Matrix Isolation Spectroscopy: Aqueous p-Toluenesulfonic Acid Solvation.

Interaction between p-toluenesulfonic acid (pTSA) and water is studied at -20 °C in a CCl4 matrix. In CCl4 water exists as monomers with restricted rotational motion about its symmetry axis. Additionally, CCl4 is transparent in the hydrogen-bonded region; CCl4 thus constitutes an excellent ambient thermal energy matrix isolation medium for diagnosing interactions with water. Introducing pTSA-nH2O gives rise to two narrow resonances at 3642 cm-1 and at 2835 cm-1 plus a broad 3000-3550 cm-1 absorption. In addition, negative monomer symmetric and asymmetric stretch features relative to nominally dry CCl4 indicate that fewer water monomers exist in the cooled (-20 °C) acid solution than in room-temperature anhydrous CCl4. The negative peaks along with the broad absorption band indicate that water monomers are incorporated into clusters. The 3642 cm-1 resonance is assigned to the OH-π interaction with a cluster containing many water molecules per acid molecule. The 2835 cm-1 resonance is assigned to the (S-)O-H stretch of pTSA-dihydrate. The coexistence of these two species provides insights into interactions in this acid-water CCl4 system.

Static density functional study of graphene-hexagonal bilayer ice interaction.

Periodic static ab initio studies are conducted of hexagonal bilayer ice (HBL) and basal layers of ice-1h adsorbed on graphene using the model BLYP-D in CRYSTAL09. Eight high-symmetry periodic forms of HBL are optimized, of which four have lower energy; their electronic binding energy to graphene is ∼1.6 kcal/mol per abutting H2O. Optimized geometries have the property of maximizing the occurrence of a certain O-H-C alignment motif. One lattice is selected for more detailed study. Its 2-D shear translation potential energy surface is found to have barrier heights in two zigzag directions of ∼140 cal/mol per abutting H2O. A second hexagonal bilayer can be added and the electronic binding energy drops from ∼1.7 to ∼1.0 kcal/mol per abutting H2O. For ice-1h monolayer adsorbed on graphene, a proton-ordered form in which half of the O's nearest the graphene carry a proton pointing toward graphene is preferred over proton-ordered forms in which either all or none of those O's have H's pointing toward graphene. Cohesive energy for two-layer ice-1h on graphene is 0.66 kcal/mol of H2O higher than for HBL, supporting experimental evidence that the graphene+HBL isomer is more stable. However, the HBL and two-HBL structures are unstable or at best metastable with respect to four layers of ice-1h.

Ab initio molecular dynamics study of the aqueous HOO(-) ion.

The properties of the hydroperoxide anion, HOO(-), in water play a key role in many biological systems and industrial processes. However the dynamics of HOO(-) and its solvation shell are largely unknown. We have undertaken an ab initio molecular dynamics study of aqueous HOO(-) at ambient temperature in liquid water. Two solvation structures for the hydroperoxide anion account for 90% or more of the configurations in a 25 ps NVT run at 300 K: these have four hydrogen bond donors to the terminal oxygen atom of HOO(-) and either one or two hydrogen bond donors to its middle oxygen atom. The H of HOO(-) is essentially always a donor in an H-bond to a water molecule. Two structures with three donors to the terminal O and either one or two at the middle O are also important. A set of five NVE runs totaling 74 ps found considerable variability in the proportions of time spent in each type of solvation pattern. Mean lifetimes of these patterns ranged from 54 to 109 fs, after which the complexes were observed to transform into different, sometimes less favorable structures. Analysis of the electronic structure associated with different solvation patterns indicates that a traditional Lewis-type picture of hydrogen bonding at the middle oxygen and non-Lewis behavior at the terminal oxygen coexist in aqueous HOO(-). The non-Lewis character of the terminal oxygen is compared to similar observations of the oxygen in the hydrated hydroxide ion from previous ab initio molecular dynamics of OH(-)(aq).

Comparison of hydrated hydroperoxide anion (HOO-)(H2O)n clusters with alkaline hydrogen peroxide (HOOH)(OH-)(H2O)(n-1) clusters, n = 1-8, 20: an ab initio study.

