化学•材料最新文献

{"title":"Mechanism and Origin of Regio- and Stereoselectivity in the Synthesis of Benzazocines via Palladium-Catalyzed [6+2] Annulation of Allenyl Benzoxazinanones with Terminal Allenes","authors":"Jinglong Xin,Aili Feng,Jihong Xu,Yanling Zhao,Dongju Zhang","doi":"10.1021/acs.joc.6c01402","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01402","url":null,"abstract":"Density functional theory calculations were carried out to elucidate the mechanism and the origin of regio- and stereoselectivity in the palladium-catalyzed [6+2] annulation of allenyl benzoxazinanones with terminal allenes. An unconventional oxidative addition–reductive elimination mechanism was revealed. The reaction starts with SN2-type oxidative addition of the substrate to Pd0, followed by decarboxylation to afford a π-allylpalladium intermediate. Pathway bifurcation leads to competing [6+2] and [4+2] annulations, and the more stable seven-membered palladacycle kinetically favors the [6+2] pathway and inhibits the [4+2] side reaction. Distortion/interaction analysis indicates that the exclusive Z-selectivity originates from the larger structural distortion of the E-configured transition state. Different from conventional three-center reductive elimination, the reaction proceeds via a zwitterionic-intermediate-mediated nucleophilic coupling pathway, which acts as the rate-limiting step with an overall barrier of 21.3 kcal/mol. This work rationalizes experimental selectivity and offers theoretical guidance for the design of related Pd-catalyzed annulation reactions.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Native Chemical Ligation-Driven Formation of Hyaluronic Acid-Based Injectable Hydrogels","authors":"Camille Vantou,&nbsp;Nolwenn Vigneron,&nbsp;Benoit Keromnes,&nbsp;Romain Brusini,&nbsp;Michel Marquet,&nbsp;François Bourdon,&nbsp;Sébastien Vidal,&nbsp;Jimmy Faivre","doi":"10.1021/acs.bioconjchem.6c00139","DOIUrl":"https://doi.org/10.1021/acs.bioconjchem.6c00139","url":null,"abstract":"<p>We report the development of an injectable hyaluronic acid (HA)-based hydrogel using native chemical ligation (NCL) as a biocompatible and chemoselective crosslinking strategy for potential biomedical applications. High-molecular-weight HA was pre-modified with a glycinyl thioester derivative, while a <em>bis</em>-cysteine peptide served as the crosslinker, enabling rapid hydrogel formation under physiological conditions. After optimization of NCL parameters, the resulting hydrogel exhibits all key attributes for biomedical hydrogel injectables: cytocompatibility, injectability, tunable rheology adapted for soft-tissue delivery (e.g., skin and subcutaneous tissue), enzymatic degradability by hyaluronidase, adjustable swelling, and long-term shelf-life stability. It can be sterilized by autoclaving for injection purposes and also functions as a drug delivery matrix for localized, in situ release. This study presents a robust and scalable HA-based platform, available as either an injectable hydrogel or an in situ cross-linkable solution, with broad potential in drug delivery, regenerative medicine, and aesthetic applications.</p>","PeriodicalId":29,"journal":{"name":"Bioconjugate Chemistry","volume":"37 10","pages":"1963–1974"},"PeriodicalIF":4.5,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221995","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Glycosylated Diarylmethyloxy-Triazines: Facile Synthesis and Aqueous Self-Assembly for Supramolecular Hydrogel Formation","authors":"Shuto Okuda,&nbsp;Honoka Samizo,&nbsp;Shintaro Sugiura,&nbsp;Fumiko Nakagawa,&nbsp;Aya Shibata,&nbsp;Sayuri L. Higashi,&nbsp;Natsuhisa Oka,&nbsp;Koichiro M. Hirosawa,&nbsp;Kenichi G. N. Suzuki,&nbsp;Masato Ikeda","doi":"10.1021/acs.bioconjchem.6c00313","DOIUrl":"https://doi.org/10.1021/acs.bioconjchem.6c00313","url":null,"abstract":"<p>Glycosylated self-assembling molecules enable the construction of nanostructures whose surfaces are decorated with saccharides under aqueous conditions, reminiscent of biological systems at both the molecular and cellular levels. Such glyco-nanostructures thus hold great promise as soft materials for biological applications. Herein, we report the facile synthesis of glycosylated diarylmethyloxy-triazines, which serve as new building blocks for fabricating self-assembled nanostructures in aqueous media and forming supramolecular hydrogels. The triazine scaffold enables the protecting-group-free synthesis of glycosylated compounds with reasonable β-anomer selectivity. Notably, both the substituents on the aryl groups attached to the triazine core and the geometry of the glycosidic linkages in the disaccharides strongly influence the hydrogelation behavior.