Effect of dangling chains on the structure and physical properties of a tightly crosslinked poly(ethylene glycol) network

Major imperfections in crosslinked polymers include loose or dangling chain ends that lower the crosslink d., thereby reducing elastic recovery and increasing the solvent swelling. These imperfections are hard to detect, quantify and control when the network is initiated by free radical reactions. As an alternative approach, the sol-​gel synthesis of a model poly(ethylene glycol) (PEG-​2000) network is described using controlled amts. of bis- and mono-​triethoxy silyl Pr urethane PEG precursors to give silsesquioxane (SSQ, R-​SiO1.5) structures as crosslink junctions with a controlled no. of dangling chains. The effect of the no. of dangling chains on the structure and connectivity of the dried SSQ networks has been detd. by step-​crystn. differential scanning calorimetry. The role that micelle formation plays in controlling the sol-​gel PEG network connectivity has been studied by dynamic light scattering of the bis- and mono-​triethoxy silyl precursors and the networks have been characterized by 29Si solid state NMR, sol fraction and swelling measurements. These show that the dangling chains will increase the mesh size and water uptake. Compared to other end-​linked PEG hydrogels, the SSQ-​crosslinked networks show a low sol fraction and high connectivity, which reduces solvent swelling, degree of crystallinity and the crystal transition temp. The increased degree of freedom in segment movement on the addn. of dangling chains in the SSQ-​crosslinked network facilitates the packing process in crystn. of the dry network and, in the hydrogel, helps to accommodate more water mols. before reaching equil.

Outsider board activity, ownership structure and firm value : evidence from Korea

Using a sample of publicly listed firm in Korea from 2002 to 2006, this article examines the impact of board monitoring on firm value and productivity. We use outsider's attendance of board meetings as a proxy for board monitoring. Consistent with the commitment hypothesis, we find that outsider's attendance rate increases firm value, suggesting that attending board meeting itself is a strong signal that reflects outsider's intention to monitor insiders. While ownership of controlling shareholders negatively affects firm value, this relationship is not moderated by increased monitoring by outsiders. Our findings provide further evidence that the outside director system is less effective in chaebol-affiliated firms. Results also indicate that the effect of outsider's board monitoring activity on investor's valuation of the firm is greater than on productivity improvement of the firm. Our conclusions are robust for possible endogeneity in the relationship between firm value and board attendance by outside directors.

Improving work and life balance : building a multilevel model of work-life balance focusing on group structure and relational job design

One in five Australian workers believes that work doesn’t fit well with their family and social commitments. Concurrently, organisations are recognising that to stay competitive they need policies and practices that support the multiple aspects of employees’ lives. Many employees work in group environments yet there is currently little group level work-life balance research. This paper proposes a new theoretical framework developed to understand the design of work groups to better facilitate work-life balance. This new framework focuses on task and relational job designs, group structures and processes and workplace culture.

High-efficiency silencing of a β-glucuronidase gene in rice is correlated with repetitive transgene structure but is independent of DNA methylation

Two transgenic callus lines of rice, stably expressing a β-glucuronidase (GUS) gene, were supertransformed with a set of constructs designed to silence the resident GUS gene. An inverted-repeat (i/r) GUS construct, designed to produce mRNA with self-complementarity, was much more effective than simple sense and antisense constructs at inducing silencing. Supertransforming rice calluses with a direct-repeat (d/r) construct, although not as effective as those with the i/r construct, was also substantially more effective in silencing the resident GUS gene than the simple sense and antisense constructs. DNA hybridisation analyses revealed that every callus line supertransformed with either simple sense or antisense constructs, and subsequently showing GUS silencing, had the silence-inducing transgenes integrated into the plant genome in inverted-repeat configurations. The silenced lines containing i/r and d/r constructs did not necessarily have inverted-repeat T-DNA insertions. There was significant methylation of the GUS sequences in most of the silenced lines but not in the unsilenced lines. However, demethylation treatment of silenced lines with 5-azacytidine did not reverse the post-transcriptional gene silencing (PTGS) of GUS. Whereas the levels of RNA specific to the resident GUS gene were uniformly low in the silenced lines, RNA specific to the inducer transgenes accumulated to a substantial level, and the majority of the i/r RNA was unpolyadenylated. Altogether, these results suggest that both sense- and antisense-mediated gene suppression share a similar molecular basis, that unpolyadenylated RNA plays an important role in PTGS, and that methylation is not essential for PTGS.

