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Two Kinds of Water
and their importance to living organisms


This web page is about the work of
Philippa Wiggins
retired from the Department of Medicine,
University of Auckland Medical School,
Auckland, New Zealand.

16th of July 1925 - 16th of March 2017.
An obituary may be found
at the bottom of this page




Philippa Wiggins at Otago University in 1964
Published in University of Otago 150 years
The Hocken Collections, Department of Biochemistry records, MS-4113/009,
S14.512b. Permission applied for.





In 1986 Dr Wiggins published the results of her experiments showing that water
exists in two distinct structural forms. She used infrared spectroscopy to study
the strength of hydrogen bonding in water trapped in membranes. This showed two
distinct bond strengths instead of the wide range of bond strengths that would
be expected for a single type of water structure (Wiggins and van Ryn,1986).

Recently a group of scientists using the synchrotron at Stanford University, and
other groups in Japan and Sweden, showed that liquid water exists simultaneously
in two forms. This finally gives independent solid support for a theory which Dr
Wiggins proposed many years ago to explain the behavior of water in biological
systems. (See the Stanford News article by Tuttle, and the scientific
publication by Huang et. al., Aug 2009 given in the reference list below.)

Dr Wiggins has spent most of her life studying the properties of water. She
started out as a physical chemist and discovered that silica gel was capable of
selectively taking up potassium and excluding sodium (Wiggins 1973). In fact the
absorption of ions into water trapped in tiny cavities or pores inside the
silica gel followed the same pattern as the selective uptake of ions in living
cells, following the order   Mg2+ <   Ca2+ <   Li+ <   Na+ <   K+ <   Rb+ <  
Cs+.    She proposed that the structure of water inside these pores was
different to bulk water and that it behaved as a different solvent, taking up
potassium in preference to sodium.

This discovery led in the mid-1970s to her proposal that the sodium-potassium
ATP-ase, known as the sodium pump, operated by forming a pocket of 'ordered'
water at the same time as a channel openned in the ATP-ase. This allowed solutes
such as sodium to diffuse out of the pocket of 'ordered' water, through the
channel, into the bulk water outside the cell. The channel closed as the ordered
water collapsed and the conformational structure of the ATP-ase also changed.
This model has required only minor refinements as more is learned about the
actual protein stuctures of these pumps and about the properties of water.

The discovery that water exists in two structural forms led to the gradual
development and evolution of a theory which explains many previously unexplained
phenomena in biology. The wide range of biological processes that can be
explained by this theory, ranges from how the sodium-potassium pump and other
pumps work; how enzymes work to catalyze chemical reactions which would
otherwise require extremely high temperatures and pressures; how proteins fold
(Wiggins, 2009a) or in some cases misfold causing diseases such as Alzheimers
Disease, Parkinson's Disease and Huntington's Disease; how prion diseases such
as Creutzfeldt-Jakob Disease and "mad cow disease" occur (Wiggins, 2008a); how
DNA spirals into such an elegant double helix and how certain crucial steps in
the origins of life may have occurred.

She is a meticulous laboratory worker and an honest scientist dedicated only to
discovering the truth about water and its role in all living things, while
avoiding politics and publicity. She has numerous publications in peer reviewed
journals, and for the list of references below she has selected a handful of
articles that were written after 1986 when she confirmed that water exists in
two forms. At that time all her work had focused on the properties of water near
surfaces or in small cavities. In 1994 Wilse Robinson proposed that bulk liquid
water also existed in two forms and called it 'The Modern Mixture Model' to
distinguish it from an older model apparently proposed by Roentgen in 1891.
Since 1994 Dr Wiggins' work has incorporated the modern mixture model into all
her publications and her recent contribution has been to explain the importance
of these discoveries to biological systems and to explain the thermodynamics of
the equilibrium between two structural forms of water.

