Journal Club – “Can low-temperature thermoluminescence cast light on the nature of ultra-high dilutions?”

January 1st, 2000 by Ben Goldacre in journal club | 5 Comments »

This is part of the Homeopathy journal club described here:

www.badscience.net/?p=490

doi:10.1016/j.homp.2007.05.004 How to Cite or Link Using DOI (Opens New Window)
Copyright © 2007 Elsevier Ltd All rights reserved. Can low-temperature thermoluminescence cast light on the nature of ultra-high dilutions?

Louis ReyCorresponding Author Contact Information, a, E-mail The Corresponding Author
aChemin de Verdonnet 2, CH-1010 Lausanne, Switzerland
Received 2 May 2007; revised 8 May 2007; accepted 16 May 2007. Available online 31 July 2007.

Abstract

Low-temperature thermoluminescence has been used in attempt to understand the particular structure of ultra high dilutions. Samples are activated by irradiation after freezing at the temperature of liquid nitrogen (77°K). Experimental results show that, in the course of rewarming, the thermoluminescent glow is susbtantially different between dilutions of different substances. It is suggested that the dispersed gas phase might play a role in this process.

Keywords: irradiation; frozen dilutions; nanobubbles; low-temperature glow

Article Outline

Introduction
Research objective
Method
Results
New prospects
Acknowledgements
References


Introduction

No chemical is more common on earth than water: it covers 75% of the earth’s surface with a total mass of 1.4 billion megatons. A very simple molecule, with one central, negatively charged, oxygen atom and two positively charged hydrogen atoms 0.1 nm apart at an angle of 104°1 water is, nevertheless, a most atypical compound. In the liquid state, it is an abnormal fluid which should be a gas by comparison with other similar chemicals. Among other unusual properties, it increases in volume when crystallizing into solid ice at 0°C and boils at 100°C: both these temperatures are abnormally high for a substance which is neither a metal nor an ionic compound. Its dielectric constant as well as its increasing fluidity with rising pressure is equally odd.

In fact, liquid water is not a simple association of independent molecules; the molecules are actively interconnected by hydrogen bonds[2] and [3]. Liquid water is, indeed, a structured fluid which behaves as a polymer. In an ever-moving universe, individual water molecules link to each other, most often in tetrahedral geometry, building evanescent clusters which are continuously formed and dissociated again at random in a pico-second timeframe. When an ionic compound is dissolved in H2O, each ion is immediately surrounded by a spherical shell of water molecules so intensely that, should the concentration of the solute be high enough (over about 10%) all the shells come into contact and there is no more truly liquid water.

It can, thus, be understood that, in the preparation of an homeopathic medicine, any compound dispersed in water gives rise, from the outset, to a specific structure. When successive dilutions are made the violent turbulence created in the liquid by each succussion, helps to both maintain and possibly spread the original structure despite, progressively, the solute content of the dilution dropping by a factor of 100 with each centesimal step. However, Brownian motion is still very active and these ‘remnant structures’ fade away and reconstitute continuously. In other terms, we could say that homeopathic dilutions are ‘statistically structured’ and could remain so beyond the Avogadro number. Succussion appears to be an essential part of the overall process.

Research objective

It is easy to understand why, based upon this succession of dilutions–succussions, many scientists believe that eventually—and definitely beyond the Avogadro number—the resulting ‘solutions’ are no more than the dilution fluid itself. However, numerous physiological and clinical tests have demonstrated for decades, since Hahnemann himself, that this is not the case. Our research objective has been to try to demonstrate that the high dilutions are physically different from the diluent and have, indeed, an ‘individual personality’.

Method

Since any investigation is always difficult in an highly dynamic system we assumed that, should some specific ‘patterns’ exist in the liquid dilution they might be fixed when it is frozen giving rise to specific defects in the crystal lattice of ice, which could be investigated by appropriate means.

To perform this type of studies we selected low-temperature thermoluminescence. This technique, which is well known for archaeological and geological dating,4 has been adapted by us to low temperatures5 and described in detail in previous publications.[6] and [7] I will here only summarize here its main features.