Hydroperoxide anion (HOO(-)), the conjugate base of hydrogen peroxide (HOOH), has been relatively little studied despite the importance of HOOH in commercial processes, atmospheric science, and biology. The anion has been shown to exist as a stable species in alkaline water. This project explored the structure of gas phase (HOO(-))(H(2)O)(n) clusters and identified the lowest energy configurations for n ≤ 8 at the B3LYP/6-311++G** level of theory and for n ≤ 6 at the MP2/aug-cc-pVTZ level of theory. As a start toward understanding equilibration between HOO(-) and HOOH in an alkaline environment, (HOOH)(OH(-))(H(2)O)(n-1) clusters were likewise examined, and the lowest energy configurations were determined for n ≤ 8 (B3LYP/6-311++G**) and n ≤ 6 (MP2/aug-cc-pVTZ). Some studies were also done for n = 20. The two species have very different solvation behaviors. In low energy (HOOH)(OH(-))(H(2)O)(n-1) clusters, HOOH sits on the surface of the cluster, is 4-coordinated (each O is donor once and acceptor once), and donates to the hydroxide ion. In contrast, in low energy (HOO(-))(H(2)O)(n) clusters, (HOO(-)) takes a position in the cluster center surrounded on all sides by water molecules, and its optimum coordination number appears to be 7 (one O is donor-acceptor-acceptor while the other is a 4-fold acceptor). For n ≤ 6 the lowest (HOOH)(OH(-))(H(2)O)(n-1) cluster lies 1.0-2.1 kcal/mol below the lowest (HOO(-))(H(2)O)(n) cluster, but the lowest clusters found for n = 20 favor (HOO(-))(H(2)O)(20). The results suggest that ambient water could act as a substantial kinetic brake that slows equilibration between (HOOH)(OH(-)) and (HOO(-))(H(2)O) because extensive rearrangement of solvation shells is necessary to restabilize either species after proton transfer.

Topology-energy relationships and lowest energy configurations for pentagonal dodecahedral (H2O)20X clusters, X = empty, H2O, NH3, H3O+: the importance of O-topology.

For (H(2)O)(20)X water clusters consisting of X enclosed by the 5(12) dodecahedral cage, X = empty, H(2)O, NH(3), and H(3)O(+), databases are made consisting of 55-82 isomers optimized via B3LYP/6-311++G(**). Correlations are explored between ground state electronic energy (Ee) or electronic energy plus zero point energy (Ee+ZPE) and the clusters' topology, defined as the set of directed H-bonds. Linear regression is done to identify topological features that correlate with cluster energy. For each X, variables are found that account for 99% of the variance in Ee and predict it with a rms error under 0.2 kcal/mol. The method of analysis emphasizes the importance of an intermediate level of structure, the "O-topology," consisting of O-types and a list of O pairs that are bonded but omitting H-bond directions, as a device to organize the databases and reduce the number of structures one needs to consider. Relevant variables include three parameters, which count the number of H-bonds having particular donor and acceptor types; absolute value(M)(2), where M is the cluster's vector dipole moment; and the projection of M onto the symmetry axis of X. Scatter diagrams for Ee or Ee+ZPE versus absolute value(M) show that clusters fall naturally into "families" defined by the values of certain discrete parameters, the "major parameters," for each X. Combining "family" analysis and O-topologies, a small group of clusters is identified for each X that are candidates to be the global minimum, and the minimum is determined. For X = H(3)O(+), one cluster with central hydronium lies just 2.08 kcal/mol above the lowest isomer with surface hydronium. Implications of the methodology for dodecahedral (H(2)O)(20)(NH(4)(+)) and (H(2)O)(20)(NH(4)(+))(OH(-)) are discussed, and new lower energy isomers are found. For MP2/TZVP, the lowest-energy (H(2)O)(20)(NH(4)(+)) isomer features a trifurcated H-bond. The results suggest a much more efficient and comprehensive way of seeking low-energy water cluster geometries that may have wide applicability.

Enzyme stabilization by glass-derived silicates in glass-exposed aqueous solutions.

