Understanding the Reshaping of Fluorinated Polyester Vitrimers by Kinetic and DFT Studies of the Transesterification Reaction

Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Following up on a recent report on catalyst-free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in α- or β-position, parallel DFT calculations and an experimental kinetic study on model molecules are presented in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate.     

Some Isoperimetric Inequalities in Electrochemistry and Hele Shaw Flows

Isoperimetric inequalities are applied to a moving-boundaryproblem for doubly-connected domains. This problem occurs forexample in electrochemistry, in which case the domains in questionare the electrolyte of an electrolytic cell. The two electrodessurrounding the electrolyte are assumed to grow or dissolve,at different rates in general, by electrochemical reaction.We obtain optimal estimates showing, for example, that the leastchange in volume of each electrode always occurs in sphericalsymmetry.     

Path-integral Monte Carlo simulations of electron localization in water clusters

Path-integral Monte Carlo simulations are used to investigate the possibility of binding of an excess electron to water clusters. Model potentials are used to characterize the interaction between the excess electron and a water monomer and between two water molecules. The simulations reveal that two water molecules can bind an electron. In addition, it is found that the excess electron can be trapped in the field of three water molecules arranged in a linear configuration. The results are used to comment on recent molecular beam experiments.     

Drying and hydrophobic collapse of paraffin plates

We perform molecular dynamics simulations of the hydrophobic collapse of two paraffin plates to examine how the collapse is mediated by realistic paraffin-water attractive van der Waals forces. We explore several aspects of the drying transition between the plates, including the critical separation for drying and the critical size of the vapor bubble required for the nucleation of the drying event. We also investigate the kinetics of hydrophobic collapse and find that the hydrophobic collapse occurs in about 100 ps. We compare these results with the simulations with the plate-water van der Waals attractions turned off and with recent results on the hydrophobic collapse of multidomain proteins. Last, we discuss the relationship among the dewetting transition critical distance, van der Waals potential well depth, and water contact angle on solute surface using a simple macroscopic theory.     

Dynamics of water confined in the interdomain region of a multidomain protein

Molecular dynamics simulations are performed to study the dynamics of interfacial water confined in the interdomain region of a two-domain protein, BphC enzyme. The results show that near the protein surface the water diffusion constant is much smaller and the water-water hydrogen bond lifetime is much longer than that in bulk. The diffusion constant and hydrogen bond lifetime can vary by a factor of as much as 2 in going from the region near the hydrophobic domain surface to the bulk. Water molecules in the first solvation shell persist for a much longer time near local concave sites than near convex sites. Also, the water layer survival correlation time shows that on average water molecules near the extended hydrophilic surfaces have longer residence times than those near hydrophobic surfaces. These results indicate that local surface curvature and hydrophobicity have a significant influence on water dynamics.     

Why is the partial molar volume of CO2 so small when dissolved in a room temperature ionic liquid? Structure and dynamics of CO2 dissolved in [Bmim+] [PF6(-)

When supercritical CO2 is dissolved in an ionic liquid, its partial molar volume is much smaller than that observed in most other solvents. In this article we explore in atomistic detail and explain in an intuitive way the peculiar volumetric behavior experimentally observed when supercritical CO2 is dissolved in 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim+] [PF6(-)]). We also provide physical insight into the structure and dynamics occurring across the boundary of the CO2 ionic liquid interface. We find that the liquid structure of [Bmim+] [PF6(-)] in the presence of CO2 is nearly identical to that in the neat ionic liquid (IL) even at fairly large mole fractions of CO2. Our simulations indicate, in agreement with experiments, that partial miscibilities of one fluid into the other are very unsymmetrical, CO2 being highly soluble in the ionic liquid phase while the ionic liquid is highly insoluble in the CO2 phase. We interpret our results in terms of the size and shape of spontaneously forming cavities in the ionic liquid phase, and we propose that CO2 occupies extremely well-defined locations in the IL. Even though our accurate prediction of cavity sizes in the neat IL indicates that these cavities are small compared with the van der Waals radius of a single carbon or oxygen atom, CO2 appears to occupy a space that was for the most part a priori "empty".     

Elastic bag model for molecular dynamics simulations of solvated systems: application to liquid water and solvated peptides

The fluctuating elastic boundary (FEB) model for molecular dynamics has recently been developed and validated through simulations of liquid argon. In the FEB model, a flexible boundary which consists of particles connected by springs is used to confine the solvated system, thereby eliminating the need for periodic boundary conditions. In this study, we extend this model to the simulation of bulk water and solvated alanine dipeptide. Both the confining potential and boundary particle interaction functions are modified to preserve the structural integrity of the boundary and prevent the leakage of the solute-solvent system through the boundary. A broad spectrum of structural and dynamic properties of liquid water are computed and compared with those obtained from conventional periodic boundary condition simulations. The applicability of the model to biomolecular simulations is investigated through the analysis of conformational population distribution of solvated alanine dipeptide. In most cases we find remarkable agreement between the two simulation approaches.     

Central neurocytoma: typical magnetic resonance spectroscopy findings and atypical ventricular dissemination

PURPOSE: Central neurocytomas (CNCs) are rare neuronal tumors that have a favorable prognosis and lower rate of recurrence compared with other intraventricular neoplasms. Although it may be difficult to distinguish CNC on conventional neuroimaging, typical MR spectroscopy (MRS) features have been reported. We describe the MRI and MRS features of CNC. MATERIALS AND METHODS: Eight patients with CNC were reviewed. Three patients underwent presurgical in vivo single-voxel MRS at short echo time (TE, 35 ms) and multi-voxel MR spectroscopic imaging at long TE (144 ms). The surgically resected tumor specimen of one of these patients was also studied ex vivo using high-resolution magic angle spinning (HRMAS) nuclear magnetic resonance. RESULTS: All eight tumors were located in the lateral ventricles. In six patients, CNC extended into the third ventricle, and in two patients the tumor showed further contiguous intraventricular dissemination into the fourth ventricle. In all three patients who underwent MRS, a characteristic metabolite peak was detected at 3.55 parts per million (ppm) at both long and short TE. HRMAS confirmed the presence of elevated glycine (Gly) at 3.55 ppm, without increase in the concentration of myo-inositol found at the same chemical shift. Elevated choline (at 3.2 ppm) was also seen in all three patients. CONCLUSION: On MRS, CNCs have a typical appearance with a metabolite peak at 3.55 ppm due to increased Gly, and this feature may be helpful in presurgical diagnosis. Although they are rare benign intraventricular tumors, in atypical cases, CNCs can show extensive intraventricular dissemination into the fourth ventricle.     

Collective properties of polyatomic gases in a magnetic field: Effects on light scattering spectrum

The effect of magnetic fields on collective properties of polyatomic gases has been extended outside the hydrodynamic regime. The calculations are based on a linearized Waldmann-Snider equation. The Waldmann-Snider collision operator is truncated yielding a finite matrix equation. The resulting matrix equation is solved on a computer to yield the polarized and depolarized light scattering spectra. These spectra are calculated in the absence and presence of a magnetic field. For long wavelengths it is found that the magnetic effects are of the same order of magnitude as in the Senftleben-Beenakker effects. For shorter wavelengths the effects disappear due to Doppler effects.This work was supported by NSF GP22881.Alfred P. Sloan Foundation Fellow.NIH Predoctoral Fellow.