Latest ArticlesSuzuki coupling reactions between symmetrical monomers were conducted in various mesoporous silica nanoreactors grafted with palladium catalysts, enabling the selective formation of [12]cycloparaphenylene precursor with separate yield up to 25% in one-pot reactions, much higher than that in homogeneous reaction. The spatial nanoconfinement of the nanoreactors promotes the macrocyclization while limits the concomitant linear oligomer formation, offering more possibilities for the synthesis of macrocycles from symmetrical monomers in one-pot reaction.
Voriconazole (VZL) is a second-generation and broad-spectrum triazole against fungal infections. Being a BCS (biopharmaceutics classification system) class Ⅱ compound, the poor aqueous solubility has limited its bioavailability and clinical efficacy. Aims to overcome this disadvantage, a cocrystallization strategy based on crystal engineering principles has resulted in five new multi-component crystals of VZL with maleic acid, L-tartaric, protocatechuic, gallic, and 3,5-dinitrobenzoic acids. Structure analysis revealed that the hydroxyl/carboxylic acid···triazole N3 hydrogen bonding interaction appears as a main supramolecular heterosynthon in the VZL multi-component crystals with organic acids. And VZL molecule has a flexible conformation in each of the five multi-component structures. The newly synthesized multi-component crystals showed impressive solubility improvement compared to that of the raw material of VZL. Molecular electrostatic potential surfaces (MEPS) analysis based on density functional (DFT) calculations revealed that hydrogen bond interactions in cocrystals mainly involved pairwise interactions in the global maxima and minima sites, but this rule is not always followed. This study indicates the potential of cocrystals to improve the solubility and dissolution rate of VZL
Organic-inorganic hybrid perovskites (OIHPs) materials with high phase transition temperature (Tp) have been widely studied in the field of molecular switches, solar energy and electric power. At present, the OIHPs with high Tp are generally constructed through molecular design, which can be applied to a wide temperature range. Here, three one-dimensional (1D) OIHPs [R-ClEQ]PbCl3 (Tp = 442 K), [R-ClEQ]PbBr3 (Tp= 499 K) and [R-ClEQ]PbI3 (Tp above m.p.) (R-ClEQ = (R)-N-chloroethyl-3-quinuclidinol) with different Tp are obtained by regulating the halogen-halogen interaction and hydrogen bonding in the system. Especially in [R-ClEQ]PbX3 (X = Cl, Br and I) crystal system, all the halogen bonds tend to form at approximately 180°angles and the strength of halogen bonding is found to be increased from 1.59 × 10–3 Hartree to 2.35 × 10–3 Hartree with increased atom number from Cl to I. The synergistic effect of halogen bonding and hydrogen bonding provide a useful strategy for the design OIHPs phase transition materials with high Tp.
Nitrogen electro-reduction reaction (NERR) is a promising alternative method for ammonia production to the Haber–Bosch approach due to mild reaction conditions and free harmful by-product emission. A formidable challenge in bringing NERR closer to the practical application is developing an electro-catalyst which can simultaneously improve the Faraday efficiency and reduce the reaction over-potential. Herein, we fabricated a catalyst of nitrogen-doped carbon dots modified copper-phosphate nanoflower petals (CuPo-NCDs NF) via a self-assembly method. The flower structure endowed the CuPo-NCDs NF with large specific surface area, and thus enabled more active sites to be exposed. In particular, we demonstrated that the NCDs modified CuPo petals with flower-like structure can accelerate the interfacial proton-electron transfer, suppressing the competing hydrogen evolution reaction and promoting the desired NERR process. Ultimately, for the CuPo-NCDs NF catalyzed NERR, the FENH3 and the reaction potential both were boosted, the resultant energy efficiency of NERR reached a record-breaking value of 56.5%, and the NH3 yield rate increased by 7 times compared to NCDs. This study provides a novel catalyst with a new pathway to boost the NERR.
The Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM811) layered cathodes endow Li-ion batteries (LIBs) with high energy density. However, they usually suffer from limited ion-diffusion and structural instability during cycling. Although doping strategy can effectively alleviate these issues, the coupling effects of multi-element doping and the corresponding performance enhancement mechanism have been yet unclear. Here, we report a Zr/Ti dual-doped NCM811 cathode material (ZT-NCM811), in which Zr-ion is doped into both transition metal (TM) layers and lithium layers and Ti-ion is only distributed in TM layers. The dual-doping can effectively enhance crystal structure stability via inhibiting the lattice collapse along c-axis and decreasing the Li/Ni disorder. Meantime, the lattice oxygen escape is also greatly reduced due to the presence of stronger Zr-O and Ti-O bonds, further mitigating the crystal surface parasitic reactions with electrolyte. The resultant ZT-NCM811 exhibits high specific capacity of 124 mAh/g at even 10 C, much higher than undoped and single-doped NCM811, and a retention of 98.8% at 1 C after 100 cycles. The assembled ZT-NCM811/graphite full cell also delivers superior battery performances and durability.
Sodium-ion batteries (SIBs) have received significant attention in large-scale energy storage due to their low cost and abundant resources. To obtain high-performance SIBs, many intensive studies about electrode materials have been carried out, especially the cathode material. As various types of cathode material for SIBs, a 3D open framework structural Na3V2(PO4)2F3 (NVPF) with Na superionic conductor (NASICON) structure is a promising cathode material owing to its high operating potential and high energy density. However, its electrochemical properties are severely limited by the poor electronic conductivity due to the insulated [PO4] tetrahedral unit. In this review, the challenges and strategies for NVPF are presented, and the synthetic strategy for NVPF is also analyzed in detail. Furthermore, recent developments of modification research to enhance their electrochemical performance are discussed, including designing the crystal structure, adjusting the electrode structure, and optimizing the electrolyte components. Finally, further research and application for future development of NVPF are prospected.
Difluorocarbene has emerged as a valuable intermediate to synthesize fluorides. However, difluorocarbene-derived synthesis of 19F/18F-trifluoromethyl triazoles has not been explored. Herein, we reported the Cu(I)-promoted difluorocarbene-derived 19F/18F-trifluoromethylation of iodotriazoles using KF/K18F as the fluorine source. This approach rapidly generated a wide range of 5-trifluoromethyl-1, 2, 3-triazoles in good yields showing high functional group compatibility. The reaction was effective for late-stage functionalization of bioactive molecules and 18F-trifluoromethylation of iodotriazoles. This work provides a practical synthetic methodology for the development of triazole drugs and 18F-radiotracers for positron emission tomography.
Activity-based Ubiquitin probes (Ub-ABPs) carrying a reporter group have emerged as effective tools for the investigation of deubiquitinating enzymes (DUBs), such as studying the molecular mechanism of DUBs, profiling new DUBs. But so far, the synthesis of commonly used biotin-bearing Ub-ABPs is a technical challenge. Here, we report a one-pot semi-synthetic strategy for the acquiring of Ub-ABPs carrying a biotin tag through sequential enzymatic ligation, N-S acyl transfer and aminolysis reaction without any purification steps. These probes enable to capture the different family of DUBs for enrichment and immunoblotting using the attached biotin tag.
Developing efficient photosensitizers for C–P bond construction is highly important and remains a challenge due to the urgently needed for the synthesis of modified nucleosides, nucleotides, and other phosphine-containing ligands. Herein, two pyrene-tethered bismoviologen derivatives (Py-BiV2+) were designed and synthesized for visible-light-induced C–P bonds formation. The photochemical and electrochemical properties of Py-BiV2+ were studied systemically, certifying fine-tunable opto-electronic properties through the number of pyrene groups (4, n = 1; 6, n = 2). The prepared Py-BiV2+ showed strong light absorption, while retaining good redox features and chromic response features that were inherent to viologens. 4 exhibited accelerated photoinduced electron transfer in the presence of the electron donor (pyrene) and the generated 4' (radical cation) showed higher stability. Accordingly, Py-BiV2+ directly served as photosensitizers for the first time in the visible-light-induced C(sp3)–P and C(sp2)–P bonds formation. As expected, these novel viologen derivatives exhibited good catalytic performance and good substrate expansibility under ambient conditions.
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