Stereocontrolled chemical glycosylation remains a major challenge despite vast efforts reported over many decades and so far still mainly relies on trial and error. Now it is shown that the relative reactivity value (RRV) of thioglycosides is an indicator for revealing stereoselectivities according to four types of acceptors. Mechanistic studies show that the reaction is dominated by two distinct intermediates: glycosyl triflates and glycosyl halides from N‐halosuccinimide (NXS)/TfOH. The formation of glycosyl halide is highly correlated with the production of α‐glycoside. These findings enable glycosylation reactions to be foreseen by using RRVs as an α/β‐selectivity indicator and guidelines and rules to be developed for stereocontrolled glycosylation.
Electrotransfection is a technique utilized for gene delivery in both preclinical and clinical studies. However, its mechanisms are not fully understood. The goal of this study was to investigate specific pathways of endocytosis involved in electrotransfection. In the study, three different human cell lines (HEK293, HCT116, and HT29) were either treated with ice cold medium postelectrotransfection or endocytic inhibitors prior to electrotransfection. The inhibitors were pharmacological agents (chlorpromazine, genistein, and amiloride) or different small interfering RNA (siRNA) molecules that could knockdown expression of clathrin heavy chain (CLTC), caveolin-1, and Rab34, respectively. The reduction in gene expressions was confirmed with western blot analysis at 48-72h post-siRNA treatment. It was observed that treatments with either ice cold medium, chlorpromazine, or genistein resulted in significant reductions in electrotransfection efficiency (eTE) in all three cell lines, compared to the matched controls, but amiloride treatment had insignificant effects on eTE. For cells treated with siRNA, only CLTC knockdown resulted in eTE reduction for all three cell lines. Together, these data demonstrated that the clathrin-mediated endocytosis played an important role in electrotransfection.
A recent theory suggests that endocytosis is involved in uptake and intracellular transport of electrotransfected plasmid DNA (pDNA). The goal of the current study was to understand if approaches used previously to improve endocytosis of gene delivery vectors could be applied to enhancing electrotransfection efficiency (eTE). Results from the study showed that photochemically induced endosomal escape, which could increase poly-L-lysine (PLL)-mediated gene delivery, decreased eTE. The decrease could not be blocked by treatment of cells with endonuclease inhibitors (aurintricarboxylic acid and zinc ion) or antioxidants (L-glutamine and ascorbic acid). Chemical treatment of cells with an endosomal trafficking inhibitor that blocks endosome progression, bafilomycin A1, resulted in a significant decrease in eTE. However, treatment of cells with lysosomotropic agents (chloroquine and ammonium chloride) had little effects on eTE. These data suggested that endosomes played important roles in protecting and intracellular trafficking of electrotransfected pDNA.
The effects of cathode buffer layers on the bulk-heterojunction solar cells are investigated. Comparing with the device without buffer layer, obvious enhancements of Voc from 0.38 to 0.65 V and fill factor from 44% to 63% have been achieved by using 2 nm bathocuproine layer, which make the efficiency of the devices improved from 1.63% to 4.11%. Alternatively, lithium fluoride and/or tris(8-hydroxyquinolinato) aluminum were also introduced for clarification purpose. X-ray photoelectron spectroscopy study indicates that the degradation caused by the outer diffusion of carbon from active layers plays a crucial role in the device performance.
An investigation of carbodicarbenes, the less explored member of the carbenic complex/ligand family has yielded unexpected electronic features and concomitant reactivity. Observed 1,2-addition of E-H bonds (E = B, C, Si) across the carbone central carbon and that of the flanking N-heterocyclic carbene (NHC) fragment, combined with single-crystal X-ray studies of a model Pd complex strongly suggests a significant level of π-accepting ability at the central carbon of the NHC moiety. This feature is atypical of classic NHCs, which are strong σ-donors, with only nominal π-accepting ability. The unanticipated π-acidity is critical for engendering carbodicarbenes with reactivity more commonly observed with frustrated Lewis pairs (FLPs) rather than the more closely related NHCs and cyclic (alkyl)(amino)carbenes (CAACs).
Magnetic ordering and Kondo behavior coexist in three (Ce,Al)-based compounds: CeAl2, Ce3Al, and Ce3Al11. A common feature apparently independent of crystal structures also prevails in terms of the size-induced transition between these two magnetic phenomena. As the particle size is reduced to nanoscale, the specific heat anomaly associated with the magnetic ordering diminishes. Although the Kondo temperature also decreases, the entropy associated with Kondo anomaly exhibits a large increase. This results in an enhancement of the Kondo behavior and an increased coefficient gamma of the linear term in specific heat. For example, in 80 A CeAl2 the extrapolated r(0) reaches 9000 mJ mol Ce-1 K-2.
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