Periodic and high-temperature disordered conformations of polytetrafluoroethylene chains: an ab initio modeling

We report here the main results of a successful attempt to predict some macroscopic properties of representative polymers of technological relevance both in regular and disordered forms by using first principle quantum mechanical approaches at microscopic level. Until now, the prediction of the structural and thermal properties of those polymers has been mostly a domain of molecular mechanics methods. To overcome the limits of those classical computational tools whenever physical properties are significantly influenced by stereoelectronic effects (e.g., electron rich substituents), we employed methods rooted in the Density Functional Theory (DFT). A general computational strategy including the proper choice of periodic boundary conditions (PBC), functional, basis set, and model system size, has been tested and validated for saturated polymers such as polyethylene and isotactic/syndiotactic polypropylenes. On the basis of these results, a comprehensive study of poly(tetrafluoroethylene) (PTFE) chains in both regular periodic and disordered conformations has been performed. A statistical approach has been next applied to obtain the thermal concentration of defects and to reproduce the thermal behavior of the investigated polymer. At the end, a very good agreement with experimental X-ray diffraction and IR results has been achieved, definitely reaching a good understanding of the widely studied disorder phenomenon determining the main technological properties of poly(tetrafluoroethylene) (the trade Teflon) and, at the same time, identifying the proper computational tools to investigate perfluoro-compounds and other complex polymeric systems.     

Study of flexible joints and permanent bends in DNA fragments by brownian dynamics simulations

The use of Brownian dynamics simulations to investigate the presence of structural (kinks) and dynamic (bulges) anomalies in short DNA stretches is analyzed in connection with a string-of-beads model. A scaling method to choose the hydrodynamic translational and rotational parameters of the beads is proposed and tested on straight, kinked and bulged DNA fragments 17 nm long. The model reproduces the rigid-body rotational diffusion for the straight DNA and for the fluorescence polarization anisotropy decay of the kinked and bulged DNAs the model predicts a different behavior which is found experimentally. Received: 24 March 1998 / Accepted: 3 September 1998 / Published online: 23 November 1998     

Large‐scale Two‐dimensional MoSx Catalyst Prepared under Mild Conditions for Enhancing Electrocatalytic Hydrogen Evolution Reaction

As an electrocatalyst with abundant resources and great potential, molybdenum disulfide is regarded as one of the most likely alternatives to expensive noble‐metals catalysts. However, it is still a challenge to achieve large scale production of few‐layer MoS₂ with enhancing activity of electrocatalytic hydrogen reaction at ambient conditions. Herein, we developed a simple environmentally friendly two‐step method, which included intercalation reaction and a subsequent electrochemical reduction reaction for mass preparation of defect‐rich desulfurized MoS_x (D?MoS_x) nanosheets with plentiful sulfur vacancies. The ratio of sulfur‐molybdenum atoms can be adjusted from 2 : 1 to 1.4 : 1 by regulating the desulfurization voltage. It was found that the HER catalytic activity of the D?MoS_x was enhanced compared with that of pristine MoS₂ (P?MoS₂), the current density of D?MoS_x (desulfurization at ?1.0 V) at ?0.3 V versus RHE was about 169% of the P?MoS₂, and the Tafel slope decreased to 136 mV dec^?1. This method can be widely applied to large‐scale preparation of other two‐dimensional materials.     

Role of surface oxygen vacancies in photoluminescence of tin dioxide nanobelts

The role of surface oxygen vacancies in the optical properties of tin dioxide nanobelts is investigated in this paper. Using a first-principles approach, based on the density functional theory combined to a very accurate exchange correlation functional, we characterize SnO₂ (1 0 1), that is the nanobelt largest surface. We show that the presence of surface oxygen vacancies leads to the appearance of (i) occupied states located at about 1 eV above the valence band and (ii) unoccupied states lying in resonance with the conduction band. Photoluminescence characterization performed on samples of SnO₂ nanobelts at low temperature shows that the basic spectral features of luminescence are in excellent agreement with theoretical predictions.     

Towards a mesoscopic model of water-like fluids with hydrodynamic interactions

We present a mesoscopic lattice model for non-ideal fluid flows with directional interactions, mimicking the effects of hydrogen bonds in water. The model supports a rich and complex structural dynamics of the orientational order parameter, and exhibits the formation of disordered domains whose size and shape depend on the relative strength of directional order and thermal diffusivity. By letting the directional forces carry an inverse density dependence, the model is able to display a correlation between ordered domains and low density regions, reflecting the idea of water as a denser liquid in the disordered state than in the ordered one.     

