Latest ArticlesProtein recognition using host-guest recognition approach is of great interest but has been limited mainly to the protein N-terminal residues. Here, we site-specific incorporated two novel non-canonical amino acids containing supramolecular guest motifs into protein via an expanded genetic code. Through Staudinger reduction reactions, the encoded unnatural residues on protein becoming activated and can be specifically recognized by cucurbit[7]uril (CB[7]) and cucurbit[8]uril (CB[8]). We demonstrated that enzyme containing guest amino acid incorporated near the active site can be reversibly regulated by CB[7] recognition, and CB[8] recognition induces protein dimerization. These amino acids will make useful addition to the supramolecular toolbox for protein targeting using molecular recognition approaches.
A water-soluble macrocycle that bears four carboxylate anions has been designed and prepared, which forms a rectangular cavity that can efficiently encapsulate discrete electron-deficient aromatic compounds, including berberine and palmatine. This macrocycle is revealed to be highly biocompatible and able to inhibit the bitter taste of the two drugs.
Zinc-based batteries (ZBs) have been deemed as a potential substitute for lithium-ion batteries due to its unique advantages of abundant resources, low cost and acceptable energy density. Despite great progress in designing electrode materials has been made, the development of high-performance ZBs still remain challenges, such as the dendrite growth of zinc anode, hydrogen evolution reaction, limited electrochemical stability window, water evaporation and liquid leakage. Gel polymer electrolytes (GPEs), including hydrous GPEs with low content of active water and anhydrous GPEs without the presence of water, are proposed to avoid these problems. Furthermore, employing GPEs is conductive to fabricate flexible devices owing to the good mechanical strength. To date, most of researches focus on discovering new GPEs and exploring its application on flexible or wearable devices. Recent reviews also have outlined the polymer matrixes and advances of GPEs in various battery systems. Given this, herein, we seek to summarize the gelation mechanisms of GPEs, involving physical gel of polymer, chemical crosslinking of polymer and chemical polymerization of monomers. Peculiarly, the preparation methods are also classified. In addition, not only the features and central conundrum of GPEs are analyzed but also the corresponding strategies are discussed, contributing to design GPEs with ideal properties for high-performance ZBs.
Photosensitization related to energy/electron transfer process is of great importance to natural photosynthesis. Herein, we proposed a promising strategy to improve the sensitizing ability of the typical photoactive MOFs (UiO-Ir) by engineering its metal coordination center with NBI (1, 8-naphthalenebenzimidizole) chromophore. The resulting MOFs (UiO-Ir-NBI) exhibited a strong sensitizing ability for significantly boosting photosynthesis. Impressively, the catalytic yield of 2-chloroethyl ethyl sulfoxide with UiO-Ir-NBI can reach 99%, over 6 times higher than that with UiO-Ir (16.4%). Moreover, UiO-Ir-NBI exhibited an excellent catalytic stability and a broad substrate tolerance, highlighting its great application prospect. Systematic investigations revealed that the strong visible light absorption, long excited state lifetime and efficient electron-hole separation of UiO-Ir-NBI greatly contributed to harvesting visible light and facilitating interface electron/energy transfer for efficient solar energy utilization. This work provides a new horizon to boost photosythesis of MOFs by engineering their metal sensitizing centers at a molecular level.
Mg-doped manganese oxide octahedral molecular sieve (Mg-OMS-2) catalysts were prepared by hydrothermal method. The photothermal degradation performance of these catalysts for formaldehyde (HCHO) in batch system and continuous system was investigated. The light absorption of OMS-2 was increased by Mg-doped, especially for near infrared light, which promoted surface temperature reach a maximum of 214.8 ℃ under xenon irradiation. At this temperature, the reinforced surface lattice oxygen and oxygen vacancy that formed by lattice distortion via Mg-doped were activated. The best HCHO elimination efficiency was achieved over Mg0.2/OMS-2 catalyst with Mg2+/Mn2+ = 1/5, which could reduce HCHO from 250 ppm to 10 ppm within 20 min. The in situ DRIFTS was also carried out to monitor the changes in the content of reaction intermediates and analyze the degradation paths of HCHO. It was found the HCHO was attacked by formed •OH and •O2− to generate formate species and carbonate species, and finally transformed to CO2 and H2O. This photothermal catalytic oxidation process exhibited a high efficiency purification of HCHO without the help of extra energy consumption.
