Journal of the American Chemical Society最新文献

Semiconducting Carbon Nanotube Extraction Enabled by Alkylated Cellulose Wrapping. 通过烷基化纤维素包裹提取半导体碳纳米管。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-06-27 DOI: 10.1021/jacs.4c05468

Tomoko Yagi, Kazuhiro Yoshida, Shunsuke Sakurai, Tsuyoshi Kawai, Yoshiyuki Nonoguchi

引用次数: 0

Switchable and Chemoselective Arene Hydrogenation for Efficient Late Stage Applications.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-06-27 DOI: 10.1021/jacs.4c05883

Fuhao Zhang, Himadri Sekhar Sasmal, Debanjan Rana, Frank Glorius

引用次数: 0

Tailoring Interface Energies via Phosphonic Acids to Grow and Stabilize Cubic FAPI₃ Deposited by Thermal Evaporation.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-06-27 DOI: 10.1021/jacs.4c03911

Andrés-Felipe Castro-Méndez, Farzaneh Jahanbakhshi, Diana K LaFollette, Benjamin J Lawrie, Ruipeng Li, Carlo A R Perini, Andrew M Rappe, Juan-Pablo Correa-Baena

{"title":"Tailoring Interface Energies via Phosphonic Acids to Grow and Stabilize Cubic FAPI3 Deposited by Thermal Evaporation.","authors":"Andrés-Felipe Castro-Méndez, Farzaneh Jahanbakhshi, Diana K LaFollette, Benjamin J Lawrie, Ruipeng Li, Carlo A R Perini, Andrew M Rappe, Juan-Pablo Correa-Baena","doi":"10.1021/jacs.4c03911","DOIUrl":"https://doi.org/10.1021/jacs.4c03911","url":null,"abstract":"Coevaporation of formamidinium lead iodide (FAPbI3) is a promising route for the fabrication of highly efficient and scalable optoelectronic devices, such as perovskite solar cells. However, it poses experimental challenges in achieving stoichiometric FAPbI3 films with a cubic structure (α-FAPbI3). In this work, we show that undesired hexagonal phases of both PbI2 and FAPbI3 form during thermal evaporation, including the well-known 2H-FAPbI3, which are detrimental for optoelectronic performance. We demonstrate the growth of α-FAPbI3 at room temperature via thermal evaporation by depositing phosphonic acids (PAc) on substrates and subsequently coevaporating PbI2 and formamidinium iodide. We use density-functional theory to develop a theoretical model to understand the relative growth energetics of the α and 2H phases of FAPbI3 for different molecular interactions. Experiments and theory show that the presence of PAc molecules stabilizes the formation of α-FAPbI3 in thin films when excess molecules are available to migrate during growth. This migration of molecules facilitates the continued presence of adsorbed organic precursors at the free surface throughout the evaporation, which lowers the growth energy of the α-FAPbI3 phase. Our theoretical analyses of PAc molecule-molecule interactions show that ligands can form hydrogen bonding to reduce the migration rate of the molecules through the deposited film, limiting the effects on the crystal structure stabilization. Our results also show that the phase stabilization with molecules that migrate is long-lasting and resistant to moist air. These findings enable reliable formation and processing of α-FAPbI3 films via vapor deposition.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453716","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}

引用次数: 0

Controlling Charge Percolation in Solutions of Metal Redox Active Polymers: Implications of Microscopic Polyelectrolyte Dynamics on Macroscopic Energy Storage. 控制金属氧化还原活性聚合物溶液中的电荷渗流：微观聚电解质动力学对宏观能量存储的影响。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-06-26 Epub Date: 2024-06-11 DOI: 10.1021/jacs.4c05102

Adolfo I B Romo, Liliana Bello, Sanja Pudar, Nafisa Ibrahim, Yilin Wang, Miranda J Baran, Qianwen Wu, Randy H Ewoldt, Brett A Helms, Charles Sing, Joaquín Rodríguez-López