A 1 cc sample of the dilution under investigation is placed in an aluminum cup and frozen down to liquid nitrogen temperature (−196°C=77°K) following a well defined multi-step process. The frozen 1 mm thick ice disk is then ‘activated’ by radiation (Gamma rays, X-rays or electron beams) which displace electrons from their quantum ground states. The sample is then rewarmed at constant rate (3°C/min) from 77°K to melting point. During that process the electrons, powered by ‘thermal activation’ leave their respective traps and recombine with the empty quantum ‘holes’ releasing their ‘activation energy’ in the form of light as they do so. This light is the thermoluminescent glow that we record.

The analysis of the emitted light shows two main peaks around 120 and 166°K for deuterium oxide and 115 and 162°K for H2O.5 Their relative intensity and shape vary both with the radiation dose and also with the nature of the radiant beam. In particular peak 2 displays a complex structure which can be resolved in a set of individual components by a deconvolution technique.[8] and [9] It is assumed that the ‘defects’ present in the ice crystalline lattice are active luminescent centers, hence that thermoluminescence might be an appropriate tool to study the ‘image’ of the initial liquid samples.

Results

Thermoluminescence is known to be a very sensitive technique and has been used to identify trace compounds. For example see Figure 1, the thermoluminescence emissions of very dilute alumina colloidal sols which show major differences between the 10−8 g/ml, 10−9 and 10−10 g/ml solutions.


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Figure 1. Thermoluminescence glow of colloidal sols of alumina irradiated by gamma rays (10 kGy) at liquid nitrogen temperature (77°K).

For homeopathic high dilutions we use deuterium oxide (D2O, heavy water) as the solute since the signal is 50 times more intense than that of H2O, due to the more rigid nature of the two ‘arms’ of the molecule. As diluted substances we selected two ionic compounds: sodium chloride (NaCl) and lithium chloride (LiCl). The latter was selected because, like urea and ethanol, it is known to impact on and suppress the hydrogen bonds10 which are thought to be involved into the high temperature peak (ca 166°K) of the thermoluminescence glow.6 Figure 2 shows that the curves recorded for successive dilutions of LiCl (3c, 5c, 7c, 9c) prepared by the classical Hahnemannian method and following the French Homeopathic Pharmacopoeia (150 strokes of 2 cm amplitude in 7.5 s, delivered by mechanical succussion machine) are substantially different.


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Figure 2. Thermoluminescence glow of successive dilutions (3c, 5c, 7c, 9c) of lithium chloride in D2O irradiated by a 2.2 Mev electron beam (6 kGy) at 77°K.

Subsequently, since it appeared that we had a reliable tool for assessing the dilutions we applied the same method to ultra-high dilutions beyond Avogadro’s number.6 Figure 3 gives the results and shows evidence that the ‘signature’ peak of LiCl 15c is substantially lower than that of NaCl 15c and lower than succussed pure D2O. This demonstrates that: ultra-high dilutions are different from their dilution fluid.


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Figure 3. Thermoluminescence glow of ultra-high dilutions (15c) in D2O of LiCl, NaCl and of pure D2O, diluted and succussed to 15c irradiated by gamma rays (19 kGy) at 77°K.

The high temperature components of the glow (ca 166°K) is linked to the hydrogen bond network. These results have been recently confirmed by another research group.11

In recent and still unpublished experiments we found the same type of ‘scaling’ between increasing dilutions of other compounds, among which potassium dichromate looks particularly interesting.12

New prospects

As I said above, in the homeopathic preparation scheme, succussion is an important component of the preparation process of homeopathic medicines, releasing considerable energy in the fluid. In view of this I became interested in recent research on the role of ‘nanobubbles’ in water.13 Part of the ‘message’ transferred from one dilution step to the next one might be linked to the nanobubbles created into the liquid by the successive strong mechanical agitation which creates turbulence.