</p>","PeriodicalId":29,"journal":{"name":"Bioconjugate Chemistry","volume":"37 10","pages":"1949–1956"},"PeriodicalIF":4.5,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221964","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Porphyrin−Peptide Bioconjugates: Photophysical Properties and Targeted Singlet Oxygen-Mediated Photooxidation of Amyloid-β","authors":"Cristina Parisi,&nbsp;Francesco Attanasio,&nbsp;Giuseppina Sabatino,&nbsp;Sonia Covaceuszach,&nbsp;Giuseppe Pappalardo,&nbsp;Giuseppe Di Natale,&nbsp;Salvatore Sortino","doi":"10.1021/acs.bioconjchem.6c00426","DOIUrl":"https://doi.org/10.1021/acs.bioconjchem.6c00426","url":null,"abstract":"<p>The aberrant self-assembly of amyloid β (Aβ) peptides into toxic oligomers is a central event in Alzheimer’s disease, motivating the development of molecular systems capable of modulating or degrading these species. Porphyrins and porphyrin−peptide bioconjugates have emerged as promising photoactive platforms due to their known ability to generate the highly oxidant singlet oxygen (¹O₂) upon light excitation. Still, the mechanisms underlying their oxidative effects on Aβ remain unclear. Here, we investigate the photophysical properties and the ¹O₂-mediated oxidation capability of two porphyrin−peptide conjugates, <strong>Ph-Pep</strong> and its Zn-metallated analogue <strong>ZnPh-Pep</strong>, both incorporating the Aβ recognition motif KLVFF. Steady-state and time-resolved spectroscopic studies reveal the good preservation of the photophysical and photochemical properties of the porphyrin chromophore units after their conjugation with the peptide appendage. Population of the long-lived triplet state of both compounds under visible-light excitation results in an effective generation of ¹O₂. High-resolution mass spectrometry shows that the ¹O₂ photogenerated by <strong>ZnPh-Pep</strong> induces extensive oxidation, yielding peroxidic and hydroperoxidic species, and provides evidence of partial Aβ42 degradation. In contrast, <strong>Ph-Pep</strong> leads to a rapid loss of detectable Aβ signal, suggesting the formation of higher-order aggregates rather than peptide cleavage. These distinct outcomes highlight the roles of Zn²⁺ coordination and peptide conjugation in modulating the ¹O₂-driven pathways. Overall, this study provides a mechanistic insight into designing photoactivatable porphyrin-based constructs capable of degrading or modulating toxic Aβ assemblies, opening intriguing prospects for light-mediated therapeutic strategies for neurodegenerative diseases.</p>","PeriodicalId":29,"journal":{"name":"Bioconjugate Chemistry","volume":"37 10","pages":"2084–2091"},"PeriodicalIF":4.5,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Co-delivery of siPD-L1 and Tat-HSPB1 by G5PBA Enhances the Efficacy of Antitumor Therapy in Clear Cell Renal Cell Carcinoma","authors":"Kui Xiong,&nbsp;Lili Xia,&nbsp;Lin Zhang,&nbsp;Weiyuan Li,&nbsp;Yan An,&nbsp;Xiangyang Shi,&nbsp;Guang-Zhi Jin","doi":"10.1021/acs.bioconjchem.6c00488","DOIUrl":"https://doi.org/10.1021/acs.bioconjchem.6c00488","url":null,"abstract":"<p>Clear cell renal cell carcinoma (ccRCC) is the most common subtype of renal cell carcinoma and remains challenging to treat at advanced stages due to immune evasion and inefficient intracellular delivery of therapeutic agents. In this study, we synthesized a modified generation 5 (G5) poly(amidoamine) dendrimer (G5PBA) to co-deliver small-interfering RNA targeting programmed death-ligand 1 (siPD-L1) and the antitumor peptide Tat-HSPB1, forming the G5PBA/siPD-L1/Tat-HSPB1 nanocomplex. The agarose gel retardation assay demonstrated that G5PBA efficiently condensed siPD-L1. Furthermore, the peptide encapsulation efficiency and loading capacity were measured, confirming the loading of Tat-HSPB1 into G5PBA/siPD-L1. Flow cytometry showed that G5PBA enhanced the cellular uptake of siPD-L1, while confocal microscopy demonstrated that G5PBA promoted lysosomal escape in Caki-1 cells. Western blot analysis further confirmed that G5PBA effectively reduced the PD-L1 protein expression. In cellular experiments, CCK-8, EdU, and wound-healing assays demonstrated that G5PBA/siPD-L1/Tat-HSPB1 inhibited the viability and migration of ccRCC cells. G5PBA/siPD-L1/Tat-HSPB1 suppressed tumor growth, downregulated PD-L1 expression, enhanced CD4⁺ and CD8⁺ T-cell infiltration, and elevated serum levels of IL-2, IL-6, TNF-α, and IFN-γ in mice. Major organs exhibited no obvious histopathological abnormalities upon H&amp;E staining. Serum ALT, AST, and BUN levels showed no significant changes compared with the PBS group, suggesting the preliminary safety profile of G5PBA/siPD-L1/Tat-HSPB1. Collectively, the nanocomplex achieved efficient peptide/siPD-L1 co-delivery and demonstrated significant antitumor activity. This system thus provides a promising strategy and experimental basis for local administration of ccRCC.