Latest ArticlesA general, facile and eco-friendly iron catalysis enables oxidation of unstrained tertiary aromatic alcohols to ketones through C−C bond cleavage even with H2O2 as the oxidant. Notably, this transformation can tolerate oxidation-labile functional groups. The robustness of this method is further demonstrated on the late-stage oxidation of complex bioactive molecules.
The synthesis of degradable polymers with easy-to-break in-chain carbon-oxygen bonds has attracted much attention. This minireview introduces the synthesis of a variety of degradable polymers from the (co)polymerizations of several typical oxygenated monomers such as epoxides, cyclic carbonates, cyclic esters, carbon dioxide (CO2), carbonyl sulfide (COS), and cyclic anhydrides. We highlight the catalysts and mechanisms for these (co)polymerizations. The ring-opening copolymerization of five-membered carbonate with cyclic anhydride or COS has been introduced. We also highlight the synthesis of block copolymers and cyclic copolymers with well-defined sequences by the method of growing center switching. We hope that these new polymerization systems can provide new ideas for the development of degradable low-carbon polymers in the future.
The recent advances in accelerated polymerization of N-carboxyanhydrides (NCAs) offer an effective strategy to simplify the preparation of polypeptide materials. However, the fine-tuning of polymerization kinetics, which is critical to differentiate the main polymerization and the side reactions, remains largely unexplored. Herein we report the modulation of polymerization rate of NCA in a water/oil biphasic system. By altering the aqueous pH, the initial location of the initiators, and the pKa of initiating amines, we observed the change in polymerization time from several minutes to a few hours. Due to the high interfacial activity and low pKa value, controlled polymerization was observed from multi-amine initiators even if they were initially located in the aqueous phase. This work not only improves our understanding on the biphasic polymerization mechanism, but also facilitates preparation of versatile polypeptide materials.
The development of molecular probes or systems with the ability of multiple orthogonal responses is an effective approach to precisely detect biomolecules with similar chemical structures. Herein, we report the synthesis of a water-soluble TPE-based octacationic cage (1) with the compressed TPE-containing bilayer, which endows it with good fluorescence properties and potential conformation chirality. As a result, 1 exhibits molecular recognition for anionic nucleotides within its two “claw”-like cavities to form 1:2 host-guest complexes in water, companying with selective turn-off fluorescence and turn-on CD responses to G/GTP over other nucleotides.
Immobilizing enzyme to nano interfaces has demonstrated to be a favorable strategy for prompting the industrialized application of enzyme. Despite tremendous endeavor has been devoted to using gold nanoparticles (AuNPs) as conjugation matrix due to its fascinating physico-chemical properties, maintaining enzymatic activity while circumventing cumbersome modification remains a formidable challenge. Herein, the freezing-directed conjugation of enzyme/nano interfaces was constructed without extra reagent. As the proof of concept, glucose oxidase (GOx) was chosen as model enzyme. The one-pot conjugation process can be facilely completed at −20 ℃ under aqueous solution. Moreover, with the loading of GOx on AuNP at freezing, the enzyme exhibited superior catalytic activity and stability upon thermal and pH perturbation. The mechanism of boosted activity was then discussed in detail. It was found that higher loading density under freezing condition and more enzyme tending to bind AuNPs via Au-S bond were the main factors for the superior activity. More importantly, this methodology was universal and can also be applied to other enzyme which contains natural cysteine, such as horseradish peroxidase (HRP) and papain. This facile conjugation strategy accompanied by remarkable bioactivity expand the possibilities for enzymatic biosensing, microdevice and even drug delivery.
