Haolin Du, Qi Yu, Yucong Miao, Junli Ao, Jiale Wu, Kun Fu, Yang Shi, Jun Li, Jun-An Ma, Jie Wu
In carbonylation reactions, a carbonyl source is typically required, often supplied by carbon monoxide (CO) gas or CO surrogates that release CO via decarbonylation. Herein, we report a novel carbonylative reductive coupling reaction utilizing pivaldehyde as a facile and cost-effective carbonyl source with water serving as an environmentally benign reductant. A polymeric carbon nitride semiconductor functionalized with high-density single-atom palladium was designed as a multifunctional catalytic system, simultaneously driving a cascade decarbonylation–CO migration–carbonylative coupling process while enabling photocatalytic water oxidation to supply electrons for the reductive coupling. Life cycle assessment analysis further supports the economic viability of our carbonylative reductive coupling strategy. The spatial proximity of Pd atoms is crucial in promoting efficient CO migration, and computational studies offer atomic-level insights into this high-density configuration in the reaction. The heterogeneous single-atom photocatalyst exhibits exceptional stability, maintaining its catalytic activity over 10 consecutive cycles with minimal loss in performance. The practical utility of this method was demonstrated through the efficient synthesis of pharmaceutical compounds, including a decagram-scale synthesis of AdipoRon in a high-speed circulation flow system. This work seamlessly integrates decarbonylation, photocatalytic water splitting, and reductive coupling reactions, underscoring the tremendous potential of single-atom photocatalysts in advancing sustainable cascade organic transformations.
{"title":"High-Density Palladium Single-Atom Catalysts for Photoinduced Tandem Decarbonylation/Carbonylative Reductive Coupling","authors":"Haolin Du, Qi Yu, Yucong Miao, Junli Ao, Jiale Wu, Kun Fu, Yang Shi, Jun Li, Jun-An Ma, Jie Wu","doi":"10.1021/jacs.5c12630","DOIUrl":"https://doi.org/10.1021/jacs.5c12630","url":null,"abstract":"In carbonylation reactions, a carbonyl source is typically required, often supplied by carbon monoxide (CO) gas or CO surrogates that release CO via decarbonylation. Herein, we report a novel carbonylative reductive coupling reaction utilizing pivaldehyde as a facile and cost-effective carbonyl source with water serving as an environmentally benign reductant. A polymeric carbon nitride semiconductor functionalized with high-density single-atom palladium was designed as a multifunctional catalytic system, simultaneously driving a cascade decarbonylation–CO migration–carbonylative coupling process while enabling photocatalytic water oxidation to supply electrons for the reductive coupling. Life cycle assessment analysis further supports the economic viability of our carbonylative reductive coupling strategy. The spatial proximity of Pd atoms is crucial in promoting efficient CO migration, and computational studies offer atomic-level insights into this high-density configuration in the reaction. The heterogeneous single-atom photocatalyst exhibits exceptional stability, maintaining its catalytic activity over 10 consecutive cycles with minimal loss in performance. The practical utility of this method was demonstrated through the efficient synthesis of pharmaceutical compounds, including a decagram-scale synthesis of AdipoRon in a high-speed circulation flow system. This work seamlessly integrates decarbonylation, photocatalytic water splitting, and reductive coupling reactions, underscoring the tremendous potential of single-atom photocatalysts in advancing sustainable cascade organic transformations.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"15 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732554","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lifan Hu, Wenwu Peng, Jiyao Yu, Lisa Förch, Stephen Mann, Seah Ling Kuan, Tanja Weil
Artificial cells (ACs) offer a powerful platform to reprogram metabolic signaling in complex tissue environments by replicating key biological functions without the full complexity of living cells. However, achieving autonomous metabolite exchange and stable integration with living tissues remains a major challenge. Here, we report the development of proteinosome-based ACs equipped with a minimal metabolism to mediate bidirectional communication with glycolytic tumor cells. These tumors accumulate lactate, a metabolic byproduct that promotes immunosuppression and metastasis. Although lactate oxidase (LOx) can degrade lactate, its oxidation product, pyruvate, may inadvertently fuel tumor growth. To overcome this limitation, we engineered dual-processor ACs coencapsulating LOx and pyruvate decarboxylase (PDC), enabling selective conversion of lactate into cytotoxic acetaldehyde while suppressing pyruvate and hydrogen peroxide accumulation. These ACs demonstrate sustained catalytic activity, maintain reactive oxygen species homeostasis, and remain functional when integrated in 3D tumor spheroids. Crucially, they engage in autonomous, bidirectional metabolite exchange, preferentially with cancer cells over normal cells, dynamically rewiring important metabolites of the tumor microenvironment and suppressing cell viability. This work establishes synthetic metabolic biointerfaces as programmable actuators capable of reshaping pathological signaling in cancer tissues.