</p>","PeriodicalId":29,"journal":{"name":"Bioconjugate Chemistry","volume":"37 10","pages":"2101–2112"},"PeriodicalIF":4.5,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222049","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Design, Synthesis, and Biological Evaluation of a Novel Gedatolisib−Phospholipid Conjugate and Liposomal Formulations Based Thereon","authors":"Irina P. Fonareva,&nbsp;Anna S. Alekseeva,&nbsp;Elena V. Svirshchevskaya,&nbsp;Elena L. Vodovozova,&nbsp;Vyacheslav E. Safonov,&nbsp;Alexey Yu. Fedorov,&nbsp;Ekaterina S. Shchegravina","doi":"10.1021/acs.bioconjchem.6c00278","DOIUrl":"https://doi.org/10.1021/acs.bioconjchem.6c00278","url":null,"abstract":"<p>Herein, we report the synthesis and biological evaluation of the first phospholipid prodrug of gedatolisib, a dual PI3K/mTOR inhibitor, and liposomal nanoparticles based on this conjugate. The liposomes were designed for selective cleavage by phospholipase A₂, enabling the release of the active drug from the gedatolisib−phospholipid conjugate. Compared with free gedatolisib, the liposomal formulation demonstrated cytotoxicity that was 2−3 orders of magnitude lower across several cancer cell lines. In vivo studies using the EMT6 breast cancer model showed that the liposomal prodrug exhibited superior antitumor efficacy while being substantially less hepatotoxic than free gedatolisib, which displayed negligible antitumor activity. This phospholipid conjugation strategy represents a promising approach for potentially improving the therapeutic index of gedatolisib.</p>","PeriodicalId":29,"journal":{"name":"Bioconjugate Chemistry","volume":"37 10","pages":"1999–2010"},"PeriodicalIF":4.5,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222051","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nanozyme-Based Analytical Platforms for Environmental Pollutants: Classification, Catalytic Mechanisms, and Multimodal Strategies","authors":"Fan Zhang,Tianyu Guo,Liwen Feng,Yingshan Yin,Yuanshuo Zhang,Chunyan Hao,Tiangang Luan","doi":"10.1021/acs.est.6c03991","DOIUrl":"https://doi.org/10.1021/acs.est.6c03991","url":null,"abstract":"The precise trace pollutant analysis within complex environmental matrices demands robust, highly specific, and anti-interference analytical platforms. Nanozymes, possessing tunable enzyme-like catalytic activities, superior thermodynamic stability, and cost effectiveness, have emerged as innovative tools in environmental analytical chemistry. This Review systematically discusses the integration of diverse nanozymes (metal, metal oxide, carbon, hybrid-structured, and multimetallic alloy) across foundational analytical methodologies, including colorimetric, fluorometric, electrochemical, chemiluminescence, and surface-enhanced Raman scattering assays. To overcome the matrix interference present in real-world samples, this Review highlights the pivotal evolution from conventional single-signal detection to advanced multimodal sensing approaches. The incorporation of molecular imprinting, microfluidics, and photothermal technologies effectively mitigates matrix interference, enhances mass transfer, and eliminates false positives through multidimensional cross-validation. Furthermore, atomic-level regulation strategies including defect engineering, asymmetric coordination, and high-entropy synergistic effects are presented to address inherent limitations such as catalytic passivation and nanoparticle aggregation. A unified standardization metric framework is also proposed for rigorous analytical performance evaluation. Finally, a perspective is provided on coupling artificial intelligence and machine learning with the nanozyme-based sensing platform, guiding a pathway from empirical trial-and-error to the rational and data-driven design of next-generation intelligent environmental analytical systems.