To investigate this, we built special equipment to perform dynamization in gas atmosphere or vacuum. We dynamize the dilution at room temperature (20°C) under a moderate vacuum (2337 Pa=24 mbar) which corresponds to the saturated water vapour pressure at 20°C. Time to reach vacuum is approximately 20 seconds. Dynamization is 150 strokes in 7.5 sec followed by stabilization under reduced pressure for 3 minute. The vacuum is broken reverting to atmospheric pressure in 20 seconds. Figure 4 gives preliminary results which show that the gas-phase seems to play a major role in the ‘personalization’ of the dilutions. Bearing in mind that the number of nanobubbles created into the fluid is of the order of billions (which represents a very large ‘contact’ surface with the surrounding liquid) and that, due to their size, they may remain stable and undisturbed in the dilution for months or even much longer, this might open some new perspectives on our understanding of the homeopathic preparation process.


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Figure 4. Thermoluminescence glow of LiCl 15c in D2O dynamized in a vacuum and in a pure O2 at 15 bars pressure and irradiated by a 2.2 Mev electron beam (6 kGy) at 77°K. We dynamize the dilution at room temperature (20°C) under moderate vacuum (2337 Pa=24 mbar) which corresponds to the saturated water vapour pressure at 20°C. The time to reach vacuum is approximately 20 seconds, we use our standard dynamization: 150 strokes of approximately 2 cm amplitude in 7.5 sec, followed by stabilization under reduced pressure for 3 minutes. The vacuum is then broken, reverting to atmospheric pressure in approximately 20 seconds.


Acknowledgments

The author thanks Laboratoires BOIRON and the AREVA Nuclear Center of Marcoule for their interest and support.

References

1 J. Teixeira, Can water possibly have a memory? A sceptical view, Homeopathy 96 (2007), pp. 158–162. SummaryPlus | Full Text + Links | PDF (366 K)

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

3 J. Teixeira, A. Luzar and S. Longeville, Dynamic of hydrogen bonds: how to probe their role in unusual properties of liquid water, J Phys Condens Matter 18 (2006), pp. S2353–S52362.

4 Gartia RK. Thermoluminescent materials: past, present and future. In: Sarma HNK, Sumitra P, Basantakumar Sharma H, (eds). Proceedings of Regional Conference on Materials and their Applications (RCMA), February 18–19, 2005, Manipur University, Imphal, India, 2005, p 33–40.

5 L. Rey, Thermoluminescence de la Glace, CR Physi I (2000), pp. 107–110.

6 L. Rey, Thermoluminescence of ultra-high dilutions of lithium chloride and sodium chloride, Physica A 323 (2003), pp. 67–74. SummaryPlus | Full Text + Links | PDF (306 K) | View Record in Scopus | Cited By in Scopus

7 L. Rey, Thermoluminescence of deuterated amorphous and crystalline ices, Rad Phys Chem 72 (2005), pp. 587–594. SummaryPlus | Full Text + Links | PDF (467 K) | View Record in Scopus | Cited By in Scopus

8 B.A. Sharma, Th. Basanta Sing and R.K. Gartia, Critical evaluation of goodness of fit of computerised glow curve deconvolution, Indian J Pure Appl Phys 42 (2004), pp. 492–497.

9 Rey L, Gartia RK, Belon P. Trap Spectroscopic Characterization of D2O ice and its potentialities in homeopathy. In: Selvasekarapandian S, Murthy KVR, Natarajan V, Malathi J, Brahmanandhan GM, Khanna D, (eds). Macmillan Advanced Research Series. Proceedings of the National Conference on Luminescence and Its Applications (NCLA, 2007) January 18–20, Bharathiar University, India. New Delhi: Macmillan India Ltd., 2007, p 12–17.

10 Ourisson G. Personal communication, 2000.

11 R. van Wijk, S. Basman and E. van Wijk, Thermoluminescence in ultra-high dilution research, J Alternative Complementary Med 12 (2006), pp. 437–443. View Record in Scopus | Cited By in Scopus

12 Rey L, Muchitsch I. Recent unpublished results, 2007.

13 Ph. Vallée, J. Lafait, L. Legrand, P. Mentré, M-O. Monod and Y. Thomas, Effects of pulsed low-frequency electromagnetic fields on water characterized by light scattering techniques: role of bubbles, Langmuir 21 (6) (2005), pp. 2293–2299. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus

Corresponding Author Contact InformationCorresponding author. Louis Rey, Chemin de Verdonnet 2, CH-1010 Lausanne, Switzerland.



