123rliu

This review summarizes the latest research advances in the PISA of nonlinear polymers, focusing on typical nonlinear polymer systems including star, graft, bottlebrush, branched, and cyclic polymers. It systematically elaborates on the core idea of achieving the controlled synthesis of nonlinear block copolymer nanoparticles through precise topological structure design, details the mainstream synthetic strategies and technical methods for preparing nonlinear polymer nanoparticles currently, and presents an outlook on the existing limitations, potential challenges, and future development directions in this field.

ABSTRACT

Polymerization-induced self-assembly (PISA) has become a scalable route to block copolymer nanoparticles with tunable morphologies, but most established PISA formulations focus on linear architectures. This review surveys recent progress in extending PISA to nonlinear polymers—highlighting how polymer topology reshapes nucleation, packing, interfacial curvature, and ultimately nanoparticle morphology—while also positioning PISA as a practical method for synthesizing architecturally complex macromolecules. Key advances are summarized across star, graft, bottlebrush, branched, and cyclic polymers. Finally, we also discuss future opportunities of PISA of nonlinear polymers that may provide some inspirations for researcher in this area.

Proceedings of the National Academy of Sciences, Volume 123, Issue 13, March 2026.
SignificanceWater’s anomalous properties emerge from its complex hydrogen-bond networks in the liquid phase, which are difficult to model accurately. Quantum-level accuracy typically entails prohibitive computational costs, limiting large-scale ...

The exocytosis-inspired behaviour was demonstrated in a temperature sensitive hybrid bi-microcompartment system. Due to the universal loading capacity and excellent biocompatibility, the proliferation and temperature-programmed fast release of living cells were realized, which provided a robust platform for the on-demand transportation of various living organisms.

Abstract

Inspired by the unique characteristics of living cells, the creation of life-inspired functional ensembles is a rapidly expanding research topic, enabling transformative applications in various disciplines. Herein, we report a facile method for the fabrication of phospholipid and block copolymer hybrid bi-microcompartments via spontaneous asymmetric assembly at the water/tributyrin interface, whereby the temperature-mediated dewetting of the inner microcompartments allowed for exocytosis to occur in the constructed system. The exocytosis location and commencement time could be controlled by the buoyancy of the inner microcompartment and temperature, respectively. Furthermore, the constructed bi-microcompartments showed excellent biocompatibility and a universal loading capacity toward cargoes of widely ranging sizes; thus, the proliferation and temperature-programmed transportation of living organisms was achieved. Our results highlight opportunities for the development of complex mesoscale dynamic ensembles with life-inspired behaviors and provide a novel platform for on-demand transport of various living organisms.

The "magic methyl" effect describes the change in potency, selectivity, and/or metabolic stability of a drug candidate associated with addition of a single methyl group. We report a synthetic method that enables direct methylation of C(sp³)–H bonds in diverse drug-like molecules and pharmaceutical building blocks. Visible light–initiated triplet energy transfer promotes homolysis of the O–O bond in di-tert-butyl or dicumyl peroxide under mild conditions. The resulting alkoxyl radicals undergo divergent reactivity, either hydrogen-atom transfer from a substrate C–H bond or generation of a methyl radical via β-methyl scission. The relative rates of these steps may be tuned by varying the reaction conditions or peroxide substituents to optimize the yield of methylated product arising from nickel-mediated cross-coupling of substrate and methyl radicals.

Cycling between molybdenum(I)‐dinitrogen and molybdenum(IV)‐nitride complexes was investigated under ambient reaction conditions. A kinetic study of the second‐order reaction rate for the conversion of the molybdenum‐dinitrogen complex into the molybdenum‐nitride complex indicates that the formation of the dinitrogen‐bridged dimolybdenum complex is involved in the rate‐determining step. A new modified reaction pathway has been proposed based on the findings of our experimental and theoretical results.

