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MICROCLUSTERING: The Making of a Myth (part 1. Facts, Claims and History)

Water Clusters

wc

Physical chemists are well aware of water’s mysterious nature1 and the many different forms of water clusters2 due to hydrogen bonding.3 Very little about water clusters in bulk phase (i.e. water not at the surface or edges of another material) is understood.4 In fact, it is considered to be one of the unsolved problems in chemistry.5  These clusters have been experimentally detected6-8 or predicted from theoretical computational models in bulk liquid water.9-11

It seems clear that water manifests itself in fleeting clusters rather than in a uniform isotropic arrangement.2 Water molecules associate with adjacent molecules12  to form rapidly changing polymeric units.13 The simplest unit is a water dimer cluster.14 There are also pentamers,15 hexamers,16 octamers,17 decamers18 and many other types (e.g. cyclic, chair and linear forms).19 Clusters are denoted as (H2O)n where n=2 to 1000.20,-22  There is also the fullerene-like cluster (H2O)28, which is referred to as the ‘water buckyball’.23 There is also a large network of water clusters  (each water molecule  coordinating with four others) to form the monster 280 molecule cluster in the form of an icosahedron.24,25

However, as mentioned, these are all unstable fleeting arrangements.26 Many of them have never actually been detected, but predicted via computational molecular modeling theories.2 There are numerous studies on the properties of water and recent advances in science have allowed us to analyze the structure of liquid water in great detail,26 but still have not provided definitive answers27 to an increasing number of questions.28

Scientific Tools to Investigate Water

Water studies employ a vast array of methods including, Far-infrared vibration-rotation tunneling spectroscopy,29 X-ray diffraction,30 linear and nonlinear spectroscopy,31 dielectric spectroscopy,32 nuclear magnetic resonance,33 Raman34 and Vibrational spectroscopy,35 and many other methods.  Although we have learned a lot of things that are not true,36 the structural dynamics and arrangements of liquid water remain elusive.27,28

Pseudoscientific Claims

This fact has not stopped the frequent claims, by marketers of “healthy water” (e.g. ionized water, microwater, vortex water, etc.), that their water somehow contains stabilized micro-clustered water,37 which is purported to have  numerous health benefits.38 clusters

Generally the claim is that tap water contains water clusters of 15 or more;39 ionized water is electrically restructured to have smaller cluster size of only 3-5 H2O molecules per cluster.40 This makes the water have faster absorption and because of its smaller size, it can more easily enter the cells and increase cellular hydration.41 Numerous benefits are ascribed to microclustering,38 even that it is the most important property of ionized water.42

Silver Fleece Award

Microclustering of water actually won The Silver Fleece Award43 for “Anti-Aging Quackery” for being the product “with the most ridiculous, outrageous, scientifically unsupported or exaggerated assertions about aging or age-related diseases.”44 This is a big reason why many ridicule the concept of ionized water.

The Facts

Unfortunately no valid scientific evidence exists45 either for its occurrence46 or for its benefits.47 I have done an exhaustive search for the past five years in many databases including: PubMed, HighWire, SciFinder, Web of Science, Scopus, etc. in search of evidence to support either its existence or its benefits, but scientific research refutes these claims.48

In fact, one scientific article, by pro-ionized water researchers, specifically set out to evaluate the claims of microclustering in these products.49 Their results show that there was absolutely no difference between the claimed “microclustered water” and the controls. In the paper the authors conclude:  “The claims in the advertisements of the manufacturers concerning the cluster size of H2O molecules have not been confirmed by the results of our experiments.”49

History

flickering

It is uncertain as to exactly how and when the claim of microclustering began, but it occurred at least back in the 1950’s with “flickering clusters”50 of H2O molecules in bulk phase (figure on the left).51 However, these clusters were estimated to only last on the order of a pico-second.52

This myth gained popularity in the 1990s with the introduction of silica-hydride microclusters.53  However, facts were quickly misrepresented both within and without markets of this product.54

 