{"title":"Bioactive Artificial Cells as Autonomous Metabolic Actuators Enable Bidirectional Communication with Tumor Cells","authors":"Lifan Hu, Wenwu Peng, Jiyao Yu, Lisa Förch, Stephen Mann, Seah Ling Kuan, Tanja Weil","doi":"10.1021/jacs.5c14609","DOIUrl":"https://doi.org/10.1021/jacs.5c14609","url":null,"abstract":"Artificial cells (ACs) offer a powerful platform to reprogram metabolic signaling in complex tissue environments by replicating key biological functions without the full complexity of living cells. However, achieving autonomous metabolite exchange and stable integration with living tissues remains a major challenge. Here, we report the development of proteinosome-based ACs equipped with a minimal metabolism to mediate bidirectional communication with glycolytic tumor cells. These tumors accumulate lactate, a metabolic byproduct that promotes immunosuppression and metastasis. Although lactate oxidase (LOx) can degrade lactate, its oxidation product, pyruvate, may inadvertently fuel tumor growth. To overcome this limitation, we engineered dual-processor ACs coencapsulating LOx and pyruvate decarboxylase (PDC), enabling selective conversion of lactate into cytotoxic acetaldehyde while suppressing pyruvate and hydrogen peroxide accumulation. These ACs demonstrate sustained catalytic activity, maintain reactive oxygen species homeostasis, and remain functional when integrated in 3D tumor spheroids. Crucially, they engage in autonomous, bidirectional metabolite exchange, preferentially with cancer cells over normal cells, dynamically rewiring important metabolites of the tumor microenvironment and suppressing cell viability. This work establishes synthetic metabolic biointerfaces as programmable actuators capable of reshaping pathological signaling in cancer tissues.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"150 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732555","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cecilia A. Zito, Lars Klemeyer, Francesco Caddeo, Brian Jessen, Sani Y. Harouna-Mayer, Lise-Marie Lacroix, Malte Langfeldt, Tjark L. R. Gröne, Jagadesh K. Kesavan, Chia-Shuo Hsu, Alexander Schwarz, Ann-Christin Dippel, Fernando Igoa Saldaña, Blanka Detlefs, Dorota Koziej
Iron sulfides (FexSy), including greigite (Fe3S4), are key materials in geological processes and technological applications. However, in the context of colloidal synthesis, the mechanism by which these nanoparticles form remains unexplored. Here, we employ in situ X-ray diffraction and photon-in photon-out spectroscopic studies to elucidate the reaction pathway of Fe(acac)3 and thioacetamide (TAA) in benzyl alcohol (BA), which yields crumpled Fe3S4 nanosheets. Using powder X-ray diffraction (PXRD), we identify FeS (mackinawite) as a crystalline intermediate whose anisotropic growth, driven by its layered crystal structure, governs the crumpled nanosheet-like morphology of Fe3S4 (greigite) through a topotactic transition. By performing high-resolution fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) spectroscopy, we show that the formation of Fe3S4 proceeds through a multistep mechanism involving two intermediates. Supported by density functional theory (DFT), we find that Fe(acac)3 is initially reduced in the presence of TAA in BA, forming a molecular intermediate [Fe(acac)2(BA)2], which subsequently transforms into FeS and ultimately into Fe3S4. Complementary valence-to-core X-ray emission spectroscopy (vtc-XES) reveals the evolution of the coordination environment from Fe–O to Fe–S throughout the reaction. Our work provides a comprehensive understanding of the formation mechanism of Fe3S4 nanosheets in solution, shedding light on how crystal growth dynamics and electronic structure evolution dictate their unique crumpled nanosheet morphology.
