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Hydration of ions/molecules in nanometer-sized clusters or nanoscopic pores is ubiquitous and plays a key role in many chemical and physical systems. In this work, guanidine-H2O reactions with n = 1-8 water molecules were systematically studied by ab initio methods. The result suggests that the reduced availability of water molecules greatly inhibits the strong base guanidine from producing OH-. That is, guanidine exhibits the behavior of a weak bases in low-humidity nanoscale environments. Intriguingly, this effect is not limited to guanidine but could be applied to other strong bases. Furthermore, we demonstrate that the direction of guanidine-CO2 reactions can be controlled by changing the number of water molecules present, which in turn responds to the humidity change in air. These findings not only shed some light on unconventional chemical reactions of strong bases in atmospheric clusters and on solid porous surfaces, but also provide insights into the development of guanidine-based CO2 air-capture sorbents.The total synthesis of the natural product coralmycin A/epi-coralmycin A, as well as a desmethoxy analogue is described. Synthesis was achieved via a divergent, bidirectional solid-phase strategy, including a key on-resin O-acylation, O to N acyl shift, and O-alkylation protocol to incorporate the unusual 4-amino-2-hydroxy-3-isopropoxybenzoic acid motifs. Autophinib Autophagy inhibitor The synthetic natural product was generated as a 1 1 mixture of epimers at the central β-methoxyasparagine residue and exhibited potent antibacterial activity against a panel of ten Gram-negative and seven Gram-positive organisms. The desmethoxy analogue possessed significantly more potent antimicrobial activity against this panel with minimal inhibitory concentrations (MICs) as low as 50 nM.Though liposome-based drugs are in clinical use, the mechanism of cell internalization of liposomes is yet an object of controversy. The present experimental investigation, carried out on human glioblastoma cells, indicated different internalization routes for two diastereomeric liposomes. Molecular dynamics simulations of the lipid bilayers of the two formulations indicated that the different stereochemistry of a lipid component controls some parameters such as area per lipid molecule and fluidity of lipid membranes, surface potential and water organization at the lipid/water interface, all of which affect the interaction with biomolecules and cell components.Cyclohexanone is a simple and widely available raw material that can be obtained from lignin biomass, highlighting its renewable and sustainable features. Cyclohexanone, as an important synthon in organic chemistry, has been demonstrated to be viable for constructing functionalized arenes and benzoheteroarenes, with recent extensive development on transition metal-free oxidative dehydrogenative aromatization. This review focuses on recent research progress on the transition metal-free derivation of cyclohexanones via oxidative dehydrogenative aromatization.Hollow metal-organic frameworks (MOFs) with only a shell may be used for efficient catalysis. In this work, a general sequential synthesis was employed to successfully create Hf-based hollow MOFs, such as UiO-66, MOF-808, and PCN-223. Etchants including monocarboxylic acids and H2O are required to remove the interior of the MOFs to form hollow structures, while the different stability of the interior and surface of the MOFs partly resulting from surface epitaxy protection was responsible for the selective etching. With these insights, scale-up of hollow octahedral UiO-66 was realized. This work paves a way to rationally design hollow MOFs.The design and synthesis of crystalline materials have been a subject of intensive research because of their interesting structures, physicochemical properties, and potential applications. However, the crystalline structure of organic-inorganic hybrid materials collapses to lose the structural features of the original networks and/or frameworks when exposed to different stimuli such as pH, vapor, water, high temperature, and organic solvents. This hampers further studies focusing on practical applications. Although several review articles provide reasonable pathways for the preparation of stable metal-organic frameworks (MOFs) and coordination polymers (CPs), the synthesis and design of stable materials containing organic species remain challenging. In this frontier article, we discuss the development of crystalline MOF, CP, metallophosphate, and metallophosphite materials, and provide a feasible approach for the formation of stable organic-inorganic hybrid compounds that combine MOFs (or CPs) and phosphate (or phosphite) building elements. In addition to their interesting structures, the synthetic strategies and structural stabilities of such hybrid composites are also presented.GaN-ZnO alloys are more promising semiconductors than their counterparts for optoelectronic applications due to the abrupt red shift in the visible-light range. Unfortunately, the strong internal electrostatic field (IEF) seriously hinders to further improve the optoelectronic performance due to the charge density of surface states. We point out a structural model to extremely improve the visible-light absorption by overcoming the bottleneck of the IEF in the two-dimensional (2D) nonisovalent alloys. The novel haeckelite (8|4) configuration with the nearly zero IEF shows much better optoelectronic performances than the conventional wurtzite configuration. Meanwhile, we explore the thickness-driven structural transitions from the planar hexagonal to the 8|4 and to the wurtzite configurations. The visible-light absorption efficiency quickly rises up from the bulk wurtzite to the bulk 8|4 to the 2D 8|4 and to the MoS2-based heterostructures with the different-layer 8|4 configurations. The heterointerfacial coupling is an effective way to further reduce the IEF and hence to significantly improve the visible-light absorptions by enlarging the population of band edge states in the 8|4 configuration. We suggest that the 8|4 configuration is more prospective for diverse optoelectronic applications in 2D GaN-ZnO alloys than in binary counterparts.
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