Reformation Instability in Elastic Solids

The reformation of a body fundamentally involves the mapping of one natural reference configuration of it into another natural reference configuration. The mass and the constitutive properties of the material remain unaltered, but the overall shape of the reference configuration generally changes. If, when a natural reference configuration is distorted, there is a portion of the boundary of the body that is displacement controlled, then a reformation of the body must be such that the original displacement controlled part of the boundary and its reformation are identical. In common applications that involve reformation, the remainder of the boundary is traction-free and a reformation essentially involves a change of the morphology of this traction-free surface. For example, undulations are often a characteristic feature of the reformation of a free, plane boundary surface. Reformations are a result of a material instability and they may associate with a chemically induced diffusive processes in which particles of the body move into preferred places. Fundamentally, a reformation is generated in response to the drive to lower the total stored energy of the body. In this work we are not concerned with the physical processes that take place during reformation, but rather we are concerned with characterizing the onset of the instability. We develop a variational characterization of the reformation instability for a nonlinear elastic body and we include the effect of surface energy. As an example, we consider the axial deformation of a circular cylinder and argue that small scale nano-wires, for which the diameter-to-length ratio is sufficiently small, are expected to be stable with respect to spatial variations when extended. Moreover, we observe that if the surfacial energy function is sufficiently convex at the undistorted state such wires may also be stable with respect to spatial variations when compressed. We then show that such small scale nano-wires are unstable with respect to reformation when either extended or compressed.     

First synthesis and full characterization of mexiletine N-carbonyloxy β-d-glucuronide

A simple, convergent synthesis of the N-carbonyloxy β-d-glucuronide of mexiletine (sodium salt) in moderate yield is described. The compound is now available as an authentic reference standard for analytical studies, enabling more detailed investigation on the metabolism of mexiletine.     

Design of Liposomes Carrying HelixComplex Snail Mucus: Preliminary Studies

In recent decades liposomes have been used in different field thanks to their ability to act as a vehicle for a wide range of biomolecules, their great versatility and their easy production. The aim of this study was to evaluate liposomes as a vehicle for the actives present in the HelixComplex (HC) snail mucus for topical delivery. Liposomes composed of a mixture of phosphatidylcholine, cholesterol and octadecylamine were prepared with and without HC (empty liposomes) and their biological efficacy was tested by evaluating cell viability and migration. HC-loaded liposomes (LHC) were stable throughout 60 days of observation, and showed interesting effects on wound healing reconstitution. In particular, we observed that 25 µg/mL LHC were already able to induce a higher cell monolayer reconstitution in comparison to the untreated samples and HC treated samples after only 4 h (28% versus 10% and 7%, p = 0.03 and p= 0.003, respectively). The effect was more evident at 24 h in comparison with the untreated control (54% versus 21.2% and 41.6%, p = 0.006 and p = NS, respectively). These results represent a preliminary, but promising, novelty in the delivery strategy of the actives present in the HelixComplex mucus.     

In vivo synthesized proteins with monoexponential fluorescence decay kinetics

Tryptophan, when in a protein, typically shows multiexponential fluorescence decay kinetics. Complex kinetics prevents a straightforward interpretation of time-resolved fluorescence protein data, particularly in anisotropy studies or if the effect of a dynamic quencher or a resonance energy transfer (RET) acceptor is investigated. Here, time-resolved fluorescence data are presented of an isosteric tryptophan analogue, 5-fluorotryptophan, which when biosynthetically incorporated in proteins shows monoexponential decay kinetics. Data are presented indicating that the presence of a fluoro atom at the 5-position suppresses the electron transfer rate from the excited indole moiety to the peptide bond. This process has been related to the multiexponential fluorescence decay of tryptophan in proteins. The monoexponential decay of 5-fluorotryptophan makes it possible to measure simultaneously multiple distances between 5-fluorotryptophan and a RET acceptor. We demonstrate that for an oligomeric protein, consisting of two single-tryptophan-containing subunits, the individual distances between 5-fluorotryptophan and the single substrate binding site can be resolved using a substrate harboring a RET acceptor.     

Electronic properties of mononuclear, dinuclear, and polynuclear cobaltacarboranes: electrochemical and spectroelectrochemical studies

Electronic interactions and metal-metal communication in a wide range of cobaltacarborane-hydrocarbon complexes containing one to six metal centers, and exhibiting a variety of modes of inter-cage connectivity and molecular architectures, have been investigated via cyclic voltammetry, controlled potential coulometry, and UV-visible spectroelectrochemistry. The properties of mixed-valent Co(III)/Co(IV) and Co(II)/Co(III) species that are generated on oxidation or reduction of dinuclear and polynuclear Co(III) complexes were examined and classified as Robin-Day Class I (localized), Class II (partially delocalized), or Class III (fully delocalized) systems. The extent of metal-metal communication between metallacarborane cage units is strongly influenced by the type of intercage connection (e.g., cage B-B or Cp-Cp); the vertexes involved (equatorial vs apical); the nature of the linking unit, if any; and the presence of substituents on the carborane cages. In multi-tripledecker complexes where three CpCo(C(2)B(3)H(4))CoCp units are linked through a central triethynyl benzene connector, the data suggest that Co-Co electronic communication is extensive (Class III) within individual sandwich units while intersandwich delocalization is weak or absent. An extended Hückel study of CpCoC(2)B(4)H(6) double-decker and CpCo(C(2)B(3)H(5))CoCp triple-decker sandwich model complexes shows significant differences in the orbital contributions involved in the HOMO and LUMO of the former vs the latter type. The calculations afford additional insight into the electronic structures and properties of these systems as elucidated by the experimental studies.