Molecular dynamics study of a new metastable allotropic crystalline form of gallium—supertetrahedral gallium

A new metastable crystalline form of gallium has been computationally designed using density functional calculations with imposing periodic boundary conditions. The geometric and electronic structures of the predicted new allotrope were calculated on the basis of a diamond lattice in which all carbon atoms are replaced by gallium Ga₄ tetrahedra. This form does not have any imaginary phonons, thus it is a metastable crystalline form of gallium. The new form of gallium is a metal and shows high plasticity and low-melting temperature. Molecular dynamics simulations show that this form of gallium will melt at about 273 K with a sharp increase in temperature in the system during the melting process from 273 to 1800 K. This melting process is very different from conventional melting, where temperature stays the same until complete melting. That unusual melting can be explained by the fact that supertetrahedral gallium is a metastable structure that has an excess of strain energy released during melting. If made this new material may find many useful applications as a new low density metal with stored internal energy. © 2019 Wiley Periodicals, Inc.     

Core level study of alanine and threonine

Core level X-ray photoemission spectra (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectra of alanine and threonine in the gas phase have been measured at the carbon, nitrogen, and oxygen K edges and interpreted in the light of theoretical calculations. For the computations, a set of approximations is made which allows sufficiently accurate calculations of several conformers to be performed in reasonable computing time. The accuracy has been checked by comparing results obtained for proline to our previous, higher level calculations. The photoemission spectra at the carbon and oxygen edges are assigned and compared. The nitrogen 1s photoemission peaks show anomalous broadening which we relate to the populations and types of conformers. The carbon K-edge NEXAFS spectra of alanine and threonine are compared with our previous data on glycine and resonances assigned accordingly. The nitrogen K-edge NEXAFS spectra of alanine and threonine do not show measurable effects due to the population of conformers, in contrast to the photoemission results. At the oxygen K edge, the spectra of these amino acids are similar with two prominent peaks assigned to transitions of O 1s electrons from the oxo and hydroxyl groups to vacant pi* and sigma* orbitals and additional intensity for threonine due to the second OH group. Conformer effects are observable in photoemission but appear to be more difficult to resolve in photoabsorption. We explain this by energetic shifts of opposite sign for the core hole states and unoccupied orbitals, which causes partial cancelation in NEXAFS but not in photoemission.     

Energetics and kinetics of primary charge separation in bacterial photosynthesis

We report the results of molecular dynamics (MD) simulations and formal modeling of the free-energy surfaces and reaction rates of primary charge separation in the reaction center of Rhodobacter sphaeroides. Two simulation protocols were used to produce MD trajectories. Standard force-field potentials were employed in the first protocol. In the second protocol, the special pair was made polarizable to reproduce a high polarizability of its photoexcited state observed by Stark spectroscopy. The charge distribution between covalent and charge-transfer states of the special pair was dynamically adjusted during the simulation run. We found from both protocols that the breadth of electrostatic fluctuations of the protein/water environment far exceeds previous estimates, resulting in about 1.6 eV reorganization energy of electron transfer in the first protocol and 2.5 eV in the second protocol. Most of these electrostatic fluctuations become dynamically frozen on the time scale of primary charge separation, resulting in much smaller solvation contributions to the activation barrier. While water dominates solvation thermodynamics on long observation times, protein emerges as the major thermal bath coupled to electron transfer on the picosecond time of the reaction. Marcus parabolas were obtained for the free-energy surfaces of electron transfer by using the first protocol, while a highly asymmetric surface was obtained in the second protocol. A nonergodic formulation of the diffusion-reaction electron-transfer kinetics has allowed us to reproduce the experimental results for both the temperature dependence of the rate and the nonexponential decay of the population of the photoexcited special pair.     

High-energy sub-nanosecond optical pulse generation with a semiconductor laser diode for pulsed TOF laser ranging utilizing the single photon detection approach

Bulk and quantum well laser diodes with a large equivalent spot size of d _a /Γ _a  ≈ 3 µm and stripe width/cavity length of 30 µm/3 mm were realized and tested. They achieved a pulse energy and pulse length of the order of ~1 nJ and ~100 ps, respectively, with a peak pulse current of 6–8 A and a current pulse width of 1 ns. The 2D characteristics of the optical output power versus wavelength and time were also analyzed with a monochromator/streak camera set-up. The far-field characteristics were studied with respect to the time-homogeneity and energy distribution. The feasibility of a laser diode with a large equivalent spot size in single photon detection based laser ranging was demonstrated to a non-cooperative target at a distance of a few tens of meters.     