{"title":"In situ X-ray Synchrotron Studies Reveal the Nucleation and Topotactic Transformation of Iron Sulfide Nanosheets","authors":"Cecilia A. Zito, Lars Klemeyer, Francesco Caddeo, Brian Jessen, Sani Y. Harouna-Mayer, Lise-Marie Lacroix, Malte Langfeldt, Tjark L. R. Gröne, Jagadesh K. Kesavan, Chia-Shuo Hsu, Alexander Schwarz, Ann-Christin Dippel, Fernando Igoa Saldaña, Blanka Detlefs, Dorota Koziej","doi":"10.1021/jacs.5c15843","DOIUrl":"https://doi.org/10.1021/jacs.5c15843","url":null,"abstract":"Iron sulfides (Fe<sub><i>x</i></sub>S<sub><i>y</i></sub>), including greigite (Fe<sub>3</sub>S<sub>4</sub>), are key materials in geological processes and technological applications. However, in the context of colloidal synthesis, the mechanism by which these nanoparticles form remains unexplored. Here, we employ <i>in situ</i> X-ray diffraction and photon-in photon-out spectroscopic studies to elucidate the reaction pathway of Fe(acac)<sub>3</sub> and thioacetamide (TAA) in benzyl alcohol (BA), which yields crumpled Fe<sub>3</sub>S<sub>4</sub> nanosheets. Using powder X-ray diffraction (PXRD), we identify FeS (mackinawite) as a crystalline intermediate whose anisotropic growth, driven by its layered crystal structure, governs the crumpled nanosheet-like morphology of Fe<sub>3</sub>S<sub>4</sub> (greigite) through a topotactic transition. By performing high-resolution fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) spectroscopy, we show that the formation of Fe<sub>3</sub>S<sub>4</sub> proceeds through a multistep mechanism involving two intermediates. Supported by density functional theory (DFT), we find that Fe(acac)<sub>3</sub> is initially reduced in the presence of TAA in BA, forming a molecular intermediate [Fe(acac)<sub>2</sub>(BA)<sub>2</sub>], which subsequently transforms into FeS and ultimately into Fe<sub>3</sub>S<sub>4</sub>. Complementary valence-to-core X-ray emission spectroscopy (vtc-XES) reveals the evolution of the coordination environment from Fe–O to Fe–S throughout the reaction. Our work provides a comprehensive understanding of the formation mechanism of Fe<sub>3</sub>S<sub>4</sub> nanosheets in solution, shedding light on how crystal growth dynamics and electronic structure evolution dictate their unique crumpled nanosheet morphology.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"45 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729253","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yabing Wen, Andreas Rosnes, Bo Jiang, Øystein Prytz, Truls Norby, Reidar Haugsrud, Jonathan M. Polfus
Nickel provides essential catalytic properties for hydrogen electrodes in proton-conducting ceramic electrochemical cells. However, Ni diminishes the hydration capability and proton conductivity when incorporated into electrolyte materials including BaZr0.8Yb0.2O3−δ studied here. Through semiquantitative atomic-resolution scanning transmission electron microscopy, density functional theory simulations, X-ray total scattering, and absorption spectroscopy, we reveal that Ni forms point defect clusters with the Yb acceptors wherein oxygen vacancies are trapped and resist hydration. The resulting effective acceptor concentration is described by point defect reactions in quantitative agreement with thermogravimetric measurements of hydration for samples substituted with 2–5 mol % Ni by BaNiO2 addition. Moreover, excess B-site cations due to NiO addition induce the formation of antiphase boundaries (APBs) that are enriched in Yb and thereby deplete the bulk of acceptors, further suppressing hydration. The adverse effects of Ni are thereby resolved into two novel mechanisms, opening new avenues in point defect engineering for high-performance electrolytes.
{"title":"Nickel-Induced Lattice Defects Limit Proton Uptake in Barium Zirconate Electrolytes","authors":"Yabing Wen, Andreas Rosnes, Bo Jiang, Øystein Prytz, Truls Norby, Reidar Haugsrud, Jonathan M. Polfus","doi":"10.1021/jacs.5c13935","DOIUrl":"https://doi.org/10.1021/jacs.5c13935","url":null,"abstract":"Nickel provides essential catalytic properties for hydrogen electrodes in proton-conducting ceramic electrochemical cells. However, Ni diminishes the hydration capability and proton conductivity when incorporated into electrolyte materials including BaZr<sub>0.8</sub>Yb<sub>0.2</sub>O<sub>3−δ</sub> studied here. Through semiquantitative atomic-resolution scanning transmission electron microscopy, density functional theory simulations, X-ray total scattering, and absorption spectroscopy, we reveal that Ni forms point defect clusters with the Yb acceptors wherein oxygen vacancies are trapped and resist hydration. The resulting effective acceptor concentration is described by point defect reactions in quantitative agreement with thermogravimetric measurements of hydration for samples substituted with 2–5 mol % Ni by BaNiO<sub>2</sub> addition. Moreover, excess B-site cations due to NiO addition induce the formation of antiphase boundaries (APBs) that are enriched in Yb and thereby deplete the bulk of acceptors, further suppressing hydration. The adverse effects of Ni are thereby resolved into two novel mechanisms, opening new avenues in point defect engineering for high-performance electrolytes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"9 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732158","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fullerene (C60) exhibits rich redox chemistry but suffers from severe dissolution of reduced fulleride species in carbonate electrolytes, leading to poor reversibility and rapid capacity fading. Here, we demonstrate covalent bridging as a general strategy to stabilize the fullerene framework using Mg4C60. Mg atoms promote intercage covalent connections through C–C single bonds and [2 + 2] cycloaddition bonds, transforming a van der Waals molecular solid into a layered polymeric framework. Comprehensive characterizations reveal that such bridging effectively suppresses dissolution, preserves structural integrity, and enables a reversible Li+ storage process. Interestingly, unlike pristine C60 that undergoes multiple phase transitions, Mg4C60 exhibits slope-type electrochemical profiles reminiscent of soft carbon yet originates from an ordered two-dimensional framework. Comprehensive mechanistic studies reveal reversible fullerene cage distortions accompanied by the dynamic reconstruction of sp2 electronic states, while the covalently bridged scaffold remains intact. This work establishes covalently bridged fullerenes as a new class of durable carbonaceous anodes and provides a general pathway for designing ordered carbon frameworks with enhanced stability for next-generation rechargeable batteries.
