Controllable synthesis of nanoscale high-entropy alloys (HEAs) with specific morphologies and tunable compositions is crucial for exploring advanced catalysts. The present strategies either have great difficulties to tailor the morphology of nanoscale HEAs or suffer from narrow elemental distributions and insufficient generality. To overcome the limitations of these strategies, here we report a robust template-directed synthesis to programmatically fabricate nanoscale HEAs with controllable compositions and structures via independently controlling the morphology and composition of HEA. As a proof of concept, 12 kinds of nanoscale HEAs with controllable morphologies of zero-dimension (0D) nanoparticles, 1D nanowires, 2D ultrathin nanorings (UNRs), 3D nanodendrites, and vast elemental compositions combining five or more of Pd/Pt/Ag/Cu/Fe/Co/Ni/Pb/Bi/Sn/Sb/Ge are synthesized. Moreover, the as-prepared HEA-PdPtCuPbBiUNRs/C demonstrates the state-of-the-art electrocatalytic performance for the ethanol oxidation reaction, with 25.6- and 16.3-fold improvements in mass activity, relative to commercial Pd/C and Pt/C catalysts, respectively, as well as greatly enhanced durability. This work provides a myriad of nanoscale HEAs and a general synthetic strategy, which are expected to have broad impacts for the fields of catalysis, sensing, biomedicine, and even beyond.

Biocatalyzed asymmetric reduction of ketones is an environmentally friendly approach and one of the most cost-effective routes for producing chiral alcohols. In comparison with the well-studied reduction of prochiral ketones to generate chiral alcohols with one chiral center, resolution of racemates by ketoreductases (KREDs) to produce chiral compounds with at least two chiral centers is also an important strategy in asymmetric synthesis. The development of protein engineering and the combination with chemo-catalysts further enhanced the application of KREDs in the efficient production of chiral alcohols with high stereoselectivity. This review discusses the advances in the research area of KRED catalyzed asymmetric synthesis for biomanufacturing of chiral chemicals with at least two chiral centers through the kinetic resolution (KR) approach and the dynamic kinetic resolution (DKR) approach.

Biocatalysis can be defined as the use of isolated enzymes or enzymes inside cells to convert substrates into products. The term “biocatalysis” is often used in modern organic synthesis in connection with the environmentally friendly manufacture of chemicals and pharmaceuticals, where biocatalysis has achieved great success in recent years. Here, we review the potential use of biocatalysis in cancer therapy. We summarize the common biocatalytic reactions for activation of anticancer prodrugs, generation of excessive reactive oxygen species (ROS), and deletion of essential/immunosuppressive components in cancer therapy. We also describe the biocatalytic release of small molecule drugs from antibody–drug conjugates (ADCs) and the application of biocatalysis in living cells for cancer treatment. The diverse application of biocatalysis is an exciting and ongoing strategy that holds great promise for cancer therapy.

Multiple stereoisomers can be found when a substance contains chiral carbons in its chemical structure. To obtain the desired stereoisomers, asymmetric synthesis was proposed in the 1970s and developed rapidly at the beginning of this century. Stereodivergent synthesis, an extension of asymmetric synthesis in organic synthesis with the hope to produce all stereoisomers of chiral substances in high conversion and selectivity, enriches the variety of available products and serves as a reference suggestion for the synthesis of their derivatives and other compounds. Since biocatalysis has outstanding advantages of economy, environmental friendliness, high efficiency, and reaction at mild conditions, the biocatalytic reaction is regarded as an efficient strategy to perform stereodivergent synthesis. Thus, in this review, we summarize the stereodivergent synthesis catalyzed by enzymes or chemo-enzymes in cases where a compound contains two or three chiral carbons, i.e., at most four or eight stereoisomers are present. The types of reactions, including reduction of substituent ketones, cyclization reactions, olefin addition, and nonredox transesterification reactions, are also discussed for the understanding of the progress and application of biocatalysis in stereodivergent synthesis.

Ene‐reductase (ERED)‐catalyzed asymmetric reduction of α,β‐unsaturated ketones is an attractive method in organic synthesis. Through the discovery and further structure‐guided protein engineering of BsER, an ERED from Bacillus subtilis, the selective bio‐reduction of the well‐known building blocks Hajos‐Parrish ketone (HPK, 1 a) and Wieland‐Miescher ketone (WMK, 1 b) was achieved in this study. The optically pure (R)‐HPK ((R)‐1 a) and (R)‐WMK ((R)‐1 b) with corresponding >99% and 98% enantiomeric excess (ee) values were obtained by kinetic resolution of the racemic substrates. To the best of our knowledge, this is the first example of ERED mediated kinetic resolution of rac‐HPK and rac‐WMK. In addition, the reduction products cis‐7a‐methylhexahydro‐1H‐indene‐1,5(4H)‐dione (cis‐2 a) and cis‐8a‐methylhexahydronaphtha‐ lene‐1,6(2H,5H)‐dione (cis‐2 b) with high diastereomeric ratios (dr) were also obtained. We also developed four routes of biocatalytic cascade reduction involving BsER and ketoreductases (KREDs). Using optimized ERED‐KRED and KRED‐ERED cascades, (S)‐HPK ((S)‐1 a) and (S)‐WMK ((S)‐1 b) could be reduced stepwise, yielding the bioactive products all with >91% purity. This study presents a biocatalytic strategy for the kinetic resolution and cascade reduction of HPK and WMK (1 a and 1 b).magnified image