On the Propensity of Excess Hydroxide Ions at the Alcohol Monolayer-Water Interface.

Atomistic molecular dynamics simulations have been employed to study the self-ion (H+ and OH-) distribution at the interface between long-chain C16-OH alcohol (cetyl alcohol) monolayer and water. It is well known that the free air-water interface is acidic due to accumulation of the hydronium (H3O+) ions at the interface. In the present study, we have observed that contrary to the air-water interface, at the long-chain alcohol monolayer-water interface, it is the hydroxide (OH-) ion, not the hydronium ion (H3O+) that gets accumulated. By calculating the potential of mean forces, it is confirmed that there is extra stabilization for the OH- ions at the interface relative to the bulk, but no such stabilization is observed for the H3O+ ions. By analyzing the interaction of the self-ions with other constituents in the medium, it is clearly shown that the favorable interaction of the OH- ions with the alcoholic -OH groups stabilizes this ion at the interface. By calculating coordination numbers of the self-ions it is observed that around 50% water neighbors are substituted by alcoholic -OH in case of the hydroxide ion at the interface, whereas in the case of hydronium ions, only 15% water neighbors are substituted by the alcoholic -OH. The most interesting observation about the local structure and H-bonding pattern is that the hydroxide ion acts solely as the H-bond acceptor, but the hydronium ion acts only as the H-bond donor.

The surgical management of cutaneous abscesses: A UK cross-sectional survey.

AIM: Cutaneous abscesses are one of the most common acute general surgery presentations. This study aimed to understand the current practice in the management of cutaneous abscesses in the United Kingdom (UK), once the decision has been made that acute surgical incision and drainage (I&D) is required. METHOD: General surgeons from across the UK were surveyed on their opinions on the optimum management of cutaneous abscesses. Outcomes measured included anaesthesia, incision technique, antibiotic administration, departmental abscess pathways, and post-drainage management. A combination of Likert scales, multiple-choice questions, and short answer questions were used. Comparisons were made of Likert scales between regions using a two-sample independent t-test. The survey was peer reviewed and distributed through the Association of Coloproctology of Great Britain and Ireland (ACPGBI) network between April and June 2018. RESULTS: Sixty-one responses were collected from surgeons throughout the UK. Of these respondents, 69% indicated that cutaneous abscesses would always or usually require a General Anaesthetic (GA) for treatment, and 82% indicated that abscesses were at least sometimes not treated until the next day due to a lack of resources. While 79% of surgeons stated that pus swabs are always or are usually taken, 44% of respondents never or rarely chased the results. The main indications for giving antibiotics were sepsis/systemically unwell patients, and cellulitis. 31% of responding centres had an abscess management protocol, and 82% of respondents confirmed that they would always pack the abscess wound post-operatively. CONCLUSION: 'Incision and drainage' is currently the most widely used technique for the surgical management of cutaneous abscess. However, this study demonstrates the significant variability in the use of anaesthesia, antibiotics, packing and the use of protocols to guide and streamline patient management.

How Different Are the Characteristics of Aqueous Solutions of tert-Butyl Alcohol and Trimethylamine- N-Oxide? A Molecular Dynamics Simulation Study.

Atomistic molecular dynamics simulations have been used to investigate differences in the characteristics of the aqueous solutions of two structurally similar, biologically important molecules, namely, tert-butyl alcohol (TBA) and trimethylamine- N-oxide (TMAO). By analyzing radial distribution functions, preferential solvation factors, and the number of nearest neighbors, structural characteristics of the two aqueous solutions are found to be dramatically different. By examining the distribution of nearest neighbor solute and solvent molecules in these two solutions, it is found that the aqueous solution of TMAO is homogeneous, whereas that of TBA is not. Further scrutiny of TBA-TBA radial distribution function at a high concentration by splitting the surrounding TBA molecules into two hemispheres demonstrates that the TBA aggregation occurs not only from the side of methyl moieties of TBA as expected in hydrophobicity-induced aggregation, but also from the side of the polar C-OH group. To analyze the effect of concentration of the two solute molecules (TBA and TMAO) on the local structure of water, tetrahedral order parameter and distributions of tetrahedral angles and hydrogen-bonding angles have been calculated for both the solutions. It is surprising to see that at high concentrations, the local water structure in the TMAO solution is more disrupted compared to the same in the TBA solution. Finally, the action of these two solutes on the folding-unfolding behavior of Trp-cage miniprotein has been analyzed and their contrasting activities toward the protein stability are correlated to the strikingly different behavior of their aqueous solutions.

