Journal Club – “The silica hypothesis for homeopathy: physical chemistry”

January 1st, 2000 by Ben Goldacre in journal club | 1 Comment »

This is part of the Homeopathy journal club project described here:

www.badscience.net/?p=490

doi:10.1016/j.homp.2007.03.005 How to Cite or Link Using DOI (Opens New Window)
Copyright © 2007 Elsevier Ltd All rights reserved. The silica hypothesis for homeopathy: physical chemistry

David J. Anick1, Corresponding Author Contact Information, E-mail The Corresponding Author and John A. Ives2
1Harvard Medical School, McLean Hospital, Belmont, MA, USA
2Samueli Institute for Information Biology, 1700 Diagonal Road, Alexandria, VA, USA
Received 22 February 2007; accepted 27 July 2007. Available online 31 July 2007.

The ‘silica hypothesis’ is one of several frameworks that have been put forward to explain how homeopathic remedies, which often are diluted beyond the point where any of the original substance remains, might still be clinically effective. We describe here what the silica hypothesis says. From a physical chemistry viewpoint, we explore three challenges that the hypothesis would have to meet in order to explain homeopathy: thermodynamic stability of a large number of distinct structures, pattern initiation at low potencies, and pattern maintenance or gradual evolution at higher potencies. We juxtapose current knowledge about silicates with some of the conventional wisdom about homeopathic remedies, to see how well the latter might be a consequence of the former. We explore variants of the hypothesis including some speculations about mechanisms. We outline laboratory experiments that could help to decide it.

Keywords: homeopathy; mechanism; silica; silicate; physical chemistry

Article Outline

Introduction
Brief overview of silicates
Generation and perpetuation of remedy-specific silicates
Experiments to test the silica hypothesis
Conclusion
References


Introduction

Homeopathy has been called the third-most commonly used system of healing on the planet, and for that reason alone it deserves serious attention from the modern scientific community. As the reader of this article undoubtedly knows, many conventional scientists and doctors dismiss homeopathy as physically impossible because of the high dilutions that are commonly used. If a mother tincture (MT) contains a 1 M solution of starting substance (typically the concentration will be considerably smaller, eg sodium chloride in sea water is only 0.5 M), then a 20 ml bottle of its 12c potency has only a 1% chance of containing even a single solute molecule from that MT. For higher potencies like 30c, figures like 10−60 have been given but it is meaningless to call the concentration anything other than ‘zero’. Within conventional chemistry, a solution at concentration zero must be identical with the unprepared solvent (water or ethanol-water). The challenge is to explain or justify how one sample of concentration zero can be different from another sample of concentration zero.

The challenge is greater than scientists working on the physics or chemistry of homeopathy usually admit. There are three physical chemistry puzzles that will have to be solved before homeopathy can be considered to be ‘explained’, and this does not even include explaining how remedies influence biological systems. Generally researchers have focused on finding some measurement or test according to which remedies and controls can be told apart. As significant as a consistent finding of this kind would be, it would not be enough for homeopathy. According to homeopathic theory, the ‘vibration’ of each living thing is different, and remedies of different potencies made from the same MT are subtly different too. Helios pharmacy [www.helios.co.uk] sells 2320 different remedies, each at three to eight (or more) different potencies. It would not be enough to demonstrate that liquid water can exist in a few distinct thermodynamically stable (or meta-stable) forms. Theoretically there should be a nearly infinite variety of ‘waters,’ each one constant over a time scale of at least several minutes. In one minute the H-bond network of liquid water will undergo literally trillions of rearrangements, yet something about the sample has to be recognizably the same at the end as at the start of that minute, and yet different from ‘other remedy’ and from ‘control.’ This is the first challenge: to describe thermodynamically stable parameter(s) that not only show how remedies might differ from controls, but also how thousands of remedies can all be different from each other.

Consider two vials of pure water (in practice doubly deionized distilled water is used) each containing 198 drops (about 4 ml). To the first, two drops of pure water (from the same source) are added, making 200 drops. To the second, two drops of Sepia 29c are added. Each vial is covered and succussed. At the end, one is Sepia 30c, and the other is succussed water. To a homeopath, Sepia 30c and shaken water are as different as night and day. From a scientist’s perspective, the only difference between these samples is the 2-drop ‘seed’ added just before succussion. Other than the seed representing 1% by volume, 99% of the two samples (before succussion) were identical. If Sepia 30c is different from succussed water, then something in that seed causes the whole sample, once succussed, to come out different from what we get if the seed is not first added. And the seed is Sepia 29c, which means it too contains nothing of the starting material, and its only difference from pure water is whatever arose from succussing a seed of Sepia 28c placed in 99 parts pure water.

So this is the second challenge: whatever pattern or information is in a remedy, it must somehow ‘survive’ being mixed into 99 parts of water, and then ‘convert’ the whole sample to that same pattern (or a slightly different pattern) when the whole is succussed. The 198 drops of unprocessed fresh water must never ‘convert’ the two added drops to its ‘ordinary’ pattern.

Finally let us describe the third challenge: generation of the pattern in the first place. The first few dilutions and succussions of the MT may consist principally of diluting and mixing, since these samples would still differ from controls (and each other) by virtue of their solutes. At some stage, however, the solute must act as a seed that initiates a ‘pattern’ in the diluent to which it has been added. Perhaps this starts just as the last molecules are disappearing, around 11c, or perhaps it starts much earlier in the sequence. If it starts earlier, then some low potencies will contain both low-concentration solute and ‘patterned solvent’. It is conceivable that low-concentration solute and ‘incipient pattern’ work together to establish the ‘mature pattern’ during succussion.

Hahnemann made his remedies using glass vials, and the practice of always using glass has continued. Small amounts of silicon dioxide and ions dissolve from the glass walls into aqueous solution, during succussion. The quantities dissolved are larger for soda glass, and smaller for borosilicate glass, but there is always some. The silicates and minerals have usually been ignored as unavoidable contaminants, as something to be minimized. However Milgrom1 demonstrated that differences in T1 relaxation times between remedies and controls could be explained by different levels of dissolved silicates. Demangeat et al2 found higher than expected silica content in remedies prepared in glass vials, and more silica in certain remedies than in succussed controls.

Could vial-derived silicates be the long-sought active ingredients in remedies?

This idea, the silica hypothesis, is the subject of this article. Others have noted a possible role for silica[3], [4] and [5] in homeopathy, but it has not previously been examined at the level of detail given here. After a brief discussion of silicate structures, we will state the hypothesis and explore how well it can meet the three challenges listed above. Consideration of how biological systems might ‘read’ the information in structured silicates is beyond the scope of this article.

Brief overview of silicates

Silicon dioxide SiO2, the principal ingredient in glass, dissolves in water by combining with two H2O molecules to form a molecule of silicic acid, Si(OH)4 (Figure 1a). The solubility of silica depends on many factors. Alexander et al. demonstrated a strong temperature dependence for solubility of amorphous silica and gave a figure of around 0.010% (or 47 ppm Si) at 20 °C.6 Quartz exhibits a much lower solubility than amorphous, and the addition of small amounts of Na2O or other alkali can dramtically increase solubility.7 Two molecules of Si(OH)4 can link up, forming the dimer H6Si2O7 (Fig. 1b) by expelling a single H2O and forming a Si–O–Si bond. The Si–O–Si bond is called a siloxane bond. This reaction is called condensation or polymerization, and its reverse reaction (the splitting of a siloxane bond by H2O to make Si–OH and HO–Si) is called hydrolysis or depolymerization. The dimer can join another Si(OH)4 unit to make a trimer, and so on. The minimum-energy configuration for the gas-phase dimer has the siloxane bond bent at about 140°, but the strain is not great for angles anywhere from 130° to 150°. As a result, chains of polymerized Si(OH)4 can close, making rings, and can branch by allowing up to four siloxane bonds at each Si, creating a virtually infinite variety of polymeric species. Quartz and cristabolite are crystalline forms of (SiO2)x, and glass is an amorphous form that incorporates small quantities of other materials such as sodium or borate. ‘Silica’ is a general term for any bulk material consisting of polymerized, condensed, or crystallized SiO2. Removing one H+ from Si(OH)4 produces the H3SiO4 anion; likewise the dimer can dissociate to H+ and H5Si2O7, and so on for the more complex forms. A ‘silicate’ is any of these anionic forms, generally combined with one or more cations, or a crystalline or amorphous material composed of cations and HzSixOy anions. (Obviously we cannot pretend to do justice in a few sentences to the complexity of silica and silicate chemistry, which accounts for most of the variety of minerals in Earth’s crust.) We will refer to any HzSixOy (charge would be 4x−2y+z) that is held together entirely by Si–O and O–H covalent bonds as a ‘silicate’, regardless of its dissociation state, charge, hydration, or extent of association with cations. Our interest is in the behavior of silicates in aqueous solution, or in ethanol-water solution.


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Fig. 1. (a) Si(OH)4 monomer, optimized at B3LYP/6-311++G(3d,3p) level. (b) Si(OH)3–O–Si(OH)3 dimer, optimized at B3LYP/6-311++G(3d,3p) level.

A notation that has been used to characterize the connectivity of a Si in a silicate is Qx, with the superscript indicating the number of siloxane bonds.8 Thus Q0 is the monomer, Q1Q1 is a notation for the dimer (since each of the Si atoms is involved in a single siloxane bond), and the linear trimer would be Q1Q2Q1. The cyclic trimer is Q23; branched polymers would contain Q3‘s or Q4‘s. Q0 through Q4 have distinct signatures when a sample is examined with 29Si-NMR. The cyclic trimer is also denoted 3R for ‘3-membered ring’, and the 4R, 5R, 6R, and 8R structures are also often seen. Commonly two rings combine into a prism (‘double ring’), for which the notation would be D3R, D4R, etc. The D4R motif or cube is shown in Figure 2a.


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Fig. 2. (a) D4R cube (H’s omitted). (b) Two representations of ACO zeolite showing how the cube of Fig. 2a occurs in a repeating 3-D structure. Siloxane bonds are shown as straight rods even though they actually include an angle. One O atom is implied on each siloxane bond.

Silicate patterns that occur in natural minerals include: monomer (nesocilicates), dimer (sorosilicates), single and double chains (inosilicates including rings of 3–8 SiO2 units, the cyclosilicates), sheet (honeycomb pattern of hexagonal rings, or phyllosilicates), and framework silicate (complex 3D or tectosilicates). The last category includes the quartz group (minerals that are just (SiO2)x) and zeolites (crystals containing large pores that are typically occupied by cations). Figure 2b shows how the cube is a subunit in one zeolite structure called ACO.9

Condensation of aqueous silicic acid is slow under conditions of 20°C, 1 atm, and neutral pH. In a system with only silica and water, equilibrium of dissolved monomers with a condensed (amorphous) silica phase can take months to establish. A low-concentration system without a condensed phase produces few dimers,10 and the amount of dimer increases with pressure.[11] and [12] In a concentrated potassium silicate solution, Harris et al found 11 distinct oligomers via 29Si-NMR analysis,8 and oligomers containing up to 12 Si atoms have been identified.13 Polymerization is favored by low temperatures, high Si concentration, and low alkalinity.[14] and [15] Catalysis of polymerization by other solutes can be dramatic and will be addressed in the next section. Depolymerization and interconversion of silicate species occurs slowly at 20°C, so for practical purposes most silicate polymers can be considered to be ‘stable’ over a time frame of hours or longer.

When a sample is succussed, it is subjected to a series of brief intense shocks during which the pressure jumps for perhaps a millisecond to hundreds and probably thousands of atmospheres. Our premise is as follows. The first few succussion strokes agitate the glass walls by mechanical action and generate a saturated or supersaturated solution of silicic acid. During later succussion strokes, the momentary high-pressure shifts the equilibrium for silicic acid in favor of condensation, and polymers form. (Demangeat et al2 reported a mean Si concentration of 6 ppm for their remedies, near the solubility limit for quartz,7 with certain remedies showing consistently higher concentrations than others. Our laboratory obtained Si concentrations of 1.3 to 4.0 ppm in succussed solutions [unpublished data]. These measurements are obtained after a remedy has had some time to “settle” in its glass vial so there could be higher concentrations during and immediately after the succussion strokes.) We will later discuss how, in remedies, specific condensation patterns might be catalyzed. As the high-pressure abates, the polymers remain as polymers.

(There is also some evidence that succussion may cause larger silica units as well as Si(OH)4 to enter solution.16 We have unpublished light-microscopy and EM observations from our laboratory that indicate relatively large particles in succussed solutions. Although these are possibly due to condensation of silica units during the sample preparations, it is also likely that some large particles exist immediately after succussion.)

The ‘silica hypothesis’ for homeopathy states that remedies differ from succussed water controls and from each other, in the structure (not primarily in the quantity) of their dissolved silicates. At this point we lack experimental evidence to be more specific, but the differences could include the distribution of polymer sizes, the degree of arborization (Q3 and Q4 vs Q2), the frequency of specific motifs like 6R or D5R, or quite specific long-range patterns in larger units such as particular crystalline or zeolite forms. Characteristics such as these would be stable enough to last for at least a few minutes at ambient temperature and pressure while a remedy was being transferred to begin the next potency, or while being transferred onto lactose pellets (which would absorb the water and cease any further hydrolysis or condensation) for clinical use. In a glass bottle that would provide a baseline Si(OH)4 concentration, these ‘identifying characteristics’ of a remedy could quite possibly last for days or months, though we would expect it eventually to degrade.

Interestingly, the fact that liquid remedies are normally kept for long-term storage in 87% ethanol rather than plain water might help their stability. Hydrolysis consumes H2O, so hydrolysis incurs a higher free energy cost in hygroscopic ethanol than in water. Ethanol should slow the degradation of the ‘information’ in dissolved silicate structures, though the formation of some ethoxysilicates might be expected instead.17

Generation and perpetuation of remedy-specific silicates

Having seen how the silica hypothesis could address the first challenge, viz. the thermodynamic stability of a remedy’s ‘information’ encoded in its silicate structures, let us turn to the third challenge: generation of remedy-specific information. How feasible is it that components in the original MT could direct or catalyze remedy-specific silicate structures?

This turns out to be extremely feasible. An extensive literature already documents the capacity for both organic and inorganic solutes to direct the condensation of silicic acid into solute-specific patterns.18 Indeed, this capacity is the basis for numerous natural and commercial processes to generate specific silicate and organosilicate structures. We will review only a small part of this literature, emphasizing its relevance to pattern initiation in low-potency remedies.