In reality, adding really small pieces (i.e. micro-pieces) of silica to water, results in “microclusters” of water.55  Similarly, if you added just one ion (like calcium) to the water, the water molecules would also surround it,56 but this is much smaller then a micrometer. It’s on the nano scale, so the resulting cluster would be a nano cluster.57 Similarly, if you add something the size of a millimeter to water, then you would get a water “millicluster”. The use of microclustered minerals has been very common and refers to mineral colloids.58

This simple idea of “hydration spheres”59 or “solvation spheres”60 eventually and rapidly grew to the idea that it was the microcluster itself that exerted therapeutic benefits not the ion (or solute) it contained.61 Eventually, the ions (or solute) was abandoned altogether and marketers just propagated the myth that water microclusters are healthy and increase hydration, nutrient delivery, etc.37-42

Perhaps the fact that it wasn’t until recently that molecular hydrogen  was found to be the primary benefit of ionized water, marketers held on to the idea of microclustering to help explain the therapeutic benefits of the water.

 

References: Click Here

  1. Earis, Philip. (2005) The mysterious nature of water. Highlights in Chemical Science.4, 23-23.
  2. Ludwig, R. (2001). Water: from clusters to the bulk. Angewandte Chemie International Edition, 40(10), 1808-1827.
  3. Xantheas, S. S. (1996). Quantitative description of hydrogen bonding in chloride-water clusters. The Journal of Physical Chemistry, 100(23), 9703-9713.
  4. Keutsch, F. N., & Saykally, R. J. (2001). Water clusters: Untangling the mysteries of the liquid, one molecule at a time. Proceedings of the National Academy of Sciences, 98(19), 10533-10540.
  5. First 25 of 125 big questions that face scientific inquiry over the next quarter-century". Science 309 (125th Anniversary). 1 July 2005.
  6. Gruenloh, C. J., Carney, J. R., Arrington, C. A., Zwier, T. S., Fredericks, S. Y., & Jordan, K. D. (1997). Infrared spectrum of a molecular ice cube: the S4 and D2d water octamers in benzene-(water) 8. Science, 276(5319), 1678-1681.
  7. Buck, U., Ettischer, I., Melzer, M., Buch, V., & Sadlej, J. (1998). Structure and spectra of three-dimensional (H_ {2} O) _ {n} Clusters, n= 8, 9, 10. Physical review letters, 80(12), 2578.
  8. Viant, M. R., Cruzan, J. D., Lucas, D. D., Brown, M. G., Liu, K., & Saykally, R. J. (1997). Pseudorotation in water trimer isotopomers using terahertz laser spectroscopy. The Journal of Physical Chemistry A, 101(48), 9032-9041.
  9. Saykally, R. et al. (2005) Unified Description of Temperature-Dependent Hydrogen Bond Rearrangements in Liquid Water, PNAS, Vol. 102, ? 40, pp. 14171–14174.
  10. Fowler, P. W., Quinn, C. M., Redmond, D. B. (1991) Decorated fullerenes and model structures for water clusters, The Journal of Chemical Physics, Vol. 95, No 10, p. 7678.
  11. Ignatov, I., Mosin, O. V. (2013) Structural Mathematical Models Describing Water Clusters, Journal of Mathematical Theory and Modeling, Vol. 3, No 11, pp. 72-87.
  12. Chaplin, M. (2006). Do we underestimate the importance of water in cell biology?. Nature Reviews Molecular Cell Biology, 7(11), 861-866.
  13. Del Bene, J., & Pople, J. A. (1970). Theory of Molecular Interactions. I. Molecular Orbital Studies of Water Polymers Using a Minimal Slater?Type Basis. The Journal of Chemical Physics, 52, 4858.
  14. Buckingham, A. D. The hydrogen bond, and the structure and properties of water and the water dimer. Journal of Molecular Structure 1991, 250, 111-18.
  15. Liu, K., Brown, M. G., Cruzan, J. D., & Saykally, R. J. (1996). Vibration-rotation tunneling spectra of the water pentamer: Structure and dynamics. Science, 271(5245), 62-64.