Generic Mechanism for Pattern Formation in the Solvation Shells of Buckminsterfullerene.

Accurate description of solvation structure of a hydrophobic nanomaterial is of immense importance to understand protein folding, molecular recognition, drug binding, and many related phenomena. Moreover, spontaneous pattern formation through self-organization of solvent molecules around a nanoscopic solute is fascinating and useful in making template-directed nanostructures of desired morphologies. Recently, it has been shown using polarizable atomistic models that the hydration shell of a buckminsterfullerene can have atomically resolved ordered structure, in which C60 atomic arrangement is imprinted. In analyzing any peculiar behavior of water, traditionally, emphasis has been placed on the long-ranged and orientation-dependent interactions in it. Here, we show through molecular dynamics simulation that the patterned solvation layer with the imprints of the hydrophobic surface atoms of the buckminsterfullerene can be obtained from a completely different mechanism arising from a spherically symmetric, short-ranged interaction having two characteristic lengthscales. The nature of the pattern can be modified by adjusting solvent density or pressure. Although solute-solvent dispersion interaction is the key to such pattern formation adjacent to the solute surface, the ordering at longer lengthscale is a consequence of mutual influence of short-range correlations among successive layers. The present study thus demonstrates that the formation of such patterned solvation shells around the buckminsterfullerene is not restricted to water, but encompasses a large class of anomalous fluids represented by two-lengthscale potential.

Is Solute Rotation in an Ionic Liquid Influenced by the Addition of Glucose?

Fluorescence anisotropy measurements and molecular dynamics (MD) simulations have been performed to understand the specific interactions of two structurally similar nondipolar solutes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP), with neat 1-butyl-3-methylimidazolium dicyanamide ([BMIM][N(CN)2]) and also in the presence of glucose. It has been observed that the measured reorientation times of DMDPP in neat [BMIM][N(CN)2] follow the predictions of the Stokes-Einstein-Debye hydrodynamic theory with slip boundary condition. Addition of glucose (0.075 and 0.15 mole fraction) has no bearing on the rotational diffusion of the solute apart from the viscosity related effects. In contrast, the reorientation times of DPP in neat [BMIM][N(CN)2] obey stick boundary condition as the hydrogen bond donating solute experiences specific interactions with the dicyanamide anion. No influence of the additive can be noticed on the rotational diffusion of DPP at 0.075 mole fraction of glucose. However, at 0.15 mole fraction of glucose, the reorientation times of the solute at a given viscosity and temperature decrease by 15-40% compared to those obtained in the neat ionic liquid. MD simulations indicate that each DPP molecule hydrogen bonds with two dicyanamide anions in neat ionic liquid. The simulations also reveal that, at 0.15 mole fraction of glucose, the concentration of anions hydrogen bonded to glucose increases significantly; therefore, the percentage of solute molecules that can form hydrogen bonds with two dicyanamide anions decreases to 84, which leads to faster rotation of DPP.

Effects of Concentration on Like-Charge Pairing of Guanidinium Ions and on the Structure of Water: An All-Atom Molecular Dynamics Simulation Study.

Like-charge ion-pair formation in an aqueous solution of guanidinium chloride (GdmCl) has two important facets. On one hand, it describes the role of the arginine (ARG) side chain in aggregation and dimer formation in proteins, and on the other hand, it lends support for the direct mechanism of protein denaturation by GdmCl. We employ all-atom molecular dynamics simulations to investigate the effect of GdmCl concentration on the like-charge ion-pair formation of guanidinium ions (Gdm(+)). From analyses of the radial distribution function (RDF) between the carbon atoms of two guanidinium moieties, the existence of both contact pairs and solvent-separated pairs has been observed. Although the peak height corresponding to the contact-pair state decreases, the number of Gdm(+) ions in the contact-pair state actually increases with increasing GdmCl concentration. We have also investigated the effect of the concentration of Gdm(+) on the structure of water. The effect of GdmCl concentration on the radial and tetrahedral structures of water is found to be negligibly small; however, GdmCl concentration has a considerable effect on the hydrogen-bonding structure of water. It is demonstrated that the presence of chloride ions, not Gdm(+), in the first solvation shell of water causes the distortion in the hydrogen-bonding network of water. In order to establish that Gdm(+) not only stacks against another Gdm(+) but also directly attacks the ARG residue of a protein or peptide, simulation of an ARG-rich peptide in 6 M aqueous solution of GdmCl has been performed. The analyses of RDFs and orientation distributions reveal that the Gdm(+) moiety of the GdmCl attacks the same moiety in the ARG side chain with a parallel stacking orientation.

