The benzylidene acetal group is one of the most important protecting groups not only in carbohydrate chemistry but also in general organic chemistry. In the case of 4,6-O-benzylidene glycosides, we previously found that the stereochemistry at 4-position altered the reaction rate constant for hydrolysis of benzylidene acetal group. However, a detail of the acceleration or deceleration factor was still unclear. In this work, the hydrolysis reaction of benzylidene acetal group was analyzed using the Arrhenius and Eyring plot to obtain individual parameters for glucosides (Glc), mannosides (Man), and galactosides (Gal). The Arrhenius and Eyring plot indicated that the pre-exponential factor (A) and ΔS⧧ were critical for the smallest reaction rate constant of Gal among nonacetylated substrates. On the other hand, both Ea/ΔH⧧ and A/ΔS⧧ were influential for the smallest reaction rate constant of Gal among diacetylated substrates. All parameters obtained suggested that the rate constant for hydrolysis reaction was regulated by protonation and hydration steps along with solvation. The obtained parameters support wide use of benzylidene acetal group as orthogonal protection of cis- and trans-fused bicyclic systems through the fast hydrolysis of the trans-fused benzylidene acetal group.Amphotericin B (AmB) is an antifungal agent that poses a challenge for intravenous drug delivery due to its hydrophobicity and severe side effects that are attributed to the self-aggregation of AmB in aqueous solution. To overcome this problem, we have rationally designed an ionic-liquid-in-water nanoemulsion drug delivery system that harnesses the unique properties of ionic liquids. The complex drug AmB serves as a model pharmaceutical agent to demonstrate the robustness of ionic-liquid-in-water nanoemulsions. High concentrations of AmB were solubilized in a new hydrophobic dicholinium-based ionic liquid. The absorption spectrum of AmB in an ionic liquid mixture and prepared nanoemulsion indicates AmB solubilization in the monomeric form. The hydrophobic ionic liquid exhibits high in vivo biocompatibility with zebrafish. The hemolytic activity of the AmB nanoemulsion was negligible, yet it maintained antifungal activity against Candida albicans. The preliminary results presented in this Communication indicate that ionic-liquid-in-water nanoemulsions may allow for the delivery of a variety of pharmaceuticals intravenously, broadening the scope of ionic liquids in the pharmaceutical sciences.The stereochemistry of the substitution product formed when (1s,3s)-3-(tert-butyl)-1-methylcyclobutyl methanesulfonate, 7, reacts in trifluoroethanol is one of retention of configuration. This is consistent with the intermediacy of a nonclassical bicyclobutonium cation 8N. As the solvent becomes less highly ionizing, the product contains increasing amounts of the isomeric inverted product. This is indicative of the competitive involvement of a classical cation 8C that captures solvent from both sides. Solvolytic rate studies show no large rate enhancements due to the t-butyl group in 7. However, computational studies suggest that the combined stabilization of the bicyclobutonium cation 8N by C-C σ-interactions and the t-butyl group amounts to 10.8 kcal/mol in the gas phase. Computationally, the t-butyl group contributes to stabilization of 8N, but this stabilization is not revealed by kinetic studies. This discrepancy suggests caution when relating computational studies on carbocations to solvolytic studies in common solvents.The clinical aminoglycoside antibiotic gentamicin is a mixture of several difficult-to-separate major and minor components. The relative inaccessibility of the minor components in particular complicates efforts to separate antibacterial activity from nephro- and/or ototoxicity and to clarify the origin of the potentially therapeutically important read-through activity. With a view to facilitating such studies, the synthesis of a fully and selectively protected garamine-based acceptor has been developed from readily available sisomicin. Glycosylation of this acceptor with a 6-azido-6,7-dideoxy-d-glycero-d-glucoheptopyranosyl donor affords gentamicin B1 after deprotection, whereas employment of a 2-azido-2-deoxy-d-glucopyranosyl donor under N,N-dimethylformamide-directed glycosylation conditions affords gentamicin X2 after deprotection.Perovskite nanocrystal light-emitting devices (PNC LEDs) exhibit great potential in display and lighting applications. Balanced hole and electron injection in the light-emitting layer is undoubtedly an effective way to improve LED performance. Here, bismuth (Bi) was introduced into PNC LEDs to form a silver-bismuth (Ag-Bi) bilayer anode. Ag diffused into a defective 2 nm thick Bi layer to form an alloy-like state that promoted hole injection, reduced the charge transfer resistance, and enhanced charge transfer, leading to more balanced hole-electron carriers in the emission layer through hole injection enhancement. As a result, the turn-on voltage and brightness changed from 2.41 V and 2200 cd m-2, respectively, for CsPb1-xZnxI3-based LEDs with a Ag monolayer anode to 2.2 V and 3714 cd m-2, respectively, for devices with a Ag-Bi bilayer anode. In addition, the performance of CsPbI3 and CsPbBrI2 PNC-based LEDs has also been effectively improved by using a Ag-Bi bilayer anode.Interaction with the dopaminergic system in the central nervous system is either therapeutically intended or it is a side effect. In both cases, dopamine-receptor agonists (DRA) like the ergoline derivative bromocriptine and dopamine-receptor antagonists (DRAn) like metoclopramide have to cross the blood-brain barrier (BBB). The organic anion transporting polypeptides (OATP) 1A2 and 2B1 are cellular uptake carriers for a variety of endogenous and xenobiotic compounds. As both transporters are expressed in endothelial cells of the BBB, the aim of the present study was to determine whether the DRA bromocriptine, cabergoline, and pergolide and the DRAn metoclopramide and domperidone are interacting with OATP1A2 and 2B1 and could therefore be candidate genes modifying wanted and unwanted effects of these drugs. Localization of both transporters in the brain was confirmed using LC-MS/MS and immunofluorescence stainings. selleck For the functional studies, MDCKII cells stably expressing OATP1A2 or 2B1 were used. Initial interaction studies with the well-characterized transporter substrate estrone 3-sulfate revealed that all tested compounds except pergolide inhibit the transport function of both proteins with the most potent effect for bromocriptine (IC50 = 2.