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Main observation and conclusion: Block copolymers not only combine properties of different segments but also generate new application prospects. Poly(α‐amino acid)‐b‐poly(tetrahydrofuran)‐b‐poly(α‐amino acid) (PAA‐PTHF‐PAA) is one of the copolymers. In this contribution, di‐hydroxyl‐ended HO‐PTHF‐OH is transferred into di‐oxyamino‐ended H2NO‐PTHF‐ONH2 quantitatively, which is used as a macroinitiator to polymerize sarcosine N‐thiocarboxyanhydride (Sar‐NTA) and N‐phenyoxycarbonyl N‐ε‐carbobenzyloxy‐D‐lysine (ZDL‐NPC). Well‐defined triblock PAA‐NHO‐PTHF‐ONH‐PAA is produced with high molecular weight (up to 25.3 kg/mol) and narrow dispersity. The amphiphilic PSar‐NHO‐PTHF‐ONH‐PSar (STS) self‐assembles into micelles with uniform diameters of 30—40 nm according to DLS. Owing to oxygen amide groups inside the backbone of these copolymers, the polyether‐poly(amino acid)s block copolymers are cleavable under an acidic environment and therefore have potential applications in smart biomedicine and engineering. [ABSTRACT FROM AUTHOR]

Developing chiral electrode catalysts for enantioselective electrosynthesis is a great challenge, as it requires catalysts that possess both high activity and enantioselectivity. Precise synthesis of nanoclusters and single atoms coexisting chiral catalysts provide a promising pathway for enhancing asymmetric catalytic performance. Herein, chiral electrode catalysts are fabricated comprising gold clusters (R‐AuC) and single atoms (R‐AuS) on graphene oxide (R‐AuC/S@GO) through an assembly‐irradiation strategy. Thereinto, the R‐Aus is in situ generated from R‐AuC under light irradiation. The monoatomization process can be precisely regulated by changing the wavelength of the light, resulting in four Au‐based chiral electrode (R‐Au@GO) catalysts with different ratios of nanoclusters and single atoms. These chiral electrodes are applied in the electrocatalytic enantioselective hydrogenation of methyl benzoylformate (MB) to chiral methyl mandelate (S‐MM), and the R‐AuC/S‐2@GO with ≈26% R‐AuC and 74% R‐AuS achieve the highest catalytic activity (35 µmol cm−2 h−1 productivity) and enantioselectivity [97% enantiomeric excess (ee)]. Detailed experimental analysis and density functional theory calculations reveal that the R‐AuS on GO promotes the in situ generation of H* species, and R‐AuC mainly drives the enantioselective conversion of MB by transferring the H* species to the carbonyl group of MB, ultimately yielding chiral S‐MM. [ABSTRACT FROM AUTHOR]