For inorganic solutes, Kinradet and Pole 19 observed effects of metal cations on silicate condensation. Paired cations facilitated the approach of the negatively charged silicates so that condensation could occur. Alkali metals from Na+ to Cs+ stabilized different oligomers, with Li+–H2O interactions further enhancing polymerization in the case of Li+. Tossell 20 has explained the role of fluoride ion F in promoting the formation of D4R cubes. A comparative study of substituted ammonium, NA4+, shows markedly different results depending on whether the alkyl group A is methyl, ethyl, or propyl.[13] and [21] If A is methyl the preference is for D4R, whereas ethyl makes D3R and propyl guides the formation of the zeolite ZSM-5 [22], [23] and [24] but does not make double rings.

Organic solutes can choreograph the production of highly specific crystalline (repetitive) silicates. Diatoms, single-celled plants that live inside a silicate coat called a frustule, ‘produce an enormous variety of biosilica structures’.25 The number of known species exceeds 20,000. The silica-condensing molecules are long-chain poly-amines (LCPAs) and modified proteins called silaffins, which generate the same species-specific structures from silicic acid solutions when used in vitro. [25] and [26] Working with LCPAs including spermine and spermidine, Belton et al27 determined that ‘chain length, intramolecular N–N spacing and C:N ratio of the additives’ was responsible for ‘the combination of unique catalytic effects and aggregation behaviours’ that determined the materials’ properties. Working with amino acid silicate solutions, Belton and coworkers found that 11 of the 20 amino acid residues ‘affect the kinetics of small oligomer formation, the growth of aggregate structures and the morphology and surface properties of the silicas produced’.28

Given this information, it is tempting to imagine that almost any inorganic or organic material could guide the formation of specific silicates. Focusing on plants, which are the source of the majority of remedies in clinical use, could the particular proteins or N-containing alkaloids in a plant account for plant-specific silicates appearing in remedies made from that plant? Obviously some compounds will be more effective than others at condensing silica, eg silaffins evolved specifically for that purpose. In a low-potency remedy like a diluted 3c being succussed to make a 4c, perhaps silicic acid ‘ignores’ most plant components while allowing particular ‘active ingredients’ to catalyze the relevant structures. It would be interesting if the silica-condensing ingredients were the same as the pharmacologically active ingredients. If so, it could explain why, say, the atropine in Belladonna plays the key role in determining the properties of potentized Bell, and it would suggest that remedy made from whole plant should be essentially identical to remedy made by starting with purified atropine. It is widely believed that the homeopathic remedies Bell and Atropinum have very similar clinical activity.

We should also express some notes of caution. While it is true that inorganic and organic solutes guide silicate formation, in many cases these solutes are incorporated into the final product, eg the cations occupy the pores in a zeolite, or organic matter remains embedded in the final silicate. Or, the concentration of ‘catalyst’ is comparable to that of silicate, eg, Belton et al28 used a 2:1 molar ratio of Si to amino acid. This poses a problem for the silica hypotheses. As the remedy becomes progressively more dilute, there is less and less catalytic material available. To our knowledge, the question of how low the solute concentrations can get, and still generate significant quantities of solute-specific silica structures, has never been studied. Nor is it known how a pulse of high pressure, as in succussion, would affect the process. For the silica hypothesis to work, it would be essential that some components of the MT act as true catalysts, yielding many structured silicates per molecule, and not become trapped in individual silicate complexes. Questions can also be raised about how far the specificity of the catalysts can extend. For example atropine and hyoscyamine are enantiamers, differing solely in their orientation at a single C locus, yet Bell and Hyos are considered to be rather different remedies. Most silicates that have been studied are achiral, but some, like trigonal quartz, can be chiral.

Let us turn now to the second challenge: perpetuation of the pattern after all of the MT has been diluted away. Let us assume that a 12c remedy sample contains a measurable population of remedy-specific silicates. What happens when that remedy is diluted 1:100 and succussed? The process can begin the same way: the early succussion strokes release silicic acid from the vial walls. However there is no catalyst to condense the silicic acid—or is there? Clearly we would require that the remedy-specific silicate polymers from the prior potency serve as the catalyst. Suppose the relevant structure in the 12c were nanocrystals of a particular zeolite. We would be saying that diluting this zeolite solution 1:100, adding silicic acid, and succussing, should generate more zeolite. Indeed, we would need to have about 100 times as much zeolite nanocrystal at the end of the succussion cycle, as we had just after the 1:100 dilution. If we do not amplify the active ingredient by a factor of 100 each time, then with subsequent dilutions the amount of structured silicate will soon diminish to zero.

How feasible is it to generate particular silicates from silicic acid, by using only a seed containing already-structured silicate, and then succussing? We admit this is the weakest point of the silica hypothesis, but it is not impossible. We propose four ways it could happen. First, some silica motifs may be inherently amenable to self-replication. Perhaps a double ring like D5R has a tendency to split (hydrolyze) into two single 5R rings when vigorously shaken, and perhaps the two resulting single rings have a tendency to attract a second layer of condensation, re-creating the double ring. If so, a single succussion stroke could double the amount of D5R, and repeated succussion strokes could amplify the amount of D5R as much as 100 times. This hypothetical process would be comparable to the polymerase chain reaction for DNA. Building on the DNA analogy, in addition to double rings we could imagine a double form of any flat linear or branched silicate polymer. As noted above, single and double chains are among the naturally occurring forms of silicate in minerals. (Some cycles could be allowed too but joined rings and highly branched topologies cannot be ‘doubled’ without introducing a lot of bond angle strain.) If the double form were to ‘unzip’ like DNA, and if each half were then to act as a template to re-create the double form, we would have a mechanism for preserving the structure from one potency to the next.

This idea also permits us to see a way that remedies might change gradually with potency. For instance, if the ‘replication’ described above were not 100% perfect, but instead there was a tendency for small but predictable changes to occur, then the 13c might be subtly different from the 12c, the 14c might be slightly changed from the 13c, and so on. By ‘small but predictable changes’ we mean things like lengthening a chain by one or two units or adding a short side-branch. Small changes could function like point mutations in DNA: alterations that leave the structure mostly unchanged, and do not interfere with the capacity for replication, but which would be inherited and maintained by subsequent dilution/succussion cycles. Small changes might occur with low probability but might accumulate over many cycles, like DNA mutations, to result in a noticeably different structure with different clinical benefits. This would fit with the conventional wisdom of homeopaths that a 12c and a 13c and a 14c are not much different, but with passage of enough cycles, the 200c and the 12c can be quite different.

Second, we have alluded to silica nanocrystals as the information-carrying component. Crystals are well known for acting as seeds that can extend their pattern as other molecular units crystallize onto them. Once a particular silica crystal pattern got started, could it grow more of its own pattern when added to a silicic acid solution and succussed? We would be saying that of the 200+ known zeolite structures, if tiny nanocrystals of one zeolite are added to silicic acid and succussed, the result would be 100 times as much of that very same zeolite. This strikes us as a priori unlikely, yet it might work for at least some zeolite or other crystalline forms. We doubt the question has ever been studied.

Third, an intriguing mechanism could involve transfer of information from the silicates to structure the water during succussion, and transfer of information back from the structured water onto silicate particles, which then ‘hold’ the information when the succussion pressure abates. Zeng and coworkers29 proposed such a mechanism when they studied the well known ‘memory effect’ of water. The ‘memory effect’ does not involve homeopathy: it says that a water sample that has been crystallized under pressure into a gas hydrate, and then melted, will more quickly re-form the clathrate hydrate structure when mixed with gas and re-pressurized, compared to a water sample that did not previously experience the hydrate state. Analysis of water samples with neutron scattering could not find any structural basis for a ‘memory effect’.30 When Zeng and coworkers discovered that low concentrations of certain ice nucleation inhibitors could destroy the memory effect, they inferred that the effect was due to small impurity particles that received the ‘imprint’ of the clathrate state and, by holding that imprint long after melting and degassing, supplied a template for rapid nucleation back to the clathrate state.

Quoting Zeng et al, the memory effect ‘must be ascribed to an alteration of the surface states of the impurity particles that amplifies their nucleating action. This could occur because of an imprinting of the surface of the impurities by the growth of a hydrate crystal on the particle surfaces. For instance, if the impurities are hydrated or hydroxylated silicon or iron oxides, a hydrate crystal may well alter the surface geometry so that when the hydrate melts, the surface is now a better nucleator of hydrate than it was during the first nucleation cycle’ (emphasis added). They are explicitly postulating that silicate particles could be the information carriers that cause water, when pressurized, to form a particular pattern, and that the pattern could imprint other silicate particles. We are not proposing that water forms a momentary clathrate hydrate during succussion, but there could be other structural alterations. These alterations could start at (be nucleated by) silicate particles, could spread throughout the sample, and then imprint other silicate particles throughout the sample. The result would be an amplification, conceivably by the needed factor of 100, of the specific surface pattern on silica particles. Although the structural change in the water would be lost when the pressure returns to 1 atm, the information would persist in the silica surface changes. This explanation works best if silica is released into solution as nanoparticles, rather than as monomeric silicic acid, when agitated during succussion.

Fourth, if we postulate that silica surface carries the information, could the glass vial wall itself be that carrier? Some commercial remedies are prepared by the Korsakoff method. In this method, a single vial is used, and dilution is achieved by decanting most of the liquid and then refilling. Then the vial is succussed. A thin layer of water that wets the inside vial walls stays there when most of the liquid is decanted. This layer is estimated to be about 1% of the vial volume; so subsequent refilling accomplishes the 1:100 dilution. Asay and Kim31 found that water adsorbing onto glass at 20°C forms a three-molecule thick layer of ice. The pattern of the water adjacent to the glass will certainly be affected by alterations in the glass surface. Once a pattern is established on the vial walls, subsequent Korsakoff cycles might do nothing or might slowly alter the pattern. In order to transmit this information after the final potency is removed, however, it would have to contain some imprinted silica particles as well.

Experiments to test the silica hypothesis

The silica hypothesis and its variants are amenable to experiment and measurement to verify or negate them. Its challenges are the low concentrations at which silicates occur, and the difficulty of teasing apart chemically similar oligomers or surface features. A starting point will be to measure the amount of monomeric and polymeric silicates in remedies, in succussed water, and in diluted remedies after 0, 2, 8, 20, and 40 succussion strokes (or any similar sampling sequence). Alexander et al6 successfully used a molybdic acid assay to measure the amount of monomeric silicate, while mass spectroscopy can provide the total Si content of a sample. Obviously we would want to repeat these measurements for several different types of glass vials, and for ethanol-water vs water for the solvent.

Raman spectroscopy and 29Si-NMR provide insight into the degree of polymerization of silicates. 29Si-NMR will tell us ratios among Qx loci. Assuming we see some consistent differences among remedies or between remedies and controls, we can use these methods to ask how well homeopathically relevant substances such as atropine can serve as silicate polymerizers, and whether their condensed silicate products have consistent and substance-specific properties. The protocol would be to add a known concentration of atropine to a silicic acid solution of known concentration (in plastic vial) and succuss. Electron microscopy of frozen and cracked samples or very thin frozen layers is one way to look for suspended silica nanoparticles and to examine their surface. If surface features seem to be the information-carrying aspect, we will ultimately need to develop assays that detect particular features. Such an assay might measure adsorption of particular molecules, or enhancement or stabilization of a particular enzyme.

If early experiments lead us to suspect that remedy-specific oligomers are the information-carrying ingredient, we will ultimately need to make remedies enriched in 29Si in order to identify them via 29Si-NMR. To make a vial out of 29SiO would be prohibitively expensive, but here is an alternative. Remedies could be made by succussing them in polypropylene vials, and silica could be added in the form of small (not, vert, similar1 mm diameter) recoverable beads. The total surface of the beads could be calculated to equal that of the vial (typically an 8-, 12-, or 20-ml vial). Beads would be strained away after the last succussion stroke. It would be an open question whether such beads can be immediately reused for another remedy or potency, or whether they would be ‘imprinted’ in some way that would carry information that could affect the next remedy made with them. If remedies made via ‘succuss with silica beads in plastic’ appear via 29Si-NMR to yield similar results to ‘succuss in glass,’ the idea would be to replace the beads with 29Si-enriched beads. Now, even that would get expensive when 95% 29SiO2 runs $3 to $5 per mg. But one could coat ceramic beads with melted 29SiO2 making a layer perhaps 10–30 μm thick. This would not require too much 29SiO2 and would allow us to simulate exposure to a 29SiO2 vial. All of the resulting silicate structures would then be 29SiO2-enriched. Note that only the potencies we intend to study would have to be made with the 29SiO2 beads.

Conclusion

The clichéd scientific objection to homeopathy is that it cannot work because ‘remedies have nothing in them chemically,’ besides water. The silica hypothesis turns this objection on its head. It declares that remedies made in glass do have something else in them chemically, namely silicates, and that the silicates are not irrelevant contaminants but meaningfully structured active ingredients. According to the hypothesis, succussion releases silicic acid monomers into the solution, which are then polymerized into remedy-specific patterns by catalytic action of MT components. For potencies above 12c, structured silicates themselves act as the catalysts or templates for perpetuation of the remedy-specific patterns. In a variant on the hypothesis, silica delaminates from the glass walls in the form of nanoparticles rather than Si(OH)4 monomers, and the information is carried via silica surface alterations.

In this brief overview of the silica hypothesis we have begun to ask how the hypothesis might be able to meet three physical chemistry challenges that any explanation for homeopathy will have to overcome. Silicates can indeed form a huge variety of distinct and thermodynamically stable (for minutes or longer) structures in aqueous solution. Organic and inorganic MT components can guide selective silicate pattern formation. Structured silica seeds may be able to direct the formation of more copies of themselves, and may be capable of slowly changing or ‘evolving’ over the course of repeated dilution-succussion cycles. Gradual ‘evolution’ of silicate properties would explain the widely believed-in gradual change in clinical properties of remedies as the potency is increased.

Our overview contains many ideas that are speculations and extrapolations, and where this is the case we have admitted it. Rather than argue these points, it seems wisest to begin to collect experimental evidence that will support or negate various claims and versions of the hypothesis.

References

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8 R.K. Harris, C.T.G. Knight and W.E. Hull, Nature of species present in an aqueous solution of potassium silicate, J Amer Chem Soc 103 (1981), pp. 1577–1578. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

9 Source: www.iza-structure.org/databases/.

10 R.H. Busey and R.E. Mesmer, Ionization equilibria of silicic acid and polysilicate formation in aqueous sodium chloride solutions to 300 °C, Inorg Chem 16 (10) (1977), p. 2444. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

11 Manning CE. Polymeric silicate complexing in aqueous fluids at high pressure and temperature. In: Wanty RB, (ed.). Water–Rock Interaction I, Taylor & Francis, 2004; pp. 45–52.