Increasing environmental pollution and shortage of conventional fossil fuels have made it urgent to develop renewable and clean energy sources. Electrocatalytic water splitting, with its abundant raw materials, simple process, and zero carbon emission, is considered one of the most promising processes for producing carbon-neutral hydrogen which has excellent energy conversion efficiency and high gravimetric energy density. Among them, oxygen evolution reaction (OER) electrocatalysts and hydrogen evolution reaction (HER) electrocatalysts are critical to decreasing the intrinsic reaction energy barrier and boosting the hydrogen evolution efficiency. Therefore, it is imperative to develop and design low-cost, highly active, and stable OER and HER electrocatalysts to lower the overpotential and drive the electrocatalytic reactions. Transition metal sulfides, especially iron-based sulfides, have attracted extensive exploration by researchers as a result of its high abundance in the Earth's crust and near-metallic conductivity. Consequently, in this review, we systematically and comprehensively summarize the progress in the application of iron-based sulfides and their composites as OER and HER electrocatalysts in electrocatalysis. Detailed descriptions and illustrations of the special relationships among their composition, structure, and electrocatalytic performance are presented. Finally, this review points out the challenges and future prospects of iron-based sulfides in practical applications for designing and fabricating more promising iron-based sulfide OER and HER electrocatalysts. We believe that iron-based sulfide materials will have a wide range of application prospects as OER and HER electrocatalysts in the future.
Molecular doping has become a widely used method to modulate the electric performance of organic semiconductors (OSC). Highly effective charge transfer during molecular doping is desired to achieve ideal electrical conductivity. Two types of charge transfer mechanisms are widely accepted in molecular doping process: integer charge transfer (ICT) and charge transfer complex (CTC). In this review, fundamental principles of two mechanisms are revisited and the characterization methods are depicted. The key points for the formation of two mechanisms are highlighted from aspects of molecular structure and process engineering. Then, the strategies to improve the proportion of ICT are discussed. Finally, the challenges and perspectives for future developments in the molecular doping of polymer semiconductors are provided.
Carbon nanofibers (CNFs) have received extensive and in-depth studied as anodes for sodium-ion batteries (SIBs), and yet their initial Coulombic efficiency and rate capability remain enormous challenge at practical level. Herein, CNFs anchored with cobalt nanocluster (CNFs-Co) were prepared using chemical vapor deposition and thermal reduction methods. The as-prepared CNFs-Co shows a high initial Coulombic efficiency of 91% and a high specific discharge capacity of 246 mAh/g at 0.1 A/g after 200 cycles as anode for SIBs. Meanwhile, the CNFs-Co anode still delivers a high cycling stability with 108 mAh/g after 1000 cycles at 10 A/g. These excellent electrochemical properties could be attributed to the involved spin state Co, which endows CNFs with large interplanar spacing (0.39 nm) and abundant vacancy defects. Importantly, the spin state Co downshifts the p-band center of carbon and strengthens the Na+ adsorption energy from −2.33 eV to −2.64 eV based on density functional theory calculation. This novel strategy of modulating the carbon electronic structure by the spin state of magnetic metals provides a reference for the development of high-performance carbon-based anode materials.
It is challenging to cooperatively improve the nonlinear optical (NLO) efficiency and the laser-induced damage threshold (LIDT). This work reports a novel IR NLO materials CsInP2S7 (CIPS) designed by combination the strategies of alkali metals substitution and microscopic NLO units PS4 introduction based on AgGaS2. CIPS was composed of strongly distorted [InS6]9- octahedra and [P2S7]4- dimers constructed by corner-sharing [PS4]3-, which increase the NLO efficiency and decrease thermal expansion anisotropy simultaneously. Compared with AgGaS2, CIPS exhibited strong phase matchable NLO response ca. 1.1 × AGS@2.1 µm, high LIDT ca. 20.8 × AgGaS2, and IR transparency up to 15.3 µm. Structural analysis and theoretical investigation confirmed that large SHG effect and ultrahigh LIDT of CIPS originated from the synergistic contribution of [InS6]9- octahedra and [P2S7]4- dimers. These results indicate that CIPS is a promising NLO candidate in the mid-IR region, and this study provides a new approach for developing potential NLO-LIDT compatible materials.
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