Spermatogenesis, maturation, capacitation and fertilization are precisely regulated by glycosylation. However, the relationship between altered glycosylation patterns and the onset and development of reproductive disorders is unclear, mainly limited by the lack of in situ imaging techniques for spermatozoa glycosylation. We developed an efficient and highly specific spermatozoa glycan imaging technique based on the robust chemoselective labeling of sialic acid (Sia) and N-acetyl-d-galactosamine (Gal/GalNAc). We further proposed a "tandem glycan chemoselective labeling" strategy to achieve simultaneous imaging of two types of glycans on spermatozoa. We applied the developed method to the spermatozoa from oligozoospermic patients and diabetic mice and found that these spermatozoa showed higher levels of Sia and Gal/GalNAc expression than the normal groups. Moreover, spermatozoa from diabetic mice showed a severe decrease in number, viability, and forward motility, suggesting that in vivo glucose metabolism disorders may lead to an elevated level of spermatozoa glycosylation and have a correlation with the development of oligoasthenotspermia. Our work provides a research tool to reveal the relationship between glycosylation modification and spermatozoa quality, and a promising clue for the development of glycan-based reproductive markers.
Liposomes are one of the significant classes of antitumor nanomaterials and the most successful nanomedicine drugs in clinical translation. However, it is difficult to accurately reveal liposome delivery modes and drug release rates at different pH values to assess the biodistribution and drug delivery pathways in vivo. Here, we established a strategy to integrate Bi-doped carbon quantum dots (CQDs) with liposomes to produce fluorescence visualization and therapeutic effects, namely lipo/Bi-doped CQDs. Lipo/Bi-doped CQDs show good water solubility and physicochemical properties, which can be used for in vitro labeling of colon cancer (CT26) cells and in vivo imaging localization tracking tumors for monitoring. Simultaneously, thanks to the excellent pH sensitivity and ion doping characteristic of Bi-doped CQDs, lipo/Bi-doped CQDs can be used to reveal the drug release rate of liposomes at different pH values and exhibit potential effects in vivo antitumor therapy.
Sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) are the most promising alternatives to lithium-ion batteries, and thus have drawn intensive research attention. Porous carbon materials from different precursors have been widely used as anode materials owing to their compatible storage effectiveness of both larger radii sodium and potassium ions. However, the differential bonding behaviors of Na and K ions with porous carbon-based anode are the significant one worth investigating, which could provide a clean picture of alkali ions storage mechanism. Therefore, in this work, we prepare a porous carbon network derived from sawdust (SDC) wastes, to further analyze the differences on sodium and potassium ions storage behaviors in terms of bond-forming process. It is found that, as-prepared SDC anodes could deliver stable sodium and potassium storage capacities, however, there are notable distinctions in terms of electrochemical behaviors and diffusion processes. By virtue of ex-situ XRD and Raman spectroscopy, the phase transition reaction of potassium ions could be well-observed, and the results shows that the multiple intercalated compounds was formed in SDC network during ions insertion, further resulting in slower diffusion kinetics and larger resistance compared to non-bonded process of sodium ions storage. This study provides more insights into the differences between sodium and potassium ions storage, as well as the energy storage mechanism of porous carbon as anodes for secondary batteries.
A rhodium/diphosphine-catalyzed asymmetric cross-dehydrogenative coupling between sulfoximines and dihydrosilanes has been achieved. This is the first report on the enantioselective N-silylation of sulfoximines. The protocol gives access to a variety of Si-stereogenic N-silylated sulfoximines in decent yield (up to 99%) with excellent stereoselectivity (up to 99%), featuring high atom economy, and a cleaner manner with H2 as the sole byproduct. The obtained bis-Si-stereogenic monohydrosilane product can be further converted into the corresponding chiral polymer with pendant sulfoximine groups.
Doyle-Kirmse rearrangement reactions have received continuous attention as an important method for constructing complex chemical structures. Herein, we disclosed an efficient rhodium-catalyzed Doyle-Kirmse rearrangement reaction, which can simultaneously construct CC bonds and CX (X = S/Se) bonds using sulfoxonium ylides as starting materials to obtain sulfur- or selenium-containing compounds. This strategy is characterized by the safer and greener carbene precursor, high yields and broad substrate scope, possessing a wide range of application.