12 N. Zotov and H. Keppler, Silica speciation in aqueous fluids at high pressures and high temperatures, Chem Geol 184 (2002), pp. 71–82. SummaryPlus | Full Text + Links | PDF (249 K) | View Record in Scopus | Cited By in Scopus

13 W.M. Hendricks, A.T. Bell and C.J. Radke, Effects of organic and alkali metal cations on the distribution of silicate anions in aqueous solutions, J Phys Chem 95 (1991), pp. 9513–9518. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

14 S.D. Kinradet and T.W. Swaddle, Silicon-29 NMR studies of aqueous silicate solutions. 1. Chemical shifts and equilibria, Inorg Chem 27 (1988), pp. 4253–4259.

15 X. Xue, J.F. Stebbins, M. Kanzaki, P.F. McMillan and B. Poe, Pressure-induced silicon coordination and tetrahedral structural changes in alkali oxide-silica melts up to 12 GPa: NMR, Raman, and infrared spectroscopy, Amer Mineral 76 (1991), pp. 8–26.

16 R.D. Ennis, R. Pritchard and C. Nakamura et al., Glass vials for small volume parenterals: influence of drug and manufacturing processes on glass delamination, Pharm Dev Technol 6 (3) (2001), pp. 393–405. View Record in Scopus | Cited By in Scopus

17 P.K. Jal, M. Sudarshan and A. Saha et al., Synthesis and characterization of nanosilica prepared by precipitation method, Colloids Surf A: Physicochem Eng Aspects 240 (2004), pp. 173–178. SummaryPlus | Full Text + Links | PDF (131 K) | View Record in Scopus | Cited By in Scopus

18 A. Corma and M.E. Davis, Issues in the synthesis of crystalline molecular sieves: towards the crystallization of low framework-density structures, Chemphyschem 5 (3) (2004), pp. 305–313.

19 S.D. Kinradet and D.L. Pole, Effect of alkali-metal cations on the chemistry of aqueous silicate solutions, Inorg Chem 31 (1992), pp. 4558–4563.

20 Tossell JA, Calculation of 19F and 29Si NMR shifts and stabilities of F encapsulating silsesquioxanes, preprint.

21 R.F. Mortlock, A.T. Bell and C.J. Radke, Incorporation of aluminum into silicate anions in aqueous and methanoic solutions of TMA silicates, J Phys Chem 95 (1991), pp. 7847–7851. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

22 S.L. Burkett and M.E. Davis, Mechanism of structure direction in the synthesis of Si-ZSM-5: an investigation by intermolecular 1H-29Si CP MAS NMR, J Phys Chem B 98 (1994), p. 4647. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

23 Burkett SL, Davis ME, Mechanisms of structure direction in the synthesis of pure-silica zeolites. 1. Synthesis of TPNSJ-ZSM-5, 2. hydrophobic hydration and structural specificity. Chem Mater 1995; 7: 920-928, 1453-1463.

24 C.J.Y. Houssin, C.E.A. Kirschhock and P.C.M.M. Magusin et al., Combined in situ 29Si NMR and small-angle X-ray scattering study of precursors in MFI zeolite formation from silicic acid in TPAOH solutions, Phys Chem Chem Phys 5 (2003), pp. 3518–3524. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

25 N. Poulsen, M. Sumper and N. Kröger, Biosilica formation in diatoms: characterization of native silaffin-2 and its role in silica morphogenesis, Proc Nat Acad Sci 100 (2003), pp. 12075–12080. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

26 N. Poulsen and N. Kröger, Silica morphogenesis by alternative processing of silaffins in the diatom thalassiosira pseudonana, J. Biol Chem 279 (41) (2004), pp. 42993–42999. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

27 D.J. Belton, S.V. Patwardhan and C.C. Perry, Spermine, spermidine and their analogues generate tailored silicas, J Mater Chem 15 (2005), pp. 4629–4638. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

28 D.J. Belton, G. Paine, S.V. Patwardhan and C.C. Perry, Towards an understanding of (bio)silicification: the role of amino acids and lysine oligomers in silicification, J Mater Chem 14 (2004), pp. 2231–2241. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

29 H. Zeng, L.D. Wilson, V.K. Walker and J.A. Ripmeester, Effect of antifreeze proteins on the nucleation, growth, and the memory effect during tetrahydrofuran clathrate hydrate formation, J Am Chem Soc 128 (2006), pp. 2844–2850. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

30 P. Buchanan, A.K. Soper and J. Thompson et al., Search for memory effects in methane hydrate: Structure of water before hydrate formation and after hydrate decomposition, J Chem Phys 123 (2005), p. 164507. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

31 D.B. Asay and S.H. Kim, Evolution of the adsorbed water layer structure on silicon oxide at room temperature, J Phys Chem B 109 (2005), pp. 16760–16763. View Record in Scopus | Cited By in Scopus

Corresponding Author Contact InformationCorresponding author. DJ Anick, Harvard Medical School, McLean Hospital, Centre Bldg 11, Belmont, MA 02478, USA.



Homeopathy
Volume 96, Issue 3, July 2007, Pages 189-195
The Memory of Water

Journal Club – “The possible role of active oxygen in the Memory of Water”

January 1st, 2000 by Ben Goldacre in journal club | 2 Comments »

This is part of the Homeopathy journal club described here:

www.badscience.net/?p=490

doi:10.1016/j.homp.2007.05.003    How to Cite or Link Using DOI (Opens New Window)
Copyright © 2007 Elsevier Ltd All rights reserved. The possible role of active oxygen in the Memory of Water

Vladimir L. VoeikovCorresponding Author Contact Information, a, E-mail The Corresponding Author
aFaculty of Biology, Lomonosov Moscow State University, Moscow 119234, Russia
Received 13 April 2007;  accepted 4 May 2007.  Available online 31 July 2007.

Abstract

Phenomena of long-term ‘memory of water’ imply that aqueous systems possessing it remain for a long period after the initial perturbation in an out-of equilibrium state without a constant supply of energy from the environment. It is argued here that various initial perturbations initiate development of a set of chain reactions of active oxygen species in water. Energy, in particular high grade energy of electronic excitation, released in such reactions can support non-equilibrium state of an aqueous system. In principle, such reactions can continue indefinitely due to specific local structuring of water with even minute ‘impurities’ that are always present in it and by continuous supply of oxygen amounts due to water splitting. Specific properties of several real aqueous systems, in particular, homeopathic potencies in which such processes could proceed, are discussed. The role of coherent domains in water in maintenance of active oxygen reactions and in emergence of oscillatory modes in their course is considered.

Keywords: active (reactive) oxygen species; water splitting; electronic excitation; homeopathy; nanoparticles; coherent domains

Article Outline

Introduction
Long-term effects of physical factors upon the properties of water
Water, a two-faced Janus: Pro- and anti-oxidant activity of water
Water participation in chain reactions
Oscillatory nature of reactions with active oxygen participation
Conclusion
References


Introduction

‘Memory of water’ is a popular idiom meaning long-term effects of various physical factors upon physical–chemical properties and biological activity of aqueous systems. The phenomenon of ‘water memory’ is on area of heated debate. The particular case of ‘water memory’ controversy is homeopathy. Its assertion that a homeopathic preparation can hardly contain a single molecule of an initial biologically active material but retain biological activity cannot be explained in the frame of the current biochemical and pharmacological paradigm. According to the latter a medicine exerts its action due to local interactions of active substantial principles present in a medication with appropriate biomolecules (enzymes, receptors, etc.). Specificity of these interactions is due to complementarities of electronic landscapes of interacting due to species. Specific binding of an appropriate ligand to the particular ‘receptor’ induces its conformational change, necessary for the development of a downstream chain of reactions.

It is generally considered that there is no problem in energy supply and transformation for performance of this chemical work. Conformational change in the receptor is supposed to be provided by energy released as a drug binds to it. Chemical work associated with all the downstream reactions of a cell is supported by energy supplied by metabolism. This reasoning tacitly implies the initial non-equilibrium state of the whole system: drug+a target cell.

From this perspective homeopathy seems improbable for several reasons. One of them is bewilderment about how a preparation not containing a single biologically active molecule from its original solution or tincture exerts any specific biological effect (the problem of specificity). Claims that the original molecular principle somehow leaves its imprint in water contradicts the textbook model of water, according to which water cannot retain any ‘memory’ after a perturbation due to fast relaxation to an equilibrium state for the given ambient conditions.

Thus, one of the key questions related to the problem of ‘water memory’ is the question whether water is a substance that after a perturbation does not easily relax to the original state and under special circumstances can even further move away from the equilibrium state? If so, what mechanisms provide for its stable non-equilibrium state? If one can answer these questions, the question of the specificity of homeopathic preparations may be solved more easily.

Here the hypothesis is presented that due to water’s capability to transform low grade energy (eg, mechanical) into high grade energy of electronic excitation and due to its dual oxidant–reductant nature, water may remain in a non-equilibrium (dissipative) state for a very long time.

However, before we go further clarity about the word ‘water’ should be introduced. ‘Water’ is never pure H2O. Real water always contains impurities: products of its ionization (H+ and OH), ions, dissolved gases, and traces of other substances. Even ultra-pure water is kept in a vessel. Water properties in the vicinity of its walls (interfacial water) may significantly differ from those in ‘bulk’ water and from those at a water/gas (air) interface. Unlike common belief that effects of solid surfaces with which water is in contact vanish on a nanometre scale, new evidence shows that they may propagate at distances of tens and hundreds of microns.1

Long-term effects of physical factors upon the properties of water

Currently there is no shortage in evidence of long-term effects of physical factors, such as static and oscillating magnetic and electromagnetic fields, mechanical stirring and vibrations, sonication, etc. upon the properties of water. Here we will refer to only few of these studies that are seriously substantiated and relevant for further discussion of the role of active oxygen species in water memory.

In more than a decade of study of the effects of vigorous succussion and extreme serial dilutions in bi-distilled water or different aqueous solutions. Elia and co-workers found that already the third centesimal dilutions prepared with vigorous succussion demonstrated significant excess in heat release upon mixing with dilute alkali or acid and significant increase in electrical conductivity over unsuccussed solvent or dilutions.2 Even more important was that these differences did not attenuate or vanish with time, but rather magnified in all the samples during several weeks of storage. Differences did not disappear even after several years of storage, and the smaller the volume of stored samples, the larger was the deviation.3 Elia et al establish that “these extremely diluted solutions (EDS), after strong agitation (succussion), enter a far from equilibrium state and remain there or get even farther by dissipating energy in the form and amount necessary to stay in a far from equilibrium state. What is the source of dissipating energy that does not exhaust for several years?

Elia et al acknowledge that in the process of vigorous succussion of aqueous samples traces of substances may be released by the glass of the containers, and these traces are able to ‘activate’ the EDS. Strong support for the suggestion that a long-term perturbation of aqueous systems treated by a physical factor depends on nano-‘impurities’ is provided by the recent seminal paper of Katsir and co-authors.4 They demonstrated that radio-frequency treatment (in the megahertz frequency range) of aqueous solutions can dramatically change their properties expressed, in particular, in peculiar patterns of electrochemical deposition of zinc sulphate solutions. Again, it takes some time after irradiation for the aqueous system to change its properties. The effects of radio-frequency treatment of solutions lasted for hours. If ultra-pure water used as a solvent was doped under radio-frequency treatment with barium titanate nanoparticles (diameter range 10–100 nm) special properties of zinc sulphate solutions prepared on such water were amplified and lasted for months. Saturation concentration for nanoparticles in irradiated water did not exceed 10−12 M; at higher concentrations they clump and sediment. As it takes many hours for the emergence of special properties of nanoparticle-doped water (NPD) the authors assume that water goes through a self-organization process.

The findings of Katzir and co-authors have much in common with the research into physical–chemical properties and biological activity of aqueous dispersions of Fullerene C60. Since the discovery of fullerenes a lot of surprising biomedical effects both in vivo and in vitro were reported. Those include antiviral (in particular, anti-HIV), anti-bacterial, anti-tumour, anti-oxidant, and anti-apoptosis effects among others.5 In most cases hydrophilic C60 derivatives were used because pristine fullerenes C60 are considered to be water-insoluble. Andrievsky et al developed a procedure for preparing molecular–colloidal solution of pristine C60, with the help of ultrasonic treatment of fullerene water suspension. It contains both single fullerene molecules and small clusters.6 In such ‘fullerene–water-systems’ (FWS) single C60 molecules and their clusters do not precipitate because they are covered with water shells in which water molecules are absorbed so strongly that water is not completely lost even in vacuum of 10−3 Pa. FWS do not have toxic effects and possess strong biological activity even in dilutions down to 10−9 M.7 Andrievsky ascribes the wide spectrum of beneficial biological effects of FWS to their strong ‘anti-oxidant’ activity that is also ascribed to aqueous solutions of hydrophilic fullerenes5 (we will discuss below what ‘antioxidant activity’ really means).

Water systems described above: ‘EDS’ of Elia et al, ‘NPD’ of Katzir et al, and ‘FWS’ of Andrievsky et al have much in common, though they are prepared using quite different procedures and have completely different chemical composition. On the one hand, in the course of their preparation basically the same procedure is used—physical treatment of water causing cavitation in it (‘cavitation’ is the emergence of gas-filled cavities and bubbles in a liquid and vigorous change of their volume and behaviour depending upon local pressure changes). Katzir et al, ascribe the “anomalous effects of radio-frequency treatments of water and aqueous solution to the formation of pliable network of gas nanobubbles that has special hierarchical organization effect”. They suggest that much more long-term changes in the properties of NPD than in irradiated water or simple aqueous solutions is explained by replacement of less stable nanobubbles with stable barium titanate nanoparticles. Succussion used for the preparation of EDS and ultrasound treatment of water used for the preparation of FWS also produce cavitation in water. In all three systems water becomes ‘doped’ with nanoparticles. In the case of EDS they are supposedly represented by silica oxide, in NPD—with barium titanate, and in the third case—with fullerenes. At least in the last two cases it has been demonstrated that nanoparticles serve ‘kernels’ around which water shells with properties very different from those characteristic for usual ‘bulk’ water originate. And for FWS so-called ‘anti-oxidant’ properties were demonstrated.

Water forming shells around nanoparticles is ‘gel-like’ and the shell may extend up to a micron in range (at least in the case of NPD). Thus, it is difficult to explain physical–chemical (‘anti-oxidant’) and biological activity of all these aqueous systems by chemical properties of ‘impurities’—nanoparticles that are so chemically different and rather inert. It is much more plausible that this activity is based on a specific structuring of interfacial water. But how can such ‘gel-like’ (or ‘ice-like’) water structures provide for stable non-equilibrium, energy dissipative properties of aqueous systems?