{"title":"Covalent Bridges Enabling Layered C60 as an Exceptionally Stable Anode in Lithium-Ion Batteries","authors":"Shijian Wang, Heng Liu, Yaojie Lei, Dongfang Li, Yameng Fan, Liang Hong, Xin Guo, Meng Wang, Zefu Huang, Yong Chen, Xu Yang, Jinqiang Zhang, Hao Li, Guoxiu Wang","doi":"10.1021/jacs.5c17338","DOIUrl":"https://doi.org/10.1021/jacs.5c17338","url":null,"abstract":"Fullerene (C<sub>60</sub>) exhibits rich redox chemistry but suffers from severe dissolution of reduced fulleride species in carbonate electrolytes, leading to poor reversibility and rapid capacity fading. Here, we demonstrate covalent bridging as a general strategy to stabilize the fullerene framework using Mg<sub>4</sub>C<sub>60</sub>. Mg atoms promote intercage covalent connections through C–C single bonds and [2 + 2] cycloaddition bonds, transforming a van der Waals molecular solid into a layered polymeric framework. Comprehensive characterizations reveal that such bridging effectively suppresses dissolution, preserves structural integrity, and enables a reversible Li<sup>+</sup> storage process. Interestingly, unlike pristine C<sub>60</sub> that undergoes multiple phase transitions, Mg<sub>4</sub>C<sub>60</sub> exhibits slope-type electrochemical profiles reminiscent of soft carbon yet originates from an ordered two-dimensional framework. Comprehensive mechanistic studies reveal reversible fullerene cage distortions accompanied by the dynamic reconstruction of <i>sp</i><sup>2</sup> electronic states, while the covalently bridged scaffold remains intact. This work establishes covalently bridged fullerenes as a new class of durable carbonaceous anodes and provides a general pathway for designing ordered carbon frameworks with enhanced stability for next-generation rechargeable batteries.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"206 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718436","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dynamic and spatially graded mechanical microenvironments are essential for guiding the regeneration of hierarchical osteochondral tissue. Although hydrogels are widely used in stem cells-based tissue regeneration, conventional platforms cannot deliver precisely controlled spatiotemporal mechanical cues required for osteochondral repair. Herein, a self-evolving hydrogel (SE gel) is reported that incorporates a secondary cross-linking network catalyzed by alkaline phosphatase (ALP), formed by the reaction between 2-cyanobenzothiazole (CBT) and cysteine (Cys). This enzymatic cross-linking increases network density and complements the primary photo-cross-linking structure, resulting in a 4-fold increase in the storage modulus from 2.73 to 11.08 kPa. The increased stiffness induces a morphological transition in cell spreading from fusiform to polygonal shapes, promotes a 2.2-fold increase in nuclear localization of yes-associated protein (YAP), and triggers osteogenic differentiation. SE gel exploits the endogenous ALP gradient to form a spatially graded, dual-cross-linked network. In the subchondral bone region, a higher ALP activity (∼294.5 U mg–1) catalyzes the extensive formation of a dual-cross-linked structure, whereas the articular cartilage region, with a lower ALP activity (∼15.0 U mg–1), generates a less dense network. This ALP-gradient-driven evolution delivers spatially and temporally dynamic mechanical cues, ranging from soft to stiff, which are transduced through extended integrin-mediated mechanosignaling and subsequently activate the PI3K/AKT/GSK-3β/β-catenin pathway. This cascade regulates key cell functions, such as spreading, migration, and differentiation. The dynamic and gradient-responsive SE gel supports osteochondral regeneration with tissue-specific heterogeneity. To the best of our knowledge, this is the first study to integrate an adaptive hydrogel with an ALP activity gradient, demonstrating its potential in osteochondral regeneration and highlighting the pivotal role of mechanobiology.