A satellite RNA of barley yellow dwarf virus contains a novel hammerhead structure in the self-cleavage domain

An RNA molecule with properties of a satellite RNA was found in an isolate of barley yellow dwarf virus (BYDV), RPV serotype. It is 322 nucleotides long, single-stranded, and does not hybridize to the viral genome. Dimers of the RNA, which presumably represent replicative intermediates, were able to self-cleave into monomers. In vitro transcripts from cDNA clones were capable of self-cleavage in both the plus (encapsidated) and minus orientations. The sequence flanking the minus strand cleavage site contained a consensus " hammerhead" structure, similar to those found in other self-cleaving satellite RNAs. Although related to the hammerhead structure, sequences flanking the plus strand termini showed differences from the consensus and may be folded into a different structure containing a pseudoknot. © 1991.

Advantages of exploiting projection structure for segmenting dense 3D point clouds

Timely and comprehensive scene segmentation is often a critical step for many high level mobile robotic tasks. This paper examines a projected area based neighbourhood lookup approach with the motivation towards faster unsupervised segmentation of dense 3D point clouds. The proposed algorithm exploits the projection geometry of a depth camera to find nearest neighbours which is time independent of the input data size. Points near depth discontinuations are also detected to reinforce object boundaries in the clustering process. The search method presented is evaluated using both indoor and outdoor dense depth images and demonstrates significant improvements in speed and precision compared to the commonly used Fast library for approximate nearest neighbour (FLANN) [Muja and Lowe, 2009].

Tuning the surface structure of nitrogen-doped TiO2Nanofibres : an effective method to rnhance photocatalytic activities of visible-light-driven green synthesis and degradation

Nitrogen-doped TiO2 nanofibres of anatase and TiO2(B) phases were synthesised by a reaction between titanate nanofibres of a layered structure and gaseous NH3 at 400–700 °C, following a different mechanism than that for the direct nitrogen doping from TiO2. The surface of the N-doped TiO2 nanofibres can be tuned by facial calcination in air to remove the surface-bonded N species, whereas the core remains N doped. N-Doped TiO2 nanofibres, only after calcination in air, became effective photocatalysts for the decomposition of sulforhodamine B under visible-light irradiation. The surface-oxidised surface layer was proven to be very effective for organic molecule adsorption, and the activation of oxygen molecules, whereas the remaining N-doped interior of the fibres strongly absorbed visible light, resulting in the generation of electrons and holes. The N-doped nanofibres were also used as supports of gold nanoparticle (Au NP) photocatalysts for visible-light-driven hydroamination of phenylacetylene with aniline. Phenylacetylene was activated on the N-doped surface of the nanofibres and aniline on the Au NPs. The Au NPs adsorbed on N-doped TiO2(B) nanofibres exhibited much better conversion (80 % of phenylacetylene) than when adsorbed on undoped fibres (46 %) at 40 °C and 95 % of the product is the desired imine. The surface N species can prevent the adsorption of O2 that is unfavourable for the hydroamination reaction, and thus, improve the photocatalytic activity. Removal of the surface N species resulted in a sharp decrease of the photocatalytic activity. These photocatalysts are feasible for practical applications, because they can be easily dispersed into solution and separated from a liquid by filtration, sedimentation or centrifugation due to their fibril morphology.

Supplementary information : weighted tree kernels for sequence analysis

Genomic sequences are fundamentally text documents, admitting various representations according to need and tokenization. Gene expression depends crucially on binding of enzymes to the DNA sequence at small, poorly conserved binding sites, limiting the utility of standard pattern search. However, one may exploit the regular syntactic structure of the enzyme's component proteins and the corresponding binding sites, framing the problem as one of detecting grammatically correct genomic phrases. In this paper we propose new kernels based on weighted tree structures, traversing the paths within them to capture the features which underpin the task. Experimentally, we and that these kernels provide performance comparable with state of the art approaches for this problem, while offering significant computational advantages over earlier methods. The methods proposed may be applied to a broad range of sequence or tree-structured data in molecular biology and other domains.

Performance of buried tunnels subjected to surface blast incorporating fluid structure interaction

This paper uses finite element techniques to investigate the performance of buried tunnels subjected to surface blasts incorporating fully coupled Fluid Structure Interaction and appropriate material models which simulate strain rate effects. Modelling techniques are first validated against existing experimental results and then used to treat the blast induced shock wave propagation and tunnel response in dry and saturated sands. Results show that the tunnel buried in saturated sand responds earlier than that in dry sand. Tunnel deformations decrease with distance from explosive in both sands, as expected. In the vicinity of the explosive, the tunnel buried in saturated sand suffered permanent deformation in both axial and circumferential directions, whereas the tunnel buried in dry sand recovered from most of the axial deformation. Overall, response of the tunnel in saturated sand is more severe for a given blast event and shows the detrimental effect of pore water on the blast response of buried tunnels. The validated modelling techniques developed in this paper can be used to investigate the blast response of tunnels buried in dry and saturated sands.