Water, a two-faced Janus: Pro- and anti-oxidant activity of water

Until recently water was considered just as a solvent in which biochemical processes go on and as a fluid used to transport different substances throughout the body. Though ‘anomalous’ properties of water, its role in base–acid equilibrium, its direct participation in the reactions of hydrolysis and photosynthesis is generally acknowledged, the much deeper fundamental role of water in practically all chemical reactions is neglected. Yet the discovery that water is the catalyst of at least oxidative reactions was made as long ago as in 18th century. In 1794 a British researcher, Elizabeth Fulhame published in London a book entitled ‘An Essay on Combustion’. Based on her own studies she stated that “hydrogen of water is the only substance, that restores oxygenated bodies to their combustible state; and that water is the only source of the oxygen, which oxygenates combustible bodies” (cited after [8]). For example, to explain the combustion of charcoal she suggested that “the carbon attracts the oxygen of the water, and forms carbonic acid, while the hydrogen of the water unites with oxygen of the vital air, and forms a new quantity of water equal to that decomposed”:

Click to view the MathML source

Thus, water according to Fulhame is both pro-oxidant (it oxidizes a fuel) and anti-oxidant (it reduces oxygen).

Though the discovery of Fulhame was soon forgotten, chemists of the 19th century acknowledged that water is necessary for oxidation (oxygenation) even of easily combustible bodies. They knew that metallic sodium and potassium do not lose their metallic luster in an atmosphere of dry oxygen, and that carbon, sulphur, and phosphorus burn under very dry conditions at much higher temperatures than in humid air.9 However, until the beginning of the 21st century, when it was rediscovered that water can ‘burn’—be oxidized by singlet oxygen10 this ‘mysterious’ property of water was neglected. It was also proved by quantum chemical modelling that water oxygenation is catalysed by water.11

Water participation in chain reactions

How are catalytic and red/ox properties of water related to the phenomenon of water memory? Above it has been argued that water forming shells around nanoparticles is ‘gel-like’, so it has features of a polymeric substance. It is well known that polymers can undergo chemical transformations under the action of mechanical impacts, freezing–thawing and fast temperature variations, action of audible sound and ultrasound, and of other low density energy forces too weak to induce chemical reactions in monomers or short oligomers. Polymers may accumulate and concentrate mechanical energy to densities that comprise energy quanta sufficient to excite and break down their internal covalent bonds. Unpairing of electrons and appearance of a pair of free radicals results in the development of new reactions.12

Based on the presumption that liquid water contains quasi-polymeric structures Domrachev et al investigated the effect of low density energy physical factors on homolytic water dissociation (H—O—H→HOradical dot+radical dotH, cf. ionic water dissociation: H—O—H→H++OH). It was shown that water freezing–thawing, evaporation–condensation, sonication even with audible sound, filtration through narrow capillaries resulted in an increase of H2O2 even in ultra-pure and carefully degassed water. Efficiency of water splitting resulting from water filtration through narrow capillaries (where a significant part of it forms interfacial water) was more than 100 times greater than photodissociation with far UV-light.13 Yield of H2O2 in water containing ions and dissolved oxygen was much higher, and notably, H2O2 concentration continued to grow in water containing dissolved oxygen for some time after the completion of any treatment, as if it ‘remembered’ it.

In the case of a single water molecule in a mechanically excited polymeric entity being split:

(H2O)n(H–|–OH)(H2O)m→(H2O)n(H↓)+(↑OH)(H2O)m, (1)

the initial products of water splitting are free radicals H↓ and ↑OH (here we symbolize a given electron as ↑ or ↓ to stress their alternative spin states). In most cases this singlet pair of radicals recombines back to water:

H↓+↑OH→H2O. (2)

However, even in such a case this is not just a reverse, equilibrium reaction because water splitting has been achieved under the action of mechanical forces while back recombination of radicals gains an energy quantum of 5.2 eV. In condensed and organized media (such as water), long-range energy transfer of electronic and vibrational excitation has been demonstrated already in 1930s–1950s by J. Perrin, S. Vavilov, Th. Foerster, A. Szent-Giorgyi, and others. This phenomenon was recently confirmed with new techniques.14

The probability of radicals moving away from each other significantly increases when dissolved gases and other molecules and particles are present in water, especially in cases when multiple layers of water are organized by surfaces which it hydrates and when these layers move relative to each other at different rates (consider a vortex as an example). Here, a rich set of reactions may proceed, for example:

HO↑+HO↓→H2O2, (3)

H↑+↓H→H2, (4)

Hradical dot+O2→HO2radical dot, (5)

HO2↑+HO2↓→H2O2+O2, (6)

2H2O2→2H2O+O2. (7)

Besides these more or less stable products exotic metastable substances may appear, for example: HOOOH, H2O4, HOO–HOOO, HOOH–OOO, etc. Reactions 6 and 7 in which oxygen molecules are released are notable as they provide evidence that oxygen may abiogenically arise from water under very mild conditions. What is also important is that this ‘newborn’ oxygen arises in an activated, singlet state.

It should be reminded that O2 is unique among molecules because in its ground state its two electrons are unpaired [O2(↑↓)2↑↑ or O2(↑↓)2↓↓] (besides, an oxygen atom also has two unpaired electrons). Thus, oxygen molecule is a bi-radical (in fact it is a tetra-radical) and it represents a vast store of energy. But the laws of quantum physics forbid direct reactions of bi-radicals (they are also called particles in a triplet state) with molecules in which all electrons are paired (singlet state particles). That is why oxygen needs to be activated to release its energy reserve.

There are a few ways for O2 to be activated. It may be excited by an appropriate energy quantum (greater-or-equal, slanted1 eV) and turn into a highly reactive singlet oxygen (O2(↑↓), also denoted, 1O2). A peculiar feature of 1O2 is that this electronically excited species may relax only to triplet state because oxygen, unlike other substances does not have ground singlet state. Since singlet–triplet transition is ‘forbidden’ by quantum physics laws, the lifetime of excited singlet oxygen is usually much longer than that of any other molecule in an excited singlet state. Probably that is why the reaction of singlet oxygen with water goes with sufficiently high probability—1O2 is long-living enough to find an appropriate catalytic environment for water oxidation.

On the other hand, triplet oxygen easily reacts with free radicals—atoms and molecular particles with an odd number of electrons. In these reactions oxygen gains an electron, turns into a mono-radical which can easily take new electrons releasing large quanta of energy at each consecutive step of one-electron reduction.

The principal property of free radical reactions in which O2 participates is that they may easily turn into a branching (or run-away) process.15 Several specific features distinguish branching chain reactions (BCRs) from ‘normal’ chemical reactions.16

First, the quantum yield (the ratio of the quantity of reaction events to the quantity of quanta that initiated the initial reaction events) is extremely high.

Second, BCR often start to develop after an induction period, long after the completion of the initiating stimulus impact. (Development of BCR is expressed in exponential growth of reaction centres represented usually by free radicals, until the rates of their production and annihilation equalize).

Third, the reaction proceeds at a very low rate below and above threshold values of critical parameters: temperature, volume of the reaction mixture or ratio of the reaction mixture volume to the surface of the reaction vessel, concentrations of reagents, etc.

The fourth specific feature of BCR is a very strong accelerating or rate-retarding effect of certain minute admixtures in the reaction mixture.

Fifth, large deviation of kinetics of BCR from classical laws of chemical kinetics—Arrhenius temperature law and the law of mass action—is observed at certain stages of BCR development.

Finally, as long as a BCR proceeds it serves as a source of high density energy—energy of electronic excitation, equivalent to quanta of visible or UV light, because free radical recombination events (recombination of unpaired electrons) are highly exergonic. That is why the reaction systems in which such reactions occur are often chemiluminescent.

In the gaseous phase BCRs usually develop as explosions. However, in condensed phases a lot of red/ox-reactions with O2 participation meet many criteria of the BCRs though they develop and proceed without termination for an extremely long time. Semyonov16 suggested that these reactions go on as linear chain reactions in which chains do not branch:

Rradical dot+RH→RH+Rradical dot;Rradical dot+RH→RH+Rradical dot;Rradical dot+Rtriple primeH→Rtriple primeradical dot+cdots, three dots, centered,

where Rn· is a free radical with an unpaired electron, and RmH is a molecule which it oxidizes.But if a free radical is in turn oxidized with a bi-radical molecule oxygen, a peroxide radical, ROO·, is produced. When it oxidizes a certain molecule, a metastable and energy-rich peroxide (ROOH) is produced in addition to a new radical, which provides for chain propagation. Usually low energy of activation is needed for decomposition of peroxides at which two new active centres, RO· and ·OH emerge. Thus, even if a ‘parent’ chain is eliminated, the system in which peroxides appear stays ‘charged’ and new chains arise in it sometimes after a very slight perturbation. Such reactions are named “chain reactions with delayed branching” (CRDB). Systems in which CDRB go on are intrinsically non-equilibrium, though at a first sight may seem to be at rest.

Evidence is accumulating that very slow CRDB may under ‘appropriate conditions’ readily develop in water. As mentioned above, quantum chemical calculations show that if water is organized in a favourable way (water molecules are arranged in space, in particular, in relation to singlet oxygen and to each other), the energy of activation for oxidation of a water molecule with singlet oxygen diminishes to reasonable values. The immediate products of water oxidation are exotic and highly energy-rich peroxides such as HOOOH, HOOOOH, HOO–HOOO.11 All these peroxides are typical active oxygen species. They easily decompose giving birth to new free radicals, initiating propagation of new chains, or to ozone, generating new singlet oxygen molecules. Stationary levels of all these active oxygen species are extremely low due to their instability, but since water is never devoid of molecular oxygen (recall that any perturbation of water gives birth to oxygen and hydrogen at a non-zero probability), high energy quanta-generating processes never completely fade out.

We observed that in the course of CRDB of slow oxidation of amino acids in aqueous solutions initiated with H2O2 addition or with low intensity UV-irradiation, concentration of H2O2 increases to levels that can be explained only by water oxidation with O2.17 Recently, it has been shown that in water containing carbonates and phosphates18 or in water bubbled with noble gases, such as argon,19 concentration of H2O2 spontaneously increases and its augmentation goes on faster if water is stirred. Using chemiluminescent methods we also found that such processes spontaneously develop and proceed for an indefinitely long time in aerated mineral waters from natural sources.20 Also is it was mentioned above H2O2 yield in pure water equilibrated with air under the conditions favourable for its splitting13 occurs faster, continues longer after initial perturbation, and reaches higher levels than in degassed water.

Oscillatory nature of reactions with active oxygen participation

At the beginning of this essay a question was asked: is water a special case of a substance that can stay after a perturbation for a sufficiently long time out of equilibrium with the environment required by the second law of thermodynamics, and if it can, what mechanisms provide its stable non-equilibrium state? According to the theory developed by Del Giudice et al based on the principles of quantum electro-dynamics coherent domains of sub-micron (‘nano’) dimensions spontaneously emerge in water and coexist in it together with non-coherent dense water ‘gas’.21 According to this theory water particles within a coherent domain oscillate coherently between two states belonging to individual spectrum of these states. Calculations show that two relevant levels involved in a coherent oscillation are separated by an energy of 12.06 eV whereas the ionization threshold of the water molecule is 12.6 eV, that is only 0.54 eV below ionization threshold.22 Del Guidice pointed my attention to the fact that, provided that this threshold is overcome, coherent domains (CD) may tunnel ‘hot’ electrons in the non-coherent surroundings where they stick to oxygen molecules thus initiating chain reactions described above.23

Turning back to the three examples of stable non-equilibrium aqueous system mentioned earlier: ‘extremely diluted solutions’, ‘nanoparticle doped water’, and ‘FWS’, one may suggest that water shells surrounding nanoparticles present in these systems represent stable coherent domains that may supply electrons to oxygen. Energy of electronic excitation released due to oxygen reduction and free radical reactions may serve as activation energy for additional release of electrons from a CD. When too many electrons are extracted from a CD, it dissipates. Chain reactions terminate though metastable products of CDRB stay in a system. During this period water shells begin to build up around nanoparticles and as soon as they turn into CDs the latter again start to supply electrons to oxygen. This hypothetical scenario shows how complex oscillations of energy of electronic excitation generation, of red/ox potentials, and of other properties of aqueous systems may originate in systems where coherent water domains reduce oxygen, and its active species are present. The frequency range of oscillations varies from the optical region, characteristic for electronic excitation, to extremely low frequencies of oscillations of other parameters of the system. Thus, aqueous systems in which chain reactions with the participation of active oxygen proceed may serve as emitters and receivers of oscillatory signals in an extremely wide frequency range.24 This to our mind is a necessary condition for homeopathic potencies to exert its action on living systems.

Conclusion

It is now evident that a substantial part of oxygen consumed by all aerobic organisms is one-electron reduced, and that all the processes in which active oxygen species participate described above in connection with inanimate aqueous systems in principle take place in living systems. The indispensable role of active oxygen species in regulation of practically all physiological processes is no longer disputed. According to our point of view their ubiquitous regulatory role is paradoxically provided by extremely fast elimination of active oxygen by multiple ‘anti-oxidant’ systems as soon as they emerge. As we reasoned elsewhere25 evidence is accumulating that the energy of electronic excitation generated by unpaired electrons pairing may be utilized as energy of activation of particular biochemical reactions, as regulatory signals, and in special cases as the major source of energy for performing physiological functions. Since oscillatory patterns are characteristic for all processes in which active oxygen participate, both insufficient production of active oxygen and distortions in its use may result in derangement of oscillatory patterns of biochemical and physiological processes and their malfunction. External resonators such as homeopathic medicines may restore normal patterns of deranged processes. However, the problem of high specificity of particular homeopathic medicines needs further reflection.

References

1 J. Zheng and G.H. Pollack, Solute exclusion and potential distribution near hydrophilic surfaces. In: G.H. Pollack, I.L. Cameron and D.N. Wheatley, Editors, Water and the Cell, Springer, Dordrecht (2006), pp. 165–174.

2 V. Elia, S. Baiano and I. Duro et al., Permanent physico-chemical properties of extremely diluted aqueous solutions of homeopathic medicines, Homeopathy 93 (2004), pp. 144–150. SummaryPlus | Full Text + Links | PDF (154 K) | View Record in Scopus | Cited By in Scopus

3 V. Elia, L. Elia and E. Napoli et al., Conductometric and calorimetric studies of serially diluted and agitated solutions: the dependence of intensive parameters on volume, Int J Ecodyn 1 (2006), pp. 1–12.