OBJECTIVES: To analyze the solutes leaching from glass containers into aqueous solutions, and to show that these solutes have enzyme activity stabilizing effects in very dilute solutions. METHODS: Enzyme assays with acetylcholine esterase were used to analyze serially succussed and diluted (SSD) solutions prepared in glass and plastic containers. Aqueous SSD preparations starting with various solutes, or water alone, were prepared under several conditions, and tested for their solute content and their ability to affect enzyme stability in dilute solution. RESULTS: We confirm that water acts to dissolve constituents from glass vials, and show that the solutes derived from the glass have effects on enzymes in the resultant solutions. Enzyme assays demonstrated that enzyme stability in purified and deionized water was enhanced in SSD solutions that were prepared in glass containers, but not those prepared in plastic. The increased enzyme stability could be mimicked in a dose-dependent manner by the addition of silicates to the purified, deionized water that enzymes were dissolved in. Elemental analyses of SSD water preparations made in glass vials showed that boron, silicon, and sodium were present at micromolar concentrations. CONCLUSIONS: These results show that silicates and other solutes are present at micromolar levels in all glass-exposed solutions, whether pharmaceutical or homeopathic in nature. Even though silicates are known to have biological activity at higher concentrations, the silicate concentrations we measured in homeopathic preparations were too low to account for any purported in vivo efficacy, but could potentially influence in vitro biological assays reporting homeopathic effects.

The silica hypothesis for homeopathy: physical chemistry.

The 'silica hypothesis' is one of several frameworks that have been put forward to explain how homeopathic remedies, which often are diluted beyond the point where any of the original substance remains, might still be clinically effective. We describe here what the silica hypothesis says. From a physical chemistry viewpoint, we explore three challenges that the hypothesis would have to meet in order to explain homeopathy: thermodynamic stability of a large number of distinct structures, pattern initiation at low potencies, and pattern maintenance or gradual evolution at higher potencies. We juxtapose current knowledge about silicates with some of the conventional wisdom about homeopathic remedies, to see how well the latter might be a consequence of the former. We explore variants of the hypothesis including some speculations about mechanisms. We outline laboratory experiments that could help to decide it.

The octave potencies convention: a mathematical model of dilution and succussion.

Several hypothesized explanations for homeopathy posit that remedies contain a concentration of discrete information-carrying units, such as water clusters, nano-bubbles, or silicates. For any such explanation to be sustainable, dilution must reduce and succussion must restore the concentration of these units. Succussion can be modeled by a logistic equation, which leads to mathematical relationships involving the maximum concentration, the average growth of information-carrying units rate per succussion stroke, the number of succussion strokes, and the dilution factor (x, c, or LM). When multiple species of information-carrying units are present, the fastest-growing species will eventually come to dominate, as the potency is increased. An analogy is explored between iterated cycles dilution and succussion, in making homeopathic remedies, and iterated cycles of reseeding and growth, in bacterial cultures. Drawing on this analogy, the active ingredients in low and medium potency remedies may be present at early dilutions but only gradually come to 'dominate', while high potencies may develop from the occurrence of low-probability but faster-growing 'mutations.' Conclusions from this model include: 'x' and 'c' potencies are best compared by the amount of dilution, not the amount of succussion; the minimum number of succussion strokes needed per cycle is proportional to the logarithm of the dilution factor; and a plausible interpretation of why potencies at approximately regular ratios are traditionally used (the octave potencies convention).

O-H stretch modes of dodecahedral water clusters: a statistical ab initio study.

Infrared frequencies calculations were carried out for 20 (H2O)20 water clusters obeying the 5(12) dodecahedral geometry, optimized at the B3LYP/6-311++G** level. Their combined spectra contained 800 O-H stretch modes, ranging from 2181 to 3867 cm(-1) (unscaled), which were treated and studied as a database. Of these, 752 modes (94%) could be assigned to a single dominant O-H stretch. These 752 were classified into five subdatabases depending on the local H-bond type of the dominant stretch. The frequency (nu) was correlated with the O-H distance (b(OH)), with H-bond length (R(OO)) where applicable, and with other variables. The parameter b(OH) alone accounted for 96-99% of the variance in nu for stretches in H-bonds. The correlation with R(OO) is substantially weaker. Normal modes were classified as "high ratio" or "low ratio" depending upon the mode's distribution of kinetic energy among the O-H bonds. High-ratio modes (389 modes, or 49% of our sample) are modeled well as a single oscillator undergoing small perturbations by weak coupling from other oscillators. Low-ratio modes involve strong coupling with at least one other O-H stretch for which b(OH2) is close to b(OH). The IR intensities of modes vary widely but can be explained in terms of a single equation giving dipole moment derivatives as a function of b(OH). For the lowest-energy (H2O)20 clusters, their IR stretch spectra contained eight distinguishable absorption bands. An explanation for eight bands in terms of the theory of polyhedral water clusters is offered.

