30 resultados para EPSILON-CAPROLACTAM

em Deakin Research Online - Australia


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"Networking of Multimedia Women" event is a continuation of an on-going conversation in the multimedia research community and efforts by the ACM SIGMM to engage and promote female researchers in multimedia community, enable networking of junior and senior female researchers, and give insights towards successful professional careers based on examples. This year, the event will have a theme, called "Beyond Epsilon Science", where preeminent senior female researchers from academia, industry and government, Svetha Venkatesh, Nalini Venkatasubramanian, Dulce Ponceleon, Susanne Boll, and Maria Zemankova will present and discuss how to go beyond epsilon science, where to look for big ideas with high social impact, as well as how to obtain funding to realize these ideas, innovations and opportunities. Their current research projects and funding efforts, and their personal experiences will drive the event's discussions, awareness of major research and funding initiatives, answers to open questions and insights into successful professional careers.

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Biodegradable polyesters such as poly(epsilon-caprolactone) (PCL) have a number of biomedical applications; however, their usage is often limited by a lack of biological functionality. In this paper, a PCL-based polymer containing pendent groups activated by 4-nitrophenyl chloroformate (NPC) and reactive toward primary amines has been cast into thin films. The reactivity of the films toward poly(l-lysine) and the cell adhesion peptide, GRGDS, was assessed, and their cell adhesive capabilities were characterized. ATR-FTIR analysis found that NPC functional groups were present on the surface of the cast film, and the synthesis, conjugation, and visualization of a fluorescent molecule on these films further demonstrated the success of this functionalization methodology. The immersion of these films into a solution of either poly(l-lysine) (PLL) or GRGDS in PBS (pH 7.4) and subsequent 3T3 fibroblast adhesion studies demonstrated significant improvement in cell adhesion and spreading over films cast from unmodified PCL. This investigation has shown that this novel NPC-containing polymer can be utilized in many applications where increased cellular adhesion is required, or the coupling of specific molecules to polymer surfaces is of interest.

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In the present study, the effect of nominal equivalent strain (between 0 and 1.2), deformation temperature (790– 750°C) and carbon content (0.06 – 0.35%C) was investigated on ferrite grain refinement through dynamic strain induced transformation (DSIT) in plain carbon steels in single pass rolling. The microstructural evolution of the transformation of austenite to ferrite has been evaluated through the thickness of the strip. The results showed a number of important microstructural features as a function of strain, which could be classified into three regions; no DSIT region, DSIT region, and ultrafine ferrite (UFF) grain region. Hence, two critical strains; dynamic strain induced transformation (εC, DSIT) and ultrafine ferrite formation (εC, UFF) were determined. These strains were increased significantly with an increase in carbon content. The critical strain for UFF formation reduced with decrease in deformation temperature. The UFF microstructure consisted of ultrafine, equiaxed ferrite grains (<2 μm) with very fine cementite particles. In the centre of the rolled strip, there was a conventional ferrite– pearlite microstructure, although ferrite grain refinement and the volume fraction of ferrite increased with increase in the nominal equivalent strain.

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The post-deformation softening behaviour of austenite has been studied for various compositions and deformation conditions. The strain at which the transition from strain dependent to strain independent post-deformation softening behaviour occurs (ε*) has been found to coincide closely with the strain to the peak stress (εp) under certain conditions but not under others. It has been proposed that the relationship between ε* and εp may be described geometrically using the initial grain size and the dynamically recrystallised grain size.

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In this article, we explore the role of the C-terminus (V5 domain) of PKCvar epsilon plays in the catalytic competence of the kinase using serial truncations followed by immune-complex kinase assays. Surprisingly, removal of the last seven amino acid residues at the C-terminus of PKCvar epsilon resulted in a PKCvar epsilon-Δ731 mutant with greatly reduced intrinsic catalytic activity while truncation of eight amino acid residues at the C-terminus resulted in a catalytically inactive PKCvar epsilon mutant. Computer modeling and molecular dynamics simulations showed that the last seven and/or eight amino acid residues of PKCvar epsilon were involved in interactions with residues in the catalytic core. Further truncation analyses revealed that the hydrophobic phosphorylation motif was dispensable for the physical interaction between PKCvar epsilon and 3-phosphoinositide-dependent kinase-1 (PDK-1) as the PKCvar epsilon mutant lacking both the turn and the hydrophobic motifs could still be co-immunoprecipitated with PDK-1. These results provide fresh insights into the biochemical and structural basis underlying the isozyme-specific regulation of PKC and suggest that the very C-termini of PKCs constitute a promising new target for the development of novel isozyme-specific inhibitors of PKC.

