Development of metal-containing polymers for optoelectronic applications

Most of the work in organic electroluminescent polymers has been focused on organic conjugated polymers. However, polymers attached with transition metal complex have received relatively less attention. We have synthesized and studied the light emitting properties of some metal containing polymers based on the polypyridine complexes of rhenium and ruthenium. These complexes exhibit long-lived excited states caused by the metal to ligand charge transfer transitions. By varying the structure of the ligand and/or the transition metal, we are able to fine-tune the electronic properties of the resulting metal complexes.We have synthesized a series of poly(phenylenevinylene) (PPV) derivatives which are functionalized with ruthenium polypyridine complexes at the polymer mainchain or side chain. These complexes are able to act as photosensitizers which enhance the photoconductivity of these polymers at longer wavelength. Both the conjugatedbackbone and the metal complex can emit light upon excitation. As a result, it is possible to tune the color by loading different amount of ruthenium complex to the polymer. Luminescence studies showed that the ruthenium complex could quench the emission of the conjugated backbone in some polymers, which suggests an energy transfer processbetween the backbone and the metal complexes. It was also found that the presence of metal complexes could enhance the charge carrier mobilities of the polymers, as the metal and/or ligands can act as extra charge carriers in the charge transport process.published_or_final_versio

Micromechanical analysis of kinematic hardening in natural clay

This paper presents a micromechanical analysis of the macroscopic behaviour of natural clay. A microstructural stress-strain model for clayey material has been developed which considers clay as a collection of clusters. The deformation of a representative volume of the material is generated by mobilizing and compressing all the clusters along their contact planes. Numerical simulations of multistage drained triaxial stress paths on Otaniemi clay have been performed and compared the numerical results to the experimental ones in order to validate the modelling approach. Then, the numerical results obtained at the microscopic level were analysed in order to explain the induced anisotropy observed in the clay behaviour at the macroscopic level. The evolution of the state variables at each contact plane during loading can explain the changes in shape and position in the stress space of the yield surface at the macroscopic level, as well as the rotation of the axes of anisotropy of the material

Superconductivity as a probe of magnetic switching and ferromagnetic stability in Nb/Ni multilayers

The temperature and field dependences of the AC and DC magnetic moment of superconducting and ferromagnetic Nb/Ni multilayers were measured using a SQUID magnetometer with magnetic field applied parallel to the multilayer plane. Periodic kinks in the superconducting upper critical field are evidence for nucleation of a hierarchy of Abrikosov vortex lattices aligned parallel to the multilayer. Small cusps in the low-field, isothermal DC magnetization are evidence that supercurrents are sensitive to extremely small changes in the Ni layer magnetization. Smooth ferromagnetic hysteresis is observed in the normal state, but is supplanted below the superconducting transition by two reproducible discontinuities that indicate magnetic switching of the Ni layers is tightly coupled to the supercurrents. The discontinuities are attributed to the non-dipole character of the moment near switching fields and, therefore, cannot be analyzed by standard magnetometer software. Ferromagnetic resonance spectra were measured in parallel and perpendicular DC magnetic fields at room temperature and 4.2 K, and resulting data suggest that Ni layers interact magnetically in the superconducting state

Analysis of bolted flanged panel joint for GRP sectional tanks

Peer reviewedPublisher PD

Human neutrophil clearance of bacterial pathogens triggers anti-microbial gamma delta T cell responses in early infection

Human blood Vc9/Vd2 T cells, monocytes and neutrophils share a responsiveness toward inflammatory chemokines and are rapidly recruited to sites of infection. Studying their interaction in vitro and relating these findings to in vivo observations in patients may therefore provide crucial insight into inflammatory events. Our present data demonstrate that Vc9/Vd2 T cells provide potent survival signals resulting in neutrophil activation and the release of the neutrophil chemoattractant CXCL8 (IL-8). In turn, Vc9/Vd2 T cells readily respond to neutrophils harboring phagocytosed bacteria, as evidenced by expression of CD69, interferon (IFN)-c and tumor necrosis factor (TNF)-a. This response is dependent on the ability of these bacteria to produce the microbial metabolite (E)-4-hydroxy-3-methyl-but-2-enyl pyrophosphate (HMB-PP), requires cell-cell contact of Vc9/Vd2 T cells with accessory monocytes through lymphocyte function-associated antigen-1 (LFA-1), and results in a TNF-a dependent proliferation of Vc9/Vd2 T cells. The antibiotic fosmidomycin, which targets the HMB-PP biosynthesis pathway, not only has a direct antibacterial effect on most HMB-PP producing bacteria but also possesses rapid anti-inflammatory properties by inhibiting cd T cell responses in vitro. Patients with acute peritoneal-dialysis (PD)-associated bacterial peritonitis – characterized by an excessive influx of neutrophils and monocytes into the peritoneal cavity – show a selective activation of local Vc9/Vd2 T cells by HMB-PP producing but not by HMB-PP deficient bacterial pathogens. The cd T celldriven perpetuation of inflammatory responses during acute peritonitis is associated with elevated peritoneal levels of cd T cells and TNF-a and detrimental clinical outcomes in infections caused by HMB-PP positive microorganisms. Taken together, our findings indicate a direct link between invading pathogens, neutrophils, monocytes and microbe-responsive cd T cells in early infection and suggest novel diagnostic and therapeutic approaches.Martin S. Davey, Chan-Yu Lin, Gareth W. Roberts, Sinéad Heuston, Amanda C. Brown, James A. Chess, Mark A. Toleman, Cormac G.M. Gahan, Colin Hill, Tanya Parish, John D. Williams, Simon J. Davies, David W. Johnson, Nicholas Topley, Bernhard Moser and Matthias Eber

Modeling recursive RNA interference.