动态和空间梯度的机械微环境是指导分层骨软骨组织再生的必要条件。尽管水凝胶广泛应用于干细胞组织再生，但传统的平台无法提供骨软骨修复所需的精确控制的时空机械线索。本文报道了一种自进化的水凝胶（SE凝胶），该凝胶包含由2-氰苯并噻唑（CBT）和半胱氨酸（Cys）反应形成的碱性磷酸酶（ALP）催化的二级交联网络。这种酶交联增加了网络密度，并补充了主要的光交联结构，导致存储模量从2.73增加到11.08 kPa，增加了4倍。增加的硬度诱导细胞从梭形向多边形扩散的形态转变，促进yes相关蛋白（YAP）的核定位增加2.2倍，并引发成骨分化。SE凝胶利用内源性ALP梯度形成空间梯度的双交联网络。在软骨下骨区域，较高的ALP活性（~ 294.5 U mg-1）催化双交联结构的广泛形成，而具有较低ALP活性（~ 15.0 U mg-1）的关节软骨区域产生较不密集的网络。这种由alp梯度驱动的进化提供了空间和时间上动态的机械信号，从柔软到坚硬，这些信号通过扩展整合素介导的机械信号转导，随后激活PI3K/AKT/GSK-3β/β-catenin途径。这个级联调节关键的细胞功能，如扩散、迁移和分化。动态和梯度响应的SE凝胶支持骨软骨再生具有组织特异性异质性。据我们所知，这是第一个将适应性水凝胶与ALP活性梯度相结合的研究，证明了其在骨软骨再生中的潜力，并强调了机械生物学的关键作用。
{"title":"Enzyme-Responsive Self-Evolving Hydrogel for Osteochondral Regeneration through Mechanosignaling Pathway","authors":"Yaling Zhuang, Enbo Liu, Yu Gao, Jianxun Ding, Xuesi Chen","doi":"10.1021/jacs.5c09022","DOIUrl":"https://doi.org/10.1021/jacs.5c09022","url":null,"abstract":"Dynamic and spatially graded mechanical microenvironments are essential for guiding the regeneration of hierarchical osteochondral tissue. Although hydrogels are widely used in stem cells-based tissue regeneration, conventional platforms cannot deliver precisely controlled spatiotemporal mechanical cues required for osteochondral repair. Herein, a self-evolving hydrogel (SE gel) is reported that incorporates a secondary cross-linking network catalyzed by alkaline phosphatase (ALP), formed by the reaction between 2-cyanobenzothiazole (CBT) and cysteine (Cys). This enzymatic cross-linking increases network density and complements the primary photo-cross-linking structure, resulting in a 4-fold increase in the storage modulus from 2.73 to 11.08 kPa. The increased stiffness induces a morphological transition in cell spreading from fusiform to polygonal shapes, promotes a 2.2-fold increase in nuclear localization of yes-associated protein (YAP), and triggers osteogenic differentiation. SE gel exploits the endogenous ALP gradient to form a spatially graded, dual-cross-linked network. In the subchondral bone region, a higher ALP activity (∼294.5 U mg<sup>–1</sup>) catalyzes the extensive formation of a dual-cross-linked structure, whereas the articular cartilage region, with a lower ALP activity (∼15.0 U mg<sup>–1</sup>), generates a less dense network. This ALP-gradient-driven evolution delivers spatially and temporally dynamic mechanical cues, ranging from soft to stiff, which are transduced through extended integrin-mediated mechanosignaling and subsequently activate the PI3K/AKT/GSK-3β/β-catenin pathway. This cascade regulates key cell functions, such as spreading, migration, and differentiation. The dynamic and gradient-responsive SE gel supports osteochondral regeneration with tissue-specific heterogeneity. To the best of our knowledge, this is the first study to integrate an adaptive hydrogel with an ALP activity gradient, demonstrating its potential in osteochondral regeneration and highlighting the pivotal role of mechanobiology.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"11 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729257","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lisi Xie, Jie Li, Guohao Wang, Wei Sang, Mengze Xu, Wenxi Li, Jie Yan, Bei Li, Zhan Zhang, Qi Zhao, Zhen Yuan, Quli Fan, Yunlu Dai
In the original publication, in Figure S45A in the Supporting Information, the image for G6 was inadvertently duplicated as the image for G2. We have replaced the image for G2 with the correct one in the replacement Figure S45, shown below. A complete, corrected Supporting Information file is provided herein. This change does not affect the conclusions of the manuscript. Figure S45. (A) Photographs of spleens in different groups. (B) The mice spleen weight on day 14 in different groups. Data was presented as mean ± s.d (n = 5). All data was analyzed with one-way ANOVA with Tukey’s post hoc test. Significance was presented as *p < 0.05, **p < 0.01, ***p < 0.001 and ****p < 0.0001. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.5c18626. Experimental materials and methods for the synthesis, preparation, and characterization of the nanoparticles, in vitro antitumor efficiency, in vivo imaging, exosome isolation, immune activation, and in vivo animal experiments (corrected) (PDF) Correction to “Phototheranostic Metal-Phenolic Networks with Antiexosomal PD-L1 Enhanced Ferroptosis for Synergistic Immunotherapy” 2 views 0 shares 0 downloads Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.
