The ablation of metal surfaces in the presence of a precursor gas produces reaction products which are often difficult to predict and highly dependent on ablation conditions. This article describes the successful development and implementation of a laser ablation source-equipped Fourier transform microwave spectrometer capable of observing 4 GHz regions of spectra in a single data acquisition event. The dramatically increased speed with which regions may be searched, when compared to other high resolution microwave techniques, allows the source conditions to be the prime variable in laser ablation microwave spectroscopic studies. A second feature of the technique is that observed spectral features have correct relative intensities. This is advantageous when assigning observed spectra. The study of two metal chlorides, AgCl and AuCl, illustrate the instrument's benefits.
Tissue engineered vascular grafts (TEVGs) using scaffolds fabricated from braided poly(glycolic acid) (PGA) fibers coated with poly(glycerol sebacate) (PGS) are developed. The approach relies on in vivo tissue engineering by which neotissue forms solely within the body after a scaffold has been implanted. Herein, the impact of altering scaffold braid design and scaffold coating on neotissue formation is investigated. Several combinations of braiding parameters are manufactured and evaluated in a Beige mouse model in the infrarenal abdominal aorta. Animals are followed with 4D ultrasound analysis, and 12 week explanted vessels are evaluated for biaxial mechanical properties as well as histological composition. Results show that scaffold parameters (i.e., braiding angle, braiding density, and presence of a PGS coating) have interdependent effects on the resulting graft performance, namely, alteration of these parameters influences levels of inflammation, extracellular matrix production, graft dilation, neovessel distensibility, and overall survival. Coupling carefully designed in vivo experimentation with regression analysis, critical relationships between the scaffold design and the resulting neotissue that enable induction of favorable cellular and extracellular composition in a controlled manner are uncovered. Such an approach provides a potential for fabricating scaffolds with a broad range of features and the potential to manufacture optimized TEVGs.
Vimentin intermediate filaments form part of the cytoskeleton of mesenchymal cells, but under pathological conditions often associated with inflammation, vimentin filaments depolymerize as the result of phosphorylation or citrullination, and vimentin oligomers are secreted or released into the extracellular environment. In the extracellular space, vimentin can bind surfaces of other cells and the extracellular matrix, and the interaction between extracellular vimentin and other cell types can trigger changes in cellular functions, such as activation of fibroblasts to a fibrotic phenotype. The mechanism by which extracellular vimentin binds external cell membranes and whether vimentin alone can act as an adhesive anchor for cells is largely uncharacterized. Here, we show that various cell types (normal and vimentin null fibroblasts, mesenchymal stem cells, A549 lung carcinoma cells) attach to and spread on polyacrylamide hydrogel substrates covalently linked to vimentin. Using traction force microscopy and spheroid expansion assays, we characterize how different cell types respond to extracellular vimentin. Cell attachment to and spreading on vimentin-coated surfaces is inhibited by hyaluronic acid (HA) degrading enzymes, HA synthase inhibitors, soluble heparin, or N-acetyl glucosamine, treatments that have little or no effect on the same cell types binding to collagen-coated hydrogels. These studies highlight the effectiveness of substrate-bound vimentin as a ligand for cells and suggest that carbohydrate structures, including the glycocalyx and glycosylated cell surface proteins that contain N-acetyl glucosamine, form a novel class of adhesion receptors for extracellular vimentin.
The overall rate constant for H + CH 3 SH has been studied over 296− 1007 K in an Ar bath gas using the laser flash photolysis method at 193 nm. H atoms were generated from CH 3 SH and in some cases NH 3 . They were detected via timeresolved resonance fluorescence. The results are summarized as k = (3.45 ± 0.19) × 10 −11 cm 3 molecule −1 s −1 exp(−6.92 ± 0.16 kJ mol/RT) where the errors in the Arrhenius parameters are the statistical uncertainties at the 2σ level. Overall error limits of ±9% for k are proposed. In the overlapping temperature range there is very good agreement with the resonance fluorescence measurements of Wine et al. Ab initio data and transition state theory yield moderate accord with the total rate constant, but not with prior mass spectrometry measurements of the main product channels leading to CH 3 S + H 2 and CH 3 + H 2 S by Amano et al.
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