Effect of nanoparticle dispersion on glass transition in thin films of polymer nanocomposites

We present spectroscopic ellipsometry measurements on thin films of polymer nanocomposites consisting of gold nanoparticles embedded in poly(styrene). The temperature dependence of thickness variation is used to estimate the glass transition temperature, T(g). In these thin films we find a significant dependence of T(g) on the nature of dispersion of the embedded nanoparticles. Our work thus highlights the crucial role played by the particle polymer interface morphology in determining the glass transition in particular and thermo-mechanical properties of such nanocomposite films.

Anomalous X-ray scattering study of local structures in the superionic conducting glass (AgBr)0.4 (Ag2O)0.3 (GeO2)0.3

The local structural information in the near-neighbor region of superionic conducting glass (AgBr)0.4(Ag2O)0.3(GeO2)0.3 has been estimated from the anomalous X-ray scattering (AXS) measurements using Ge and Br K absorption edges. The possible atomic arrangements in the near-neighbor region of this glass were obtained by coupling the results with the least-squares variational method so as to reproduce two differential intensity profiles for Ge and Br as well as the ordinary scattering profile. The coordination number of oxygen around Ge is found to be 3.6 at a distance of 0.176 nm, suggesting the GeO4 tetrahedral unit as the probable structural entity in this glass. Moreover, the coordination number of Ag around Br is estimated as 6.3 at a distance of 0.284 nm, suggesting an arrangement similar to that in crystalline AgBr.

Mode-coupling glass transition in a fluid confined by a periodic potential

We show that a fluid under strong spatially periodic confinement displays a glass transition within mode-coupling theory at a much lower density than the corresponding bulk system. We use fluctuating hydrodynamics, with confinement imposed through a periodic potential whose wavelength plays an important role in our treatment. To make the calculation tractable we implement a detailed calculation in one dimension. Although we do not expect simple 1d fluids to show a glass transition, our results are indicative of the behavior expected in higher dimensions. In a certain region of parameter space we observe a three-step relaxation reported recently in computer simulations [S. H. Krishnan, Ph.D. thesis, Indian Institute of Science (2005); Kim et al., Eur. Phys. J. Special Topics 189, 135 (2010)] and a glass-glass transition. We compare our results to those of Krakoviack [Phys. Rev. E 75, 031503 (2007)] and Lang et al. [Phys. Rev. Lett. 105, 125701 (2010)].

Enhancement of photoluminescence intensity by photoinduced interdiffusion in nanolayered a-Se/As2S3 films

Optical parameters of chalcogenide glass multilayers with 12–15 nm modulation lengths prepared by thermal evaporation can be changed by laser irradiation. Photoluminescence (PL) studies were carried out on such nonirradiated and irradiated multilayered samples of a-Se/As2S3 (sublayer thickness of a-Se is 4–5 nm for one set of samples and 1–2 nm for the other set. However As2S3 sublayer thickness is 11–12 nm for both sets of samples.) PL intensity can be increased by several orders of magnitude by reducing the Se well layer (lower band gap) thickness and can be further increased by irradiating the samples with appropriate wavelengths in the range of the absorption edge. The broadening of luminescence bands takes place either with a decrease in Se layer thickness or with irradiation. The former is due to the change in interface roughness and defects because of the enhanced structural disorder while the latter is due to photoinduced interdiffusion. The photoinduced interdiffusion creates defects at the interface between Se and As2S3 by forming an As–Se–S solid solution. From the deconvoluted PL spectrum, it is shown that the peak PL intensity, full width half maximum, and the PL quantum efficiency of particular defects giving rise to PL, can be tuned by changing the sublayer thickness or by interdiffusion.

Modified McMurray Inverter with Pulse Forming Network Commutation Circuits

The modified McMurray Inverter with Pulse Forming Network (PFN) has been explained. The current and voltage waveshapes of the PFN commutation ci rcuit have been compared with conventional L-commutation circuit. The design method of PFN has been explained. Advantages of this type of commutation have been discussed. Experimental results are given.

