ACS Earth and Space Chemistry最新文献

{"title":"Defect-Engineered Coordination Compound Nanoparticles Based on Prussian Blue Analogues for Surface-Enhanced Raman Spectroscopy","authors":"Xingxing Yu,&nbsp;Xuke Tang,&nbsp;Jun-Yu Dong,&nbsp;Yunjie Deng,&nbsp;Mitsuhiro Saito,&nbsp;Zhanglei Gao,&nbsp;Pablo Martinez Pancorbo,&nbsp;Machiko Marumi,&nbsp;Walker Peterson,&nbsp;Huanhuan Zhang,&nbsp;Naoki Kishimoto,&nbsp;Abdullah N. Alodhayb,&nbsp;Prabhat K. Dwivedi,&nbsp;Yuichi Ikuhara,&nbsp;Yasutaka Kitahama,&nbsp;Ting-Hui Xiao* and Keisuke Goda*,&nbsp;","doi":"10.1021/acsnano.4c0697210.1021/acsnano.4c06972","DOIUrl":"https://doi.org/10.1021/acsnano.4c06972https://doi.org/10.1021/acsnano.4c06972","url":null,"abstract":"<p >Surface-enhanced Raman spectroscopy (SERS) is a powerful tool for label-free chemical analysis. The emergence of nonmetallic materials as SERS substrates, offering chemical signal enhancements, presents an exciting direction for achieving reproducible and biocompatible SERS, a challenge with traditional metallic substrates. Despite the potential, the realm of nonmetallic SERS substrates, particularly nanoparticles, remains largely untapped. Here, we present defect-engineered coordination compounds (DECCs) based on Prussian blue analogues (PBAs) as a class of nonmetallic nanoparticle-based SERS substrates. We demonstrate the utility and flexibility of the DECC template by incorporating various metal (M) elements into PBAs to synthesize nanoparticles that deliver substantial chemical mechanism (CM)-based enhancements to the Raman signal with a ∼ 10⁸-fold increase. The introduction of the M-PBA-based DECC nanoparticles as a class of SERS substrates represents a pioneering stride, enabling the straightforward and systematic exploration of a library of compounds for SERS-based analysis of a wide range of target molecules, especially biomolecules.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"30987–31001 30987–31001"},"PeriodicalIF":15.8,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609548","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-Entropy Multiple-Anion Aqueous Electrolytes for Long-Life Zn-Metal Anodes","authors":"Shisheng Hou,&nbsp;Jie Luo*,&nbsp;Wenbin Gong,&nbsp;Yucheng Xie,&nbsp;Xuhui Zhou,&nbsp;Fan Yue,&nbsp;Jiaxin Shen,&nbsp;Chen Li,&nbsp;Lei Wei,&nbsp;Feng Xu* and Qichong Zhang*,&nbsp;","doi":"10.1021/acsnano.4c1266010.1021/acsnano.4c12660","DOIUrl":"https://doi.org/10.1021/acsnano.4c12660https://doi.org/10.1021/acsnano.4c12660","url":null,"abstract":"<p >Aqueous zinc-ion batteries (AZIBs) hold great promise for large-scale energy storage applications, however, their practical use is significantly hindered by issues such as zinc dendrite growth and hydrogen evolution. To address these challenges, we propose a high-entropy (HE) electrolyte design strategy that incorporates multiple zinc salts, aimed at enhancing ion kinetics and improving the electrochemical stability of the electrolyte. The interactions between multiple anions and Zn²⁺ increase the complexity of the solvation structure, resulting in smaller ion clusters while maintaining weakly anion-rich solvation structures. This leads to improved ion mobility and the formation of robust interphase layers on the electrode–electrolyte interface. Moreover, the HE electrolyte effectively suppresses hydrogen evolution and corrosion side reactions while facilitating uniform and reversible Zn plating/stripping processes. Impressively, the optimized electrolyte enables dendrite-free Zn plating/stripping for over 3000 h in symmetric cells and achieves a high Coulombic efficiency of 99.5% at 10 mA cm^–2 in asymmetric cells. Inspiringly, full cells paired with Ca-VO₂ cathodes demonstrate excellent performance, retaining 81.5% of the initial capacity over 1800 cycles at 5 A g^–1. These significant findings highlight the potential of this electrolyte design strategy to improve the performance and lifespan of Zn-metal anodes in AZIBs.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31524–31536 31524–31536"},"PeriodicalIF":15.8,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Single-Molecule-Based, Label-Free Monitoring of Molecular Glue Efficacies for Promoting Protein–Protein Interactions Using YaxAB Nanopores","authors":"Minju Ryu,&nbsp;Sohee Oh,&nbsp;Ki-Baek Jeong,&nbsp;Sungbo Hwang,&nbsp;Jin-Sik Kim,&nbsp;Minji Chung and Seung-Wook Chi*,&nbsp;","doi":"10.1021/acsnano.4c1143610.1021/acsnano.4c11436","DOIUrl":"https://doi.org/10.1021/acsnano.4c11436https://doi.org/10.1021/acsnano.4c11436","url":null,"abstract":"<p >Modulating protein–protein interactions (PPIs) is an attractive strategy in drug discovery. Molecular glues, bifunctional small-molecule drugs that promote PPIs, offer an approach to targeting traditionally undruggable targets. However, the efficient discovery of molecular glues has been hampered by the current limitations of conventional ensemble-averaging-based methods. In this study, we present a YaxAB nanopore for probing the efficacy of molecular glues in inducing PPIs. Using YaxAB nanopores, we demonstrate single-molecule-based, label-free monitoring