Espectroscopia de alta sensibilidad de resonancia magnética nuclear en protones (H-NMR) de medicamentos homeopáticos hechos en agua (Parte 4) / High-sensitivity spectroscopy of proton nuclear magnetic resonance (H-NMR) of homeopathic water facts (Part 4)

Lo que sí es prioritario informar, es que los medicamentos que provienen de los laboratorios HELIOS poseen una mayor concentración de estos iones con respecto a los medicamentos preparados en el laboratorio de análisis (medias de 55 y 44 contra un máximo de 30)

Espectroscopia de alta sensibilidad de resonancia magnética nuclear en protones (H-NMR) de medicamentos homeopáticos hechos en agua (Parte 4) / High-sensitivity spectroscopy of proton nuclear magnetic resonance (H-NMR) of homeopathic water facts (Part 4)

Lo que sí es prioritario informar, es que los medicamentos que provienen de los laboratorios HELIOS poseen una mayor concentración de estos iones con respecto a los medicamentos preparados en el laboratorio de análisis (medias de 55 y 44 contra un máximo de 30)

Espectroscopia de alta sensibilidad de resonancia magnética nuclear en protones (H-NMR) de medicamentos homeopáticos hechos en agua (Parte 3) / High-sensitivity spectroscopy of proton nuclear magnetic resonance (H-NMR) of homeopathic water facts (Part 3)

El objetivo de este proyecto fue encontrar picos o marcas discretas y fuertes que los encontrados previamente. Posteriormente se examinaron 35 posiciones no esperadas para explicar si existen algún tipo de señales en esas posiciones. Quince de las 35 señales fueron consideradas artefactos, lo que quiere decir que son señales que probablemente generadas por el mismo aparato y las cuales no se relacionaron con la muestra.

Espectroscopia de alta sensibilidad de resonancia magnética nuclear en protones (H-NMR) de medicamentos homeopáticos hechos en agua (Parte 3) / High-sensitivity spectroscopy of proton nuclear magnetic resonance (H-NMR) of homeopathic water facts (Part 3)

El objetivo de este proyecto fue encontrar picos o marcas discretas y fuertes que los encontrados previamente. Posteriormente se examinaron 35 posiciones no esperadas para explicar si existen algún tipo de señales en esas posiciones. Quince de las 35 señales fueron consideradas artefactos, lo que quiere decir que son señales que probablemente generadas por el mismo aparato y las cuales no se relacionaron con la muestra.

Espectroscopia de alta sensibilidad de resonancia magnética nuclear en protones (H-NMR) de medicamentos homeopáticos hechos en agua (Parte 2) / High-sensitivity spectroscopy of proton nuclear magnetic resonance (H-NMR) of homeopathic water facts (Part 2)

En este estudio se formularon los remedios minerales mas haya de la 12C, comezando desde la tintura madre que consistía en una solución hecha por nosotros conformada por Cloruro de Sodio 1M y Nitrato de Plata 0.1N.

Espectroscopia de alta sensibilidad de resonancia magnética nuclear en protones (H-NMR) de medicamentos homeopáticos hechos en agua (Parte 2) / High-sensitivity spectroscopy of proton nuclear magnetic resonance (H-NMR) of homeopathic water facts (Part 2)

En este estudio se formularon los remedios minerales mas haya de la 12C, comezando desde la tintura madre que consistía en una solución hecha por nosotros conformada por Cloruro de Sodio 1M y Nitrato de Plata 0.1N.

Esctroscopia de alta sensibilidad de resonancia magnética nuclear en protones (H-NMR) de medicamentos homeopáticos hechos en agua (parte 1) / Esctroscopia high sensitivity proton nuclear magnetic resonance (H-NMR) of homeopathic water facts (part 1)

El mecanismo de acción de los medicamentos homeopáticos ha sido confuso para sus practicantes y científicos estudiosos por más de dos siglos. Donde una sucusión debe alterar el solvente, proporcionándole una "memoria" o "información" que los sistemas biológicos pueden detectar. Algunos experimentos han tratado de demonstrar o documentar como es que la alteración del solvente ocurre mediante estudios físicos y químicos de los cuales han fallado en la obtención de resultados positivos en pruebas independientes y por duplicado.

Esctroscopia de alta sensibilidad de resonancia magnética nuclear en protones (H-NMR) de medicamentos homeopáticos hechos en agua (parte 1) / Esctroscopia high sensitivity proton nuclear magnetic resonance (H-NMR) of homeopathic water facts (part 1)

El mecanismo de acción de los medicamentos homeopáticos ha sido confuso para sus practicantes y científicos estudiosos por más de dos siglos. Donde una sucusión debe alterar el solvente, proporcionándole una "memoria" o "información" que los sistemas biológicos pueden detectar. Algunos experimentos han tratado de demonstrar o documentar como es que la alteración del solvente ocurre mediante estudios físicos y químicos de los cuales han fallado en la obtención de resultados positivos en pruebas independientes y por duplicado.

