Effects of translational and rotational degrees of freedom on the properties of model water

Molecular dynamics simulations with separate thermostats for rotational and translational motions were used to study the effects of these degrees of freedom on the structure of water at a fixed density. To describe water molecules, we used the SPC/E model. The results indicate that an increase of the rotational temperature, $T_\textrm{R}$, causes a significant breaking of the hydrogen bonds. This is not the case, at least not to such an extent, when the translational temperature, $T_\textrm{T}$, is raised. The probability of finding an empty spherical cavity (no water molecule present) of a given size, strongly decreases with an increase of $T_\textrm{R}$, but this only marginally affects the free energy of the hydrophobe insertion. The excess internal energy increases proportionally with an increase of $T_\textrm{R}$, while an increase of $T_\textrm{T}$ yields a much smaller effect at high temperatures. The diffusion coefficient of water exhibits a non-monotonous behaviour with an increase of the rotational temperature.Comment: 9 pages, 9 figure

Cavity-ligand binding in a simple two-dimensional water model

By means of Monte Carlo computer simulations in the isothermal-isobaric ensemble, we investigated the interaction of a hydrophobic ligand with the hydrophobic surfaces of various curvatures (planar, convex and concave). A simple two-dimensional model of water, hydrophobic ligand and surface was used. Hydration/dehidration phenomena concerning water molecules confined close to the molecular surface were investigated. A notable dewetting of the hydrophobic surfaces was observed together with the reorientation of the water molecules close to the surface. The hydrogen bonding network was formed to accommodate cavities next to the surfaces as well as beyond the first hydration shell. The effects were most strongly pronounced in the case of concave surfaces having large curvature. This simplified model can be further used to evaluate the thermodynamic fingerprint of the docking of hydrophobic ligands.Comment: 6 pages, 5 figure

Primitive model electrolytes. A comparison of the HNC approximation for the activity coefficient with Monte Carlo data

Accuracy of the mean activity coefficient expression (Hansen-Vieillefosse-Belloni equation), valid within the hypernetted chain (HNC) approximation, was tested in a wide concentration range against new Monte Carlo (MC) data for +1:-1 and +2:-2 primitive model electrolytes. The expression has an advantage that the excess chemical potential can be obtained directly, without invoking the time consuming Gibbs-Duhem calculation. We found the HNC results for the mean activity coefficient to be in good agreement with the machine calculations performed for the same model. In addition, the thermodynamic consistency of the HNC approximation was tested. The mean activity coefficients, calculated via the Gibbs-Duhem equation, seem to follow the MC data slightly better than the Hansen-Vieillefosse-Belloni expression. For completeness of the calculation, the HNC excess internal energies and osmotic coefficients are also presented. These results are compared with the calculations based on other theories commonly used to describe electrolyte solutions, such as the mean spherical approximation, Pitzer's extension of the Debye-H\"uckel theory, and the Debye-H\"uckel limiting law.Comment: 15 pages, 6 figure

Modelling the ion-exchange equilibrium in nanoporous materials

Distribution of a two component electrolyte mixture between the model adsorbent and a bulk aqueous electrolyte solution was studied using the replica Ornstein-Zernike theory and the grand canonical Monte Carlo method. The electrolyte components were modelled to mimic the HCl/NaCl and HCl/CaCl_2 mixtures, respectively. The matrix, invaded by the primitive model electrolyte mixture, was formed from monovalent negatively charged spherical obstacles. The solution was treated as a continuous dielectric with the properties of pure water. Comparison of the pair distribution functions (obtained by the two methods) between the various ionic species indicated a good agreement between the replica Ornstein-Zernike results and machine calculations. Among thermodynamic properties, the mean activity coefficient of the invaded electrolyte components was calculated. Simple model for the ion-exchange resin was proposed. The selectivity calculations yielded qualitative agreement with the following experimental observations: (i) selectivity increases with the increasing capacity of the adsorbent (matrix concentration), (ii) the adsorbent is more selective for the ion having higher charge density if its fraction in mixture is smaller.Comment: 12 pages, 9 figure

Novel nano-composite biomaterials that respond to light

Composites of nanoparticles and polymers are finding wide applications to alter material properties, conductivity, and utility. Here, we show that nano-composites can be designed to heat in the presence of near infrared light. This process is useful in transitioning materials through a transition temperature for a range of applications. For example, shape-memory materials (including polymers, metals, and ceramics) are those that are processed into a temporary shape and respond to some external stimuli (e.g., temperature) to undergo a transition back to a permanent shape and may be useful in a range of applications from aerospace to fabrics, to biomedical devices and microsystem components. In this work, we formulated composites of gold nanorods (\u3c1% by volume) and biodegradable networks, where exposure to infrared light induced heating and consequently, shape transitions. The heating is repeatable and tunable based on nanorod concentration and light intensity

Application of Replica Ornstein-Zernike equations in studies of the adsorption of electrolyte mixtures in disordered matrices of charged particles

