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## Cf. JR Van Wazer American Scientist 1962 50 450 describing ‘Structural Reorganization
Throughout The Periodic Table’ indicated that stochastic behaviour is widespread and first became
associated with PolyP and related chemical systems when 31P NMR became available
Van Wazer (later when working at Vanderbilt University
together with colleagues elsewhere) found evidence that NMR
absorptions of simple phosphorus-oxy-acid units which
constitute PolyPi, vary in a counter-ion-dependent manner with
aqueous solution concentrations apparently via an induced a
major change in adjacent ‘water structure’ (the puzzling
complex linking together of often many individual water (H2O)
molecules within liquid water. This linking between phosphate
related compounds is likely to play an important part in their
detergency but also may be a part of the reason why liquid water
in contact with pro-life phosphorus oxy-acid systems of which
PolyPi is a key member, is the reason why both liquid water and
phosphate are essential for life. This is now further
hypothesized to be because PolyPi changes water quality in
subtle ways which are probably related to how
liquid water also supports stochastic Brownian
motion where the second law of thermodynamics is
now known to be unequivocally breached. This breach
can be interpreted (Searles et al. 2002) as a brief
reversal of time (cf. Wang GM et al. Phys Rev Lett 2002 89
050601) and its application to the Eyring complex (Appendix).
Perhaps PolyPi and similar phosphorus oxy-acid ‘detergency’
enhances this breach.
Numerous biologically-relevant chemical reactions in water
have been found to display what might be related (part)
stochastic behaviour which cannot be explained by classical
thermodynamics. Attempts to rationally design drugs (which
operate in biological aqueous solutions) by designed chemical
modification to improve binding of the drugs to their receptors
were most often found to be seriously mysterious hampered by a
systematic counter-force which Nature seemed to use to directly
counter these efforts; when these binding processes were
quantified by isothermal calorimetry which gave direct results
for the enthalpy and entropy changes in the binding processes a
surprising correlation was found between the binding entropy
and enthalpy. This correlation is outwith what is allowed by
classical thermodynamics.
A similar correlation had been historically found for numerous
Arrhenius pre-exponential and activation energy terms in sets of
chemical reactions; (chemical reactions go faster under higher
temperature conditions but these rates are similarly restricted by
some mysterious force: this turned out to be the same entropy
enthalpy compensation (EEC) phenomena which had later been
identified by the isothermal calorimetric studies of drug receptor
binding. (The physical origin of EEC remains one of the
outstanding puzzles in science (it also showing up in semiconductor and
photoelelectronics where it is termed the Meyer-Neldel rule ) ##.
#
Bizarrely the use of PolyPi in cosmetics may genuinely put the clock back for wrinkled aged skin
Footnotes
a
While scientists now known a great deal about DNA, a polymer system
which may have evolved from polyPi, they, until recently, have largely
ignored the latter which consists of a (often very long) helix of P-O-P
linked phosphate groups which for many animal species also contains
within its helix calcium ions and poly-β-hydroxybutyrate, a substance with
piezoelectric powers (meaning it can translate mechanical force into electricity).
PolyPi is
- O- O - O-
│ │ │
O- P -[-P-O] - P-O-
║ ║ n║
O O O
where n=0 this is pyrophosphate (PPi ) ) or where n>0 up to
several thousand in bacteria and a few tens in animals
Van Wazer found that classes of PolyPi or analogous ring polyphosphates when
examined by 31P NMR showed mixtures to be present. An organophosphurus
pesticide labelled with a molecular structure derived from classical preparative
organic chemistry logic (OMPA) showed none of the molecular structure shown on
the label of its container to be present: this organo-phosphorus hitherto-believed-to be
a specific molecular substance turned out to be an reproducible mixture consisting of
an array of different molecular substances which seemed to have been spontaneously
formed from the single substance identified on the label; (cf. American Scientist 1962
50 450 [for a more formal description of the Van Wazer stochastic processes see DW
Matula LCD Groenweghe and JR Van Wazer J Chem Phys 1964 41 3105-21]. PolyPi
similarly could be made to undergo simultaneously break up and rearrangement their
P-O-P bonds, creating a random structure reorganization (occurring most
characteristically above a critical temperature which can be decreased by catalysts).
The mixture which can have a very large number of individual molecular structures is
what nature prefers for the numbers of covalent oxidation state five P, bivalent
covalent oxygen atoms and monocovalent phosphorus oxygen anion units. A similar
stochastic-related behaviour was found to occur above a critical temperature range
throughout the periodic table but more commonly in inorganic and organometallic
compounds than for purely organic compounds. Liquid water seems also to be a Van
Wazer stochastic mixture.
