The Structure of Liquid Water

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The Structure of Liquid Water Novel Insights
from Materials Research Potential Relevance to
Homeopathy Rustum Roy1, W.A. Tiller2, Iris
Bell3, R.A. Hoover4 1 Evan Pugh Professor
of the Solid State, Emeritus, and Founding
Director of the Materials Research Laboratory at
Penn State (rroy_at_psu.edu). 2 Professor
Emeritus and former Department Chair of Materials
Science, Stanford University. 3 Professor of
Medicine, Psychiatry, Family and Community
Medicine, and Public Health, Director of
Research, Program in Integrative Medicine,
University of Arizona (ibell_at_u.arizona.edu). 4
Research Associate, Materials Research Institute,
Penn State(rickhoover_at_psu.edu)
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But What are some Facts

• Water has been known for its intimate connection
  to health in all cultures
• Getting pure drinking water and managing sewage
  are the Wests biggest by far contribution to
  health. 66 of the near doubling of U.S. life
  expectancy from 1900-2000 is due to civil
  engineering.

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More Facts Role of Ultradilute dispersions, as
colloids
Some have a profound role in health (silvers
role at 1ppm is unexplained.) What are the
possibilities for special suspended minerals
which are present in all natural waters.

• Special spas all over the world
• Lourdes
• The Ganges data
• Homeopathy

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COMPOSITION
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Fig. 1. The classical picture of the Random
Network Structure as presented by Zachariasen
(1932), which has become established as the
structure of glass on the basis of model fitting
on x-ray scattering data. The key assumption
(unrecognized by others for 7 or 8 decades) of
this model is that the structure of all glasses
is homogeneous in the same ways as crystals are.
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Fig. 2 In sharp contrast with the hypothetical
calculations based on Zachariasens random
network theory, is the direct TEM evidence. Shown
are some examples of binary and ternary glasses,
some quenched, some heat-treated which clearly
show actual phase-separation. One can confidently
assume that in many if not most glasses and in
many liquids, structural (-composition)
fluctuations must exist as precursors to such
phase separation (after Mazurin and
Porai-koshits, 1984).
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Fig. 3 The first presentation by Roy (1960) of
the theoretical argument that the non-ideality of
the liquidus (clearly shown in its shape)
indicated that the liquid phase itself was
heterogeneous in structure, and could be
induced to phase-separate in a temperature region
where it was metastable (left hand figure).
Porai-koshits and Averjanov (1968) experimentally
demonstrated exactly such an example.
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Fig. 4 p.t. Phase Diagrams for sulfur. On the
left is the subliquidus region showing the many
crystalline structures. On the right is the
liquid stable region showing at least 5 different
liquid structures separated by a phase boundary.
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Fig. 5 TEM and model there from of glassy carbon
structure showing 1 nm intergrowth of
diamond-like and graphite-like regions after Noda
and Inagaki (1964)
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Fig. 6 The paper by Kawamoto et al. (2004) shows
a projection of at least two water structures
into the stable liquid water region exactly
analogous to Fig. 4s experimental data on
several liquid structures in liquid sulfur some
35 years earlier.
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Fig. 7.a. The cartoon version of the more
generalized structure of glass clearly indicating
its heterogeneous (with respect to structure or
structure and/or composition) nature from Roy
(1971).Note that water is mentioned in The third
column. This is the new minimalist schematic
representation of the structure of water.
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Fig. 7.b. A similar representation of the water
structure by Bockris and Reddy (1998).
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Fig. 8 The enormous variety of structures of the
molecules in which almost certainly the chemical
entity H2O can exist. The well known H2O monomer
with its precisely defined tetrahedral angle is
shown on the top left and below it a series of
dimers, trimers, tetramers which can be
constructed on paper from the relatively rigid
H2O molecule, and so on. Moderate sized molecules
are on the right. See Chaplin 2004 (q.v.) for
individual references for any particular
structure pictured above.
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Fig. 9 This figure shows some of the larger
polyhedra which are presumed to exist, largely on
the calculation of likely structure of
tetrahedrally bonded units. For refs. see Chaplin
2004. The relationship of the images of
individual molecules, and how they are related to
each other, in 3-D space, in liquid water, are
rarely treated, the emphasis being on which units
are present.
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Fig. 10 Two of the molecules in inorganic
materials, illustrated in the garnet structure by
the 4-coordinated (cornered) tetrahedral (colored
yellow and orange in the middle of the four
quadrants, and the 6-coordinated or cornered
octahedra.
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Fig. 11 The final molecule in the structure,
the eight coordinated, or cornered, green cubes,
is added, and knitted into a fixed position. The
relationship of the atoms and polyhedra within
the outlined (unit cell) boundaries are fixed
and repeated ad-infinitum in 3-D space,
illustrating what materials scientists call
structure.
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Grain Boundary Structure of Y-TZP/Bi2O3-CuO-V2O5
Intergranular Nanocomposite
Y-TZP 10wt(Bi2O3-CuO-V2O5 ) , PECS 1200C,
30MPa for 5 min
ZrO2
ZrO2
G. B. Phase
ZrO2
20 nm
matrix ZrO2 grain
1nm
In some materials developed, the nano-sized
crystalline with electric conductivity were also
dispersed in the amorphous grain boundary phases.
ZrO2
ZrO2
ZrO2