Molecular dynamics simulation of aqueous urea solution: is urea a structure breaker?

An aqueous solution of urea is a very important mixture of biological relevance because of the definitive role of urea as protein denaturant at high concentrations. There has been an extended debate over the years on urea's influence on the structure of water. On the basis of a variety of analysis methods employed, urea has been described as a structure-breaker, a structure-maker, or as neutral toward water structure. Using molecular dynamics simulation and a nearest neighbor approach of analyzing water structure, we present here a detailed analysis of the effect of urea on water structure. By carefully choosing the nearest neighbors, allowing urea also to be a neighbor of a reference water molecule, we have conclusively shown that urea does not break the local tetrahedral structure of water even at high concentrations. A slight change in the distribution of tetrahedral order parameters as a function of urea concentration has been shown to be a result of change in the proportions of n-hydrogen-bonded water molecules. The present result thus suggests that urea is able to substitute for water in the hydrogen-bonded network nicely without breaking the tetrahedral, hydrogen-bonded structure of water.

Correlation of structural order, anomalous density, and hydrogen bonding network of liquid water.

We use extensive molecular dynamics simulations employing different state-of-the-art force fields to find a common framework for comparing structural orders and density anomalies as obtained from different water models. It is found that the average number of hydrogen bonds correlates well with various order parameters as well as the temperature of maximum densities across the different models, unifying apparently disparate results from different models and emphasizing the importance of hydrogen bonding in determining anomalous properties and the structure of water. A deeper insight into the hydrogen bond network of water reveals that the solvation shell of a water molecule can be defined by considering only those neighbors that are hydrogen-bonded to it. On the basis of this view, the origin of the appearance of a non-tetrahedral peak at a higher temperature in the distribution of tetrahedral order parameters has been explained. It is found that a neighbor that is hydrogen-bonded to the central molecule is tetrahedrally coordinated even at higher temperatures. The non-tetrahedral peak at a higher temperature arises due to the strained orientation of the neighbors that are non-hydrogen-bonded to the central molecule. With the new definition of the solvation shell, liquid water can be viewed as an instantaneously changing random hydrogen-bonded network consisting of differently coordinated hydrogen-bonded molecules with their distinct solvation shells. The variation of the composition of these hydrogen-bonded molecules against temperature accounts for the density anomaly without introducing the concept of large-scale structural polyamorphism in water.

Characterizing hydrophobicity at the nanoscale: a molecular dynamics simulation study.

We use molecular dynamics (MD) simulations of water near nanoscopic surfaces to characterize hydrophobic solute-water interfaces. By using nanoscopic paraffin like plates as model solutes, MD simulations in isothermal-isobaric ensemble have been employed to identify characteristic features of such an interface. Enhanced water correlation, density fluctuations, and position dependent compressibility apart from surface specific hydrogen bond distribution and molecular orientations have been identified as characteristic features of such interfaces. Tetrahedral order parameter that quantifies the degree of tetrahedrality in the water structure and an orientational order parameter, which quantifies the orientational preferences of the second solvation shell water around a central water molecule, have also been calculated as a function of distance from the plate surface. In the vicinity of the surface these two order parameters too show considerable sensitivity to the surface hydrophobicity. The potential of mean force (PMF) between water and the surface as a function of the distance from the surface has also been analyzed in terms of direct interaction and induced contribution, which shows unusual effect of plate hydrophobicity on the solvent induced PMF. In order to investigate hydrophobic nature of these plates, we have also investigated interplate dewetting when two such plates are immersed in water.

Spontaneous idiopathic subcapsular biloma.

Spontaneous biloma is an uncommon entity. We report a case of subcapsular biloma in an elderly patient with a nonobstructed biliary channel, without prior history of surgery, instrumentation, or trauma. Computed tomography (CT) and magnetic resonance imaging are described. We believe that this is the first reported case of spontaneous subcapsular biloma of idiopathic origin.