Browse Articles

Reversing Blocking Order of Trithiocarbonate‐Mediated RAFT Polymerizations Using Photocatalysis

Abstract Many acrylic–methacrylic block copolymer sequences remain inaccessible due to synthetic limitations. Herein, photoinduced electron/energy transfer (PET) catalysis is leveraged to reverse blocking order limitations in trithiocarbonate (TTC)‐mediated reversible addition–fragmentation chain transfer (RAFT) polymerization. We synthesized poly(methyl acrylate‐ b ‐methyl methacrylate) by PET‐RAFT using fac ‐Ir(ppy) 3 , achieving predictable, linear increases in molecular weight with conversion. Kinetics studies showed that adding a tertiary amine (triethanolamine) introduced a reversible redox reaction to stabilize the TTC radical during chain extensions, leading to more uniform block copolymers ( Р < 1.47) compared to block copolymers synthesized without amine ( Р < 1.56). To highlight the utility of this method, triblock copolymers of poly(methyl acrylate) and poly(methyl methacrylate) blocks were investigated. The order of acrylic and methacrylic blocks impacted the physical properties of compositionally similar polymeric materials. For example, a high molecular weight triblock copolymer (P(MMA‐ b ‐MA‐ b ‐MMA), M n  = 564 kg mol −1 ) thermoplastic elastomer showed exceptional strain (>1600%). Overall, we report (i) a new methodology to unlock synthetic access to acrylic–methacrylic block copolymers using TTCs and photocatalysis, (ii) insight into photocatalyst‐mediated radical polymerization, and (iii) synthesis of new high‐performance materials.

Investigating industrial by-product for soil conditioning addressing environmental risk and waste reduction alternatives

A cerebello-thalamo-cortical pathway transmits reward-based post-error signals for motor timing correction during learning in male mice

Titanium–Polyoxometalate Crosslinked Metallo–Supramolecular Polymer as Artificial Interfacial Layer for Highly Persistent and Low–Temperature Tolerant Lithium Metal Batteries

Abstract The uncontrolled lithium (Li) dendrite growth and fragile native solid electrolyte interphase formation have severely hindered the practical development of Li metal batteries. Herein, a coordinatively cross‐linked metallo‐supramolecular polymer as anodic interfacial protective layer (MSP‐IPL) is developed by utilizing titanium(IV)–polyoxometalates (Ti‐POMs) as hexatopic linkers to bridge organic and inorganic moieties. The constructed MSP‐IPL possesses high electrochemical stability, superior ion‐transfer ability, and good air stability. Due to its high film formation uniformity and mechanical tenacity, the MSP‐IPL can effectively avoid nonuniform Li deposition caused by the tip effect, thus inhibiting Li dendrite proliferation. The uniformly distributed Ti‐POMs in polymer skeleton can efficiently bind with PF 6 − anions, thus increasing Li + transference number and promoting homogeneous Li + distribution. The reprocessability and self‐healing ability endowed by dynamic coordination bonds enable the MSP‐IPL to accommodate electrode volume changes and maintain good interface contact. Consequently, high‐loading Li||LiFePO 4 and Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 batteries based on MSP‐IPL‐coated Li anodes demonstrate impressive cyclability and extraordinary rate capability. Even at a low temperature of −20 °C, the MSP‐IPL‐coated Li||NCM811 batteries can still cycle stably for over 500 cycles (equivalent to 138 days) with a considerable capacity retention of 86.8%. This work presents a promising solution for developing practical low‐temperature Li metal batteries.

Non-invasive evaluation of advanced glycation end products in hair as early markers of diabetes and aging

Experience-dependent maternal defense behavior mediated by profrontal cortical projections to the medial preoptic area in mice

Active Edge Sites Engineering on Amorphous Co–Mn Spinel‐Based Oxides for Efficient Peroxymonosulfate Activation

Abstract Rational modulation of edge active sites in the Fenton‐like reaction, utilizing defect engineering to form efficient catalytic activity centers, is a hot topic in the heterogeneous catalysis field, yet the applicability of large‐scale manufacturing remains a severe challenge. Herein, a general wet‐chemical approach is reported to large‐scale prepare porous CoMn 2 O 4 with abundant active edge sites for enhanced peroxymonosulfate (PMS)‐based Fenton‐like activation without using a template or heat treatment. The obtained Turing‐type structure not only can be assembled into spatially restricted domain CoMn 2 O 4 nanoreactors but also greatly facilitates the exposure of active edge sites with oxygen‐rich vacancies in promoting PMS adsorption and interfacial charge transfer. The unique CoMn 2 O 4 /PMS system exhibited efficient and stable removal of organic pollutants with dominant nonradical ( 1 O 2 ) pathways and maintained a degradation rate of 99.8% within 5 min after seven‐cycle runs. Moreover, the application prospect of the PMS‐based Fenton‐like process for large‐scale wastewater treatment, including sulfadiazine (SD) antibiotics in real river water and real pharmaceutical wastewater, was demonstrated by the fixed‐bed tower reactor and the in‐situ floating water treatment device. This work will provide guidance for the development of low‐cost and efficient heterogeneous PMS‐activation catalysts through rational defect engineering.