Zero point energy of polyhedral water clusters.

Polyhedral water clusters (PWCs) are cage-like (H2O)n clusters where every O participates in exactly three H bonds. For a database of 83 PWCs, 8 < or = n < or = 20, geometry was optimized and zero point energy (ZPE) was calculated at the B3LYP/6-311++G** level. ZPE correlates negatively with electronic energy (E0): each increase of 1 kcal/mol in E0 corresponds to a decrease of about 0.11 kcal/mol in ZPE. For each n, a set of four connectivity parameters accounts for 98% or more of the variance in ZPE. Linear regression of ZPE against n and this set gives an RMS error of 0.13 kcal/mol. The contributions to ZPE from stretch modes only (ZPE(S)) and from torsional modes only (ZPE(T)) also correlate strongly with E0 and with each other.

Proton and deuteron position preferences in water clusters: an ab initio study.

In order to explore the effect of H-to-D substitution on the zero-point energy (ZPE) of water clusters, Hessians were computed for a database of 53 optimized (H2O)n clusters, 5 < or = n < or = 21, at the B3LYP6-311 + + G** level. The 53 clusters contained 1524 protons, which were sorted into 18 categories according to the type of their donor O and (if not free) acceptor O. Letting deltaZPE[H]* denote the change in ZPE when the proton H* is replaced by D, mean values for deltaZPE[H*] for the H-bonded categories ranged from -2172 cal mol(-1) for H* in a DDAA-DDAA bond to -2118 for H* in a DAA-DDA bond. Mean value for H* free on DAA (respectively, DA) was -2018 (respectively, -1969). For DAA-DDA bonds, and for short H bonds in general, there was a strong inverse correlation between /deltaZPE[H*]/ and the O-H* distance. deltaZPE for multiple H-to-D substitutions was additive, except for a cooperativity effect of -13.7 to -19.7 cal mol(-1) when two substituted protons were in the same H2O unit and a much smaller cooperativity when one proton's donor was the other's acceptor. Implications of these data include a relative preference for D to occupy H bonded rather than free positions in finite water clusters, a value of 3.82 for the disproportionation equilibrium constant of mixed ice at 150 K, increased occupation by H at surface positions of mixed ice, and a larger average coordination number for liquid D2O than for liquid H2O.

High sensitivity 1H-NMR spectroscopy of homeopathic remedies made in water.

BACKGROUND: The efficacy of homeopathy is controversial. Homeopathic remedies are made via iterated shaking and dilution, in ethanol or in water, from a starting substance. Remedies of potency 12 C or higher are ultra-dilute (UD), i.e. contain zero molecules of the starting material. Various hypotheses have been advanced to explain how a UD remedy might be different from unprepared solvent. One such hypothesis posits that a remedy contains stable clusters, i.e. localized regions where one or more hydrogen bonds remain fixed on a long time scale. High sensitivity proton nuclear magnetic resonance spectroscopy has not previously been used to look for evidence of differences between UD remedies and controls. METHODS: Homeopathic remedies made in water were studied via high sensitivity proton nuclear magnetic resonance spectroscopy. A total of 57 remedy samples representing six starting materials and spanning a variety of potencies from 6 C to 10 M were tested along with 46 controls. RESULTS: By presaturating on the water peak, signals could be reliably detected that represented H-containing species at concentrations as low as 5 microM. There were 35 positions where a discrete signal was seen in one or more of the 103 spectra, which should theoretically have been absent from the spectrum of pure water. Of these 35, fifteen were identified as machine-generated artifacts, eight were identified as trace levels of organic contaminants, and twelve were unexplained. Of the unexplained signals, six were seen in just one spectrum each. None of the artifacts or unexplained signals occurred more frequently in remedies than in controls, using a p < .05 cutoff. Some commercially prepared samples were found to contain traces of one or more of these small organic molecules: ethanol, acetate, formate, methanol, and acetone. CONCLUSION: No discrete signals suggesting a difference between remedies and controls were seen, via high sensitivity 1H-NMR spectroscopy. The results failed to support a hypothesis that remedies made in water contain long-lived non-dynamic alterations of the H-bonding pattern of the solvent.