Wiggins' theory is based on the idea that all water exists in two forms. One is
an ice-like structure called low density water or LDW, and she has shown that
it's infrared spectrum is indeed similar to ice, while the high density water
(HDW) has a different and clearly distinct infrared spectrum. Bulk liquid water
has a mixture of these two types of water kept in an equilibrium by an
interesting energy balance described by thermodynamics. It is a balance between
entropy (or randomness) and enthalpy (or heat) in the two kinds of water. This
balance shifts with increasing temperature with more water shifting from LDW to
HDW. The balance between these two forms of water is affected by the properties
of nearby surfaces and solutes. Dr Wiggins has carefully studied the free energy
changes that occur in various situations and this analysis has proven remarkably
powerful in explaining numerous anomolies that have puzzled chemists and
biologists for a century or more.

The reader may be interested in a free on-line monograph Dr Wiggins wrote in
2007 called Life Depends upon Two Kinds of Water. This and other references with
links to web sites containing abstracts or full publications are listed below.

A. Evan Lewis PhD, MD (previously a PhD student of Dr Wiggins from 1974-1977)
DrEvanLewis@gmail.com



NEWS FLASH JUNE 2018

A news report describes experiments demonstrating that "Water exists in two
forms". The article is based on a publication in Nature which describes two
forms of isolated water molecules in a vacuum. It was found that the nuclear
spins of the two hydrogen nuclei can be either in the same direction or oposite
directions and this results in a 23% difference in the rate of a chemical
reaction. Could this finding be related to the differences in hydrogen bonding
in high density and low density water?

Another article in the popular press Water Behaves Differently From All Other
Liquids, And We Finally Know Why introduces research showing that the anomolous
behaviour of water can be explained by proposing that water forms specific
tetrahedral structures similar to diamond in some regions while remaining more
disordered in other regions. The proportion of water in each of the two states
can change, resulting in the anomolous behaviour. The full article by John Russo
et al, published in PNAS on 2nd April 2018, can be found here: Water-like
anomolies as a function of tetrahedrality. The bond angles between hydrogen and
oxygen promote the formation of tetrahedral structures with hydrogen bonding.
Professor Wiggins' early work referred to the two kinds of water as ordered and
disordered, structured or unstructured but later she preferred the terms low
density and high density structures.

Martin Chaplin of London South Bank University has compiled an amazing on-line
monograph called 'Water Structure and Science' which gives a thorough overview
of all aspects concerning the properties of water.



References


Cameron I.L., Kanal, K.M., Keener, C.R. & Fullerton, G.D. A mechanistic view of
the non-ideal osmotic and motional behavior of intracellular water. Cell Biol.
International 21 (1997) 99-113.

Cho, H.C., Singh, S. & Robinson, G.W. Understanding all of water's anomalies
with a non-local potential. J. Chem. Phys. 107 (1997) 7979-7988.

Evan A, Lewis D, Wiggins PM A simple universal mechanism of use and conservation
of energy: its application to movements of ions and other materials across cell,
mitochondrial and other membranes and to oxidative phosphorylation. Med
Hypotheses. 1977 Jan-Feb;3(1):25-32

The above reference was published with the authors listed incorrectly. It should
be A Evan Lewis and PM Wiggins. Please contact me at the email address given
below if you would like the full article.

Harrington, S,. Poole, P H Sciortino,F and Stanley, H. E. Equation of State of
Supercooled SPC/E Water. J. Chem. Phys. 107, 7443-7450 (1997)

Huang, C, K. T. Wikfeldt, T. Tokushima, D. Nordlund, Y. Harada, U. Bergmann, M.
Niebuhr, T. M. Weiss, Y. Horikawa, M. Leetmaa, M. P. Ljungberg, O. Takahashi, A.
Lenz, L. Ojamäe, A. P. Lyubartsev, S. Shin, L. G. M. Pettersson and A. Nilsson.
The inhomogeneous structure of water at ambient conditions. Proceedings of the
National Academy of Sciences, August 13, 2009, doi: 10.1073/pnas.0904743106