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"94 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Global Cropland Efficiency-Stress Divide: Typological Diagnosis and Reconciling Pathways","authors":"Tingyu Hu,Junnian Song,Wei Yang,Xian’en Wang","doi":"10.1021/acs.est.6c07911","DOIUrl":"https://doi.org/10.1021/acs.est.6c07911","url":null,"abstract":"Cropland underpins food security but faces mounting resource constraints and environmental pressures. Achieving sustainable agriculture hinges on advancing land use efficiency (LUE) and alleviating land ecological stress (LES). However, a typological framework characterizing LUE and LES remains lacking, hindering the distinction between technical efficiency and ecological sustainability in cropland use. Herein, we establish a coupled LUE-LES diagnostic framework by integrating the super-efficiency slack-based measure model with land ecological footprint accounting. This framework classifies regions into efficiency-stress typologies globally for 2011, 2015, 2019, and 2022, and identifies type-specific improvement priorities through slack and ecological footprint-biocapacity diagnostics. Results show that in 2022, LUE is below 1 in 62.5% of regions, while China and Brazil reach 1.90 and 1.81, respectively, but remain efficient-stressed due to high ecological deficits. Despite ecological deficits, Indonesia and Australia exhibit the highest outflow intensity of embodied cropland use, exporting 55.9% and 68.0% of regional production-based land ecological footprint (PLEF), respectively. Two-dimensional diagnostics identify irrigation water and energy as dominant sources of inefficiency and show that PLEF exceeds land biocapacity by approximately 5%–35% in deficit regions. Policy designs for reconciling LUE and LES should guide supply-side efficiency gains, complemented by demand- and trade-oriented measures for durable agricultural sustainability.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"13 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nickel-Catalyzed C–O Cross-coupling of N-Boc-Protected Amino Alcohols with (Hetero)aryl Halides","authors":"Zi-Han Zhao,Jia-Xin Feng,Gao-Dong Xu,Nan Ji,Liu Yang,Dong Xue,Wei He","doi":"10.1021/acs.joc.6c00945","DOIUrl":"https://doi.org/10.1021/acs.joc.6c00945","url":null,"abstract":"The aryloxyalkylamine motif is a privileged pharmacophore found in bioactive molecules. However, achieving its direct and chemoselective construction via O-arylation of amino alcohols remains a significant challenge in synthetic chemistry. Herein, we report a mild and efficient nickel-catalyzed C–O cross-coupling of N-Boc-protected amino alcohols with (hetero)aryl halides. This method employs bipyridine as the ligand and an organic amine as the base, circumventing the need for specific ligand systems and strong inorganic bases typically required in other protocols. The system exhibits excellent functional group tolerance and broad compatibility, particularly with regard to heteroaryl halides and amino alcohols derived from natural amino acids. Furthermore, the scalability of the reaction is demonstrated through gram-scale synthesis, highlighting its potential for practical applications.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221699","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Surface-Confined Pt–Ov–Mn Atomic Interfaces Promote Deep Benzene Mineralization through Coupled Electron Transfer and Lattice-Oxygen Activation","authors":"Wenbo Pei,Xinzhu Wu,Jianwei Wang,Tao Ban,Pan Zhang,Wenqiang Yang,Qi Peng,Qing Wang,Jinyao Liu,Hao Guo,Di Hu,Hongxing Dai,Haibao Huang","doi":"10.1021/acs.est.6c09929","DOIUrl":"https://doi.org/10.1021/acs.est.6c09929","url":null,"abstract":"Single-atom catalysts are promising for VOC abatement, but their application is limited by the trade-off between the stability of isolated atoms and the redox activity. Herein, we report a surface-confined Pt–Ov–Mn atomic interface constructed within the outer layer of Mn2O3 via thermal self-reconstruction. Oxygen vacancies trap isolated Pt atoms and electronically connect them with neighboring Mn centers, forming a vacancy-rich interfacial active center. For benzene oxidation, Pt1/Mn2O3 achieved a specific reaction rate of 45.70 μmol gPt–1 s–1 at 140 °C, which is 3.8 and 11.2 times those of the Pt nanocluster and nanoparticle counterparts, respectively. The catalyst also exhibited excellent thermal stability and enhanced tolerance to SO2 poisoning. Mechanistic studies reveal that the Pt–Ov–Mn interface enables electron–lattice-oxygen coupling: interfacial Pt 5d–Mn 3d electronic interaction upshifts the Pt d-band center, strengthening benzene π adsorption and promoting C–H activation and ring opening, while adjacent oxygen vacancies accelerate lattice-oxygen migration and replenishment through a Mars–van Krevelen cycle. This coupled pathway suppresses the accumulation of partially oxidized intermediates and drives deep mineralization to CO2. These findings identify surface-layer atomic interfaces as designable active centers for developing robust SACs toward hazardous VOC control.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"60 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226072","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}