在原始出版物中，在支持信息中的图S45A中，G6的图像无意中被复制为G2的图像。我们已经将G2的图片替换为替换图S45中正确的图片，如下所示。这里提供了一个完整的、正确的支持信息文件。这一变化不影响手稿的结论。图S45。(A)各组脾脏照片。(B)各组小鼠第14天脾脏重量。数据以mean±s.d表示（n = 5）。所有数据采用Tukey事后检验的单因素方差分析。显著性分别为*p <； 0.05、**p < 0.01、**p <； 0.001和****p <； 0.0001。支持信息可在https://pubs.acs.org/doi/10.1021/jacs.5c18626免费获取。纳米颗粒的合成、制备和表征的实验材料和方法，体外抗肿瘤效率，体内成像，外泌体分离，免疫激活，和体内动物实验（更正）（PDF）对“PhototheranosticMetal-PhenolicNetworks with anti - exosomal PD-L1 Enhanced Ferroptosis for SynergisticImmunotherapy”的更正2次浏览0次分享0次下载大多数电子支持信息文件无需订阅ACS网络版即可获得。这些文件可以通过文章下载用于研究用途（如果相关文章有公共使用许可链接，该许可可以允许其他用途）。如有其他用途，可通过RightsLink权限系统http://pubs.acs.org/page/copyright/permissions.html向ACS申请。这篇文章尚未被其他出版物引用。
{"title":"Correction to “Phototheranostic Metal-Phenolic Networks with Antiexosomal PD-L1 Enhanced Ferroptosis for Synergistic Immunotherapy”","authors":"Lisi Xie, Jie Li, Guohao Wang, Wei Sang, Mengze Xu, Wenxi Li, Jie Yan, Bei Li, Zhan Zhang, Qi Zhao, Zhen Yuan, Quli Fan, Yunlu Dai","doi":"10.1021/jacs.5c18626","DOIUrl":"https://doi.org/10.1021/jacs.5c18626","url":null,"abstract":"In the original publication, in Figure S45A in the Supporting Information, the image for G6 was inadvertently duplicated as the image for G2. We have replaced the image for G2 with the correct one in the replacement Figure S45, shown below. A complete, corrected Supporting Information file is provided herein. This change does not affect the conclusions of the manuscript. Figure S45. (A) Photographs of spleens in different groups. (B) The mice spleen weight on day 14 in different groups. Data was presented as mean ± s.d (n = 5). All data was analyzed with one-way ANOVA with Tukey’s post hoc test. Significance was presented as *<i>p</i> < 0.05, **<i>p</i> < 0.01, ***<i>p</i> < 0.001 and ****<i>p</i> < 0.0001. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.5c18626. Experimental materials and methods for the synthesis, preparation, and characterization of the nanoparticles, in vitro antitumor efficiency, in vivo imaging, exosome isolation, immune activation, and in vivo animal experiments (corrected) (PDF) Correction to “Phototheranostic\u0000Metal-Phenolic\u0000Networks with Antiexosomal PD-L1 Enhanced Ferroptosis for Synergistic\u0000Immunotherapy” <span> 2 </span><span> views </span> <span> 0 </span><span> shares </span> <span> 0 </span><span> downloads </span> Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"143 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Johanna-Barbara Linse, Hyun Sun Cho, Friedrich Schotte, Philip A. Anfinrud, Jochen S. Hub
The hydration shell is an integral part of proteins since it plays key roles in conformational transitions, molecular recognition, and enzymatic activity. While the dynamics of the hydration shell have been described by spectroscopic techniques, the structure of the hydration shell remains less understood due to the lack of hydration shell-sensitive structural probes with high spatial resolution. We combined temperature-ramp small-angle X-ray scattering (T-ramp SAXS) from 255 to 335 K with molecular simulations to demonstrate that the hydration shells of the IgG-binding domain of Protein G (GB3) and the villin headpiece are remarkably temperature-sensitive. For proteins in the folded state, T-ramp SAXS data and explicit-solvent SAXS predictions consistently demonstrate decays of protein contrasts and radii of gyration with increasing temperature, which are shown to reflect predominantly temperature-sensitive, depleting hydration shells. The depletion is caused not merely by enhanced disorder within the hydration shells but also by partial displacements of surface-coordinated water molecules. Together, T-ramp SAXS and explicit-solvent SAXS calculations provide a novel structural view of the protein hydration shell, which underlies temperature-dependent processes such as cold denaturation, thermophoresis, or biomolecular phase separation.