4 Y. Katsir, L. Miller and Y. Aharonov et al., The effect of rf-irradiation on electrochemical deposition and its stabilization by nanoparticle doping, J Electrochem Soc 154 (2007), pp. D249–D259. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

5 Freitas Jr RA. Fullerene-based pharmaceuticals. Nanomedicine, Vol IIA: Biocompatibility. Georgetown, TX: Landes Bioscience, 2003 [chap 15.3.2.3].

6 G.V. Andrievsky, V.K. Klochkov and A. Bordyuh et al., Comparative analysis of two aqueous–colloidal solutions of C60 fullerene with help of FTIR reflectance and UV–Vis spectroscopy, Chem Phys Lett 364 (2002), pp. 8–17. SummaryPlus | Full Text + Links | PDF (339 K) | View Record in Scopus | Cited By in Scopus

7 G.V. Andrievsky, V.K. Klochkov and L.I. Derevyanchenko, Is C60 fullerene molecule toxic?!, Fuller Nanotub Car N 13 (2005), pp. 363–376. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

8 K.J. Laidler and A. Cornish-Bowden, Elizabeth Fulhame and the discovery of catalysis. In: A. Cornish-Bowden, Editor, New Beer in an Old Bottle: Eduard Buchner and the Growth of Biochemical Knowledge, Universitat de Valencia, Valencia (1997), pp. 123–126.

9 A.N. Bach, On the role of peroxides in the processes of slow oxidation, Zh Russ Phys-Chem Soc 29 (1897), pp. 373–395.

10 P. Wentworth Jr, L.H. Jones and A.D. Wentworth et al., Antibody catalysis of the oxidation of water, Science 293 (2001), pp. 1806–1811.

11 X. Xu, R.P. Muller and W.A. Goddard 3rd, The gas phase reaction of singlet dioxygen with water: a water-catalyzed mechanism, Proc Nat Acad Sci USA 99 (2002), pp. 3376–3381. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

12 N.K. Baramboim, Mechanochemistry of High Molecular Weight Compounds, Chimiya, Moscow (1971).

13 G.A. Domrachev, G.A. Roldigin and D.A. Selivanovsky, Mechano-chemically activated water dissociation in a liquid phase, Proc Russ Acad Sci 329 (1993), pp. 258–265. View Record in Scopus | Cited By in Scopus

14 S. Woutersen and H.J. Bakker, Resonant intermolecular transfer of vibrational energy in liquid water, Nature 402 (1999), pp. 507–509. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

15 V.L. Voeikov and V.I. Naleto, Weak photon emission of non-linear chemical reactions of amino acids and sugars in aqueous solutions. In: J.-J. Chang, J. Fisch and F.-A. Popp, Editors, Biophotons, Kluwer Academic Publishers, Dordrecht (1998), pp. 93–108.

16 N.N. Semyonov, Chemical Kinetics and Chain Reactions, Oxford University Press, Oxford (1935).

17 V.L. Voeikov, I.V. Baskakov and K. Kafkialias et al., Initiation of degenerate-branched chain reaction of glycin deamination with ultraweak UV irradiation or hydrogen peroxide, Russ J Bioorg Chem 22 (1996), pp. 35–42. View Record in Scopus | Cited By in Scopus

18 V.I. Bruskov, A.V. Chernikov and S.V. Gudkov et al., Activation of reducing properties of anions in sea water under the action of heat, Biofizika 48 (2003), pp. 1022–1029.

19 V.L. Voeikov and M.V. Khimich, Amplification by argon of luminol-dependent chemiluminescence in aqueous NaCl/H2O2 solutions, Biofizika 48 (2002), pp. 5–11. View Record in Scopus | Cited By in Scopus

20 V.L. Voeikov, R. Asfaramov and V. Koldunov et al., Chemiluminescent analysis reveals spontaneous oxygen-dependent accumulation of high density energy in natural waters, Clin Lab 49 (2003), p. 569.

21 E. Del Giudice, G. Preparata and G. Vitiello, Water as a free electric dipole laser, Phys Rev Lett 61 (1988), pp. 1085–1088. Full Text via CrossRef

22 R. Arani, I. Bono and E. Del Giudice et al., QED Coherence and the thermodynamics of water, Int J Mod Phys B 9 (1995), pp. 1813–1841. Full Text via CrossRef

23 E. Del Guidice, A. De Ninno and M. Fleischmann et al., Coherent quantum electrodynamics in living matter, Electromagn Boil Med 24 (2005), pp. 199–210.

24 V.L. Voeikov, Fundamental role of water in bioenergetics. In: L.V. Beloussov, V.L. Voeikov and V.S. Martynyuk, Editors, Biophotonics and Coherent. Systems in Biology, Springer, New York (2006), pp. 89–104.

25 V.L. Voeikov, Reactive oxygen species (ROS): pathogens or sources of vital energy? Part 1. ROS in normal and pathologic physiology of living systems, J Alt Compl Med 12 (2006), pp. 111–118. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus
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Corresponding Author Contact InformationCorrespondence: Vladimir L. Voeikov, Faculty of Biology, Lomonosov Moscow State University, Moscow 119234, Russia.



Homeopathy
Volume 96, Issue 3, July 2007, Pages 196-201
The Memory of Water

Journal Club – “The octave potencies convention: a mathematical model of dilution and succussion”

January 1st, 2000 by Ben Goldacre in journal club | 2 Comments »

This is part of the Homeopathy journal club described here:

www.badscience.net/?p=490

doi:10.1016/j.homp.2007.03.008    How to Cite or Link Using DOI (Opens New Window)
Copyright © 2007 Elsevier Ltd All rights reserved. The octave potencies convention: a mathematical model of dilution and succussion

David J. AnickCorresponding Author Contact Information, a, E-mail The Corresponding Author
aHarvard Medical School, McLean Hospital, Centre Bldg. 11, 115 Mill St., Belmont, MA 02478, USA
Received 22 February 2007;  accepted 27 March 2007.  Available online 31 July 2007.

Several hypothesized explanations for homeopathy posit that remedies contain a concentration of discrete information-carrying units, such as water clusters, nano-bubbles, or silicates. For any such explanation to be sustainable, dilution must reduce and succussion must restore the concentration of these units. Succussion can be modeled by a logistic equation, which leads to mathematical relationships involving the maximum concentration, the average growth of information-carrying units rate per succussion stroke, the number of succussion strokes, and the dilution factor (x, c, or LM). When multiple species of information-carrying units are present, the fastest-growing species will eventually come to dominate, as the potency is increased.

An analogy is explored between iterated cycles dilution and succussion, in making homeopathic remedies, and iterated cycles of reseeding and growth, in bacterial cultures. Drawing on this analogy, the active ingredients in low and medium potency remedies may be present at early dilutions but only gradually come to ‘dominate’, while high potencies may develop from the occurrence of low-probability but faster-growing ‘mutations.’ Conclusions from this model include: ‘x’ and ‘c’ potencies are best compared by the amount of dilution, not the amount of succussion; the minimum number of succussion strokes needed per cycle is proportional to the logarithm of the dilution factor; and a plausible interpretation of why potencies at approximately regular ratios are traditionally used (the octave potencies convention).

Keywords: dilution factor; succussion; mathematical model; logistic curve; competition

Article Outline

Introduction
Modeling succussion
Two active ingredients
Multiple active ingredients
High potencies
Conclusion
References


Introduction

Homeopathic remedies are made by iterated dilution (in water or ethanol–water) and succussion (vigorous repeated pounding of the closed vial against a firm surface), starting from a mother tincture (‘MT’), most often a plant or animal extract. Hahnemann experimented mainly with 1:9 (‘x’), 1:99 (‘c’), and 1:50 000 (‘LM’) dilutions. These have become, by convention, the dilution ratios that are used in commercially available remedies. We will call the volume increase during dilution the ‘dilution factor’ and denote it as H. Thus, H=10 for ‘x’ remedies, H=100 for ‘c’ remedies, and H=50 001 for ‘LM’ remedies.

The number of dilution–succussion cycles is the potency of the remedy, denoted P. Within homeopathic practice, while it is theoretically possible to give a patient any potency of a remedy, only certain potencies are normally available and stocked. For the ‘x’ series these are the ‘6’, ‘12’, ‘30’, and ‘200’ potencies, while for the ‘c’ series one can get ‘6’, ‘12’, ‘30’, ‘200’, ‘1000’, and ‘10 000’. Although in other homeopathic traditions different series may be used, there is a similar progression. LM’s start with LM1 and every potency is available (i.e. LM2, LM3, LM4, etc.) up to LM10 or so. The potencies most frequenty dispensed in practice (at least in the Anglo-American tradition), by far are the 6c and 12c (‘low potencies’), 30c and 200c (‘medium potencies’), and 1000c and 10 000c (‘high potencies’). Homeopaths generally believe that remedies gain strength with more dilution–succussion cycles, although there are believed to be qualitative differences: ‘stronger’ is not necessarily ‘better’. Posology, or how to decide what potency to give, is a complex subject about which there are many theories. In general, higher potency remedies are used when the remedy choice is more certain, when the patient’s vital force is stronger, and when the problem is chronic rather than acute.

Is there any rationale for the sequence: 6, 12, 30, 200, 1000, 10 000? The sequence bears some resemblance to a geometric progression, and the use of fixed potencies with (supposedly) approximately equal ratios is called the ‘Octave potencies convention’ (OPC). I wondered, could there possibly be a rationale for the OPC? The usual thinking about this is that the remedy’s qualities change gradually with potency, eg a 12c and a 13c are nearly the same, and 13c and 14c are nearly the same, but enough small changes accumulate in going from 12c to 30c, that 30c may bring different results in the clinic from 12c. While a 12c and a 13c are ‘nearly the same’, a 1000c and a 1001c would be considered to be clinically interchangeable.

Various hypotheses have been put forward to ‘explain’ homeopathy in terms of conventional physics and chemistry. ‘Local’ hypotheses posit that remedies differ from untreated water in that they contain a population or concentration of an active ingredient. For some explanations, the active ingredient is a (hypothetical) persistent structural feature in what is chemically pure water, such as a zwitterion,1 a clathrate,2 or nano-bubble.3 The ‘silica hypothesis’ posits that SiO2 derived from the glass walls of the succussed vials is condensed into remedy-specific oligomers or nanocrystals, or else that silica nanoparticle surface is modified in patches to carry remedy-specific information.4

The mathematical model developed here is compatible with any of these explanations. Let Q denote the concentration of ‘active ingredient’. Depending on the hypothesis, Q could be the concentration of a particular zwitterion, of a particular species of nano-bubble, of a particular silica oligomer (or family of oligomers), or of a specific silica nanoparticle surface feature. Note that the concentration of active ingredient in ordinary solvent is zero or is assumed to be negligible. Right after dilution, the concentration will be Qdil=Q/H.

The fundamental assumption underlying our mathematical model is the following. Since a 1000c and 1001c are (essentially) identical, we assume that the effect of diluting a remedy of concentration Q, followed by succussion, is to regenerate (approximately) the same concentration Q of the same active ingredient. The model will shortly be made more complex by postulating multiple species of active ingredients, but let us start with the assumption of a single active ingredient. Then succussion must raise the concentration from Qdil back up to Q=HQdil. If succussion did not raise the concentration by a factor of (on average) H, then after repeated cycles the concentration would dwindle to zero.

Modeling succussion

How does succussion raise the concentration by a factor of H (typically H=100)? The answer depends on what the active ingredient is alleged to be. For the nano-bubble hypothesis, a nano-bubble might, during the pressure wave of succussion, organize the adjacent H2O into another copy of the same nano-bubble, and both bubbles might survive as structural features after the pressure wave passes.

For the silica hypothesis, silica might be released into solution as Si(OH)4 monomers by the mechanical agitation of succussion, and the specific silica nanocrystals might catalyze the formation of more copies of themselves out of the newly released monomers. It is beyond the scope of this article to assess or justify whether such notions are plausible.

Our starting point is to suppose that if any local hypothesis for homeopathy is valid, then there is some mechanism by which some structural feature replicates itself when succussed. We do not need to know what the feature is, or how it makes more copies, to develop the model.

Succussion consists of a series of ‘succussion strokes’. During each stroke several things happen: pressure rapidly surges then returns to 1 atm, the solution is turbulently mixed with air, Si(OH)4 enters solution, and so on. Let S denote the number of strokes used in each cycle. We postulate that in the course of S strokes, the concentration climbs from Qdil to HQdil. We cannot say what happens during a single stroke since we do not know the specific mechanism, but the hypothesized mechanisms suggest that each unit (ie each zwitterion, each nano-bubble, each silica nanocrystal, etc.) uses the added ‘raw material’ (ie the added water or newly dissolving air or Si(OH)4 monomers) to create more copies of itself. Thus, we assume that succussion strokes induce replication of the active units.

To call it ‘replication’ suggests a 2-for-1 process, but the process may not be 100% efficient. Instead of 2-for-1 we postulate that one succussion stroke raises the concentration of active units by a factor we call R. If Qm is the concentration after m strokes with Q0=Qdil, then Q1=RQ0, Q2=RQ1, and so on. This cannot continue forever, or Qm would blow up exponentially. Replication ceases when the solution runs out of usable raw material. For instance, if the units are nano-bubbles, there will be some limit on how closely they can crowd together, and once the population reaches the crowding limit they will not be able to replicate further. This situation is a familiar one in population biology: growth starts exponentially but then is capped by a finite carrying capacity. Mathematically it is modeled by assuming the actual growth rate is proportional to the amount of raw material accessible for further growth, which in turn is proportional to the difference between Q and a maximum concentration C. We obtain the discrete logistic equation,

Qm+1-Qm=(R-1)Qm(C-Qm)/C. (1)

This equation does not have a simple solution in its discrete form, but the very similar equation

Qm+1-Qm=(R-1)Qm(C-Qm+1)/C (2)

has the very nice exact solution

Click to view the MathML source (3)

which exhibits the expected S-shaped curve asymptotic to C as m→∞. After S succussion strokes the concentration is HQ0, ie QS=HQ0, and putting this into Eq. (3) shows that the concentration at the end of each cycle is given by

Click to view the MathML source (4)

According to Eq. (4), if RSnot double greater-than signH, then QS will be close to the maximum allowable concentration C, but if RS<H, there is no (positive) solution, and the concentration will die out to zero with repeated dilution–succussion cycles.

