Chemical Science最新文献

The hexadehydro-Diels-Alder (HDDA) reaction is a cycloisomerization between a conjugated diyne and a tethered diynophile that generates ortho-benzyne derivatives. Considerable fundamental understanding of aryne reactivity has resulted from this body of research. The multi-yne cycloisomerization substrate is typically pre-formed and the (rate-limiting) closure of this diyne/diynophile pair to produce the isomeric benzyne generally requires thermal input, often requiring reaction temperatures of >100 °C and times of 16-48 h to achieve near-full conversion. We report here that diynoic acids can be dimerized and that the resulting substrate, having a 3-atom anhydride linker (i.e., O[double bond, length as m-dash]COC[double bond, length as m-dash]O), then undergoes HDDA cyclization within minutes at or below room temperature. This allows for the novel in situ assembly and cyclization of HDDA benzyne precursors in an operationally simple protocol. Experimental kinetic data along with DFT computations are used to identify the source of this surprisingly huge rate acceleration afforded by the anhydride linker: >10⁷ faster than the analogous multi-yne having, instead, a CH₂OCH₂ ether linker.

The in situ synthesis of degradable polymer prodrug nanoparticles is still a challenge to be met, which would make it possible to remedy both the shortcomings of traditional formulation of preformed polymers (e.g., low nanoparticle concentrations) and those of the physical encapsulation of drugs (e.g., burst release and poor drug loadings). Herein, through the combination of radical ring-opening polymerization (rROP) and polymerization-induced self-assembly (PISA) under appropriate experimental conditions, we report the successful preparation of high-solid content, degradable polymer prodrug nanoparticles, exhibiting multiple drug moieties covalently linked to a degradable vinyl copolymer backbone. Such a rROPISA process relied on the chain extension of a biocompatible poly(ethylene glycol)-based solvophilic block with a mixture of lauryl methacrylate (LMA), cyclic ketene acetal (CKA) and drug-bearing methacrylic esters by reversible addition fragmentation chain transfer (RAFT) copolymerization at 20 wt% solid content. This novel approach was exemplified with two different CKA monomers and two different anticancer drugs, namely paclitaxel and gemcitabine, to demonstrate its versatility. After transferring to water, remarkably stable aqueous suspensions of core-degradable polymer prodrug nanoparticles, 56-225 nm in diameter, with tunable amounts of CKA units (7-26 mol%) and drug loadings of up to 33 wt% were obtained. The incorporation of ester groups in the copolymers was demonstrated by hydrolytic degradation of both the copolymers and the nanoparticles under accelerated conditions. The nanoparticles showed significant cytotoxicity against A549 cells, used as a lung cancer model. Fluorescence labeling of the solvophilic block also enabled effective monitoring of cell internalization by confocal microscopy, with potential for theranostic applications.

Given that proteins with minor variations in amino acid sequences cause distinct functional outcomes, identifying and quantifying similar proteins is crucial, but remains a long-standing challenge. Herein, we present a two-dimensional orthogonal fluorescence and chemiluminescence design strategy for the probe DCM-SA, which is sequentially activated by albumin-mediated hydrolysis, exhibiting light-up fluorescence and photo-induced cycloaddition generating chemiluminescence, enabling orthogonal signal amplification for discrimination of subtle differences between similar proteins. By orthogonalizing these dual-mode signals, a two-dimensional work curve of fluorescence and chemiluminescence is established to distinguish and quantify similar proteins HSA and BSA. Importantly, the dual-mode signals of DCM-SA exhibit contrary incremental trends towards HSA and BSA. Molecular docking and femtosecond transient absorbance spectroscopy reveal that the lower K _D value of DCM-SA with HSA and the longer excited-state lifetime of DCM-SA with BSA underlie the distinct dual-mode responses. Using two-dimensional orthogonal signals, for the first time, we precisely measure the HSA/BSA ratio in mixed serum. This method facilitates rapid blood source identification and trace HSA quantitation in human urine. Our two-dimensional orthogonal amplification approach offers a powerful tool for distinguishing and quantifying subtle differences among highly similar proteins, demonstrating great potential for both basic life science research and clinical applications.

In this article, we highlight the recent report of Greb et al. on the use of a structurally constrained P–P bonded system for phosphinophosphination of alkenes, alkynes, and carbonyls with high regio- and stereoselectivity (https://doi.org/10.1039/D4SC06581F).

Hybrid organic–inorganic perovskites (HOIPs) are widely studied for their potential in optoelectronic devices due to their unique semiconductor features. Porous HOIPs are extremely rare, with (APOSS)[CuCl₄]₄ being one of the very few examples, featuring 12 Å pores within its lattice. Reed and coworkers (C. W. Dalton, P. M. Gannon, W. Kaminsky and D. A. Reed, Chem. Sci., 2025, DOI: https://doi.org/10.1039/D4SC04378B) have recently shed light on the structure of this interesting material and demonstrated that these pores can incorporate large electroactive molecules such as ferrocene (Fc) and tetracyanoethylene (TCNE). Further, they showed that the ability to incorporate molecules within the pores also enables the synthesis of new crystalline phases and unlocks numerous applications, including gas sensing and photocatalysis, among others.

Thermoelectric technology plays an important role in developing sustainable clean energy and reducing carbon emissions, offering new opportunities to alleviate current energy and environmental crises. Nowadays, GeTe has emerged as a highly promising thermoelectric candidate for mid-temperature applications, due to its remarkable thermoelectric figure of merit (ZT) of 2.7. This review presents a thorough overview of the advancements in GeTe thermoelectric materials, meticulously detailing the crystal structure, chemical bonding characteristics, band structure, and phonon dynamics to elucidate the underlying mechanisms that contribute to their exceptional performance. Moreover, the phase transition in GeTe introduces unique degrees of freedom that enable multiple pathways for property optimization. In terms of electrical properties, noticeable enhancement can be realized through strategies such as band structure modulation, carrier concentration engineering, and vacancy engineering. For phonon transport properties, by incorporating defect structures with varying dimensions and constructing multi-scale hierarchical architectures, phonons can be effectively scattered across different wavelengths. Additionally, we provide a summary of current research on devices and modules of GeTe. This review encapsulates historical progress while projecting future development trends that will facilitate the practical application of GeTe in alignment with environmentally sustainable objectives.

Correction for ‘Reconstructing the phase of vanadium oxides enables redox-catalysis manipulated reversible sulfur conversion for stable Zn–S batteries’ by Hao Luo et al., Chem. Sci., 2025, https://doi.org/10.1039/d4sc06593j.