{"title":"Depletion of the Protein Hydration Shell with Increasing Temperature Observed by Small-Angle X-ray Scattering and Molecular Simulations","authors":"Johanna-Barbara Linse, Hyun Sun Cho, Friedrich Schotte, Philip A. Anfinrud, Jochen S. Hub","doi":"10.1021/jacs.5c13497","DOIUrl":"https://doi.org/10.1021/jacs.5c13497","url":null,"abstract":"The hydration shell is an integral part of proteins since it plays key roles in conformational transitions, molecular recognition, and enzymatic activity. While the dynamics of the hydration shell have been described by spectroscopic techniques, the structure of the hydration shell remains less understood due to the lack of hydration shell-sensitive structural probes with high spatial resolution. We combined temperature-ramp small-angle X-ray scattering (<i>T</i>-ramp SAXS) from 255 to 335 K with molecular simulations to demonstrate that the hydration shells of the IgG-binding domain of Protein G (GB3) and the villin headpiece are remarkably temperature-sensitive. For proteins in the folded state, <i>T</i>-ramp SAXS data and explicit-solvent SAXS predictions consistently demonstrate decays of protein contrasts and radii of gyration with increasing temperature, which are shown to reflect predominantly temperature-sensitive, depleting hydration shells. The depletion is caused not merely by enhanced disorder within the hydration shells but also by partial displacements of surface-coordinated water molecules. Together, <i>T</i>-ramp SAXS and explicit-solvent SAXS calculations provide a novel structural view of the protein hydration shell, which underlies temperature-dependent processes such as cold denaturation, thermophoresis, or biomolecular phase separation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"29 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718434","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rosalie Cresswell, Parveen Kumar Deralia, Yoshihisa Yoshimi, Tomohiro Kuga, Alberto Echevarría-Poza, W. Trent Franks, Steven P. Brown, Ray Dupree, Paul Dupree
The structure of plant cellulose microfibrils remains elusive, despite the abundance of cellulose and its utility in industry. Using 2D solid-state NMR of 13C-labeled never-dried plants, six major glucose environments are resolved, which are common to the cellulose of softwood, hardwood, and grasses. These environments are maintained in isolated holocellulose nanofibrils, allowing more detailed microfibril characterization. We show that there are only two glucose environments that reside within the microfibril core. These have the same NMR 13C chemical shifts as tunicate cellulose Iβ center and origin chains, with no cellulose Iα being detected. The third major glucose site within spectral domain 1, previously assigned to the crystalline microfibril interior, is in close proximity to water, which could indicate that it is a surface glucose environment. The NMR peak widths of all four surface glucose environments are similar to those of the core, indicating that their glucose local order is comparable; there is no significant “amorphous” cellulose in the microfibrils. Consequently, the ratio of the carbon 4 peaks at ∼89 and ∼84 ppm, which has often provided a sample cellulose crystallinity index, is not a meaningful measure of fibril crystallinity or the interior to surface ratio. The revised ratio for poplar wood microfibrils is estimated to be 1:2, which is consistent with an 18-chain microfibril having 6 core and 12 surface chains, although other microfibril sizes are possible. These advances substantially change both the interpretation of solid-state NMR studies of cellulose and the understanding of cellulose microfibril structure and crystallinity.
