Physical origin underlying the entropy loss upon hydrophobic hydration

The hydrophobic effect (HE) is commonly associated with the demixing of oil and water at ambient conditions and plays the leading role in determining the structure and stability of biomolecular assembly in aqueous solutions. On the molecular scale HE has an entropic origin. It is believed that hydrophobic particles induce order in the surrounding water by reducing the volume of con- figuration space available for hydrogen bonding. Here we show with computer simulation results that this traditional picture is not correct. Analyzing collective fluctuations in water clusters we are able to provide a fundamentally new picture of HE based on pronounced many-body correlations affecting the switching of hydrogen bonds between molecules. These correlations emerge as a non-local compensation of reduced fluctuations of local electrostatic fields in the presence of an apolar solute

NMscatt: a program for calculating inelastic scattering from large biomolecular systems using classical force-field simulations

Computational tools for normal mode analysis, which are widely used in physics and materials science problems, are designed here in a single package called NMscatt (Normal Modes & scattering) that allows arbitrarily large systems to be handled. The package allows inelastic neutron and X-ray scattering observables to be calculated, allowing comparison with experimental data produced at large scale facilities. Various simplification schemes are presented for analysing displacement vectors, which are otherwise too complicated to understand in very large systems.Comment: 13 pages, 5 figures, preprint submitted to Computer Physics Communication

Quasiperiodic Tip Splitting in Directional Solidification

We report experimental results on the tip splitting dynamics of seaweed growth in directional solidification of succinonitrile alloys with poly(ethylene oxide) or acetone as solutes. The seaweed or dense branching morphology was selected by solidifying grains which are oriented close to the {111} plane. Despite the random appearance of the growth, a quasiperiodic tip splitting morphology was observed in which the tip alternately splits to the left and to the right. The tip splitting frequency f was found to be related to the growth velocity V as a power law f V^{1.5}. This finding is consistent with the predictions of a tip splitting model that is also presented. Small anisotropies are shown to lead to different kinds of seaweed morphologies.Comment: 4 pages, 7 figures, submitted to Physical Review Letter

More than one dynamic crossover in protein hydration water

Studies of liquid water in its supercooled region have led to many insights into the structure and behavior of water. While bulk water freezes at its homogeneous nucleation temperature of approximately 235 K, for protein hydration water, the binding of water molecules to the protein avoids crystallization. Here we study the dynamics of the hydrogen bond (HB) network of a percolating layer of water molecules, comparing measurements of a hydrated globular protein with the results of a coarse-grained model that has been shown to successfully reproduce the properties of hydration water. With dielectric spectroscopy we measure the temperature dependence of the relaxation time of protons charge fluctuations. These fluctuations are associated to the dynamics of the HB network of water molecules adsorbed on the protein surface. With Monte Carlo (MC) simulations and mean--field (MF) calculations we study the dynamics and thermodynamics of the model. In both experimental and model analyses we find two dynamic crossovers: (i) one at about 252 K, and (ii) one at about 181 K. The agreement of the experiments with the model allows us to relate the two crossovers to the presence of two specific heat maxima at ambient pressure. The first is due to fluctuations in the HB formation, and the second, at lower temperature, is due to the cooperative reordering of the HB network

Hydration dynamics at fluorinated protein surfaces

Water-protein interactions dictate many processes crucial to protein function including folding, dynamics, interactions with other biomolecules, and enzymatic catalysis. Here we examine the effect of surface fluorination on water-protein interactions. Modification of designed coiled-coil proteins by incorporation of 5,5,5-trifluoroleucine or (4S)-2-amino-4-methylhexanoic acid enables systematic examination of the effects of side-chain volume and fluorination on solvation dynamics. Using ultrafast fluorescence spectroscopy, we find that fluorinated side chains exert electrostatic drag on neighboring water molecules, slowing water motion at the protein surface

GG-circulant Matrices and the Classical Maschke Theorem

In this note, we use the isomorphism of the ring of $G$-circulant matrices over a field $k$ with the group ring $k[G]$ to derive a very short proof of the Classical Maschke Theorem

Indigenous youth peer-led health promotion in Canada, New Zealand, Australia, and the United States: A systematic review of the approaches, study designs, and effectiveness

Background: Youth peer-led interventions have become a popular way of sharing health information with young people and appear well suited to Indigenous community contexts. However, no systematic reviews focusing on Indigenous youth have been published. We conducted a systematic review to understand the range and characteristics of Indigenous youth-led health promotion projects implemented and their effectiveness. Methods: A systematic search of Medline, Embase, and ProQuest Social Sciences databases was conducted, supplemented by gray literature searches. Included studies focused on interventions where young Indigenous people delivered health information to age-matched peers. Results: Twenty-four studies were identified for inclusion, based on 20 interventions (9 Australian, 4 Canadian, and 7 from the United States of America). Only one intervention was evaluated using a randomized controlled study design. The majority of evaluations took the form of pre–post studies. Methodological limitations were identified in a majority of studies. Study outcomes included improved knowledge, attitude, and behaviors. Conclusion: Currently, there is limited high quality evidence for the effectiveness of peer-led health interventions with Indigenous young people, and the literature is dominated by Australian-based sexual health interventions. More systematic research investigating the effectiveness of peer-led inventions is required, specifically with Indigenous populations. To improve health outcomes for Indigenous youth, greater knowledge of the mechanisms and context under which peer-delivered health promotion is effective in comparison to other methods of health promotion is needed