Integration of multi-omics quantitative trait loci evidence reveals novel susceptibility genes for Alzheimer’s disease

Gene regulatory activity associated with polycystic ovary syndrome revealed DENND1A-dependent testosterone production

Communicative Nanomotors Reprogram Cancer Cell Death via Pyroptosis

Abstract Nanomotors offer significant advantages over passive nanoparticles in biomedical applications. However, their potential has been largely restricted to cargo transport, with limited capacity for interaction with biological systems. Here, we present next‐generation self‐assembled nanomotors that not only exhibit chemotactic motility but also actively communicate with cells, reprogramming cell fate by inducing pyroptosis. These nanomotors are designed to respond to elevated reactive oxygen species (ROS) in the tumor microenvironment, triggering nitric oxide (NO)‐driven propulsion and selective mitochondria targeting via triphenylphosphine (TPP) surface engineering. This interaction induces mitochondrial damage, cytochrome c release, and activation of gasdermin E (GSDME)‐mediated pyroptosis. Furthermore, their chemotactic motility facilitates deeper tumor tissue penetration in 3D spheroids, demonstrating their ability to navigate physiological barriers. By shifting the paradigm from motility‐driven to interactive nanomedicine, this study establishes a transformative platform for targeted cancer therapy.

Identification of foam cell like M2 macrophages, AEBP1 biomarkers, and resveratrol as potential therapeutic in MASLD using Ecotyper and WGCNA

Adaptive loss of shortwave-sensitive opsins during cartilaginous fish evolution

Controlling Assembly of Hybrid DNA Nanostructures into Higher‐Order Structures via Hydrophobicity

Abstract Hydrophobic interactions are one of the fundamental driving forces of self‐assembly in living systems. It remains challenging to harness hydrophobicity to have a controllable and programmable assembly of DNA nanostructures. On the other hand, there is also a need to explore orthogonal hierarchical assembly strategies to be used as an additional toolset along with the traditional Watson–Crick base pairing to achieve complex superstructures. In this work, we rationally design and synthesize a series of low molecular weight hydrophobic molecules that are conjugated to single‐stranded DNA strands. By incorporating these modified DNA strands into the precisely defined locations of DNA tiles and origami nanostructures, we achieve controlled hierarchical assembly driven by hydrophobic interaction. We demonstrate a versatile hydrophobicity‐guided higher‐order assembly strategy by employing strategically engineered DNA nanostructures of increasing complexity, ranging from simple DNA tiles to complex origami structures, functionalized with these small hydrophobic molecules as programmable building blocks.

Research on the impact of artificial intelligence applications on agricultural green development

Quantum metric third-order nonlinear Hall effect in a non-centrosymmetric ferromagnet

High Turnover Frequency in the Electrocatalytic Reduction of Nitrous Oxide to Dinitrogen at a Binuclear Copper Complex of 3,5‐Diamino‐1,2,4‐Triazole

Abstract Nitrous oxide (N 2 O) is a potent greenhouse gas and an ozone‐depleting substance. Electrocatalytic N 2 O reduction (e‐N 2 ORR) is a promising approach to remove N 2 O from the air under ambient conditions. However, developing noble‐metal‐free e‐N 2 ORR electrocatalysts with high Faradaic efficiency (FE) and turnover frequency (TOF) remains a challenge because of the weak binding of N 2 O and the high kinetic barrier for deoxygenation reaction. In this work, inspired by the multinuclear copper active site of nitrous oxide reductases, a binuclear copper complex of 3,5‐diamino‐1,2,4‐triazole supported on carbon black of Ketjenblack (CuHdatrz/KB) was utilized for the e‐N 2 ORR at pH 13 and 298 K. CuHdatrz/KB achieves a high FE of ≈ 100% at −0.3 V versus reversible hydrogen electrode for the e‐N 2 ORR to N 2 and TOF up to ≈ 700 h −1 , which is one–two orders of magnitude higher than those of the previously reported molecular‐based catalysts. In situ X‐ray absorption spectroscopy confirmed that Cu(II) ions of CuHdatrz/KB are reduced to Cu(I) keeping the binuclear core, suggesting that the multinuclear copper active site is crucial to efficiently catalyze the e‐N 2 ORR like the nitrous oxide reductase.

Knowledge graph convolutional networks with user preferences for course recommendation

Chalcogen Bonding Boosts the Uptake of Small Molecules in Mammalian Cells

Abstract Chalcogen bonding, a noncovalent interaction between the chalcogen atom (S, Se, and Te) and Lewis base, plays crucial roles in catalysis, anion recognition, protein confirmation, enzyme activity, and drug design. Herein, we show that chalcogen bonding can be used as a driving force to enhance the uptake of small molecules in mammalian cells. A systematic investigation using several chalcogen‐containing fluorescent molecules reveal that the cellular uptake strongly depends on the nature of chalcogen atom and the compounds with heavier chalcogen atoms (Se and Te), which can form stronger chalcogen bonds, are preferentially taken up by the cells. This study suggests that the biological activities of chalcogen‐based compounds may depend not only on their chemical reactivity but also on their chalcogen bond forming ability with the cell membrane.

Exploring weighting schemes for the discovery of informative generalized between pathway models to uncover pathways in genetic interaction networks

Amide Chemistry Enables Redox Locking of Cyclic Disulfides for Polypeptide Assembly

Abstract A practical strategy in synthetic organic chemistry for shutting down temporarily the nucleophilicity of thiols is to exploit their redox properties by converting them into disulfides. The stability of such a thiol protection in reductive medium can be sensitive to microenvironmental changes, including chemical modifications occurring nearby. Although difficult to achieve, large shifts in disulfide stability might provide a practical mean for bringing selectivity in a reacting system comprising multiple thiol functionalities. Here we report that the stability of a cyclic disulfide increases dramatically upon acylation of an amino group placed in the vicinity of the S─S bond. The gain in stability is so pronounced that the amide bond formation acts as a redox lock. We describe the application of such a redox switch to the chemoselective assembly of polypeptides by thiol‐based peptide ligation chemistries.