An important application of the RNA interference (RNAi) pathway is its use as a small RNA-based regulatory system commonly exploited to suppress expression of target genes to test their function in vivo. In several published experiments, RNAi has been used to inactivate components of the RNAi pathway itself, a procedure termed recursive RNAi in this report. The theoretical basis of recursive RNAi is unclear since the procedure could potentially be self-defeating, and in practice the effectiveness of recursive RNAi in published experiments is highly variable. A mathematical model for recursive RNAi was developed and used to investigate the range of conditions under which the procedure should be effective. The model predicts that the effectiveness of recursive RNAi is strongly dependent on the efficacy of RNAi at knocking down target gene expression. This efficacy is known to vary highly between different cell types, and comparison of the model predictions to published experimental data suggests that variation in RNAi efficacy may be the main cause of discrepancies between published recursive RNAi experiments in different organisms. The model suggests potential ways to optimize the effectiveness of recursive RNAi both for screening of RNAi components as well as for improved temporal control of gene expression in switch off-switch on experiments

Insights from Amphioxus into the Evolution of Vertebrate Cartilage

Central to the story of vertebrate evolution is the origin of the vertebrate head, a problem difficult to approach using paleontology and comparative morphology due to a lack of unambiguous intermediate forms. Embryologically, much of the vertebrate head is derived from two ectodermal tissues, the neural crest and cranial placodes. Recent work in protochordates suggests the first chordates possessed migratory neural tube cells with some features of neural crest cells. However, it is unclear how and when these cells acquired the ability to form cellular cartilage, a cell type unique to vertebrates. It has been variously proposed that the neural crest acquired chondrogenic ability by recruiting proto-chondrogenic gene programs deployed in the neural tube, pharynx, and notochord. To test these hypotheses we examined the expression of 11 amphioxus orthologs of genes involved in neural crest chondrogenesis. Consistent with cellular cartilage as a vertebrate novelty, we find that no single amphioxus tissue co-expresses all or most of these genes. However, most are variously co-expressed in mesodermal derivatives. Our results suggest that neural crest-derived cartilage evolved by serial cooption of genes which functioned primitively in mesoderm

Chalcogenide Glass-on-Graphene Photonics

Two-dimensional (2-D) materials are of tremendous interest to integrated photonics given their singular optical characteristics spanning light emission, modulation, saturable absorption, and nonlinear optics. To harness their optical properties, these atomically thin materials are usually attached onto prefabricated devices via a transfer process. In this paper, we present a new route for 2-D material integration with planar photonics. Central to this approach is the use of chalcogenide glass, a multifunctional material which can be directly deposited and patterned on a wide variety of 2-D materials and can simultaneously function as the light guiding medium, a gate dielectric, and a passivation layer for 2-D materials. Besides claiming improved fabrication yield and throughput compared to the traditional transfer process, our technique also enables unconventional multilayer device geometries optimally designed for enhancing light-matter interactions in the 2-D layers. Capitalizing on this facile integration method, we demonstrate a series of high-performance glass-on-graphene devices including ultra-broadband on-chip polarizers, energy-efficient thermo-optic switches, as well as graphene-based mid-infrared (mid-IR) waveguide-integrated photodetectors and modulators

Centralized Modularity of N-Linked Glycosylation Pathways in Mammalian Cells

Glycosylation is a highly complex process to produce a diverse repertoire of cellular glycans that are attached to proteins and lipids. Glycans are involved in fundamental biological processes, including protein folding and clearance, cell proliferation and apoptosis, development, immune responses, and pathogenesis. One of the major types of glycans, N-linked glycans, is formed by sequential attachments of monosaccharides to proteins by a limited number of enzymes. Many of these enzymes can accept multiple N-linked glycans as substrates, thereby generating a large number of glycan intermediates and their intermingled pathways. Motivated by the quantitative methods developed in complex network research, we investigated the large-scale organization of such N-linked glycosylation pathways in mammalian cells. The N-linked glycosylation pathways are extremely modular, and are composed of cohesive topological modules that directly branch from a common upstream pathway of glycan synthesis. This unique structural property allows the glycan production between modules to be controlled by the upstream region. Although the enzymes act on multiple glycan substrates, indicating cross-talk between modules, the impact of the cross-talk on the module-specific enhancement of glycan synthesis may be confined within a moderate range by transcription-level control. The findings of the present study provide experimentally-testable predictions for glycosylation processes, and may be applicable to therapeutic glycoprotein engineering