Homeopathy
Volume 96, Issue 3, July 2007, Pages 170-174
The Memory of Water


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5 Responses



  1. wilsontown said,

    August 15, 2007 at 1:43 pm

    This paper looks very interesting. Unfortunately low-T thermoluminescence is not really my thing (I’m a structural geologist). I do have some questions, though.

    Is it a safe assumption that you can infer anything about the structure of a liquid from studying the frozen liquid?

    Were the results reproducible? The author says someone else has reproduced them, but what I really want to know is what is the variability of the samples. If I test 100 different samples of, say, 30C Nat. Mur., how much would the spectra vary? There’s no information on this in the paper.

    The claim seems to be that the graphs look different for different homeopathic ‘remedies’ [Figure 3]. However, the peaks appear at roughly the same temperatures, although they have different amplitudes. If you were seeing different structures, would you not expect to see emission at different temperatures, rather than just variation in amplitude?

    As I say, not my field.

  2. DoctorLoctor said,

    August 20, 2007 at 10:58 pm

    As a chemist with a bit of photophysics in the mix, I have to say that this looks like a very interesting technique for probing ice structure, but this paper is just a wee bit woolly for my taste. In the hands of a half-decent condensed matter physicist, you could get some really interesting science out of this.

    “Is it a safe assumption that you can infer anything about the structure of a liquid from studying the frozen liquid?”

    You might be on reasonable grounds to infer something about the structure of a liquid crystal from its solid state, crystal structure, in combination with other techniques. For an isotropic liquid like water, though, you can only really make inferences about the sort of structures you might observe at interfaces between that liquid and another phase of matter, be that gas, solid or another, immiscible liquid. These will be pretty dynamic structures in any event, even if the molecules involved exchange positions with others at a rather lower rate than occurs in the bulk.

    So much for the woo-friendly premise of the paper. Criticisms of the science would be a lack of controls, a failure to assign the peaks to the relaxation of particular excited states and a disturbingly arbitrary approach to radiation intensity selection.

    My explanations? Woolly speculation – perhaps I should steer clear – but…

    Using heavy water implies they are looking at a heavy isotope effect, so coupling to O-D stretching vibrations is probably important. Because water has basically two stretching modes, of differing symmetries (called symmetric and asymmetric stretches), I suspect we are seeing two populations of electronic excited states, of corresponding symmetries to the vibrations. For luminescent decay to be an “allowed” quantum transition, symmetries must coincide (or be related through a consistent mathematical operation – I only know a bit of photophysics…) As the temperature rises, in whichever sequence, first one of the vibration modes is thermally possible, so the corresponding excited state can decay through that state with a corresponding photon emission. The second vibration becomes allowed at a higher T, whereupon the second excitation can decay by luminescence.

    What the author observes, therefore, are variations of emission from the ice, and it is very interesting that the lower T event is pretty much constant whatever the solute. The inferences to be drawn from the author’s data are (a) increasing colloid content increases this higher T emission with a roughly logarithmic effect, (b) that dissolved ionic solids cause an decrease of this emission with increasing concentration.

    This is where the really interesting question is posed, and it would be great if someone was in a position to try and answer it. Why do ionic solutes quench, whilst the colloid intensifies the thermoluminescence at around 160K? I bet it’s down to direct coordination of O atoms to cations (and H atoms to chloride) in the ionic solutions, whilst water will build a relatively robust hydrogen bonded structure (yes, I know!) around colloid particles. Goodness knows how, though…

  3. Dr Aust said,

    August 29, 2007 at 9:49 pm

    Anyone out there with access to the Journal of Alternative and Complementary Medicine?

    I’m trying to get hold of

    Roeland van Wijk, Saskia Bosman, Eduard P.A. van Wijk. The Journal of Alternative and Complementary Medicine. 2006, 12(5): 437-443. doi:10.1089/acm.2006.12.437.

    – which apparently reproduces some of Rey’s results.

    My Univ doesn’t subscribe… not that it’s a sudden anti-woo conversion, more that we don’t seem to take Liebert journals.

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