  16. Liu, K., Brown, M. G., Carter, C., Saykally, R. J., Gregory, J. K., & Clary, D. C. (1996). Characterization of a cage form of the water hexamer. Nature, 381(6582), 501-503.
  17. Stillinger, F. H., & David, C. W. (1980). Study of the water octamer using the polarization model of molecular interactions. The Journal of Chemical Physics, 73, 3384.
  18. Karthikeyan, S., & Kim, K. S. (2009). Structure, Stability, Thermodynamic Properties, and IR Spectra of the Protonated Water Decamer H+ (H2O) 10. The Journal of Physical Chemistry A, 113(32), 9237-9242.
  19. Wang, J., Zheng, L. L., Li, C. J., Zheng, Y. Z., & Tong, M. L. (2006). Coexistence of planar and chair-shaped cyclic water hexamers in a unique cyclohexanehexacarboxylate-bridged metal-organic framework. Crystal growth & design, 6(2), 357-359.
  20. Dunn, M. E., Evans, T. M., Kirschner, K. N., & Shields, G. C. (2006). Prediction of accurate anharmonic experimental vibrational frequencies for water clusters,(H2O) n, n= 2-5. The Journal of Physical Chemistry A, 110(1), 303-309.
  21. Zakharov, V. V., Brodskaya, E. N., & Laaksonen, A. (1998). Surface properties of water clusters: a molecular dynamics study. Molecular Physics, 95(2), 203-209.
  22. Devlin, J. P., Joyce, C., & Buch, V. (2000). Infrared spectra and structures of large water clusters. The Journal of Physical Chemistry A, 104(10), 1974-1977.
  23. Ludwig, R., & Appelhagen, A. (2005). Calculation of Clathrate?Like Water Clusters Including H2O?Buckminsterfullerene. Angewandte Chemie International Edition, 44(5), 811-815.
  24. Tokmachev, A.M., Tchougreeff, A.L., Dronskowski, R. (2010) Hydrogen-Bond Networks in Water Clusters: An Exhaustive Quantum-Chemical, European Journal of Chemical Physics And Physical Chemistry, Vol. 11, ?2, pp. 384–388.
  25. Sykes, ?. (2007) Simulations of RNA Base Pairs in a Nanodroplet Reveal Solvation-Dependent Stability, PNAS, Vol. 104, ? 30, pp. 12336–12340.
  26. Bates, D. M., & Tschumper, G. S. (2009). CCSD (T) Complete Basis Set Limit Relative Energies for Low-Lying Water Hexamer Structures. The Journal of Physical Chemistry A, 113(15), 3555-3559.
  27. Geissler, P. L. (2013). Water Interfaces, Solvation, and Spectroscopy. Annual review of physical chemistry, 64, 317-337.
  28. Barnes, B. C., & Sum, A. K. (2013). Advances in molecular simulations of clathrate hydrates. Current Opinion in Chemical Engineering.
  29. Richardson, J. O., Wales, D. J., Althorpe, S. C., McLaughlin, R. P., Viant, M. R., Shih, O., & Saykally, R. J. (2013). Investigation of terahertz vibration–rotation tunneling spectra for the water octamer. The Journal of Physical Chemistry A.
  30. Takamuku, T., Tabata, M., Yamaguchi, A., Nishimoto, J., Kumamoto, M., Wakita, H., & Yamaguchi, T. (1998). Liquid structure of acetonitrile-water mixtures by x-ray diffraction and infrared spectroscopy. The Journal of Physical Chemistry B, 102(44), 8880-8888.
  31. Yagasaki, T., & Saito, S. (2013). Fluctuations and Relaxation Dynamics of Liquid Water Revealed by Linear and Nonlinear Spectroscopy. Annual review of physical chemistry, 64, 55-75.
  32. Jansson, H., & Swenson, J. (2003). Dynamics of water in molecular sieves by dielectric spectroscopy. The European Physical Journal E, 12(1), 51-54.
  33. Sabarinathan, V., Wu, Z., Cheng, R. H., & Ding, S. (2013). Multinuclear Solid State Nuclear Magnetic Resonance Investigation of Water Penetration in Proton Exchange Membrane Nafion-117 by Mechanical Spinning. The Journal of Physical Chemistry B.
  34. Maxton, P. M., Schaeffer, M. W., & Felker, P. M. (1995). Nonlinear Raman spectroscopy of intermolecular vibrations in benzene-(water)< sub> n</sub> clusters. Chemical physics letters, 241(5), 603-610.