{"title":"Controlling Charge Percolation in Solutions of Metal Redox Active Polymers: Implications of Microscopic Polyelectrolyte Dynamics on Macroscopic Energy Storage.","authors":"Adolfo I B Romo, Liliana Bello, Sanja Pudar, Nafisa Ibrahim, Yilin Wang, Miranda J Baran, Qianwen Wu, Randy H Ewoldt, Brett A Helms, Charles Sing, Joaquín Rodríguez-López","doi":"10.1021/jacs.4c05102","DOIUrl":"10.1021/jacs.4c05102","url":null,"abstract":"Soluble redox-active polymers (RAPs) enable size-exclusion nonaqueous redox flow batteries (NaRFBs) which promise high energy density. Pendants along the RAPs not only store charge but also engage in electron transfer to varying extents based on their designs. Here, we explore these phenomena in Metal-containing Redox Active Polymers (M-RAPs, M = Ru, Fe, Co). We assess by using cyclic voltammetry and chronoamperometry with ultramicroelectrodes the current response to electrolyte concentration spanning 3 orders of magnitude. Currents scaled as Ru-RAP > Fe-RAP ≫ Co-RAP, consistent with electron self-exchange trends in the small molecule analogues of the MII/III redox pair. Varying the ionic strength of the electrolyte also revealed nonmonotonic behavior, evidencing the impact of polyelectrolytic dynamics on M-RAP redox response. We developed a model to account for the behavior by combining kinetic Monte Carlo and Brownian dynamics near a boundary representing an electrode. While 1D pendant-to-pendant charge transfer along the chain is not a strong function of electrolyte concentration, the microstructure of the RAP at different electrolyte concentrations is decisively impacted, yielding qualitative trends to those observed experimentally. M-RAP size-exclusion NaRFBs using a poly viologen as negolyte varied in average potential with ∼1.54 V for Ru-RAP, ∼1.37 V for Fe-RAP, and ∼0.52 V for Co-RAP. Comparison of batteries at their optimal and suboptimal solution conditions as gauged from analytical experiments showed clear correlations in performance. This work provides a blueprint for understanding the factors underpinning charge transfer in solutions of RAPs for batteries and beyond.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141299380","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}

引用次数: 0

A Synergetic Pore Compartmentalization and Hydrophobization Strategy for Synchronously Boosting the Stability and Activity of Enzyme. 一种同步提高酶稳定性和活性的协同孔隙区隔化和疏水化策略。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-06-26 Epub Date: 2024-06-12 DOI: 10.1021/jacs.4c03286

Lihong Guo, Rongwei He, Guosheng Chen, Huangsheng Yang, Xiaoxue Kou, Wei Huang, Rui Gao, Shuyao Huang, Siming Huang, Fang Zhu, Gangfeng Ouyang

{"title":"A Synergetic Pore Compartmentalization and Hydrophobization Strategy for Synchronously Boosting the Stability and Activity of Enzyme.","authors":"Lihong Guo, Rongwei He, Guosheng Chen, Huangsheng Yang, Xiaoxue Kou, Wei Huang, Rui Gao, Shuyao Huang, Siming Huang, Fang Zhu, Gangfeng Ouyang","doi":"10.1021/jacs.4c03286","DOIUrl":"10.1021/jacs.4c03286","url":null,"abstract":"Spatial immobilization of fragile enzymes using a nanocarrier is an efficient means to design heterogeneous biocatalysts, presenting superior stability and recyclability to pristine enzymes. An immobilized enzyme, however, usually compromises its catalytic activity because of inevasible mass transfer issues and the unfavorable conformation changes in a confined environment. Here, we describe a synergetic metal-organic framework pore-engineering strategy to trap lipase (an important hydrolase), which confers lipase-boosted stability and activity simultaneously. The hierarchically porous NU-1003, featuring interconnected mesopore and micropore channels, is precisely modified by chain-adjustable fatty acids on its mesopore channel, into which lipase is trapped. The interconnected pore structure ensures efficient communication between trapped lipase and exterior media, while the fatty acid-mediated hydrophobic pore can activate the opening conformation of lipase by interfacial interaction. Such dual pore compartmentalization and hydrophobization activation effects render the catalytic center of trapped lipase highly accessible, resulting in 1.57-fold and 2.46-fold activities as native lipase on ester hydrolysis and enantioselective catalysis. In addition, the feasibility of these heterogeneous biocatalysts for kinetic resolution of enantiomer is also validated, showing much higher efficiency than native lipase.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141304825","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}

引用次数: 0

Capturing Metal Fluoride inside a Carbon Cage. 在碳笼内捕获金属氟化物

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-06-26 Epub Date: 2024-06-12 DOI: 10.1021/jacs.4c07045

