Latest ArticlesA copper(Ⅰ)-catalyzed diastereodivergent addition of phosphinothioates (HP(S)ROR') to α, β-unsaturated thioamides is disclosed, which constructs vicinal P-chiral and C-chiral centers in generally high diastereo- and enantioselectivities. In this reaction, the kinetic resolution of HP(S)ROR' occurs, which affords (R)-HP(S)PhOMe in high enantioselectivity in the addition with (R, R)-Ph-BPE as the ligand. It is found through control experiment that dual "soft-soft" interaction, indicated by both 1H and 31P NMR experiments, is indispensable in the present reaction. The first "soft-soft" interaction between copper(Ⅰ) catalyst and HP(S)ROR' enables facile deprotonation to generate nucleophilic [Cu]-SPROR' species. The second one between the [Cu]-SPROR' species and α, β-unsaturated thioamides facilitated the nucleophilic addition. Finally, both Michael adducts and (R)-HP(S)PhOMe are easily converted to synthetically useful compounds.
Utilizing CO2 for the production of bulky and valuable chemicals presents an attractive solution to address environmental and fossil energy crises. Among the various approaches, direct carboxylation of alcohols with CO2 stands out as an eco-friendly process capable of efficiently producing carboxylic acids in a sustainable manner. However, the high dissociation energy of the C-O bond poses a significant challenge in this process. Over the past few decades, several strategies have been developed to activate alcohols and establish efficient catalytic systems for carboxylation with CO2. Nevertheless, the sporadic nature of reported approaches makes it difficult to determine the most effective one. This perspective aims to provide an overview of the current state-of-the-art catalytic protocols for carboxylating alcohols with CO2, encompassing esterification, halogenation, and photocatalysis, while considering their respective advantages and limitations. We aim to discern the most promising avenues for future development in this field. The insights presented in this perspective will contribute to the advancement of efficient and sustainable carboxylation methods using CO2, leading to the production of valuable chemicals in future.
Sulfidation of zero-valent iron (ZVI) has attracted broad attention in recent years for improving the sequestration of contaminants from water. However, sulfidated ZVI (S-ZVI) is mostly synthesized in the aqueous phase, which usually causes the formation of a thick iron oxide layer on the ZVI surface and hinders the efficient electron transfer to the contaminants. In this study, an alcohothermal strategy was employed for S-ZVI synthesis by the one-step reaction of iron powder with elemental sulfur. It is found that ferrous sulfide (FeS) with high purity and fine crystallization was formed on the ZVI surface, which is extremely favorable for electron transfer. Cr(Ⅵ) removal experiments confirm that the rate constant of S-ZVI synthesized by the alcohothermal method was 267.1- and 5.4-fold higher than those of un-sulfidated ZVI and aqueous-phase synthesized S-ZVI, respectively. Systematic characterizations proved that Cr(Ⅵ) was reduced and co-precipitated on S-ZVI in the form of a Fe(Ⅲ)/Cr(Ⅲ)/Cr(Ⅵ) composite, suggesting its environmental benignancy.
Artemisinin (ART) resistance has been an emerging clinical problem, severely compromising antimalarial efficacy and threatening the global malaria elimination campaign. Albeit intensive studies about the molecular mechanism for ART resistance are under way, no effective therapeutic targets for reversing resistance have been applied. Here, we explore glutathione (GSH) as a therapeutic target to develop a thermo-responsive nanoplatform to specifically co-deliver ART and GSH synthesis inhibitor (L-buthionine sulfoximine, BSO) in a sustained manner, effectively reversing ART resistance in vivo. By combining with BSO, ART exerts increased antimalarial activity with reduced half-maximal inhibitory concentration (IC50) by 7.43-fold in ART-resistant strains. This work reveals that the GSH in ART-resistant parasites can be a promising therapeutic target for reversing ART resistance, paving the way for developing drug candidates and intelligent nanomedicines in malaria therapy.
Hybrid metal-organic framework (MOF) derivatives play a significant role in the novel catalyst development in energy conversion reactions. Here, we demonstrated the low-temperature fully fluorinated zeolitic imidazole framework (ZIF) coupled with a three-dimensional open framework Prussian blue analog (PBA) with combined advantages for electrocatalytic oxygen evolution reaction (OER) in water splitting reaction. The spectroscopic analysis and the electrochemical studies revealed the combined advantages of efficient electronic effect and active site synergism. Because of good conductivity improvement by N-doped carbon derived from ZIF and the high electrochemical surface area and active site exposure from PBA derivatives, good catalytic performance was obtained on the optimal catalyst of CoNi ZIF/CoFe-PBA-F-300, which required a low overpotential of 250 mV to reach 10 mA/cm2 loaded on the glassy carbon electrode, with Tafel slope of 47.4 mV/dec, and very high dynamic and steady stability. In addition, the multi-component with the mixed structure from highly polar metal fluorides promoted the easy formation of the active phase as revealed by the post-sample analysis. The current results showed a novel composite catalyst materials development from the hybrid MOF derivatives, which would be promising in the electrolysis of water oxidation reactions and energy-relevant catalysis reactions.