This already tells us something interesting about the number of succussion strokes needed. If our growth rate reflects ‘perfect’ replication when very dilute, ie R=2, then to get RS>H we require a minimun of 7 succussion strokes per cycle for H=100 (since 27>100 but 26<100), and a minimum of 16 strokes for the LM series. For a slower growth rate like R=1.2, we need at least 38 strokes per cycle to bring the concentration u to 90% of the maximum when H=100, and 72 strokes per cycle for LM’s. (These stroke counts are obtained by setting QS/C=0.9 in Eq. (4) and solving for S).

Although we have no experimental evidence to give us a range for R, Eq. (4) suggests that we should not skimp on succussion, with 40 strokes as a reasonable minimum when making ‘c’ potencies. Hahnemann himself held changing views about the optimum value for S. In the 5th edition of the Organon he recommended S=2 but revised the figure upward to S=100 in the 6th edition [5, p. 270].

Two active ingredients

If there were just a single active ingredient, dilution would reduce and succussion would restore the concentration each cycle. Nothing would change with dilution–succussion cycles and there would be no point in repeating dilution and succussion. But suppose there are two active ingredients, each of which would, if it were alone, increase according to Eq. (1). Approximate Eq. (1) by a continuous version, with the stroke count parameter ‘m’ being replaced by a ‘time’ parameter t. The difference equation (1) becomes the familiar logistic differential equation,6

Click to view the MathML source (5)

where we have scaled the concentration so that X=Q/C, and instead of R we encounter r =ln(R). The solution is X(t)=(1+(X(0)-1-1)e-rt)-1, which is the continuous form of Eq. (3).Let us add a second species of active ingredient, eg a different nano-bubble type or a different form of silica crystal. Let us assume that when some of each is present, the two species ignore each other. Each species replicates at its own rate as if the other were not present. There is still interaction, however, since both species draw upon the same raw material, of which there is a fixed amount. This sets up a competition scenario. The differential equations are

Click to view the MathML source (6)

where without losing generality we assume s>r. There is no elementary solution but the trajectories can be found by dividing the two equations, giving dY/dX=(s/r)(Y/X), hence

Y/Y(0)=(X/X(0))s/r. (7)

Let us further assume that the number of succussion strokes is large enough that the limiting concentrations are nearly attained; this is modeled by letting t→∞. Then the final concentrations are given by the intersection of trajectory (7) with the line 1–XY=0.

Suppose we conduct a series of dilution–succussion cycles for this two-component model. Let (XP,YP) describe the concentrations at the end of the Pth cycle, P denoting the potency. The relationship between (XP+1,YP+1) and (XP,YP) is as follows. Starting with (XP,YP), after dilution the concentrations are (XP/H,YP/H). Putting X(0)=XP/H and Y(0)=YP/H into Eq. (7), we see that (XP+1,YP+1) is found by intersecting the line X+Y=1 with the curve HY/YP=(HX/XP)s/r.

To proceed it is easier to work with the ‘pH’ values, x=−log(X) and y=−log(Y) (‘log’ is log10). Set h=log(H) (so h=2 for ‘c’ potencies). Referring to Figure 1, dilution takes us on a line of slope 1 from (xP,yP) to (xP+h,yP+h), and succussion takes us in a straight line of slope s/r from there back to the curve 10x+10y=1. (xP+1,yP+1) is the intersection of that curve and line.


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Figure 1. Log concentrations in alternating succussed and diluted stages of a two-ingredient remedy undergoing a transition from ‘X’-dominated to ‘Y’-dominated, for s/r=1.2. Succussed remedies lie on the blue curve, 10x+10y=1 (X+Y=1). Dilution raises both x and y by h=2.

Iterating the process, we ‘walk’ along the curve, at some point transitioning from values where y>x (meaning that X>Y and ‘X’ is the dominant species present) to values where x>y (ie ‘Y’ dominates). After the transition xP→∞ while yP→0, ie ‘X’ continues fade to zero while ‘Y’ converges to the maximum concentration. Before the transition, ie where y>x, the curve 10x+10y=1 is nearly vertical and a good approximate formula relating (xP+1,yP+1) to (xP,yP) is

Click to view the MathML source (8a)

while after the transition (where x>y) it is nearly horizontal and

Click to view the MathML source (8b)

Using only the fact that the curve 10x+10y =1 has a negative slope, we obtain the inequalities

Click to view the MathML source (9)

Clearly, what happens with increasing potency is that the slower-growing species ‘X’ is gradually replaced by the faster-growing species ‘Y’. Exponentiating Eq. (9) we see that the concentration ratio YP/XP increases by a factor of between 10h(s−r)/s and 10h(s−r)/r, or between H(s−r)/s and H(s−r)/r, with each dilution–succussion cycle. Pre-transition the ratio increase is very close to H(s−r)/r, while post-transition it is very close to H(s−r)/s. Thus, the transition potency can be predicted fairly easily if one knows the growth rates and the initial concentration ratio at a low potency. If s/r is only slightly bigger than 1, it takes more cycles to reach the transition and the transition occurs gradually over several cycles. If s/r is substantially bigger than 1, the transition is reached quickly and occurs abruptly. Of course, there is no transition at all if the initial concentration of ‘Y’ exceeds that of ‘X’: in this case the slower growing ‘X’ just declines, out-competed by ‘Y’.

Translating this to the clinical context, the implication is that, remedies where the two-component model applies will feature one species below the transition potency, and a different species above it. For example, if the transition occurs at P=20, then potencies below 20c should all have approximately the same clinical action, since the are all dominated by the same pre-transition active species, whereas those above 20c will be similar to each other but different from the pre-transition potencies. Because of this, having any one pre-transition remedy and any one post-transition remedy should suffice in the clinic. Having a ‘12c’ and a ‘30c’ would cover it.

The number of cycles needed to get from a potency whose concentration ratio is WP=YP/XP to the transition potency, is about −log(WP)/(h(s−r)/r). Without needing to know any values for s, r, or WP, this formula tells us that the number of cycles needed is inversely proportional to h=log(H). Starting from the same point, ‘c’ potencies attain the transition twice as fast as ‘X’ potencies, and ‘LM’ progress faster than ‘c’ by a factor of log(50 001)/log(1 0 0)=2.35. More generally, our formulas show that each ‘c’ dilution–succussion cycle has almost exactly the same effect as two ‘X’ cycles. To the extent that this type of model turns out to be valid, it appears to answer the long-standing argument in homeopathy as to whether dilution or succussion matters more in ‘potentizing’ remedies. This model predicts that it is the total amount of dilution that determines a remedy’s properties. Succussion at each stage must exceed a minimum threshold, but succussing significantly beyond that threshold will not make much difference.

Our mathematical model of two structural ‘species’ with different growth rates competing for raw material and limited by a maximum concentration has a perfect analogy in population biology. The analogy would be two living species that compete for a resource base but one reproduces faster than the other. A series of cycles occur, driven by periodic natural disasters that decimate each species’ numbers by the same factor of H each time. As they recover between disasters, the faster-growing species gains some ground each cycle and eventually replaces the slower-growing one.

Bacteriologists use this model deliberately to select for variants with desired traits. Bacteria with resistance to a toxin T will be ‘faster-growing’ in the presence of T. A baseline low mutation rate means that some low initial concentration of the bacteria is of the T-resistant ‘species’ (not necessarily a distinct species in the biological meaning). After culturing it to maximum growth with T, a small amount (eg 1%, corresponding to H=100) is re-seeded onto a new dish and then recultured. After many cycles the T-resistant species comes to dominate. ‘Dilution’ is like seeding a sterile culture dish while ‘succussion’ is like growth and selection.

Multiple active ingredients

The model can be extended to n species of active ingredient, n>2. The concentration of the ith species is denoted Xi, or if we also include the potency in the notation, as Xi,P. The growth rate of Xi is in (Ri), and −log(Xi) is denoted xi. The system of equations governing succussion is

Click to view the MathML source (10)

We omit details of its solution. The effect of one dilution–succussion cycle is described by

xi,P+1xi,P+h(rDOM-ri)/rDOM, (11)

where rDOM denotes the growth rate of whatever species happens to have the greatest concentration at potency P. Note that Eq. (11) reduces to Eqs. (8a) and (8b) when n=2. The effect of one dilution–succussion cycle on the concentration ratio for any two of the species, say for Xi,P/Xj,P, is to change the ratio by a factor of H(ri-rj)/rDOM, ie

(Xi,P+1/Xj,P+1)/(Xi,P/Xj,P)≈H(ri-rj)/rDOM. (12)

Depending on their initial concentrations, several of the n species may dominate in turn, but as P→∞, eventually only the fastest-growing species remains.Figure 2 illustrates the model with n=4 species and H=100. We suppose that the four species are present at the 4c potency, having been generated by some process that utilizes components from the MT. Perhaps compounds in the MT might catalyze the formation of specific silicates through directed polymerization of Si(OH)4 monomers. Again, how the MT and early potencies would do this is not relevant to our model. Initial (ie in the 4c potency) concentrations and growth rates (Ri) are taken to be: X1=0.99, R1=1.2; X2=0.01, R2=1.3; X3=10–8, R3=1.35; X4=10–12, R4=1.36. These are entirely made-up numbers but they are not implausible. Note that initial concentrations correlate inversely with growth rates. As a result we can expect that each species may lead the ‘race’ for an interval of several potencies, but ultimately X4 will ‘win.’


Display Full Size version of this image (19K)

Figure 2. Log (conc) vs potency, for four-component model.

Figure 2 displays log(Xi,P) as a function of P. Figure 2 was generated by a computer program that used the four-species analog of Eq. (1) to compute exact predictions of concentrations using S=40 succussion strokes per cycle. Each of the first three concentrations dominates for a while but then at a transition gives way to the next faster-growing species. Transitions correspond to points where the top two curves cross: at P=6.5, 23.5, and 79. With a log scale for the ordinate, each curve consists of a succession of nearly straight line segments. This behavior is explained by Eq. (11), which predicts that the slope should change at transition points (where rDOM changes) but should remain nearly constant between transition points.

Figure 3 shows the same information but displays Xi,P as a function of log(P). Note that for each of ‘6c’, ‘12c’, ‘30c’, and ‘200c’, a different species is dominant. Vertical lines have been added at these positions. Potency intervals are defined by which species dominates, and the potencies falling within any interval would be expected to be clinically equivalent. Interval boundaries occur at transition points: in this example the intervals are 4c to 6c, 7c to 23c, 24c to 79c, and 80c and up. Thus, there are just four essentially different remedies derivable from this MT.


Display Full Size version of this image (20K)

Figure 3. Conc vs log(potency), for four-component model.

Figure 3 illustrates the ‘best case scenario’ for the octave potencies convention: there are four species, each of which dominates one interval of potencies, and the potencies efficiently make available one potency from each interval. (For this MT, all potencies beyond 200c would be virtually identical to the 200c potency and would be unnecessary.) This illustrates what one would ideally want from a prescribing convention: one example of each dominant species is included, without redundancy. Given that the number of species and their growth rates must vary from MT to MT, it would be inconceivable that one number sequence (ie 6, 12, 30, 200, 1000, 10 000) would work in this ideal manner for every MT. Still, it may do a good enough job of balancing the need for simplification against comprehensive coverage, for the majority of MT’s.

High potencies

Dr JT Kent, developer of the octave potencies concept, [7] and [8] actually continued the sequence beyond 10 000: the continuation was 50 000, 105, 5×105, 106. These ‘very high’ potencies are not often used today. Does our model support a role for high (1000 and 10 000) and very high potencies? As we have noted, use of a potency above 200c only makes sense if there is a transition that occurs at a potency higher than 200, and likewise a potency above 1000c adds something new only if there is a species whose transition to dominance occurs above P=1000.

In Figure 2, the last transition (at 79c) resulted from two growth rates that are very close (R3=1.35 and R4=1.36), along with a very small initial concentration of X4 (10–12). For the model to yield a transition beyond 200c, there would have to be an even smaller difference in growth rates or a much smaller initial concentration (of the species whose transition to dominance occurs beyond 200c).

Tiny differences in rates are certainly a mathematical possibility, but this strikes me as unlikely to be the explanation for the majority of high potency remedies. Tiny initial concentrations likewise work in the model, but if we go below 10–17 or so we run into the Avogadro limit. (Concentrations have been scaled so that the maximum concentration C of a structural component is set to ‘1’. Measurements of silica[9] and [10] and other considerations place C in the micromolar range. If C is 10 μM then XP=10–17 means 10–22 M, and in a 10 mL sample there would be 10–24 mol, ie probably none, of this active ingredient.)

There is a way around this, and that is to suppose that the species with the late (ie >200) transition is not present in the initial low-potency mix at all: it only appears later in the potentizing process, presumably as a result of imperfect replication of one of the other species during a succussion step. Drawing on the biological analogy, the late-transitioning species would arise as a mutation of an earlier-transitioning species. If the mutation rate is low, it could take many cycles of dilution and succussion until the mutation first appears. To survive, the mutation would need to have a selective advantage (which in our model means a faster growth rate).

If this is correct, the high potency remedies (and possibly some 30c’s or 200c’s as well) feature an active ingredient that arises out of a lower-potency active ingredient and eventually replaces it. Ballpark numbers might be that the mutation has only a 0.5% chance of arising in any given succussion–dilution cycle, and once it arises it takes 50 cycles to become dominant. Many of the cycles between 200c and 1000c may be doing nothing except ‘waiting’ until the chance event of this particular mutation occurs. However, with enough repetitions even a 0.5% event is almost sure to occur eventually. It has a 1–(0.995)750=97.6% chance of occurring somewhere between the 200th and 950th cycle, and of achieving dominance between the 250th and 1000th cycle. According to this explanation, high potency remedies contain their intended active ingredient only with a certain probability, though the probability may be quite high (over 95%). The explanation for the need for a 10 000c would be that it depends upon the emergence of an even lower likelihood mutation (around 0.05% occurrence rate per cycle), and so on for the very high potencies.

Conclusion

Kent’s octave potency sequence is widely accepted in homeopathic practice. In the clinic, when homeopaths refer to ‘the next higher potency after 30c’, they mean 200c, not 31c. Our model suggests a reason this may be literally correct: the 31c is essentially identical to 30c, but somewhere between 30c and 200c a transition occurs to the ‘next’ active ingredient. One cannot derive Kent’s specific potency list from the model, but it does support Kent’s principle of stocking discrete potencies that occur at approximately geometric (‘octave’) intervals.

We started with a single assumption, namely that each succussion stroke amplifies the structural active ingredient by drawing upon finite resources (space, H2O, Si(OH)4, or silica surface). This assumption led to a relationship (Eq. (4)) among the growth rate, dilution factor, and stroke count. Based on Eq. (4) we recommended a minimum of 40 succussion strokes per cycle, for ‘c’ potencies.