Phenylboronic acids in crystal engineering: Utility of the energetically unfavorable syn,syn-conformation in co-crystal design

Phenylboronic acids can exist, in principle, in three different conformers (syn,syn; syn,anti and anti,anti) with distinct energy profiles. In their native state, these compounds prefer the energetically favored syn, anti-conformation. In molecular complexes, however, the functionality exhibits conformational diversity. In this paper we report a series of co-crystals, with N-donor compounds, prepared by a design strategy involving the synthons based on the syn, syn-conformation of the boronic acid functionality. For this purpose, we employed compounds with the 1,2-diazo fragment (alprazolam, 1H-tetrazole, acetazolamide and benzotriazole), 1,10-phenanthroline and 2,2'-bipyridine for the co-crystallization experiments. However, our study shows that the mere presence of the 1,2-diazo fragment in the coformer does not guarantee the successful formation of co-crystals with a syn, syn-conformation of the boronic acid. [GRAPHICS] The -B(OH)(2) fragment makes unsymmetrical O-H center dot center dot center dot N heterosynthons with alprazolam (ALP) and 1,10-phenanthroline (PHEN). In the co-crystals of phenylboronic acids with 1H-tetrazole (TETR) and 2,2'-bipyridine (BPY), the symmetrical boronic acid dimer is the major synthon. In the BPY complex, boronic acid forms linear chains and the pyridine compound interacts with the lateral OH of boronic acid dimers that acts as a connector, thus forming a ladder structure. In the TETR complex, each heterocycle interacts with three boronic acids. While two boronic acids interact using the phenolic group, the third molecule generates O-H center dot center dot center dot N hydrogen bonds using the extra OH group, of -B(OH)(2) fragment, left after the dimer formation. Thus, although molecules were selected retrosynthetically with the 1,2-diazo fragment or with nearby hetero-atoms to induce co-crystal formation using the syn,syn-orientation of the -B(OH)(2) functionality, co-crystal formation is in fact selective and is probably driven by energy factors. Acetazolamide (ACET) contains self-complementary functional groups and hence creates stable homosynthons. Phenylboronic acids being weak competitors fail to perturb the homosynthons and hence the components crystallize separately. Therefore, besides the availability of possible hydrogen bond acceptors in the required position and orientation, the ability of the phenyl-boronic acid to perturb the existing interactions is also a prerequisite to form co-crystals. This is illustrated in the table below. In the case of ALP, PHEN and BPY, the native structures are stabilized by weak interactions and may be influenced by the boronic acid fragment. Thus phenylboronic acids can attain co-crystals with those compounds, wherein the cyclic O-H center dot center dot center dot N hydrogen bonds are stronger than the individual homo-interactions. This can lower the lattice energy of the molecular complex as compared with the individual crystals. [GRAPHICS] Phenylboronic acids show some selectivity in the formation of co-crystals with N-heterocycles. The differences in solubility of the components fall short to provide a possible reason for the selective formation of co-crystals only with certain compounds. These compounds, being weak acids, do not follow the Delta pK(a) analysis and hence fail to provide any conclusive observation. Theoretical results show that of the three conformers possible, the syn,anti conformer is the most stable. The relative stabilities of the three conformers syn,anti,syn,syn and anti,anti are 0.0, 2.18 and 3.14 kcal/mol, respectively. The theoretical calculations corroborate the fact that only energetically favorable synthons can induce the formation of heterosynthons, as in ALP and PHEN complexes. From a theoretical and structural analysis it is seen that phenylboronic acids will form interactions with those molecules wherein the heterocyclic and acidic fragments can interrupt the homosynthons. However, the energy profile is shallow and can be perturbed easily by the presence of competing functional groups (such as OH and COOH) in the vicinity. [GRAPHICS] .

Interaction of G-Quadruplexes with Nonintercalating Duplex-DNA Minor Groove Binding Ligands

The enzyme telomerase synthesizes the G-rich DNA strands of the telomere and its activity is often associated with cancer. The telomerase may be therefore responsible for the ability of a cancer cell-to escape apoptosis. The G-rich DNA sequences often adopt tetra-stranded structure, known as the G-quadruplex DNA (G4-DNA). The stabilization of the telomeric DNA into the G4-DNA structures by small molecules has been the focus of many researchers for the design and development of new anticancer agents. The compounds which stabilize the G-quadruplex in the telomere inhibit the telomerase activity. Besides telomeres, the G4-DNA forming sequences are present in the genomic regions of biological significance including the transcriptional regulatory and promoter regions of several oncogenes. Inducing a G-quadruplex structure within the G-rich promoter sequences is a potential way of achieving selective gene regulation. Several G-quadruplex stabilizing ligands are known. Minor groove binding ligands (MGBLs) interact with the double-helical DNA through the minor grooves sequence-specifically and interfere with several DNA associated processes. These MGBLs when suitably modified switch their preference sometimes from the duplex DNA to G4-DNA and stabilize the G4-DNA as well. Herein, we focus on the recent advances in understanding the G-quadruplex structures, particularly made by the human telomeric ends, and review the results of various investigations of the interaction of designed organic ligands with the G-quadruplex DNA while highlighting the importance of MGBL-G-quadruplex interactions.

