Correlation between IR peak position and bond parameter of silica glass: Molecular dynamics study on fictive temperature (cooling rate) effect

The fictive temperature of glass is a consequence of its thermal history (cooling rate, primarily) and has a direct effect on physical and chemical properties of the glass. But, it is not easy to measure. The ability to nondestructively and spectroscopically measure it at room temperature would be of great benefit. Although empirical correlations have been established between fictive temperature and selected absorption peaks in the infrared spectra of silica glass, the fundamental understanding for this correlation has not been reported. Here, we use molecular dynamics simulations to show that the blue shift in the Si–O–Si asymmetric stretching peak of pure silica glass, which is known to correlate with a decrease in fictive temperature, can be attributed to a decrease in the average length of the Si–O bond in the silica network, not changes in the density or the Si–O–Si bond angle. The decrease in density at higher fictive temperatures of silica is associated with a decreased population of 5‐ and 6‐membered rings and broadening of the ring‐size distribution, and an increase in the average Si–O–Si bond angle.     

Influence of Cu metal on the domain structure and carrier mobility in single-layer graphene

We demonstrate that domain structure of single-layer graphene grown by ambient pressure chemical vapor deposition is strongly dependent on the crystallinity of the Cu catalyst. Low energy electron microscopy analysis reveals that graphene grown using a Cu foil gives small and mis-oriented graphene domains with a number of domain boundaries. On the other hand, no apparent domain boundaries are observed in graphene grown over a heteroepitaxial Cu(111) film deposited on sapphire due to unified orientation of graphene hexagons. The difference in the domain structures is correlated with the difference in the crystal plane and grain structure of the Cu metal. The graphene film grown on the heteroepitaxial Cu film exhibits much higher carrier mobility than that grown on the Cu foil.     

Graft copolymers of lignin from straw with 1‐ethenylbenzene: Synthesis and characterization

The synthesis of copolymers between lignin from steam‐exploded straw and 1‐ethenylbenzene is described. Beforehand, lignin from steam‐exploded straw was fully characterized by using elemental analysis, ultraviolet spectroscopy, gel permeation chromatography (GPC), Fourier transform infrared (FTIR), and both ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy. Using a previously described procedure utilizing calcium chloride and hydrogen peroxide as reagents the synthesis of the copolymers was performed. FTIR of the copolymers showed the presence of both lignin and polystyrene. GPC analysis showed the presence of a fraction with high molecular weights. These results were confirmed from both viscosity data and differential calorimetry. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 72–79, 2001     

Microwave-assisted synthesis of isosorbide-derived diols for the preparation of thermally stable thermoplastic polyurethane

In order to prepare thermally stable isosorbide-derived thermoplastic polyurethane, the synthesis of two new chiral exo–exo configured diols, prepared from isosorbide, and two types of diphenols (bisphenol A and thiodiphenol) was described. The synthesis conditions were optimized under conventional heating and microwave irradiations. To prove their suitability in polymerization, these monomers were successfully polymerized using 4,4′-diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate (HDI). Both monomers and polymers have been studied by NMR, FT-IR, TGA, DSC; intrinsic viscosity of polymers has also been determined. The results showed the effectiveness of the synthetic strategy proposed; moreover, a dramatic reduction of the reaction time and an important improvement of the monomers yield using microwave irradiation have been demonstrated. The monomers, as well as the polymers, showed excellent thermal stability both in air and nitrogen. It was also shown that the introduction of sulphur in the polyurethane backbone was effective in delaying the onset of degradation as well as the degradation rate.     

Synthesis and Biological Evaluation of CTP Synthetase Inhibitors as Potential Agents for the Treatment of African Trypanosomiasis

Acivicin analogues with an increased affinity for CTP synthetase (CTPS) were designed as potential new trypanocidal agents. The inhibitory activity against CTPS can be improved by increasing molecular complexity, by inserting groups able to establish additional interactions with the binding pocket of the enzyme. This strategy has been pursued with the synthesis of α‐amino‐substituted analogues of Acivicin and N1‐substituted pyrazoline derivatives. In general, there is direct correlation between the enzymatic activity and the in vitro anti‐trypanosomal efficacy of the derivatives studied here. However, this cannot be taken as a general rule, as other important factors may play a role, notably the ability of uptake/diffusion of the molecules into the trypanosomes.     

Graphene decoration with metal nanoparticles: towards easy integration for sensing applications

A simple and versatile method for the decoration of CVD grown graphene with metal nanoparticles is presented. The mechanism of nanoparticle formation is galvanic displacement resulting in physically adsorbed clusters. The single layer graphene obtained by this method can be easily transferred. Integration onto a gas sensing transducer is presented as proof of concept.     

Local Structure Around Nb Site of a Potential Thermoelectric Material La<Subscript>1/3</Subscript>NbO<Subscript>3</Subscript> from Temperature-Dependent Extended x-ray Absorption Fine Structure Spectroscopy

The effort to find thermoelectric materials suitable for different applications is an intense research topic of a large material science community. In this context, A-site-deficient La_1/3NbO₃, which shows an irreversible pressure-induced amorphization at above 15 GPa, has attracted recent attention. Here, we present a temperature-dependent Nb K-edge extended x-ray absorption fine structure (EXAFS) study of La_1/3NbO₃ in the range 77-500 K probing the Nb-O bond correlations. These results are compared with the Nb-O bond correlations in two related oxides NbO₂ and Nb₂O₅. In comparison with NbO₂ and Nb₂O₅, the Nb-O bond mean square relative displacements in La_1/3NbO₃ show much weaker temperature dependence revealing its enhanced spring constant. The “A” site deficiency in La_1/3NbO₃ may allow the oxygen atoms to preserve their local geometry and thus are less responsive to the external stimuli like temperature, which may be important in determining the thermal and electrical conductivity properties of this system.     

Focused ion beam-nanomachined probes for improved electric force microscopy

Nanomachining and beam-assisted Pt deposition by a focused ion beam (FIB) was used to modify AFM probes for improved electric force measurements. Si(3)N(4) cantilevers have been endowed with a nano-electrode at the tip apex to confine the electro-sensitive area at the very tip. This action results in both a marked decrease of the parasitic capacitive effect and in an improved electric force microscopy (EFM) contrast and resolution, with respect to usual, full metal-coated cantilevers. This fabrication approach is suited to the development of innovative electro-sensitive probes, useful in different scanning probe techniques.