Jason K. Holt, Hyung Gyu Park, Yinmin Wang, Michael Stadermann, Alexander B.
Artyukhin, Costas P. Grigoropoulos, Aleksandr Noy, Olgica Bakajin Fast Mass
Transport Through Sub-2-Nanometer Carbon Nanotubes. Science 19 May 2006: Vol.
312 no. 5776, pp. 1034 - 1037 (www.sciencemag.org)

Mishima, O. & Stanley, H.E. Decompression induced melting of ice iv and the
liquid-liquid transition in water. Nature (Lond.) 392 (1998) 164-168.

Mishima, O. & Stanley, H.E. (1998): The relationship between liquid, supercooled
and glassy water. Nature (Lond.) 396 (1998) 329-335.

Ridley, M, 2000. Mendelae's Demon. Phoenix, London.

Robinson, G. Wilse (1996) Water in biology, chemistry, and physics: experimental
overviews and computational methodologies. World Scientific Series in
Contemporary Chemical Physics, Vol 9. World Scientific Publishing Company,Pte
Ltd, PO Box 128, Farrer Rd, Singapore 912805.

Tuttle, Kelen. SLAC researchers reveal the internal dance of water, Stanford
University News Aug 10, 2009.

Vedamuthu, M., Singh, S. & Robinson, G.W. Properties of liquid water: origin of
the density anomalies. J. Phys. Chem. 98 (1994) 2222-2230.

Wiggins, P.M (1973). Ionic partition between surface and bulk phase water in
silica gel. Biophysical J. (1973) 13, 131-146.

Wiggins, P.M. & van Ryn, R.T. (1986) The solvent properties of water in
desalination membranes. J.Macromol. Sci. Chem. A23 (1986) 875-903.

Wiggins, PM (1995) Microosmosis, a chaotic phenomenon of water and solutes in
gels. Langmuir 11 1984-1986.

Wiggins PM. (2002a) Water in complex environments such as living cells. Physica
A 314: 485-491.

Wiggins PM (2002b) Enzymes and two-state water. J.Biol.Physics and Chemistry 2:
25-37.

Wiggins P (2007) Life Depends upon Two Kinds of Water. PLoS ONE 3(1): e1406.
doi:10.1371/journal.pone.0001406

Wiggins PM (2008a) Prions plaques and polyelectrolytes. Journal of Biological
Physics and Chemistry 8 49-54

Wiggins PM (2008b) DNA as a Darwinian self-replicator. Journal of Biological
Physics and Chemistry 8 89-93

Wiggins PM (2009a) The source of some of the extraordinary powers and properties
of enzymes. WATER 1, 35 - 41

Wiggins PM (2009b) Enzymes and surface water, WATER 1, 42 - 51

For a more comprehensive list of publications by Philippa Wiggins go to the
following site and enter Wiggins PM.

Search PubMed.



Contacts



Webmaster:
A. Evan Lewis - DrEvanLewis at gmail.com

First Posted: December 10th 2009.

Last Updated: June 6 2018.

Top



Obituary Draft
Philippa Wiggins the unsung scientist.

Professor Philippa Wiggins passed away peacefully on March 16th 2017.
Born on 16th of July 1925 she was 91 years old.



Professor Philippa Wiggins (nee Glasgow) was a very private and modest person
but in reality she was a widely recognized and respected scientist who was known
around the world for the huge impact she had on our basic understanding of the
biochemistry of life. When I told her she should be a candidate for the Nobel
Prize in Medicine and Physiology she said she was not interested in that.

Specifically her contributions to understanding the special properties of water,
in living systems, would be difficult to over-estimate. She worked tirelessly as
a particularly careful and meticulous research scientist and taught a number of
young post-graduate researchers. She was a master of the English language and
through thesis supervision she passed this skill on to her pupils.