When there are multiple species of active ingredients with different growth rates, we assumed there was no interaction other than competition for the finite resources. The choice of language was intentional, to draw attention to a parallel in mathematical biology. This assumption can be questioned or altered. For example, there could be other interactions including cooperative ones between the species. Also, instead of a small number of distinct species there could be a continuum or near-continuum of species (eg nano-bubble or nanocrystal size might be a continuous parameter) that is better handled with a diffusion–selection model.11 A ‘gradual evolution’ derived from selection among a near-continuum of homeopathically active silicates has been hypothesized.4 Our assumption of a small number of distinct active ingredients leads to a picture that in general is like Figure 2 and Figure 3: most potencies contain a single ‘dominant’ species with the other species occurring at levels one or more orders of magnitude lower. Each species remains dominant for an interval of potencies, until it is replaced by a different species that grows faster but starts at a lower level. The transitions can be predicted well using Eqs. (11) and (12). The locations of the transitions are proportional to log(dilution factor), meaning that a 60x will be equivalent to a 30c, a 200x like a 100c, and so on.

The strengths of this model are its generality—it works the same regardless of what the actual structural ingredient turns out to be—and its power to explain a complex clinical practice from simple starting assumptions. The model may not apply if the mechanism turns out to be ‘non-local,’ ie does not involve discrete information-carrying units (eg coherence or quantum entanglement[2], [10] and [12]) or, obviously, if remedies are ultimately proved to be mere placebos or markers that support the ritual of healer–client interaction. The great weakness of the model is that it is inspired solely by clinical conventions with no direct experimental support. Still, we have provided a new way to think about the dilution–succussion cycle, which could some day suggests experiments to test the model.

References

1 D.J. Anick, Stable Zwitterionic water clusters: the active ingredient in homeopathy?, J Am Inst Homeop. 93 (1999), pp. 129–135.

2 In: J. Schulte and P.C. Endler, Editors, Ultra High Dilution, Kluwer Academic Publishers, Dordrecht (1994).

3 R. Roy, W.A. Tiller, I. Bell and M.R. Hoover, The structure of liquid water; novel insights from materials research; potential relevance to homeopathy, Mater Res Innovation (9–4) (2005), pp. 93–124.

[4] D.J. Anick and J.A. Ives, The silica hypothesis for homeopathy: physical chemistry, Homeopathy 96 (2007), pp. 189–195. SummaryPlus | Full Text + Links | PDF (242 K)

5 Hahnemann S. Organon of Medicine. Fifth and sixth editions. New Delhi: Jain Publ. Pvt. Ltd.; reprinted 1995 (transl: Dudgeon RE and Boericke W).

6 L. Edelstein-Keshet, Mathematical models in biology, SIAM Classics Appl Math 46 (2004).

[7] Bhatia M. Homeopathic Potency Selection. Hpathy Ezine, April 2004: left angle bracketwww.hpathy.com/philosophy/bhatia-potency-selection2.aspright-pointing angle bracket.

[8] Thomas AL, Homeopathic Posology. Similima 18: left angle bracketwww.similima.com/org18.htmlright-pointing angle bracket.

9 J.-L. Demangeat, P. Gries, B. Poitevin and J.-J. Droesbeke et al., Low-field NMR water proton longitudinal relaxation in ultrahighly diluted aqueous solutions of silica-lactose prepared in glass material for pharmaceutical use, Appl Magn Reson 26 (2004), pp. 465–481. View Record in Scopus | Cited By in Scopus

10 H. Walach, W.B. Jonas and J. Ives et al., Research on homeopathy: state of the art, J Alternative Complementary Med 11 (2005), pp. 813–829. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

11 G.F. Webb and M.J. Blaser, Dynamics of bacterial phenotype selection in a colonized host, Proc Natl Acad Sci USA 99 (2002), pp. 3135–3140. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

12 L.R. Milgrom, Are randomized controlled trials (RCTs) redundant for testing the efficacy of homeopathy? A critique of RCT methodology based on entanglement theory, J Alternative Complementary Med 11 (2005), pp. 831–838. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

Corresponding Author Contact InformationCorresponding author. DJ Anick, Harvard Medical School, McLean Hospital, Centre Bldg. 11, 115 Mill St., Belmont, MA 02478, USA.



Homeopathy
Volume 96, Issue 3, July 2007, Pages 202-208
The Memory of Water

Journal Club – “The nature of the active ingredient in ultramolecular dilutions”

July 22nd, 2014 by Ben Goldacre in journal club | No Comments »

This is part of the Homeopathy journal club project described here:

www.badscience.net/?p=490

doi:10.1016/j.homp.2007.05.005 How to Cite or Link Using DOI (Opens New Window)
Copyright © 2007 Elsevier Ltd All rights reserved. The nature of the active ingredient in ultramolecular dilutions Otto WeingärtnerCorresponding Author Contact Information, a, E-mail The Corresponding Author
aDepartment of Basic Research, Dr. Reckeweg & Co. GmbH, Berliner Ring 32, D 64625 Bensheim, Germany
Received 8 March 2007; revised 14 May 2007. Available online 31 July 2007.

Abstract

This paper discusses the nature of the active ingredient of homeopathic ultramolecular dilutions in terms of quantitative physics.

First, the problem of the nature of an active ingredient in ultramolecular dilutions is analysed leading to the recognition of the necessity of characterizing the active ingredient as a non-local quality.

Second, non-locality in quantum mechanics, which is used as a paradigm, is formally presented.

Third, a generalization of quantum mechanics is considered, focussing on the consequences of weakening of the axioms.

The formal treatment leads to the possible extension of the validity of quantum theory to macroscopic or even non-physical systems under certain circumstances with a while maintaining non-local behaviour. With respect to the survival of entanglement in such non-quantum systems a strong relationship between homeopathy and non-local behaviour can be envisaged. I describe how several authors apply this relationship. In conclusion, the paper reviews how quantum mechanics is closely related to information theory but why weak quantum theory and homeopathy have not hitherto been related in the same way.

Keywords: potencies; non-locality; entanglement; weak quantum-theory; information

Article Outline

Introduction
Necessity of a general principle
How non-locality arose
What is entanglement?
Weakening the axioms of quantum mechanics
WQT and homeopathy
Entanglement and information in quantum physics and beyond
Discussion
Acknowledgements
Appendix A. The sequential box model (SBM)
Appendix B. Entanglement
References


Introduction

When I started basic research on homeopathy more than 20 years ago I endeavoured to describe homeopathic potencies according to the laws of physics as far as possible. This soon led me to the hypothesis of a field being responsible for the homeopathic phenomenon. In investigating this hypothesis I learned from biophysics that such a field has to be closely related to electromagnetism, because of the ability of living organisms to react in a specific way on electromagnetic signals.1 I concluded that the mechanism of homeopathic effects must be similar to resonances between electromagnetic waves and started to search for stored patterns of electromagnetic origin or, more generally, of physically measurable properties which differ between potencies and their solvent.

The results of the series of experiments that were carried out with a variety of standard physical–chemical methods2 were disappointing. Almost none of the experiments could reproduce results reported in specialist literature, and for no experimental arrangement could the results be forecast. However, the totality of experiments with nuclear magnetic resonance (NMR) showed a clear tendency in favour of a difference between potencies and their solvent in the water- and OH-portions of the ethanol–water-molecule.3 I was quite pleased with this tendency, which is now being investigated by other researchers,4 but I realized that looking for effects without having any clue of their significance is hazardous. Therefore, I started building models for the ‘Therapeutically Active Ingredient’ (TAI) and it soon became clear that models for the TAI have to have holistic character.5

While playing with models, I developed a construct which I called the ‘Sequential Box Model’ (SBM, see Appendix A). SBM is a thought experiment illustrating that the homeopathic phenomenon can be treated within physics with no consideration of the degree of dilution. Furthermore, the SBM explicitly underlines the long-standing presumption that for a TAI to emerge during the potentization procedure a quality beyond ordinary correlation between particles has to occur or be in existence already.

About this time the idea of the so-called ‘quantum computing’ was proposed in computer science.[6] and [7] This involves the idea of non-local correlations between states of entities. For my work, such non-local behaviour was the missing link between the SBM and a possible TAI, particularly as it was already known that non-local behaviour can occur in non-quantum systems under certain circumstances. The relationship between non-local behaviour of events in nature and the homeopathic phenomenon may give a clue to the ‘nature of the active ingredient in ultramolecular dilutions’ (NAIUD). It is the aim of this paper to analyse this relationship without going too far into technical details.

Necessity of a general principle

When we talk about the active ingredient of ultramolecular dilutions as used in homeopathy, we mean a non-material quality which—according to the principles of homeopathy—can be traced back to a substance. Moreover, this quality is understood to be able to make the symptoms of a patient disappear when administered via a vehicle. Many people call this quality ‘information’. Let us first look at the set of events that are required for a therapeutic active ingredient to develop out of a substance. In this context, the existence of a TAI is temporarily assumed as being proven by successful treatment (Figure 1).

1. First of all, a proving (homeopathic pathogenetic trial) must have been conducted resulting in a drug picture with specific symptoms.
2. A mother tincture is prepared from the substance.
3. Apart from some specific procedures for the preparation of low potencies that depend on the nature of the substance itself, the mother tincture is potentized stepwise with no consideration of the degree of dilution. Dilutions far beyond Avogadro’s number are used in daily practice.
4. When a homeopathic potency is prescribed, this is done according to the law of similars without consideration of the occurrence or not, of any molecule of the original substance in the medicine administered.
5. An artificial disease is triggered off resulting in healing.

These points demonstrate that the active ingredient of homeopathic potencies might have a variety of possible originators, especially when we only look at the squares and arrows in Figure 1 separately. There is no reason as to why two or more of these originators should complement one another. But if we look at Figure 1 as a whole, the necessity of a general principle becomes obvious. For such a principle, the symptoms of the homeopathic drug picture, the principle of releasing hidden energies of the substances by potentizing, the law of similars and the triggering of an artificial disease are specific projections. The problem is, how to specify this principle, especially with respect to the following questions:

1. Could such a general principle possibly be derived from the presence of a physical field?
2. For ultramolecular dilutions, interactions between molecules of the solute and those of the solvent do not make sense in terms of current scientific understanding. How can this be resolved?
3. Are there any reliable arguments for a concept of a global influence being responsible for an active ingredient in homeopathic potencies? Rupert Sheldrake’s morphogenetic field8 might serve as an example of such a concept.

In physics, fields are inevitably linked to interaction between material partners via interaction-particles. Photons, for instance, are the interaction-particles of the electromagnetic field.9 Thus, potentization as well as treatment with potencies—procedures that implicitly do not depend on matter–matter-interaction—are not primarily based on physical fields.


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Figure 1. Schema of events which are required for a TAI to: (a) develop out of a substance, and (b) proved to be existent by successful treatment. Arrows represent procedures, they map states onto states.

Both procedures, however, suggest mind–matter and matter–mind correlations.

1. Neither a specific chemical nor a specific physical property of the original substance is known to be transferred during the preparation of potencies although mother tinctures, which of course contain many molecules of the original substance, are mandatory for a starting point of this procedure. Potentization here appears to embody a procedure that relates matter to mind.
2. No common donor–acceptor-mechanism is known to be responsible for the effects of potencies. Treatment appears to embody a procedure that relates the ‘mind of matter’ to the ‘mind of illness’. The latter of course itself is strongly related to biological matter and is often looked upon as a relationship belonging to psychosomatics.

Are these correlations better described by interaction mechanisms that are not linked to particles? A possible alternative is non-local correlations, known from specific effects in quantum physics. Roughly speaking these correlations have the following characteristic:

1. Non-local correlations between systems or entities represent a real simultaneous behaviour of the correlation partners because no interacting particles (which have a finite speed and therefore cause a time delay) are necessary for interaction.
2. Non-local correlations are not able to interchange matter but only non-material information.
3. Non-local correlations are, in principle, independent of spatial distances.

How non-locality arose

Although Einstein was one of the founders of quantum physics, he did not accept quantum mechanics as to be a complete description of the phenomena of the micro world. He explained the reason for this attitude in a paper which he published with Podolsky and Rosen in 1935. In this famous paper, the three physicists described a thought experiment in which two physical quantities have simultaneous reality.10 For Einstein, this was a counter example for the completeness of quantum mechanics as a description of nature and for the rest of his life he did not change this attitude. He was not willing to accept counter-intuitive features in the description of nature. Schrödinger later on called this counter-intuitive property of quantum systems ‘entanglement’. Only three decades later, John Bell11 gave a theory-based criterion by which it was possible to decide whether a system is a quantum system or not. This criterion was applied in 1982 by Aspect and co-workers to an experimental arrangement in which they showed, for the first time, that entangled states can occur in quantum systems.12 Since then many properties of systems in micro-physics have been demonstrated in experimental arrangements based on entanglement.[5], [6] and [7] All have one thing in common: ‘Entanglement in quantum systems’.

What is entanglement?

Entanglement is a highly counter-intuitive quality of quantum systems. The fact that entanglement is irrelevant to Newtonian physics does not justify the assumption that quantum physics is the only field where entanglement occurs. At least theoretically, entanglement can occur in any system that fulfils a certain set of axioms. Entanglement comes in various guises and it is not easy for non-specialists to see whether a phenomenon belongs to the category of entangled systems or not. For our purposes, it should suffice to get a clue what entanglement is, without too much technical fuss. Readers who are interested in a more precise explanation are referred to Appendix B.

As an example let us imagine a secluded island exclusively inhabited by females. Being asked what human beings are, the inhabitants of this island would most probably point their fingers at themselves. Similarly, the inhabitants of another island exclusively inhabited by males would identify human beings with males. For the rest of the world, human beings are females as well as males. This is a description of a factual connection, where a generic quality in a system has a different meaning in its subsystems. Furthermore, if we look at pairs of human beings there might be couples among them in the rest of the world, in total contradiction to the local meaning in the two islands.

A generalization of this example leads to the following. Let p1 be a particle in a system A and let p2 be another particle in a system B. System A and system B are assumed to be disjoined, ie have no common points/particles. System A rules the behaviour of particle p1 and system B does the same for particle p2 (see Figure 2).


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Figure 2. Schema of two entangled systems A and B. p1 and p2 are assumed to be correlated. Seen from (A+B) correlation can be observed. Seen from A or B only local observations are possible.

It might be that states of the totality of the two systems occur which cannot be recognized in system A or in system B alone, but are exclusively linked to the recognition of (A+B) as a third generic system. In the above example as well as in the following generalization constellations, in which global observations are not compatible with local ones, are possible. This is the idea behind entanglement.