Ya Zhao, Ziqi Hu, Panfeng Chuai, Huaimin Jin, Shangfeng Yang, Jie Su, Zujin Shi

{"title":"Capturing Metal Fluoride inside a Carbon Cage.","authors":"Ya Zhao, Ziqi Hu, Panfeng Chuai, Huaimin Jin, Shangfeng Yang, Jie Su, Zujin Shi","doi":"10.1021/jacs.4c07045","DOIUrl":"10.1021/jacs.4c07045","url":null,"abstract":"We report here a new type of metal fluoride cluster that can be stabilized inside fullerene via in situ fluorine encapsulation followed by exohedral trifluoromethylation, giving rise to rare-earth metal fluoride clusterfullerenes (FCFs) M2F@C80(CF3) (M = Gd and Y). The molecular structure of Gd2F@C80(CF3) was unambiguously determined by single-crystal X-ray analysis to show a μ2-fluoride-bridged Gd-F-Gd cluster with short Gd-F bonds of 2.132(7) and 2.179(7) Å. The 19F NMR spectrum of the diamagnetic Y2F@C80(CF3) confirms the existence of the endohedral F atom, which exhibits a triplet with a large 19F-89Y coupling constant of 74 Hz and a high temperature sensitivity of the 19F chemical shift of 0.057 ppm/K. Theoretical studies reveal the ionic Y-F bonding nature arising from the highest electronegativity of the F element and an electronic configuration of [Y2F]5+@[C80]5- with an open-shell carbon cage, which thus necessitates the stabilization of FCFs by exohedral trifluoromethylation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141304827","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}

引用次数: 0

Selective C-H Bond Activation in Propane with Molecular Oxygen over Cu(I)-ZSM-5 at Ambient Conditions. 在环境条件下，Cu(I)-ZSM-5 上分子氧对丙烷中 C-H 键的选择性活化。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-06-26 Epub Date: 2024-06-12 DOI: 10.1021/jacs.4c03184

Hai-Sheng Su, Yiwei Liu, Hao Tian, Dinghui Chen, Qikai Shen, Xiaoxia Chang, Qi Lu, Bingjun Xu

引用次数: 0

Enhanced Photobiocatalytic Cascades at Pickering Droplet Interfaces. 增强皮克林液滴界面的光生物催化级联。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-06-26 Epub Date: 2024-06-13 DOI: 10.1021/jacs.4c01834

Ke Li, Houbing Zou, Xili Tong, Hengquan Yang

{"title":"Enhanced Photobiocatalytic Cascades at Pickering Droplet Interfaces.","authors":"Ke Li, Houbing Zou, Xili Tong, Hengquan Yang","doi":"10.1021/jacs.4c01834","DOIUrl":"10.1021/jacs.4c01834","url":null,"abstract":"Developing new methods to engineer photobiocatalytic reactions is of utmost significance for artificial photosynthesis, but it remains a grand challenge due to the intrinsic incompatibility of biocatalysts with photocatalysts. In this work, photocatalysts and enzymes were spatially colocalized at Pickering droplet interfaces, where the reaction microenvironment and the spatial distance between two distinct catalysts were exquisitely regulated to achieve unprecedented photobiocatalytic cascade reactions. As proof of the concept, ultrathin graphitic carbon nitride nanosheets loaded with Au nanoparticles were precisely positioned in the outer interfacial layer of Pickering oil droplets to produce H2O2 under light irradiation, while enzymes were exactly placed in the inner interfacial layer to catalyze the subsequent biocatalytic oxidation reactions using in situ formed H2O2 as an oxidant. In the alkene epoxidation and thioether oxidation, our interfacial photobiocatalytic cascades showed a 2.0-5.8-fold higher overall reaction efficiency than the photobiocatalytic cascades in the bulk water phase. It was demonstrated that spatial localization of the photocatalyst and the enzyme at Pickering oil droplet interfaces not only provided their respective preferable reaction environments and intimate proximity for rapid H2O2 transport but also protected the enzyme from oxidative inactivation caused by the photogenerated species. These remarkable interfacial effects contributed to the significantly enhanced photobiocatalytic cascading efficiency. Our work presents an innovative photobiocatalytic reaction system with manifold benefits, providing a cutting-edge platform for solar-driven chemical transformations via photobiocatalysis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141316073","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}

引用次数: 0

Variable Peripheral Ligand Donation Tunes Electronic Structure and NIR II Emission in Tetrathiafulvalene Tetrathiolate Diradicaloids. 可变的外围配体捐献调节了四噻吩富戊二烯四硫醇二环化合物的电子结构和近红外 II 发射。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-06-26 Epub Date: 2024-06-14 DOI: 10.1021/jacs.4c04032

Lauren E McNamara, Jan-Niklas Boyn, Sophie W Anferov, Alexander S Filatov, Miles W Maloney, David A Mazziotti, Richard D Schaller, John S Anderson