• thin amorphous layer at two phase boundaries

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Fig. 13. Comparison of changes in normal (dashed
lines) liquids with highly anomalous changes in
waters properties, which demand the existence of
many structural changes of different kinds and at
different temperatures. Notice in (a), (b) and
(c), the radical difference from normal liquids.
In (b) notice the 308319 difference. The most
dramatic departure from typical liquid behavior
is shown in (c). (Modified from DeBenedetti and
Stanley (Physics Today 6 2003 p 41)
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Fig. 14. A cartoon model of epitaxial transfer
of structural information from one crystal to
another, and to the liquid adjacent to the
crystal without any transfer of composition. The
graphite to diamond determined by the presence
of H but no H is left in the diamond.
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Fig. 15. Irregular nanobubbles shown as modified
from paper by JWG Tyrrell and P. Attard, Phys.
Rev. Lett. 87, 176104 (2001)
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Fig. 16 The change in the structure of water
caused by the subtle energies, as illustrated by
the work of Tiller, Dibble and Kohane (2001)
showing the change of pH of water only in space
conditioned by subtle energies, caused by a
static magnetic field with a specific N/S
orientation.
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Fig. 17. The change in the structure of tap
water shown in its Raman spectrum caused by the
emission of qi (subtle energy) by Dr. Yan Xin
from a distance of 7 km. The main O-H stretch
frequency is very strongly reduced and the
bending modes strongly enhanced (compare before
and after Qi, left and right). The bottom left
shows the reversion in about 2 hours as it
relaxes. The bottom right shows the sample to
sample variation possible.
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Fig. 18. Cryo-TEM image of microstructure of
ice-cream consisting of three phases water, fat,
and air. (From Hans Wildmoser (2004))
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Fig. 19 Cartoon of schematic presentation of the
kind of space-filling mixture of molecular units
which must exist in some proportion of smaller
2-4 molecule clusters (Fig. 8) and other larger
molecules up to the calculated 280 molecule units
shown in Fig. 9, to emphasize the key element of
heterogeneity of structure within water.
Unfortunately, the figure cannot easily present
the scaled spatial relations among the actual
molecules, nor the probable clusters which are
present because no such data exist.The forces
between the clusters outlined in black Must be
very much weaker than the intracluster forces,
although the bond terminations are not drawn thus.
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Penn StateBIOS-MAT-RES

• State of the Art Materials Research on Living
  Systems
• Start with samples claiming effects. e.g. Health
  Effects of Imprinted Waters, ultra fine,
  ultradilute dispersed phases in water

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Penn StateBIOS-MAT-RES (cont.)

• Do Physico-Chemical characterization from all
  directions

• Freezing Point
• Accoustic Loss Spectroscopy
• Viscosity
• Surface Tension

• UV-VIS
• FTIR
• Raman
• Spectroscopic Ellipsometry
• Attenuated Total Reflection (ATR)

3. Triangulate by correlation of anomalies across
techniques
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Ultradiluted Ag Colloidsas the Bridge

• Detailed Studies of then in vitro bioactivity and
  COMPOSITION/STRUCTURE

• ICP
• SEM
• TEM
• Raman
• ATR

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10,000 volt cell for making Ag dispersion
U.S. Patent 6,214,299 Apr. 10, 2001
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Concentrations of metallic silver in engineered
dispersions
Mfrs claim

• 10 ppm
• 32 ppm
• Our analyses
• 10-11 ppm
• 31-32 ppm

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Typical PARTICLES are 30 nm in Vacuum
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TEM of particle
All appear to be single crystal AG
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ATR-IR Spectra Water
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Figure 6 Raman Spectra of Pure Water vs Ag
Colloid on Same Instrument under Identical
Conditions
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Raman Spectrometers
Figure 6 Raman Spectra of Pure Water vs Ag
Colloid on Same Instrument under Identical
Conditions
Figure 5 Ag Colloid Run at 5 Month Interval on
Same Raman Instrument
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Raman Spectra ComparisonUsing 3 Different Lasers
On Same Sample
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Comparison of Raman Spectra Immersion Probe vs
non-Immersion Probe
Silver Dispersion