  35. Andersson, P., Steinbach, C., & Buck, U. (2003). Vibrational spectroscopy of large water clusters of known size. The European Physical Journal D-Atomic, Molecular, Optical and Plasma Physics, 24(1), 53-56.
  36. Ceponkus, J., Engdahl, A., Uvdal, P., & Nelander, B. (2013). Structure and dynamics of small water clusters, trapped in inert matrices. Chemical Physics Letters, 581, 1-9.
  37. http://www.enagic.com/blog/2011/02/22/cooking-with-kangen-water/
  38. http://www.enagic.com/watertheory_kangenbenefits.php
  39. http://g6pddeficiency.org/index.php?cmd=waterkangen
  40. http://alkalinekangenwaterfilters.wordpress.com
  41. http://www.mind2body.net/blog/kangen-water-fountain-health
  42. http://www.dailymotion.com/video/xx4eqm_micro-clustered-water-machines-water-ionizer-system_lifestyle
  43. http://www.newswise.com/articles/silver-fleece-awards-warn-consumers-of-anti-aging-misinformation
  44. Binstock, R. H. (2004). Anti-aging medicine: The history anti-aging medicine and research: A realm of conflict and profound societal implications. The Journals of Gerontology Series A: Biological Sciences and Medical Sciences, 59(6), B523-B533.
  45. Paul Shin. Water, Water Everywhere, Caveat Emptor http://www.csun.edu/~alchemy/Caveat_Emptor.pdf
  46. Hairston, James E., et al. "Drinking water and water treatment scams." Auburn, AL: Auburn University, Agronomy and Soils Department, Water Quality Timely Information, October 22 (2003).
  47. Drinking water Scams http://www.impexs.hr/slike/waterscams.pdf
  48. Roberto Car, a professor of chemistry and physics at Princeton University, says “microclustering is nonsense” Eugene Stanley, a professor of chemistry and physics at Boston University. Calls it “Rubbish” http://online.wsj.com/news/articles/SB10001424052702303404704577314182468322256
  49. Hiraoka, A., Shinohara, A., & Yoshimura, Y. (2010). Studies on the Physicochemical Properties and Existence of Water Products (as Drinks) Advertised as Having Smaller Cluster Sizes of H 2 O Molecules than Those of Regular Water. Journal of Health Science, 56(6), 717-720.
  50. H. S. Frank, W. Y. Wen, Discuss. Faraday Soc. 44, 1957,133
  51. Frank, H. S. (1967). The flickering cluster model of water. In Proceedings (Vol. 1, p. 292). US Department of the Interior, Office of Saline Water.
  52. Cohen, G. (2013). Heini, a personal recollection and appreciation. Biopolymers, 99(4), 223-224.
  53. Stephanson, C. J., Stephanson, A. M., & Flanagan, G. P. (2002). Antioxidant capability and efficacy of Mega-H™ silica hydride, an antioxidant dietary supplement, by in vitro cellular analysis using photosensitization and fluorescence detection. Journal of medicinal food, 5(1), 9-16.
  54. This is evidenced by reading the older marketing information and watching it change over the years
  55. FLANAGAN, PATRICK. "Hydrogen.... Longevity's Missing Link."
  56. Angyal, S. J. (1973). Complex formation between sugars and metal ions. Pure and Applied Chemistry, 35(2), 131-146.
  57. Harris, Daniel C. Quantitative chemical analysis. Macmillan, 2010.
  58. Stephanson, C. J., & Flanagan, G. P. (2003). Synthesis of a novel anionic hydride organosiloxane presenting biochemical properties. International journal of hydrogen energy, 28(11), 1243-1250.
  59. Ohtaki, H., & Radnai, T. (1993). Structure and dynamics of hydrated ions. Chemical Reviews, 93(3), 1157-1204.
  60. Cox, B. G., Parker, A. J., & Waghorne, W. E. (1974). Coordination and ionic solvation. The Journal of Physical Chemistry, 78(17), 1731-1740.
  61. Flanagan, P., & December, N. (1994). HYDRATION AND WATER RESEARCH. Nexus, 1995.

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