For organic substsnces, chlorinated compound were more prone to stochastic
rearrangement; cf. absolutely all perchlorcarbon compounds were found rearranged
to create an apparent equilibrium between only three final (pseudo)equilibrium
compounds: carbon tetrachloride, hexachlorobenzene and hexachloroethane.
Examined under closer experimental investigation is was confirmed to not be a
classical thermodynamics type of equilibrium (i.e. one which is microscopically
reversible).
The term ‘stochastic’ as in modern ‘stochastic thermodynamics’ theory which can
concern an aspect of fluctuation of entropy flow (which we can consider time reversal
in the Searles 2002 interpretation of the Evans fluctuation and other fluctuation
theorems)) was not used by Van Wazer and co-workers who used the words reversible
‘scrambling’ or ‘random structural reorganization’. When Dave Matula, a
mathematician, became a co-author of JR Van Wazer they then employed the
‘stochastic’ terminology. At that time, however, not fully understood that a specific
(putatively time-reversal-determined) kind of ‘stochastic’ activity which showed up as
‘Structural Reorganization Throughout the Period Table’ required a total re-think of
one-way-time thermodynamics and also required a re-think of chemical reactivity and
biochemistry.
John H Leffler (J Org Chem 1955, 20, 1202-8) in a wide-ranging review of chemical
kinetic studies carried out at about the same time as Van Wazer was finding stochastic
behaviour in inorganic substances, reported that Arrhenius rate expressions in the
peer reviewed literature surprisingly revealed that almost the rates of all chemical
reactions when arranged in sets showed up an extra-thermodynamic (i.e. non-
classical-thermodynamic) correlation between entropy and enthalpy change.
Leffler also indicated that this correlation seemed to be related to whether a reaction
was ‘clean’ or gave a range of products. The latter happened near the isothermal
temperature (obtained from the EEC plot).
The temperature range of stochastic behaviour seems the same kind of observation
also made by Van Wazer who was unaware of Lefflers work.
This indicates that the stochastic effect applies to both inorganic and organic sets of
chemical reactions.
The specific temperature (the isokinetic temperature) where all reactions in a set
proceeded at the same rate can generates apparent completely random, stochastic
behaviour as regards the products of chemically defined reaction sets of reactions
when applied to the polyphosphates, polysilicates, polysulphates etc.
Although both Van Wazer and Leffler (cf., however, the 2001 Chem Rev article by
Liu & Guo (Chem Rev 2001) showed that the isokinetic phenomena identified by
Leffler might sometimes, or often, arise artifactually). These authors had continued
the common attempts to use pure classical thermodynamics (chemical equilibrium
tied to Gibbs free energy and one-way time) to explain the observed stochastic
phenomena which they had also found to permeate the whole of chemistry, and much
of physics; these scientists, like others at that time, had, I think, critically ignored a
hundred year old statement by James Clark Maxwell had made: that the second law of
thermodynamics (and one-way time) only applies to an assemblage of molecules
(something like 1020) and should not be applied to single or perhaps the usual lab.-size
sample of molecular assemblies. This means that classical thermodynamics should
not have been blindly applied to the study of chemical reaction kinetics. The EEC
phenomenon and its apparent irrationality seems the basis of this. How EEC arises
however seems also o require both space and time distortion (relativity).
b
Other theories of the origin of life on early Earth have suggested the special water
structures occurring in pores e.g. those in silica gel were responsible for the start of
life on Earth. Evidently silica pores create the “living water” also associated with the
PolyPi family of molecules. It should be noted that both polyPi and silica gel and sols
(‘polySii’) abundantly occur in association with volcanic activity including that at
deep sea vents (cf. Wilde loc. cit.)where it is commonly assumed early life on earth
could have arisen.
Cf., in the pore water theory of life as set out by PM Wiggins in PLoS ONE 2008
3(1): e1406; Phillipa seems to have been reticent to much emphasize the part played
in her first research into the water structuring properties of silica pores perhaps
because this had been an associated scientific scandal of supposed ‘polywater’ of
water in capillary theory which was later retracted. Perhaps, in part, wrongly.
Phillipa had originally discovered the pore water effect in silica gel (i.e. this generated
the more reactive, low viscosity form of liquid water: high density water (HDW)
(“living” water); her later researches found that the same phenomenon occurred in
pores formed by those organic polymers which mimicked polysaccharides and
proteins (i.e. water niches or pores which occur in more conventional carbon-based
biological systems).