{"title":"Variable Peripheral Ligand Donation Tunes Electronic Structure and NIR II Emission in Tetrathiafulvalene Tetrathiolate Diradicaloids.","authors":"Lauren E McNamara, Jan-Niklas Boyn, Sophie W Anferov, Alexander S Filatov, Miles W Maloney, David A Mazziotti, Richard D Schaller, John S Anderson","doi":"10.1021/jacs.4c04032","DOIUrl":"10.1021/jacs.4c04032","url":null,"abstract":"Near-infrared (NIR) lumiphores are promising candidates for numerous imaging, communication, and sensing applications, but they typically require large, conjugated scaffolds to achieve emission in this low-energy region. Due to the extended conjugation and synthetic complexity required, it is extremely difficult to tune the photophysical properties of these systems for desired applications. Here, we report facile tuning of deep NIR-emitting diradicaloid complexes through simple modification of peripheral ligands. These new lumiphores are rare examples of air-, acid-, and water-stable emissive diradicaloids. We apply a simple Hammett parameter-based strategy to tune the electron donation of the capping ligand across a series of commercially available triarylphosphines. This minor peripheral modification significantly alters the electronic structure, and consequently, the electrochemical, photophysical, and magnetic properties of the tetrathiafulvalene tetrathiolate (TTFtt)-based lumiphores. The resultant ∼100 nm absorption and emission range spans common laser lines and the desirable telecom region (ca. 1260-1550 nm). Furthermore, these lumiphores are sensitive to local dielectrics, distinguishing them as promising candidates for ratiometric imaging and/or barcoding in the deep NIR region.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141316084","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}

引用次数: 0

In Situ Forming, Enzyme-Responsive Peptoid-Peptide Hydrogels: An Advanced Long-Acting Injectable Drug Delivery System. 原位形成、酶反应性肽类水凝胶：先进的长效注射给药系统。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-06-26 DOI: 10.1021/jacs.4c03751

Sophie M Coulter, Sreekanth Pentlavalli, Yuming An, Lalitkumar K Vora, Emily R Cross, Jessica V Moore, Han Sun, Ralf Schweins, Helen O McCarthy, Garry Laverty

{"title":"In Situ Forming, Enzyme-Responsive Peptoid-Peptide Hydrogels: An Advanced Long-Acting Injectable Drug Delivery System.","authors":"Sophie M Coulter, Sreekanth Pentlavalli, Yuming An, Lalitkumar K Vora, Emily R Cross, Jessica V Moore, Han Sun, Ralf Schweins, Helen O McCarthy, Garry Laverty","doi":"10.1021/jacs.4c03751","DOIUrl":"https://doi.org/10.1021/jacs.4c03751","url":null,"abstract":"Long-acting drug delivery systems are promising platforms to improve patient adherence to medication by delivering drugs over sustained periods and removing the need for patients to comply with oral regimens. This research paper provides a proof-of-concept for the development of a new optimized in situ forming injectable depot based on a tetrabenzylamine-tetraglycine-d-lysine-O-phospho-d-tyrosine peptoid-D-peptide formulation ((NPhe)4GGGGk(AZT)y(p)-OH). The chemical versatility of the peptoid-peptide motif allows low-molecular-weight drugs to be precisely and covalently conjugated. After subcutaneous injection, a hydrogel depot forms from the solubilized peptoid-peptide-drug formulation in response to phosphatase enzymes present within the skin space. This system is able to deliver clinically relevant concentrations of a model drug, the antiretroviral zidovudine (AZT), for 35 days in Sprague-Dawley rats. Oscillatory rheology demonstrated that hydrogel formation began within ∼30 s, an important characteristic of in situ systems for reducing initial drug bursts. Gel formation continued for up to ∼90 min. Small-angle neutron scattering data reveal narrow-radius fibers (∼0.78-1.8 nm) that closely fit formation via a flexible cylinder elliptical model. The inclusion of non-native peptoid monomers and D-variant amino acids confers protease resistance, enabling enhanced biostability to be demonstrated in vitro. Drug release proceeds via hydrolysis of an ester linkage under physiological conditions, releasing the drug in an unmodified form and further reducing the initial drug burst. Subcutaneous administration of (NPhe)4GGGGk(AZT)y(p)-OH to Sprague-Dawley rats resulted in zidovudine blood plasma concentrations within the 90% maximal inhibitory concentration (IC90) range (30-130 ng mL-1) for 35 days.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141449071","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}

引用次数: 0