Efficacies of multivalent vs monovalent poly(ether imine) dendritic catalysts within a generation in multiple C-C bond forming reactions

Dendrimers are ideal platforms to study multivalent effects due to the presence of uniform end groups at their peripheries. This report concerns with a study of multivalent dendritic catalysts, both within and across dendrimer generations, and their effects to mediate C-C bond forming reactions on multivalent substrates that have two and three acrylate reactive sites. As many as fourteen multivalent dendritic catalysts were prepared using 0-3 generations of poly(propyl ether imine) dendrimers, incorporated with Pd(II) catalytic sites, both within and across the dendrimer generations. C-C Bond forming reactions of these substrates with iodobenzene, mediated by uniform concentration of the metal across all catalysts, showed formation of partially and fully functionalized cinnamates in varying ratios, depending on the extent of clustering of catalytic moieties at the peripheries of dendrimers within a dendrimer generation. In a given generation, higher clustering of catalytic moieties greatly assisted multiple C-C bond formations than presenting the same in lesser number. The studies demonstrate true benefits of clustering catalytic moieties within a dendrimer generation and the beneficial effects applicable to catalysis of substrates presenting more than one reactive center. (C) 2011 Elsevier B.V. All rights reserved.

A meta-analysis of the traits affecting dispersal ability in butterflies: can wingspan be used as a proxy?

1. Dispersal ability of a species is a key ecological characteristic, affecting a range of processes from adaptation, community dynamics and genetic structure, to distribution and range size. It is determined by both intrinsic species traits and extrinsic landscape-related properties. 2. Using butterflies as a model system, the following questions were addressed: (i) given similar extrinsic factors, which intrinsic species trait(s) explain dispersal ability? (ii) can one of these traits be used as a proxy for dispersal ability? (iii) the effect of interactions between the traits, and phylogenetic relatedness, on dispersal ability. 3. Four data sets, using different measures of dispersal, were compiled from published literature. The first data set uses mean dispersal distances from capture-mark-recapture studies, and the other three use mobility indices. Data for six traits that can potentially affect dispersal ability were collected: wingspan, larval host plant specificity, adult habitat specificity, mate location strategy, voltinism and flight period duration. Each data set was subjected to both unifactorial, and multifactorial, phylogenetically controlled analyses. 4. Among the factors considered, wingspan was the most important determinant of dispersal ability, although the predictive powers of regression models were low. Voltinism and flight period duration also affect dispersal ability, especially in case of temperate species. Interactions between the factors did not affect dispersal ability, and phylogenetic relatedness was significant in one data set. 5. While using wingspan as the only proxy for dispersal ability maybe problematic, it is usually the only easily accessible species-specific trait for a large number of species. It can thus be a satisfactory proxy when carefully interpreted, especially for analyses involving many species from all across the world.

The omega phase formation during laser cladding and remelting of quasicrystal forming AlCuFe on pure aluminum

We report the formation omega phase in the remelted layers during laser cladding and remelting of quasicrystal forming Al65Cu23.3Fe11.7 alloy on pure aluminum. The omega phase is absent in the clad layers. In the remelted layer, the phase nucleates at the periphery of the primary icosahedral phase particles. A large number of omega phase particles forms enveloping the icosahedral phase growing into aluminum rich melt, which solidify as alpha-Al solid solution. On the other side it develops an interface with aluminum. A detailed transmission electron microscopic analysis shows that omega phase exhibits orientation relationship with icosahedral phase. The composition analysis performed using energy dispersive x-ray analyzer suggests that this phase has composition higher aluminum than the icosahedral phase. The analysis of the available phase diagram information indicates that the present results represent large departure from equilibrium conditions. A possible scenario of the evolution of the omega phase has been suggested.

Chemical and shifted mechanical thresholds in Al-Ge-Te glass system

We report the results of the electrical switching studies performed on the bulk Al20GexTe80-x (2.5 less than or equal to x less than or equal to 15) chalcogenide glasses. The well known topological features, mechanical and chemical thresholds are observed. Mechanical threshold is seen at a mean coordination number of atoms, < r > = 2.50 (x = 5) a clear shift rom the mean field value of < r > = 2.4 whereas the chemical threshold is observed at < r > = 2.65 (x = 12.5) as predicted by the chemically ordered covalent network model These experiments are a sequel to similar experiments on Al20AsxTe80-x glasses in which mechanical threshold was seen at < r > = 2.60 and no chemical threshold was observed These results am well understood by a chemical bond picture developed in this article.