Inspired by our previous studies to discover novel human immunodeficiency virus-1 (HIV-1) non-nucleoside reverse transcriptase inhibitors (NNRTIs) by targeting the tolerant region II of the NNRTIs binding pocket (NNIBP), a series of novel benzo[4,5]thieno[2,3-d]pyrimidine derivatives were designed through structure-based drug design as novel potent HIV-1 NNRTIs. The results showed that compound 16b was the most active inhibitor, exhibiting 50% effective concentration (EC50) values from 0.021 µmol/L to 0.298 µmol/L against wild-type (WT) and a panel of NNRTIs-resistant HIV-1 strains. Moreover, 16b was demonstrated with a significantly low 50% cytotoxicity concentration (CC50) value (> 200 µmol/L) and high selectivity index (SI) values. In addition, 16b yielded moderate reverse transcriptase (RT) enzyme inhibition with a 50% inhibition concentration (IC50) value of 0.183 µmol/L, which demonstrated that it acted as HIV-1 NNRTIs. The binding mode of 16b with RT was also illustrated via molecular docking. Overall, this work provided a novel lead compound for developing potent HIV-1 NNRTIs.
Electrocatalytic CO2 reduction at mild conditions is a promising strategy to transform greenhouse gases into fuels or value-added chemicals to solve the increasingly serious environmental and energy problems. The most crucial factor in determining the CO2 reduction performance is to develop efficient electrocatalysts with high selectivity and stability. Among the various electrocatalysts, indium-based catalysts have attracted extensive attention due to their non-toxicity, low cost, and high formic acid/formate selectivity. In this work, we comprehensively review the recent development and research progress of indium-based electrocatalysts for CO2RR. The reaction mechanism, reaction pathways, structure–activity relationship, and strategies to enhance the activity of CO2RR on indium-based catalysts have also been briefly presented and discussed. Finally, the existing challenges and future developments for indium-based high-performance catalysts for CO2RR are proposed.
All-solid-state lithium batteries (ASSLBs) based on sulfide electrolytes promise next-generation energy storage with high energy density and safety. However, the sulfide electrolytes suffer from phase instability and sluggish interfacial charge transport when pairing with layered oxide cathodes at high voltages. Herein, a simple and efficient strategy is proposed using two-dimensional Ti3C2T MXene as starting material to in-situ construct a 15 nm Li2TiO3 layer on a typical oxide cathode, LiCoO2. The in-situ transformation of Ti3C2T into Li2TiO3 layer occurs at a low temperature of 500 ℃, avoiding the phase deterioration of LiCoO2. The thin Li2TiO3 layer is Li+ conducting and electrochemically stable, thereby preventing the interfacial decomposition of sulfide electrolytes induced by LiCoO2 at high voltages and facilitating Li+ transport at the interface. Moreover, Li2TiO3 can stabilize the layer structure of LiCoO2 at high voltages. Consequently, the sulfide-based ASSLB using LiCoO2@Li2TiO3 cathode can operate stably at a high voltage of up to 4.5 V (vs. Li+/Li), delivering an outstanding initial specific discharge capacity of 138.8 mAh/g with a high capacity retention of 86.2% after 100 cycles at 0.2 C. The in-situ transformation strategy may also apply to other MXenes, offering a general approach for constructing other advanced lithiated coatings for oxide cathodes.
The first phloroglucinol-triterpenoid hybrids, myrtphlotritins A–E (1–5), were rapidly recognized and isolated from two species of Myrtaceae by employing the building blocks-based molecular network (BBMN) strategy. Compounds 1–5 featured new carbon skeletons in which phloroglucinol derivatives were coupled with lupane- and dammarane-type triterpenoids through different linkage patterns. Their structures and absolute configurations were elucidated by comprehensive analysis of spectroscopic data and quantum chemical calculations. Biosynthetic pathways for compounds 1–5 were proposed on the basis of the coexisting precursors. Guided by the biogenetic pathways, the biomimetic synthesis of compound 1 was also achieved. Additionally, compounds 2, 3, and 5 exhibited potent antiviral activities against herpes simplex virus type-1 (HSV-1) infection, and compounds 2 and 5 displayed significant anti-inflammatory activities on RAW264.7 cells.
Triphenylamine (TPA)-based aggregation-induced emission luminogens (TPA-AIEgens), a type of photoactive material utilizing the typical TPA moiety, has recently attracted increasing attention for the diagnostics and treatment of tumors due to their remarkable chemo-physical performance in optoelectronic research. TPA-AIEgens are distinguished from other photoactive agents by their strong fluorescence, good sensitivity, high signal-to-noise ratio, resistance to photobleaching, and lack of high concentration or aggregation-caused fluoresce quenching effects. In this review, we summarize the current advancements and the biomedical progress of TPA-AIEgens in tumor theranostics. First, the design principles of TPA-AIEgens photoactive agents as well as the advanced targeting strategies for nuclei, cell membranes, cell organelle and tumors were introduced, respectively. Next, the applications of TPA-AIEgens in tumor diagnosis and therapeutic techniques were reviewed. Last, the challenges and prospects of TPA-AIEgens for cancer therapy were performed. The given landscape of the TPA-AIEgens hereby is meaningful for the further design and utilization of the novel photoactive material, which could be beneficial for the development of clinic applications.
No. 86 Xueyuan South Road, Haidian District, Beijing
010-62199257
qkjq@cast.org.cn
Copyright © 2025 China Association for Science and Technology. All rights reserved. For all open access content, the relevant licensing terms apply.
Sponsored by the Office of the Leading Group for Cybersecurity and Informatization of CAST, and supported by Science and Technology Review Publishing House