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A C-Mn-Nb-Ti steel was deformed by hot torsion to study ultrafine ferrite formation through dynamic strain-induced transformation (DSIT) in conjunction with air cooling. A systematic study was carried out first to evaluate the effect of deformation temperature and prior austenite grain size on the critical strain for ultrafine ferrite formation (ε C,UFF) through single-pass deformation. Then, multiple deformations in the nonrecrystallization region were used to study the effect of thermomechanical parameters (i.e., strain, deformation temperature, etc.) on ε C,UFF. The multiple deformations in the nonrecrystallization region significantly reduced ε C,UFF, although the total equivalent strain for a given thermomechanical condition was higher than that required in single-pass deformation. The current study on a Ni-30Fe austenitic model alloy revealed that laminar microband structures were the key intragranular defects in the austenite for nucleation of ferrite during the hot torsion test. The microbands were refined and overall misorientation angle distribution increased with a decrease in the deformation temperature for a given thermomechanical processing condition. For nonisothermal multipass deformation, there was some contribution to the formation of high-angle microband boundaries from strains at higher temperature, although the strains were not completely additive.

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To improve the understanding of the heat transfer mechanism and to find a reliable and simple heat-transfer model, the gas flow and heat transfer between fluidized beds and the surfaces of an immersed object is numerically simulated based on a double particle-layer and porous medium model. The velocity field and temperature distribution of the gas and particles are analysed during the heat transfer process. The simulation shows that the change of gas velocity with the distance from immersed surface is consistent with the variation of bed voidage, and is used to validate approximately dimensional analysing result that the gas velocity between immersed surface and particles is 4.6Umf/εmf. The effects of particle size and particle residence time on the thermal penetration depth and the heat-transfer coefficients are also discussed.

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Priest Pot is an example of the abundant ponds that, collectively, contribute crucially to species diversity. Despite extensive biological study, little has been reported about the physical framework that supports its ecological richness. This article elucidates the physical character of Priest Pot’s water column and thus that of similar water bodies. Vertical thermal microstructure profiles were recorded during summer 2003 and analyzed alongside concurrent meteorological data. During summer stratification, the thermal structure appeared to be dominated by surface heat fluxes. Surface wind stress, limited by sheltering vegetation, caused turbulent overturns once a surface mixed layer was present but appeared to contribute little to setting up the thermal structure. Variations in full-depth mean stratification occurred predominantly over seasonal and ∼5-day time scales, the passage of atmospheric pressure systems being posited as the cause of the latter. In the uppermost ∼0.5 m, where the stratification varied at subdaily time scales, turbulence was active (sensu Ivey and Imberger 1991) when this layer was mixed, with dissipation values ε ∼ 10−8 m2 s−3 and vertical diffusivity KZ = 10−4 — 10−6 m2 s−1. Where the water column was stratified, turbulence was strongly damped by both buoyancy and viscosity, and KZ was an order of magnitude smaller. Vertical transport in the mixed layer occurred via many small overturns (Thorpe scale r.m.s. and maximum values were typically 0.02 m and 0.10 m, respectively), and seston were fully mixed through the water column.