• Immersion Probe

• Non-Immersion Probe

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Comparison of Raman Spectra Two Different
Immersion Probes

• Immersion Objective - Witec

• Immersion Probe - InPhotonics

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Conclusions

• 1. Classical Approach to Describing Water was
  much too Narrow and One Dimensional
• 2. The Size-Shape of the building blocks tells
  you nothing about structure
• 3. The Materials Science Approach establishes for
  certain that
• The Avogadro limit argument universally used
  against even the plausibility of homeopathy is
  simply wrong. (Our work says nothing about
  whether homeopathy works. It proves that all
  liquids can be changed in structure without
  changing composition.)

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Conclusions for Silver Colloids

• Not as simple as many think
• Effect of charge of metallic particles on the
  structure of water may hold the key

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Penn States MRI-BiosMatres Project

• Ranked 1 in the World in Materials Research Labs

• Offers the world of Whole Person Healing
  practitioners a State of the Art scientific (not
  medical, or clinical) research capability
• Specializes in
• Water Research in all aspects
• Pulsed electro-magnetic field (and acoustic)
  devices of all kinds
• Any device using or relying on minerals/materials

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ANALYSIS OF HOMEOPATHIC REMEDIES BY
SPECTROPSCOPIC METHODS
Show definitive proof that remedies are

• Different from starting solvent
• Change with potencies
• Change with remedy material

Rustum Roy and M.L. Rao The Pennsylvania State
University October 2006
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Spectroscopic Analysis of Ultra dilute Solutions

Figure 1 (a) Raman spectra of DI water wherein
duplicate runs display an excellent overlay of
the data red curve overlays the black
completely, indicative of precision in the data
collection (b) A homeopathic remedy received
from M. S. Benford wherein repeated runs prove
the reproducibility of the data.
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Figure 2 (a) UV-VIS spectra showing the
absorption of the blank polymer cuvette and (b)
blank silica glass cuvette. The nature of the
peaks obtained using DI vs DI as well as the
blank cuvette is similar clearly indicating that
the peaks observed on such a small scale are a
result of an instrumental artifact. Note that
the DI vs DI run is made on two cuvettes of the
same material filled with DI water from the same
source.
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Figure 3 (a) UV-VIS spectra analyzed on
Hahnemann 12C samples wherein the positions of
the cuvettes were interchanged and the spectra
recorded. (b) UV-VIS spectra of the blank silica
glass cuvette after 180o rotation.
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Figure 4 UV-VIS spectra analyzed by two
different people at different time frames (a)
analyzed in April, 2006, by Shakik and (b)
analyzed in August, 2006, by ML Rao. Note
Samples 6x, 30x and CM are homeopathic remedies
from Benford that have also been used for
calibration. DI is de-ionized water prepared in
our laboratory, and it is not the starting
material for any of the homeopathic remedies.
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Figure 5 UV-VIS spectra on the same remedy and
the same potency from different sample vials.
Note the distinct differences in the absorption
spectra in the UV-region (200 - 380 nm).
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(a)(b) Figure 6 Comparison of two different
homeopathic remedies Nat Mur and Nux Vomica
showing representative UV- spectra demonstrating
the differences between the remedies. Note 1 NM
indicates Nat Mur NV indicates Nux Vomica Note
2 For clarity of the data presentation, the
vertical scales are offset to separate the
results for each potency analyzed.. The red
curve represents the 6C, 12C and 30C potencies
for Nat Mur and the black curve represents 6C, 12
C and 30 C for Nux Vomica.
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Figure 7 Envelope of differences within a series
of 10 preparations supplied of each remedy Nat
Mur and Nux Vomica.
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Figure 8 FTIR comparison of Homeopathic Remedies
with different potencies and different remedies.
A clear overlay of the spectra indicates that FT
IR spectroscopy does not reflect any differences
in these homeopathic samples.
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Figure 9 (a) Raman spectra of 6C, 12C and 30C of
Nat Mur and Nux Vomica remedies
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Figure 10 Comparison of the Raman spectra of
the same potencies for the two different
remedies. Note- NM Nat Mur NV Nux Vomica.
The differences in the peaks identified as
(a)-(e) is clearly visible in 30C samples of Nat
Mur and Nux Vomica.