Weakening the axioms of quantum mechanics

Quantum mechanics deals with states zi and observables P, Q of quantum systems. Examples of observables are momentum, angular momentum, etc. Observables are thought to act as maps on the set of states. So, an observable P maps a state z1 into another state z2. Onto z2 a second observable Q may be applied resulting in a state z3. Unlike in classical mechanics in quantum mechanics one does not always have P(W(z))=Q(P(z)) or equivalently:

Pring operatorQ-Qring operatorP≠0,

where ‘ring operator’ is to be interpreted as ‘apply to’, where ‘0’ on the right-hand side of this inequality denotes the ‘zero-operator’ and where states ‘z’ have been omitted. Such a relation is known as a ‘commutation-relation’ of the two observables. Using states and observables as well as their relation to each other, quantum mechanics can be described as an algebraic system whose behaviour is ruled by a set of axioms that reflect the physical properties.In 2002, Atmanspacher et al. published13 the idea that weakening the axioms of quantum theory (weak quantum theory, WQT) could lead to theories that are no longer quantum systems or even physical systems at all, but which still have the property of possible entanglement. To be more precise, Atmanspacher et al. considered systems that comply with the following conditions (see also14):

1. Systems are any part of reality.
2. Systems are assumed to have the capacity to reside in different states. The set of states is not assumed to have the structure of the above-mentioned abstract space.
3. Observables are features of a system which can be investigated. They map states into states.
4. The composition Pring operatorQ of two observables is also an observable. P and Q are called compatible if they commute (ie Pring operatorQ-Qring operatorP=0).
5. To every observable P there is a set of different (possible) outcomes.
6. There are special observables (propositions) whose possible outcomes are either ‘yes’ or ‘no’. They follow the laws of ordinary proposition logic and have specific spectral properties (omitted here).

Within these conditions entanglement arises if global observables P pertaining to all of a system are not compatible to local observables Q pertaining to parts of the system (iePring operatorQ-Qring operatorP≠0).

WQT and homeopathy

Since WQT systems are not necessarily quantum systems, WQT could be a tool to develop models for phenomena which are not quantum but have features which resemble entanglement, for instance, homeopathy. Several authors therefore have applied WQT to the homeopathic phenomenon. Walach, one of the co-authors of the original WQT paper,15 presented a model in which the two semiotic processes ‘substance and potency’ as well as ‘drug picture and symptoms of the patient’ are assumed to be entangled by the law of similars. Milgrom has sketched a model for the homeopathic phenomenon in which the three pairs ‘Patient and practitioner’, ‘patient and remedy’ as well as ‘practitioner and remedy’ are assumed to be entangled in pairs.16 In a metaphorical way he derives, in succeeding papers, from this entanglement triangle an astonishing variety of principles of homeopathy.

Both models presuppose the validity of WQT for the specific situation in homeopathy and Milgrom, at least, deduces implications which reflect the way homeopaths think. In terms of logic, the approach of these two models is called the sufficiency part of a proof. The necessity part would be the proof that the assumptions which underlie homeopathy such as the potentization, the law of similars, etc., fit the preconditions of WQT.

I have tackled the TAI problem in a previous paper.17 This is where the SBM (see Appendix A) becomes relevant as a thought model, because it characterizes homeopathic potencies as a real physical system in which an unknown inner correlation is sought. In essence, paper17 showed that sets {Ji1,…,im·σi1,…,im·σi1,…,im} of spin-like states, where indices i1,…,im vary over permutations, fit the axioms of WQT for an arbitrary big system BN in the SBM. The sets {Ji1,…,im·σi1,…,im·σi1,…,im} are a generalization of couplings (Jik·σi·σk) of two spins, in NMR-theory, for instance. The generalization strongly suggests to investigate the possibility of global couplings instead of pair-to-pair couplings.

In summary, a number of arguments exist for non-locality being the general principle underlying the NAIUD. Quantum mechanics, however, cannot be considered, without further investigations, the theoretical frame for the NAIUD. The paradigm is rather non-locality. Quantum physics is merely the scientific discipline where non-locality has proven to occur in reality. Figure 3 gives a schematic classification of phenomena which can be treated within quantum mechanics, and those which have less structure in the set of their states and therefore need another theoretical environment, WQT. Questions concerning the NAIUD might even go beyond WQT.


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Figure 3. (I) The set of phenomena understood by quantum mechanics (essentially quantum physics); (II) the set of phenomena possibly understood by weak quantum theory (ie quantum physics and beyond); and (III) the set of phenomena belonging to homeopathy, possibly not a proper subset of II. Although quantum mechanics is an excellent paradigm for entanglement occurring in nature, quantum mechanics itself is not the frame in which NAIUD can be described.

Entanglement and information in quantum physics and beyond

It is the purpose of this section to explain the considerable difficulties one should be aware of when applying WQT instead of normal quantum mechanics to systems in nature.

This will be exemplified by the difficulties which arise when the attempt is made to translate ‘informational content’ (=entropy) in a quantum system to a system which is not quantum but which can be investigated by WQT. For formally correct representations of the factual connections given here, the reader is referred, for instance, to.6

The key concept of classical information theory is that of Shannon entropy. According to this concept, the entropy of a random variable A quantifies how much information we gain, on average, when we learn the value of A. Conversely, the entropy of A measures the amount of uncertainty about A before we learn its value. Thus, on the one hand, entropy measures the uncertainty associated with a classical probability distribution. On the other hand, in quantum ensembles density operators ρ, which represent the statistics of ensembles of different molecules in different states, formally replace probability distributions.

It was John von Neumann’s brilliant insight that in quantum mechanics the entropy S(ρ) of ρ can be expressed by the formula

Click to view the MathML source

where λx are the eigenvalues of the density operator ρ. If entanglement between two subsystems of a quantum system occurs and if one considers the density operators of these subsystems separately it can be shown that the von Neumann entropy of one of these reduced density operators is a measure of the degree of entanglement. This measure has an upper bound log(s), where s (the Schmidt-number) is the dimensionality of an abstract space in which these states ‘live’. Clearly, the bigger the s, the more the particles or states entangled. Applied to an arbitrary box BN of the SBM this suggests that the bigger the box BN is, the larger s has to be chosen and therefore the larger the measure of the amount of information.These considerations, however, presuppose entanglement of those particles being directly concerned. If we turn to a situation where WQT has to be applied instead of quantum mechanics, many of the basic constituents are no longer present or at least no longer adequately defined. For instance, if the set of states is structured so poorly then the above formula for von Neumann entropy makes no sense.

Discussion

The principle of non-local behaviour of systems in nature, first investigated in the context of the counter-intuitive phenomena of quantum physics, is not necessarily restricted to physics at the micro scale. This is the essence of WQT. Roughly speaking WQT shows that in every system where local and global observables do not commute with each other non-local behaviour is possible. For some authors, WQT was the reason for using non-locality to characterize the nature of the active ingredient of ultramolecular dilutions. Some models have simply drawn consequences from such a possible generalized non-locality, another looks at the real potentization procedure, asking what non-locality might contribute to an active ingredient. But WQT is not known to be powerful enough to describe the NAIUD entirely.

So the question arises, why considered WQT in such detail in connection with homeopathy? The answer is simple. With WQT, for the first time, special emphasis is placed quantitatively on entanglement as an idea. Moreover, WQT has shown to be a powerful tool for the characterization of the physics of the class of mathematical problems which arise when the NAIUD is to be described.

It is a great temptation to use WQT as a special way of describing the laws of quantum physics. People who do so tend to ignore the restraints given of WQT and use it as a theory applicable to everything, including the NAIUD. This is certainly not the right way to describe the NAIUD. An attempt to characterize the informational content of a system to be investigated by WQT, shows that it is not easy to generalize the concept in quantum mechanics to WQT or beyond.

Of course, all these considerations do concern the NAIUD in modelling situations. The question is, why do such work instead of looking for the TAI in experiments? The answer is that model building is a method of finding a way of thinking which allows us to understand a set of phenomena in a wider context. In contrast, experimental work tends to reductionism. I hope that both tendencies will ultimately meet.

Acknowledgement

This paper was partially done within the project ‘Modelling and simulating the therapeutically active ingredient of homeopathic potencies’ which was supported by the Carstens-Foundation.

References

1 Fröhlich H, Kremer F (eds). Coherent Excitations in Biological Systems. Berlin, Heidelberg, New York: Springer, 1983.

2 O. Weingärtner, Homöopathische Potenzen, Springer, Berlin, Heidelberg, New York (1992).

3 O. Weingärtner, Kernresonanz-Spektroskopie in der Homöopathieforschung, KVC-Verlag, Essen (2002).

4 J.L. Demangeat, P. Gries and B. Poitevin et al., Low-field NMR water proton longitudinal relaxation in ultrahighly diluted aqueous solutions of silica–lactose prepared in glass material for pharmaceutical use, Appl Magn Reson 26 (2004), pp. 465–481. View Record in Scopus | Cited By in Scopus

5 O. Weingärtner, Über die wissenschaftliche Bearbeitbarkeit der Identifikation eines ‘arzneilichen Gehalts’ von Hochpotenzen, Forsch Komplementärmed Klass Naturheilk 9 (2002), pp. 229–233. View Record in Scopus | Cited By in Scopus

6 M.A. Nielsen and I.L. Chuang, Quantum Computation and Quantum Information, Cambridge University Press, Cambridge (2000).

7 C.P. Williams and S.H. Clearwater, Explorations in Quantum Computing, Springer, New York (1998).

8 R. Sheldrake, The Presence of the Past, Times Book, New York (1988).

9 J.D. Bjorken and S.D. Drell, Relativistic Quantum Fields, McGraw-Hill Book Company, New York (1965).

10 A. Einstein, B. Podolsky and N. Rosen, Can quantum–mechanical description of physical reality be considered complete?, Phys Rev 47 (1935), pp. 777–780. Full Text via CrossRef

11 J.S. Bell, On the Einstein Podolsky Rosen paradox, Physics 1 (1964), pp. 195–200.

12 A. Aspect, P. Grangier and G. Roger, Experimental realization of Einstein–Podolsky–Rosen–Bohm–Gedanken experiment: a new violation of Bell’s inequalities, Phys Rev Lett 48 (1982), pp. 91–94. Full Text via CrossRef

13 H. Atmanspacher, H. Römer and H. Walach, Weak quantum theory: complementarity and entanglement in physics and beyond, Found Phys 32 (2002), pp. 379–406. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

14 Römer H. Weak Quantum Theory and the Emergence of Time, 2004, arXiv:quant-ph/0402011 v1, 2 February 2004.

15 H. Walach, Entanglement model of homeopathy as an example of generalized entanglement predicted by weak quantum theory, Forsch Komplementärmed Klass Naturheilk 10 (2003), pp. 192–200. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

16 L. Milgrom, Patient-practitioner-remedy (PPR) entanglement. Part 1: a qualitative, non-local metaphor for homeopathy based on quantum theory, Homeopathy 91 (2002), pp. 239–248. Abstract | Abstract + References | PDF (240 K) | View Record in Scopus | Cited By in Scopus

17 O. Weingärtner, What is the therapeutically active ingredient of homeopathic potencies?, Homeopathy 92 (2003), pp. 145–151. SummaryPlus | Full Text + Links | PDF (156 K) | View Record in Scopus | Cited By in Scopus

Appendix A. The sequential box model (SBM)

Imagine a certain volume of mother tincture is present in a box B0. Then imagine the contents of B0 are poured into another box B1, 10 times bigger than B0 and already 9/10th full of solvent. Imagine then B1 being vigorously shaken as in the preparation procedure of homeopathic potencies. Imagine then the whole content of B1 being poured into another box B2, 10 times bigger than B1 and again 9/10th full of solvent.

This procedure can be continued to an arbitrary box BN and it is clear that:

1. In every Box BN the whole volume of mother tincture is present, ie the problem of high potencies can be, at least in a thought experiment, treated physically.
2. If one attempted to conduct this experiment in reality the procedure would come to an end very soon because of the unrealizable dimensions of the boxes.
3. The higher N grows the less probable is the occurrence of a molecule in a random sample taken out of BN. This means that in BN an additional property has to be present which carries the information of B0. This property has to be non-local.

Appendix B. Entanglement

Mathematicians represent every point in the three-dimensional space of our experience as a sum of multiples of vectors of unit lengths in the x-, y- and z-axes. In the same way, they often represent objects in abstract spaces as sums of multiples of basic elements of these spaces. A direct application of this to quantum physics leads to the following.[6] and [7]

The states of quantum systems are mathematically represented by elements (points in) of an abstract Hilbert-space H. If points in this space are denoted by ψ and if the basic elements of H are denoted by phii (i=1,2,…), representations of states look like

Click to view the MathML source

This is commonly known as the principle of superposition in quantum mechanics, ie a wave function ψ is the superposition of multiples ai of basis ‘waves’ phii. In case of two particles forming two different systems we have the two representations:

Click to view the MathML source

Click to view the MathML source

where the numberings (1) and (2) are used to distinguish between the two. For the sake of clarity, we also index the Hilbert-spaces belonging to each of these representations (and get H1 and H2, respectively) although they are usually identical.The crucial point now is the consideration of a system consisting of the two particles as a whole. In this case, it is necessary to construct another Hilbert-space H=H1circle times operatorH2 out of H1 and H2 in such a way that this new system ‘lives’ in H1 and in H2 at the same time. In order to achieve this, a so-called tensor-product H1circle times operatorH2 is formed. This is a new Hilbert-space whose points have the form

Click to view the MathML source

where Φi,j denote basis elements in H=H1circle times operatorH2 and ci,j their multiples. Entangled states are those (ψ(1)ψ(2)) for which the multiples ci,j cannot be written as

ci,j=aibj,

with ai and bj being the multiples from above and independent from each other.Remarks

1. The above relation between states can be interpreted as the possible arising of additional qualities when two single systems are looked upon as a whole.
2. The set of entangled states in most of quantum systems is not empty. For many systems, the subset of possibly entangled states is much bigger than the non-entangled.
3. The above characterization is not restricted to pairs of particles.
4. States (ψ(1)ψ(2)) in H=H1circle times operatorH2 which cannot be split into products of pure states in H1 and H2, respectively, might be imagined as the pure states of the composite system.
5. The description of entanglement in quantum mechanics, which is a counter-intuitive, strongly depends on a mathematical apparatus with a rich structure.


Corresponding Author Contact InformationCorrespondence: Otto Weingärtner, Department of Basic Research, Dr. Reckeweg & Co. GmbH, Berliner Ring 32, D 64625 Bensheim, Germany.



Homeopathy
Volume 96, Issue 3, July 2007, Pages 220-226
The Memory of Water