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The oxazaphosphorines including cyclophosphamide (CPA), ifosfamide (IFO), and trofosfamide represent an important group of therapeutic agents due to their substantial antitumor and immuno-modulating activity. CPA is widely used as an anticancer drug, an immunosuppressant, and for the mobilization of hematopoetic progenitor cells from the bone marrow into peripheral blood prior to bone marrow transplantation for aplastic anemia, leukemia, and other malignancies. New oxazaphosphorines derivatives have been developed in an attempt to improve selectivity and response with reduced toxicity. These derivatives include mafosfamide (NSC 345842), glufosfamide (D19575, β-D-glucosylisophosphoramide mustard), NSC 612567 (aldophosphamide perhydrothiazine), and NSC 613060 (aldophosphamide thiazolidine). This review highlights the metabolism and transport of these oxazaphosphorines (mainly CPA and IFO, as these two oxazaphosphorine drugs are the most widely used alkylating agents) and the clinical implications. Both CPA and IFO are prodrugs that require activation by hepatic cytochrome P450 (CYP)-catalyzed 4-hydroxylation, yielding cytotoxic nitrogen mustards capable of reacting with DNA molecules to form crosslinks and lead to cell apoptosis and/or necrosis. Such prodrug activation can be enhanced within tumor cells by the CYP-based gene directed-enzyme prodrug therapy (GDEPT) approach. However, those newly synthesized oxazaphosphorine derivatives such as glufosfamide, NSC 612567 and NSC 613060, do not need hepatic activation. They are activated through other enzymatic and/or non-enzymatic pathways. For example, both NSC 612567 and NSC 613060 can be activated by plain phosphodiesterase (PDEs) in plasma and other tissues or by the high-affinity nuclear 3'-5' exonucleases associated with DNA polymerases, such as DNA polymerases and ε. The alternative CYP-catalyzed inactivation pathway by N-dechloroethylation generates the neurotoxic and nephrotoxic byproduct chloroacetaldehyde (CAA). Various aldehyde dehydrogenases (ALDHs) and glutathione S-transferases (GSTs) are involved in the detoxification of oxazaphosphorine metabolites. The metabolism of oxazaphosphorines is auto-inducible, with the activation of the orphan nuclear receptor pregnane X receptor (PXR) being the major mechanism. Oxazaphosphorine metabolism is affected by a number of factors associated with the drugs (e.g., dosage, route of administration, chirality, and drug combination) and patients (e.g., age, gender, renal and hepatic function). Several drug transporters, such as breast cancer resistance protein (BCRP), multidrug resistance associated proteins (MRP1, MRP2, and MRP4) are involved in the active uptake and efflux of parental oxazaphosphorines, their cytotoxic mustards and conjugates in hepatocytes and tumor cells. Oxazaphosphorine metabolism and transport have a major impact on pharmacokinetic variability, pharmacokinetic-pharmacodynamic relationship, toxicity, resistance, and drug interactions since the drug-metabolizing enzymes and drug transporters involved are key determinants of the pharmacokinetics and pharmacodynamics of oxazaphosphorines. A better understanding of the factors that affect the metabolism and transport of oxazaphosphorines is important for their optional use in cancer chemotherapy.

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In order to improve the understanding of the dynamic and post-dynamic recrystallization behaviours of AISI 304 austenitic stainless steel, a series of hot torsion test have been performed under a range of deformation conditions. The mechanical and microstructural features of dynamic recrystallization (DRX) were characterized to compare and contrast them with those of the post-dynamic recrystallization. A necklace type of dynamically recrystallized microstructure was observed during hot deformation at 900 °C and at a strain rate of 0.01 s−1. Following deformation, the dependency of time for 50% recrystallization, t50, changed from “strain dependent” to “strain independent” at a transition strain (ε*), which is significantly beyond the peak. This transition strain was clearly linked to the strain for 50% dynamic recrystallization during deformation. The interrelations between the fraction of dynamically recrystallized microstructure, the evolution of post-dynamically recrystallized microstructure and the final grain size have been established. The results also showed an important role of grain growth on softening of deformed austenite.

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The phase behavior, hydrogen bonding interactions and morphology of poly(hydroxyether of bisphenol A) (phenoxy) and poly(var epsilon-caprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP) were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy and atomic force microscopy (AFM). In this A-b-B/C type block copolymer/homopolymer system, both P2VP and PCL blocks have favorable intermolecular interaction towards phenoxy via hydrogen bonding. However, the hydrogen bonding between P2VP and phenoxy is significantly stronger than that between PCL and phenoxy. Selective hydrogen bonding between phenoxy/P2VP pair at lower phenoxy contents and co-existence of two competitive hydrogen bonding interactions between phenoxy/P2VP and phenoxy/PCL pairs at higher phenoxy contents were observed in the blends. This leads to the formation of a variety of composition dependent nanostructures including wormlike, hierarchical and core–shell morphologies. The blends became homogeneous at 95 wt% phenoxy where both blocks of the PCL-b-P2VP were miscible with phenoxy due to hydrogen bonding. In the end, a model was proposed to explain the microphase morphology of blends based on the experimental results obtained. The swelling of the PCL-b-P2VP block copolymer by phenoxy due to selective hydrogen bonding causes formation of different microphases