SiO2 sols are capable of self seeding and also age in a manner mimicking biological
cells. (cf. b Grant D et al., 1992 Med Hypoth. 38 46-8) and web document
‘porewateroriginoflife’ Lubbock U)
SiO2 sols present in sufficient amounts in somenatural waters can apparently allow
magnetic fields to strongly inhibit CaCO3 scale formation (cf. Szkatula A et al. Eur
Phys J Applied Phys 2002 18 41-9); cf. also the latter process per se has also been
discussed as a model for pre-biotic life in the context of the present need in physics to
revise the currently accepted rigidity of the second law of thermodynamics (cf., A
Lima-de-Faria 1987 in “Evolution without selection, form and function by
autoevolution Elsevier Science Publishers BV (Biomedical Division)). Such
autoevolution of similar complex fractal forms in both minerals and animal organs
and organisms surely must derive from common-to-all hidden electromagnetic fields
of the putative vacuum space information and structure holding system, the existence
of which seems somehow to be implicit in the above-mentioned explanation of the
enthalpy entropy compensation phenomena (which is also an alternative way of
formulating the Heisenberg Principle and the Le Chatelier Principle and perhaps also I
Ching. Cf. D Grant 2015 List-1-6 scribd.
Perhaps the pore water in SiO2 sols confers life-like water structure building
properties on these carbon-free cells and the effect upon them of artificial magnetic
fields and thereby mimics the hypothesized ability of biological water structures
associated with PolyPi etc., and bio-silica (e.g. associated with the sulphated
extracellular matrix) to interact in a pro-life manner with the natural magnetic fields
of the quantum vacuum.
(Which might conceivably the basis of the sixth sense’).
Cf. the Schrödinger quantum coherence theory of life.
It seems that for life to have evolved increasing complexity over geological timescales
(a seemingly overt breach of a simple interpretation of the second law) requires that
viable biological cells need critical amounts –O-P(O)-O and perhaps also –O-S(O)-
O22- and –O-Si-(O-)2-O- structures interspersed with organic structures (including
proteins) . This inorganic water quantum system processing system goes awry in
cancer where aberrant growth occurs by erroneous phosphorylation (related growth
factor activation (and altered sulphation and silication). Such augmented
phosphorylation apparently directly alters “living” ‘water structure’ including
HDW/LDW in a damaging way.
PolyPi may however always alter HDW/LDW beneficially if administered in a to-be-
determined controlled manner,
b-1
We might deduce that this arrangement of atoms is central to life. Perhaps because of
its unique relationship with water molecules. Perhaps is a transducer for accessing the
proposed vacuum cloud information system. (like an imaginary by ‘can-be-made-real’
DNA of space-time). Cf. the Schrödinger quantum coherence theory of life.
c
As a postgrad many years ago working with DS Payne a lecturer at Glasgow
University, I used phosphorous acid as a reagent in a chemical procedure which had
been reported to produce a high yield of P
olyPi (starting from phosphoric acid and acetic anhydride) to produce etidronate
ethane hydroxyl diphosphonic acid (now called a bisphosphonate) in quantitative
yield. As Van Wazer’s book ‘Phosphorus and its Compounds’ (Interscience 1958) did
not mention bisphosphonates or their formation by the very simple preparation
method I had used, I had difficulty getting this research result across to DSP and
others.
I also came across the common ability of phosphorus oxy-acids, their salts and
hydrates to generate hydration structures which caused infrared absorption continua
(rather than the more usual sharp absorptions which can be ascribed to a
straightforward chemical bond vibration frequency, the continuum absorption of
hydrogen in water or hydrate chemical bonds is attributable to quantum mechanical
tunnelling which is a stochastic process (cf. G Zundel publications).
The presence of PolyPi in oral tooth biofilm may impact greatly on how
dental al caries arises via removal by oral bacteria to form PolyPi. Cf.
Breland AM et al., Appl. Environ. Microbiol. 2018
doi:10.1128/AEM.02440-17
Grant D. J Appl Chem Biotechnol 1974 (1/2) 49-58; J Inorg Nucl Chem 1967 29 69-
81; D 2012 http://www/scribd.com/doc/87757336
:Liu L & Guo Q-L Chem Rev 2001 101 673-95
Appendix
Schematic of space - time distortion in Eyrng complex