{"title":"Using Solid-State NMR to Understand the Structure of Plant Cellulose","authors":"Rosalie Cresswell, Parveen Kumar Deralia, Yoshihisa Yoshimi, Tomohiro Kuga, Alberto Echevarría-Poza, W. Trent Franks, Steven P. Brown, Ray Dupree, Paul Dupree","doi":"10.1021/jacs.5c14452","DOIUrl":"https://doi.org/10.1021/jacs.5c14452","url":null,"abstract":"The structure of plant cellulose microfibrils remains elusive, despite the abundance of cellulose and its utility in industry. Using 2D solid-state NMR of <sup>13</sup>C-labeled never-dried plants, six major glucose environments are resolved, which are common to the cellulose of softwood, hardwood, and grasses. These environments are maintained in isolated holocellulose nanofibrils, allowing more detailed microfibril characterization. We show that there are only two glucose environments that reside within the microfibril core. These have the same NMR <sup>13</sup>C chemical shifts as tunicate cellulose Iβ center and origin chains, with no cellulose Iα being detected. The third major glucose site within spectral domain 1, previously assigned to the crystalline microfibril interior, is in close proximity to water, which could indicate that it is a surface glucose environment. The NMR peak widths of all four surface glucose environments are similar to those of the core, indicating that their glucose local order is comparable; there is no significant “amorphous” cellulose in the microfibrils. Consequently, the ratio of the carbon 4 peaks at ∼89 and ∼84 ppm, which has often provided a sample cellulose crystallinity index, is not a meaningful measure of fibril crystallinity or the interior to surface ratio. The revised ratio for poplar wood microfibrils is estimated to be 1:2, which is consistent with an 18-chain microfibril having 6 core and 12 surface chains, although other microfibril sizes are possible. These advances substantially change both the interpretation of solid-state NMR studies of cellulose and the understanding of cellulose microfibril structure and crystallinity.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"45 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729181","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Matthew J. Goodwin, Alexander M. Deetz, Gerald J. Meyer
Electronic coupling is one of three parameters needed to predict and model excited state electron transfer kinetics yet has never been measured for bimolecular reactions. This knowledge gap is surprising given the central role that this reaction plays in photoredox catalysis and solar energy conversion. Herein, we provide an experimental approach with an analysis based on Marcus theory that provides the electronic coupling, Hab, for electron transfer within the encounter complex. To test this approach, two photosensitizers of the general form Ir(dF-(CF3)-ppy)2(LL)]+, where LL was bipyrazine (bpz) or 4,4′-(di-tert-butyl)-2,2′-bipyridine (dtb) were characterized and utilized to photo-oxidize iodide, bromide, and chloride over a 40 °C temperature range in acetonitrile. For iodide photo-oxidation, Hab was found to be 130 cm–1 for Ir-dtb* and was 3300 cm–1 for Ir-bpz*, being sufficiently large that the nonadiabaticity of the excited state electron transfer is called into question. The stark difference in coupling is attributed, in part, to a larger average separation by the sterically bulky tert-butyl groups. Ir-bpz* was found to oxidize all three halides efficiently, and the coupling increased with the halide radius. These findings have significant implications for the design of photosensitizers with applications in photoredox catalysis and solar energy conversion.
{"title":"Elucidating Electronic Coupling of Bimolecular Excited State Electron Transfer","authors":"Matthew J. Goodwin, Alexander M. Deetz, Gerald J. Meyer","doi":"10.1021/jacs.5c16934","DOIUrl":"https://doi.org/10.1021/jacs.5c16934","url":null,"abstract":"Electronic coupling is one of three parameters needed to predict and model excited state electron transfer kinetics yet has never been measured for bimolecular reactions. This knowledge gap is surprising given the central role that this reaction plays in photoredox catalysis and solar energy conversion. Herein, we provide an experimental approach with an analysis based on Marcus theory that provides the electronic coupling, <i>H</i><sub><i>ab</i></sub>, for electron transfer within the encounter complex. To test this approach, two photosensitizers of the general form Ir(dF-(CF<sub>3</sub>)-ppy)<sub>2</sub>(LL)]<sup>+</sup>, where LL was bipyrazine (bpz) or 4,4′-(di-<i>tert</i>-butyl)-2,2′-bipyridine (dtb) were characterized and utilized to photo-oxidize iodide, bromide, and chloride over a 40 °C temperature range in acetonitrile. For iodide photo-oxidation, <i>H</i><sub><i>ab</i></sub> was found to be 130 cm<sup>–1</sup> for Ir-dtb* and was 3300 cm<sup>–1</sup> for Ir-bpz*, being sufficiently large that the nonadiabaticity of the excited state electron transfer is called into question. The stark difference in coupling is attributed, in part, to a larger average separation by the sterically bulky <i>tert</i>-butyl groups. Ir-bpz* was found to oxidize all three halides efficiently, and the coupling increased with the halide radius. These findings have significant implications for the design of photosensitizers with applications in photoredox catalysis and solar energy conversion.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"366 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729182","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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