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Nanostructured complexes were prepared from poly(ε-caprolactone)-block-poly(2-vinylpyridine) (PCL-b-P2VP) and poly(4-vinylphenol) (PVPh) in tetrahydrofuran (THF). The phase behavior, specific interactions, and morphology were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). In this A-b-B/C type block copolymer/homopolymer system, both blocks of the PCL-b-P2VP block copolymer have favorable intermolecular interaction toward PVPh via hydrogen bonding, but the interaction between P2VP block and PVPh is significantly stronger than that between PCL block and PVPh. It was found that the disparity in competitive intermolecular interactions, specifically PVPh and P2VP block interact strongly whereas PVPh and PCL block interact weakly, leads to the formation of a variety of nanostructures depending on PVPh concentration. Spherical micelles of 30−40 nm in diameter were obtained in the complex with 10 wt % PVPh, followed by wormlike micelles with size in the order of 40−50 nm in the complexes with 30−60 wt % PVPh. At low PVPh concentrations, PCL interacts weakly with PVPh, whereas in the complexes containing more than 20 wt % PVPh, the PCL block began to interact considerably with PVPh, leading to the formation of composition-dependent nanostructures. The complex becomes homogeneous with PVPh content beyond 60 wt %, since a sufficient amount of PVPh is available to form hydrogen bonds with both PCL and P2VP. Finally, a model was proposed to explain the self-assembly and microphase morphology of these complexes based on the experimental results obtained. The competitive hydrogen-bonding interactions cause the self-assembly and formation of different microphase morphologies.

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Nanostructured poly(ε-caprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP)/poly(acrylic acid) (PAA) interpolyelectrolyte complexes (IPECs) were prepared by casting from THF/ethanol solution. The morphological behaviour of this amphiphilic block copolymer/polyelectrolyte complexes with respect to the composition was investigated in a solvent mixture. The phase behaviour, specific interactions and morphology were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy (OM), dynamic light scattering (DLS) and atomic force microscopy (AFM). Micelle formation occurred due to the aggregation of hydrogen bonded P2VP block and polyelectrolyte (PAA) from non-interacted PCL blocks. It was observed that the hydrodynamic diameter (Dh) of the micelles in solution decreased with increasing PAA content up to 40 wt%. After 50 wt% PAA content, Dh again increased. The micelle formation in PCL-b-P2VP/PAA IPECs was due to the strong intermolecular hydrogen bonding between PAA homopolymer units and P2VP blocks of the block copolymer. The penetration of PAA homopolymers into the shell of the PCL-b-P2VP block copolymer micelles resulted in the folding of the P2VP chains, which in turn reduced the hydrodynamic size of the micelles. After the saturation of the shell with PAA homopolymers, the size of the micelles increased due to the absorption of added PAA onto the surface of the micelles.

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The postdeformation recrystallization behavior of a hot-deformed austenitic stainless steel was investigated based on the first part of this study, in which the microstructure development during hot deformation and, in particular, the evolution of dynamic recrystallization (DRX), was studied. The effect of different parameters such as strain, strain rate, and temperature were examined. The dependency of the time for 50 pct softening, t 50, changed from “strain dependent” to “strain independent” at a transition strain (ε*) that was in the steady-state area of the hot deformation flow curve. The fully recrystallized microstructure showed a similar transition in strain sensitivity. However, this occurred at stains greater than ε*. A mathematical model was developed to predict the transition strain under different deformation conditions. Microstructural measurements show that the transition strain corresponds to approximately 50 pct DRX in the deformed structure at the point of unloading.

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FT-IR spectroscopy has been utilized to monitor ion association in plasticized solid polymer electrolytes (SPEs). The SPEs were prepared from a random copolymer of ethylene oxide (EO) and propylene oxide (PO) and the salt lithium trifluoromethanesulfonate (lithium triflate, LiTf). Tetraethylene glycol dimethyl ether (tetraglyme) and N,N‘-dimethylformamide (DMF) were chosen as model plasticizers. Despite having a similar dielectric constant to that of the polymer host, ε ~ 5, the incorporation of tetraglyme into the SPEs resulted in increased ion association. The addition of a higher dielectric constant solvent , DMF, ε = 36.7, resulted in decreased ion association in the SPE. The effects of salt concentration (0.05−1.25 mol dm-3) and temperature (25−100 °C) upon ion association in SPEs were also investigated. At low salt concentrations, ion association was found to increase with temperature, however, at 1.25 mol dm-3 the temperature dependence of ion association was dominated by concentration effects. There appears to be a maximum in the fraction of “free” ions at a LiCF3SO3 concentration of 0.4 mol dm-3, preceded by a minimum at approximately 0.2 mol dm-3, consistent with the molar conductivity behavior previously observed in these electrolytes.