19F Magic angle spinning NMR reporter molecules: empirical measures of surface shielding, polarisability and H-bonding

Magic Angle Spinning (MAS) (19)F NMR spectra have been obtained and chemical shifts measured for 37 molecules in the gas phase and adsorbed on the surfaces of six common materials: octadecyl- and octyl-functionalised chromatography silicas, Kieselgel 100 silica, Brockmann neutral alumina, Norit activated charcoal and 3-(1-piperidino)propyl functionalised silica. From these six surfaces, octadecyl-silica is selected as a non-polar reference to which the others are compared. The change in chemical shift of a fluorine nucleus within a molecule on adsorption to a surface from the gas phase, Deltadelta(gas)(surface), is described by the empirical relationship: Deltadelta(gas)(surface) = delta(s) + (alpha(s)+pi(s))/alpha(r) (Deltadelta(gas)(reference) - delta(r)) + delta(HBA) + delta(HBD), where delta(s) and delta(r) are constants that describe the chemical shift induced by the electromagnetic field of the surface under investigation and reference surface, alpha(s) and alpha(r) are the relative surface polarisability for the surface and reference, pi(s) is an additional contribution to the surface polarisabilities due to its ability to interact with aromatic molecules, and delta(HBA) and delta(HBD) are measurements of the hydrogen acceptor and donor properties of the surface. These empirical parameters are measured for the surfaces under study. Silica and alumina are found to undergo specific interactions with aromatic reporter molecules and both accept and donate H-bonds. Activated charcoal was found to have an extreme effect on shielding but no specific interactions with the adsorbed molecules. 3-(1-Piperidino)propyl functionalised silica exhibits H-bond acceptor ability, but does not donate H-bonds.     

Advances in mucoadhesion and mucoadhesive polymers

Mucoadhesion is the ability of materials to adhere to mucosal membranes in the human body and provide a temporary retention. This property has been widely used to develop polymeric dosage forms for buccal, oral, nasal, ocular and vaginal drug delivery. Excellent mucoadhesive properties are typical for hydrophilic polymers possessing charged groups and/or non-ionic functional groups capable of forming hydrogen bonds with mucosal surfaces. This feature article considers recent advances in the study of mucoadhesion and mucoadhesive polymers. It provides an overview on the structure of mucosal membranes, properties of mucus gels and the nature of mucoadhesion. It describes the most common methods to evaluate mucoadhesive properties of various dosage forms and discusses the main classes of mucoadhesives.     

Semiconductor solar cells: Recent progress in terrestrial applications

In the last decade, the photovoltaic industry grew at a rate exceeding 30% per year. Currently, solar-cell modules based on single-crystal and large-grain polycrystalline silicon wafers comprise more than 80% of the market. Bulk Si photovoltaics, which benefit from the highly advanced growth and fabrication processes developed for microelectronics industry, is a mature technology. The light-to-electric power conversion efficiency of the best modules offered on the market is over 20%. While there is still room for improvement, the device performance is approaching the thermodynamic limit of ∼28% for single-junction Si solar cells. The major challenge that the bulk Si solar cells face is, however, the cost reduction. The potential for price reduction of electrical power generated by wafer-based Si modules is limited by the cost of bulk Si wafers, making the electrical power cost substantially higher than that generated by combustion of fossil fuels. One major strategy to bring down the cost of electricity generated by photovoltaic modules is thin-film solar cells, whose production does not require expensive semiconductor substrates and very high temperatures and thus allows decreasing the cost per unit area while retaining a reasonable efficiency. Thin-film solar cells based on amorphous, microcrystalline, and polycrystalline Si as well as cadmium telluride and copper indium diselenide compound semiconductors have already proved their commercial viability and their market share is increasing rapidly. Another avenue to reduce the cost of photovoltaic electricity is to increase the cell efficiency beyond the Shockley–Queisser limit. A variety of concepts proposed along this avenue forms the basis of the so-called third generation photovoltaics technologies. Among these approaches, high-efficiency multi-junction solar cells based on III–V compound semiconductors, which initially found uses in space applications, are now being developed for terrestrial applications. In this article, we discuss the progress, outstanding problems, and environmental issues associated with bulk Si, thin-film, and high-efficiency multi-junction solar cells.     

Diastereoselective synthesis of trans-trifluoromethyl-β-lactams and α-alkyl-β-trifluoromethyl-β-amino esters

The diastereoselective synthesis of β-lactams was examined from N-tosyl-1-chloro-2,2,2-trifluoroethylamine 3 and various nonactivated aliphatic acid chlorides in the presence of a Brønsted base. The mild reaction conditions allowed to get trifluoromethyl-β-lactams in good yields with high trans-diastereo selectivity. In addition, we also demonstrated that ring-opening of β-lactams easily provided α-alkyl-β-trifluoromethyl-β-amino esters.