Comparison of functionals for metal hexaboride band structure calculations

Density functional calculations of the electronic band structure for superconducting and semi-conducting metal hexaborides are compared using a consistent suite of assumptions and with emphasis on the physical implications of computed models. Spin polarization enhances mathematical accuracy of the functional approximations and adds significant physical meaning to model interpretation. For YB6 and LaB6, differences in alpha and beta projections occur near the Fermi energy. These differences are pronounced for superconducting hexaborides but do not occur for other metal hexaborides.

The molecular structure of the vanadate mineral mottramite [PbCu(VO4)(OH)] from Tsumeb, Namibia – a vibrational spectroscopic study

We have studied a mineral sample of mottramite PbCu(VO4)(OH) from Tsumeb, Namibia using a combination of scanning electron microscopy with EDX, Raman and infrared spectroscopy. Chemical analysis shows principally the elements V, Pb and Cu. Ca occurs as partial substitution of Pb as well as P and As in substitution to V. Minor amounts of Si and Cr were also observed. The Raman band of mottramite at 829 cm-1, is assigned to the ν1 symmetric (VO-4) ) stretching mode. The complexity of the spectra is attributed to the chemical composition of the Tsumeb mottramite. The ν3 antisymmetric vibrational mode of mottramite is observed as very low intensity bands at 716 and 747 cm-1. The series of Raman bands at 411, 439, 451 cm-1 and probably also the band at 500 cm-1 are assigned to the (VO-4) ν2 bending mode. The series of Raman bands at 293, 333 and 366 cm-1 are attributed to the (VO-4) ) ν4 bending modes. The ν3, ν3 and ν4 regions are complex for both minerals and this is attributed to symmetry reduction of the vanadate unit from Td to Cs.

The molecular structure of the borate mineral rhodizite (K, Cs)Al4Be4(B, Be)12O28 – A vibrational spectroscopic study

We have studied the borate mineral rhodizite (K, Cs)Al4Be4(B, Be)12O28 using a combination of DEM with EDX and vibrational spectroscopic techniques. The mineral occurs as colorless, gray, yellow to white crystals in the triclinic crystal system. The studied sample is from the Antandrokomby Mine, Sahatany valley, Madagascar. The mineral is prized as a semi-precious jewel. Semi-quantitative chemical composition shows a Al, Ca, borate with minor amounts of K, Mg and Cs. The mineral has a characteristic borate Raman spectrum and bands are assigned to the stretching and bending modes of B, Be and Al. No Raman bands in the OH stretching region were observed.

The molecular structure of the phosphate mineral beraunite Fe2+Fe⅗+(PO4)4(OH)5⋅4H2O– A vibrational spectroscopic study

The mineral beraunite from Boca Rica pegmatite in Minas Gerais with theoretical formula Fe2+Fe5 3+(PO4)4(OH)5⋅4H2O has been studied using a combination of electron microscopy with EDX and vibrational spectroscopic techniques. Raman spectroscopy identifies an intense band at 990 cm-1 and 1011 cm-1. These bands are attributed to the PO4 3- v, symmetric stretching mode. The m3 antisymmetric stretching modes are observed by a large number of Raman bands. The Raman bands at 1034, 1051, 1058, 1069 and 1084 together with the Raman bands at 1098, 1116, 1133, 1155 and 1174 cm-1 are assigned to the m3 antisymmetric stretching vibrations of PO4 3- and the HOPO3 2- units. The observation of these multiple Raman bands in the symmetric and antisymmetric stretching region gives credence to the concept that both phosphate and hydrogen phosphate units exist in the structure of beraunite. The series of Raman bands at 567, 582,601, 644, 661, 673, and 687 cm-1 are assigned to the PO4 3- v2 bending modes. The series of Raman bands at 437, 468, 478, 491, 503 cm-1 are attributed to the PO4 3- and OPO3 2- v4 bending modes. No Raman bands of beraunite which could be attributed to the hydroxyl stretching unit were observed. Infrared bands at 3511 and 3359 cm-1 are ascribed to the OH stretching vibration of the OH units. Very broad bands at 3022 and 3299 cm-1 are attributed to the OH stretching vibrations of water. Vibrational spectroscopy offers insights into the molecular structure of the phosphate mineral beraunite.

Solid-state structure of some substituted hexahydro-1,4:5,8-diepoxy­naphthalenes

The structure of several carboxy-substituted hexahydro-1,4:5,8-diepoxynaphthalenes have been solved with X-ray crystallography, in some cases confirming previously contentious structures. The compounds of interest are constructed in efficient one-step 2 × [4+2] cycloaddition reactions from furan and acetylene carboxylate derivatives.