Abstract

Cycling between molybdenum(I)‐dinitrogen and molybdenum(IV)‐nitride complexes was investigated under ambient reaction conditions. A kinetic study of the second‐order reaction rate for the conversion of the molybdenum‐dinitrogen complex into the molybdenum‐nitride complex indicates that the formation of the dinitrogen‐bridged dimolybdenum complex is involved in the rate‐determining step. DFT calculations indicate that the molybdenum‐dinitrogen complex transforms into the molybdenum‐nitride complex via direct cleavage of the nitrogen‐nitrogen triple bond of the bridging dinitrogen ligand of the dinitrogen‐bridged dimolybdenum complex. The corresponding reaction of the molybdenum‐nitride complex transforming into the molybdenum‐dinitrogen complex proceeds via the ligand exchange of ammonia for dinitrogen at the dinitrogen‐bridged dimolybdenum complexes. A new modified reaction pathway has been proposed based on the findings of our experimental and theoretical results.

Nature, Published online: 18 November 2019; doi:10.1038/d41586-019-03494-4

A crystal’s surface has been found to behave as a distinct material that has temperature-dependent electrical polarization — despite the rest of the crystal being non-polar.

Despite a spotty track record, companies keep trying to convert trash into energy, fuels, and chemicals

Dynamic duo: Racemic α‐allyl aldehydes undergo stereoconvergent hydroacylation to generate α,γ‐disubstituted cyclopentanones with high diastereo‐ and enantioselectivities. In this dynamic kinetic resolution, a primary amine catalyst racemizes the aldehyde substrate via enamine formation and hydrolysis while a rhodium catalyst promotes cyclization.

Abstract

We report a dynamic kinetic resolution (DKR) of chiral 4‐pentenals by olefin hydroacylation. A primary amine racemizes the aldehyde substrate via enamine formation and hydrolysis. Then, a cationic rhodium catalyst promotes hydroacylation to generate α,γ‐disubstituted cyclopentanones with high enantio‐ and diastereoselectivities.

An expedient SuFEx trifluoromethylation of sulfonyl fluorides and iminosulfur oxyfluorides is described. The efficient S−F exchange with TMSCF₃ is initiated by sub‐stoichiometric quantities of bifluoride ion [FHF]⁻ in anhydrous DMSO. The selective anticancer properties of previously inaccessible bis(trifluoromethyl)sulfur oxyimines are also demonstrated.

Abstract

SuFEx is a new‐generation click chemistry transformation that exploits the unique properties of S−F bonds and their ability to undergo near‐perfect reactions with nucleophiles. We report here the first SuFEx‐based procedure for the efficient synthesis of pharmaceutically important triflones and bis(trifluoromethyl)sulfur oxyimines from sulfonyl fluorides and iminosulfur oxydifluorides, respectively. The new process involves rapid S−F exchange with trifluoromethyltrimethylsilane (TMSCF₃) upon activation by potassium bifluoride in anhydrous DMSO. The reaction tolerates a wide selection of substrates and proceeds under mild conditions without need for chromatographic purification. A tentative mechanism is proposed involving nucleophilic displacement of S−F by the trifluoromethyl anion via a five‐coordinate intermediate. The utility of late‐stage SuFEx trifluoromethylation is demonstrated through the synthesis and selective anticancer properties of a bis(trifluoromethyl)sulfur oxyimine.

Organic radicals can play important roles potentially in diverse functional materials owing to an unpaired electron but are usually highly reactive and difficult to use. Therefore, stabilization of organic radicals is crucially important. Among organic radicals, carbon‐centered radicals are promising because of their trivalent nature that enables structural diversity and elaborate designs but they show less stabilities because of reactivities toward carbon‐carbon bond formation and atmospheric oxygen. Recently, stable carbon‐centered radicals have been increasingly explored on the basis of diverse molecular platforms. This minireview highlights these newly explored stable carbon‐centered radicals with a particular focus on porphyrinoid‐stabilized radicals owing to their remarkable spin delocalization abilities.