The Replica Ornstein-Zernike (ROZ) equations were used to study the adsorption of ions from electrolyte mixtures. The adsorbent was represented as a quenched primitive model +1:-1 size symmetric electrolyte, while the mobile particles were ions differing in charge and/or size. The ROZ equations in hypernetted-chain (HNC) approximation were tested against new Monte Carlo results in the grand canonical ensemble; good agreement between the two methods was obtained. The ROZ/HNC theory was then used to study the exclusion coefficients as a function of size and/or charge asymmetry of the annealed ions.Реплiчне рiвняння Орнштейна-Цернiке (РОЦ) застосоване для вивчення адсорбцiї iонiв iз сумiшей електролiтiв. Адсорбент розглядається у виглядi замороженої примiтивної +1:-1 моделi розмiрно симетричного електролiту, тодi як рухомi частинки – це iони, що вiдрiзняються зарядом та/або роз- мiрами. Данi, що отриманi з рiвняння РОЦ у гiперланцюжковому наближеннi (ГЛН), порiвняно з но- вими результатами Монте-Карло моделювання у великому канонiчному ансамблi i виявлено хороше узгодження мiж обома методами. Теорiю РОЦ/ГЛН далi було використано для вивчення коефiцiєнтiв виключення, в залежностi вiд параметрiв розмiрної та/або зарядової асиметрiй нерухомих iонiв

Modeling Amphiphilic Solutes in a Jagla Solvent

Methanol is an amphiphilic solute whose aqueous solutions exhibit distinctive physical properties. The volume change upon mixing, for example, is negative across the entire composition range, indicating strong association. We explore the corresponding behavior of a Jagla solvent, which has been previously shown to exhibit many of the anomalous properties of water. We consider two models of an amphiphilic solute: (i) a "dimer" model, which consists of one hydrophobic hard sphere linked to a Jagla particle with a permanent bond, and (ii) a "monomer" model, which is a limiting case of the dimer, formed by concentrically overlapping a hard sphere and a Jagla particle. Using discrete molecular dynamics, we calculate the thermodynamic properties of the resulting solutions. We systematically vary the set of parameters of the dimer and monomer models and find that one can readily reproduce the experimental behavior of the excess volume of the methanolwater system as a function of methanol volume fraction. We compare the pressure and temperature dependence of the excess volume and the excess enthalpy of both models with experimental data on methanol-water solutions and find qualitative agreement in most cases. We also investigate the solute effect on the temperature of maximum density and find that the effect of concentration isorders of magnitude stronger than measured experimentally

Influence of solvent granularity on the effective interaction between charged colloidal suspensions

We study the effect of solvent granularity on the effective force between two charged colloidal particles by computer simulations of the primitive model of strongly asymmetric electrolytes with an explicitly added hard sphere solvent. Apart from molecular oscillating forces for nearly touching colloids which arise from solvent and counterion layering, the counterions are attracted towards the colloidal surfaces by solvent depletion providing a simple statistical description of hydration. This, in turn, has an important influence on the effective forces for larger distances which are considerably reduced as compared to the prediction based on the primitive model. When these forces are repulsive, the long-distance behaviour can be described by an effective Yukawa pair potential with a solvent-renormalized charge. As a function of colloidal volume fraction and added salt concentration, this solvent-renormalized charge behaves qualitatively similar to that obtained via the Poisson-Boltzmann cell model but there are quantitative differences. For divalent counterions and nano-sized colloids, on the other hand, the hydration may lead to overscreened colloids with mutual attraction while the primitive model yields repulsive forces. All these new effects can be accounted for through a solvent-averaged primitive model (SPM) which is obtained from the full model by integrating out the solvent degrees of freedom. The SPM was used to access larger colloidal particles without simulating the solvent explicitly.Comment: 14 pages, 16 craphic

Similar Risk of Kidney Failure among Patients with Blinding Diseases Who Receive Ranibizumab, Aflibercept, and Bevacizumab:An Observational Health Data Sciences and Informatics Network Study

Purpose: To characterize the incidence of kidney failure associated with intravitreal anti-VEGF exposure; and compare the risk of kidney failure in patients treated with ranibizumab, aflibercept, or bevacizumab. Design: Retrospective cohort study across 12 databases in the Observational Health Data Sciences and Informatics (OHDSI) network. Subjects: Subjects aged ≥ 18 years with ≥ 3 monthly intravitreal anti-VEGF medications for a blinding disease (diabetic retinopathy, diabetic macular edema, exudative age-related macular degeneration, or retinal vein occlusion). Methods: The standardized incidence proportions and rates of kidney failure while on treatment with anti-VEGF were calculated. For each comparison (e.g., aflibercept versus ranibizumab), patients from each group were matched 1:1 using propensity scores. Cox proportional hazards models were used to estimate the risk of kidney failure while on treatment. A random effects meta-analysis was performed to combine each database's hazard ratio (HR) estimate into a single network-wide estimate. Main Outcome Measures: Incidence of kidney failure while on anti-VEGF treatment, and time from cohort entry to kidney failure. Results: Of the 6.1 million patients with blinding diseases, 37 189 who received ranibizumab, 39 447 aflibercept, and 163 611 bevacizumab were included; the total treatment exposure time was 161 724 person-years. The average standardized incidence proportion of kidney failure was 678 per 100 000 persons (range, 0–2389), and incidence rate 742 per 100 000 person-years (range, 0–2661). The meta-analysis HR of kidney failure comparing aflibercept with ranibizumab was 1.01 (95% confidence interval [CI], 0.70–1.47; P = 0.45), ranibizumab with bevacizumab 0.95 (95% CI, 0.68–1.32; P = 0.62), and aflibercept with bevacizumab 0.95 (95% CI, 0.65–1.39; P = 0.60). Conclusions: There was no substantially different relative risk of kidney failure between those who received ranibizumab, bevacizumab, or aflibercept. Practicing ophthalmologists and nephrologists should be aware of the risk of kidney failure among patients receiving intravitreal anti-VEGF medications and that there is little empirical evidence to preferentially choose among the specific intravitreal anti-VEGF agents. Financial Disclosures: Proprietary or commercial disclosure may be found in the Footnotes and Disclosures at the end of this article.</p