She was appointed Professor of Membrane Physiology at the Medical School in the
University of Auckland and later Emeritus Professor. She received numerous
awards and accolades but due to her modest, private, and unassuming nature,
these often went unnoticed. Her work resulted in at least 70 articles published
in respected international peer-reviewed journals. Later in her life, she worked
with companies in New Zealand developing industrial and medical applications of
her theories and had about 40 patents to her name.

She was able to explain many phenomena by more fully understanding the structure
and properties of water. She realised that water is not a random collection of
H2O molecules with little interaction between the molecules or those dissolved
in it. It was already known that water is unique in being an extremely polar
molecule which means that the two hydrogen atoms have a strong positive charge
while the single oxygen atom carries a strong negative charge. This results in
water molecules being strongly attracted to each other with connections called
hydrogen bonds.

Through this bonding, water can form huge crystal-like structures similar to ice
that have a lower density than the surrounding less-structured water. One might
expect this to cause water to become solid, and it does at low temperatures. But
at temperatures above zero degrees C, the ice-like structures break down and
form again at incredibly rapid speeds. This gives liquid water its special
properties. Without hydrogen bonding there would be only solid and gas but no
liquid. Interestingly, these two forms of water which co-exist have different
chemical properties.

The low density crystal-like structures take up potassium but not sodium. Dr
Wiggins first observed this phenomenon in the late 1960s and early 1970s when
she was studying the physical chemistry of silica gel at the University of
Otago. This material contains tiny pores or holes that are so small that huge
water structures cannot form and water exists only in the low density structured
form. Consequently, the water in silica gel takes up potassium and excludes
sodium.

A “eureka moment” occurred when she realised that this is exactly the way living
cells work. When she analyzed other chemical ions they also behaved exactly the
same way as living cells. To explain this, she proposed that water can exist in
at least two different forms as described above and that the living cells make
use of this property. She used infrared spectroscopy to demonstrate the
existence of two structures of water in biological systems, and this has been
confirmed in bulk water using the linear accelerator at Stanford University by
other researchers.

Professor Wiggins’ discovery has had a profound impact on many branches of
biochemistry and medicine. She has published papers describing how water affects
the structure of DNA and proteins and how it has influenced the evolution of
life itself. Since these interactions are fundamental to life, they can also
explain several types of diseases. She wrote about how prions cause diseases
like mad cow disease and how water influences the formation of plaques in the
brain that cause Alzheimer’s disease.

This short article cannot describe all the things that Philippa did to advance
our understanding of water and life itself, but the serious reader is referred
to a web site that includes links to many of her scientific publications,
www.PhilippaWiggins.com.

After gaining an MSc honors degree in Chemistry at Canterbury University in
1947, Philippa was awarded a scholarship to work at the Davy-Faraday Laboratory
at the Royal Institution in London, and later completed her PhD at King’s
College’ London. Philippa returned to New Zealand to work with Dr Walter Metcalf
at the University of Canterbury (who was also my teacher and PhD examiner). From
1962 to 1966. She then worked as a research scientist at the University of Otago
and that is where her lifetime interest in the role of water in living cells
began.

During times when it was difficult to obtain funding for scientific research and
when grants were usually for two years, she was awarded lifetime funding as a
Career Fellow by the New Zealand Medical Research Council. She continued her
research at the University of Auckland from 1970 to 1990. In 1994 she was
cofounder of BioStore NZ, and in 1997 she was a research scientist for Genesis
Research and Development Corporation. She continued to publish scientific papers
until at least 2009.

For all the people who knew Philippa in her professional roles, her passing is a
time of great sadness at the loss of such an important scientist and such a
wonderful personality. Our condolences go to her family who must also feel a
great sense of loss. She certainly would have been proud of her grandson, Jordan
Douglas who is embarking on a PhD in computational biology at the University of
Auckland, and thus continuing the family tradition.

Written by Evan Lewis, PhD, MD who was one of Professor Wiggins’ PhD students
1974 to 1978.