Mcclaingolden1745

We show how the powerful combination of temperature-dependent kinetics coupled with detailed statistical modeling can be used to derive dynamical information about transition state barrier heights, the importance of multiple entrance channel complexes, crossings between spin surfaces, energetics, product states, and other information for metal-ion reactions. The methods are not new, but with improved computers, ion sources, ion transport, and better detection techniques, the ability to derive such parameters from the combination of methods has improved greatly. Temperature-dependent kinetics is very sensitive to the above list of parameters because the energy is varied in a controlled way that can be easily modeled. The present measurements, performed in our variable-ion source temperature-adjustable selected-ion flow tube (VISTA-SIFT), have been enabled by advances in ion transport and injection improvements so that dim sources can be used. Replacing the quadrupole mass spectrometer detector with a time-of-f ions, mixed metal oxide ions, and a series of metallic anionic cluster reactions with small molecules such as CO, O2, CO2, N2O, CH4, and several other species. check details Particular attention was paid to reactions involving bond activation pertinent to catalysis.Area selective deposition (ASD) of films only on desired areas of the substrate opens for less complex fabrication of nanoscaled electronics. We show that a newly developed CVD method, where plasma electrons are used as the reducing agent in deposition of metallic thin films, is inherently area selective from the electrical resistivity of the substrate surface. When depositing iron with the new CVD method, no film is deposited on high-resistivity SiO2 surfaces whereas several hundred nanometers thick iron films are deposited on areas with low resistivity, obtained by adding a thin layer of silver on the SiO2 surface. On the basis of such a scheme, we show how to use the electric resistivity of the substrate surface as an extension of the ASD toolbox for metal-on-metal deposition.C70 fullerene catalyzed photoinduced oxidation of benzylic amines at ambient conditions has been explored here. The developed strategy's main feature includes the additive/oxidant-free conversion of benzylic amine to corresponding imine and aldehydes. The reaction manifests broad substrate scope with excellent function group leniency and is applicable up to the gram scale. Further, symmetrical secondary amines can also be synthesized from benzylic amine in a one-pot two-step process. Various experiments and density functional theory studies revealed that the current reaction involves the generation of reactive oxygen species, single electron transfer reaction, and benzyl radical formation as key steps under photocatalytic conditions.Spatial confinement has a great impact on the structures and dynamics of interfacial molecular and polymer liquid films. Most prior research has focused on confined liquids of fixed material compliance and often treated them in approximation to the "hard-sphere" interaction model. In this study, we microscopically investigate the structural dynamics of highly deformable poly(N-isopropylacrylamide) (PNIPAM) microgels confined between two solid surfaces in comparison to that of nearly nondeformable microgels of the same chemistry. We observe that the mobility and structural relaxation of highly deformable PNIPAM microgels at an apparent volume fraction, ϕ = 0.49-0.70, show little change with the reduction of gap spacing, in stark contrast to confinement-induced dynamic retardation of "hard-sphere"-like stiff PNIPAM microgels. The critical gap spacing, defined as the onset of confinement effect to deviate from the bulk behavior, is found to be approximately 17-22 particle layers for highly deformable microgels of ϕ = 0.56-0.70, much smaller than that of approximately 40 particle layers or larger for stiff microgels or model "hard-sphere" colloidal liquids of similar ϕ. Additionally, we observe no evident confinement-enhanced structural reorganization of deformable microgels near the confining surfaces when gap spacing approaches the critical gap spacing. Microgel deformation upon strong confinement is attributed to the disrupted confinement-induced ordering of confined microgels. Hence, it is clearly indicated that spatial confinement exhibits a much weaker effect on highly compliant microgel particles than stiff ones, resulting in a significantly less reduction in microgel interfacial dynamics. It therefore gives insights into the molecular design of polymeric thin films of variable compliance to control friction and lubrication.We fabricated bilirubin-bovine serum albumin (BR-BSA) nanocomplexes as candidates for the delivery of 5-fluoro-2-deoxyuridine (5FUdr) against experimental murine lymphoma. BR was attached to 5FUdr via acid-labile ester bonds mimicking small-molecule drug conjugates. The construct was self-assembled with BSA through strong noncovalent interactions with high drug occupancy in the core and labeled with folic acid (FA) to target cancer cells. The BR-5FUdr-BSA-FA nanoconstruct exhibits excellent biocompatibility, prevents nephrotoxicity, and is tolerated by red blood cells and mononuclear cells. The construct also showed increased accumulation in lymph nodes and tumor cells. BR-5FUdr-BSA-FA caused prolonged growth inhibition and apoptosis, enhanced mitochondrial reactive oxygen species generation, and minimized the viability of parental and doxorubicin-resistant Dalton's lymphoma cells. Treatment of tumor-bearing mice with BR-5FUdr-BSA-FA significantly increased the life span of the animals, improved their histopathological parameters, and downregulated PD-1 expression, suggesting the potential of the construct for 5FUdr delivery to treat lymphoma.There are myriad ions that are deemed too short-lived to be experimentally accessible. One of them is SF6+. It has never been observed, although not for lack of trying. We demonstrate that long-lived SF6+ can be formed by doping charged helium nanodroplets (HNDs) with sulfur hexafluoride; excess helium is then gently stripped from the doped HNDs by collisions with helium gas. The ion is identified by high-resolution mass spectrometry (resolution m/Δm = 15000), the close agreement between the expected and observed yield of ions that contain minor sulfur isotopes, and collision-induced dissociation in which mass-selected HenSF6+ ions collide with helium gas. Under optimized conditions, the yield of SF6+ exceeds that of SF5+. The procedure is versatile and suitable for stabilizing many other transient molecular ions.