of protein complex formation between mammalian target of rapamycin (mTOR) and FK506-binding proteins (FKBPs) triggered by the molecular glue, rapamycin. Owing to its wide entrance and adjustable pore size, in combination with potent electro-osmotic flow (EOF), a single funnel-shaped YaxAB nanopore enables the simultaneous detection and single-molecule-level quantification of multiprotein states, including single proteins, binary complexes, and ternary complexes induced by rapamycin. Notably, YaxAB nanopores could sensitively discriminate between the binary complexes or ternary complexes induced by rapamycin and its analogues, despite the subtle size differences of ∼122 or ∼116 Da, respectively. Taken together, our results provide proof-of-concept for single-molecule-based, label-free, and ultrasensitive screening and structure–activity relationship (SAR) analysis of molecular glues, which will contribute to low-cost, highly efficient discovery, and rational design of bifunctional modality of drugs, such as molecular glues.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31451–31465 31451–31465"},"PeriodicalIF":15.8,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnano.4c11436","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609281","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Probing Nanoscale Charge Transport Mechanisms in Quasi-2D Halide Perovskites for Photovoltaic Applications","authors":"Hongjae Shim,&nbsp;Abhinav S. Sharma,&nbsp;Rishabh Mishra,&nbsp;Jonghoon Han,&nbsp;Jihoo Lim,&nbsp;Dawei Zhang,&nbsp;Zhi Li Teh,&nbsp;Jongsung Park,&nbsp;Jan Seidel,&nbsp;Michael P. Nielsen,&nbsp;Martin A. Green,&nbsp;Shujuan Huang*,&nbsp;Jae Sung Yun* and Jincheol Kim*,&nbsp;","doi":"10.1021/acsnano.4c0700410.1021/acsnano.4c07004","DOIUrl":"https://doi.org/10.1021/acsnano.4c07004https://doi.org/10.1021/acsnano.4c07004","url":null,"abstract":"<p >Quasi-2D layered halide perovskites (quasi-2DLPs) have emerged as promising materials for photovoltaic (PV) applications owing to their advantageous bandgap for absorbing visible light and the improved stability they enable. Their charge transport mechanism is heavily influenced by the grain orientation of their crystals as well as their nanostructures, such as grain boundaries (GBs) and edge states─the formation of which is inevitable in polycrystalline quasi-2DLP thin films. Despite their importance, the impact of these features on charge transport remains unexplored. In this study, we conduct a detailed investigation on polycrystalline quasi-2DLP thin films and devices, carefully analyzing how grain orientation and nanostructures influence charge transport. Employing nondestructive atomic force microscopy (AFM) topography, along with transient absorption spectroscopy (TAS) and grazing-incidence wide-angle X-ray scattering (GIWAXS), we obtained significant insights regarding the phase purity, crystallographic information, and morphologies of these films. Moreover, our systematic investigation using AFM-based techniques, including Kelvin probe force microscopy (KPFM) and conductive AFM (c-AFM), elucidates the roles played by GBs and edge states in shaping charge transport behavior. In particular, the local band structure along the GBs and edge states within both vertical and parallel grains was found to selectively repel electrons and holes, thus facilitating charge carrier separation. These findings provide perspectives for the development of high-performance quasi-2DLP PV devices and highlight potential approaches that can leverage the intrinsic properties of quasi-2DLPs to advance the performance of perovskite solar cells.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31002–31013 31002–31013"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ultralong Compositional Gradient Perovskite Nanowires Fabricated by Source-Limiting Anion Exchange","authors":"Jing Li,&nbsp;Jianliang Li,&nbsp;Meiqi An,&nbsp;Shuai Yang,&nbsp;Yanan Bao,&nbsp;Hengshan Wang,&nbsp;Huayi Tang,&nbsp;Haotian Wang,&nbsp;Yurui Fang,&nbsp;Jijun Qiu,&nbsp;Jiming Bian,&nbsp;Jiao Xu* and Yiming Yang*,&nbsp;","doi":"10.1021/acsnano.4c0667610.1021/acsnano.4c06676","DOIUrl":"https://doi.org/10.1021/acsnano.4c06676https://doi.org/10.1021/acsnano.4c06676","url":null,"abstract":"<p >Anion exchange in halide perovskites offers prospective approaches to band gap engineering for miniaturized and integrated optoelectronic devices. However, the band engineering at the nanoscale is uncontrollable due to the rapid and random exchange nature in the liquid or gas phase. Here, we report a source-limiting mechanism in solid-state anion exchange between low-dimensional perovskites, which readily gives access to ultralong compositional gradient nanowires (NWs) with lengths of up to 100 μm. The exchanged NWs remain single-crystalline with intact morphology, while the halogen content exhibits an apparent gradient distribution, leading to a tapered energy band profile along a NW. In the dynamic study of anion behavior, it is shown that the spatial stoichiometric composition can be precisely tuned following Fick’s law of diffusion. In addition, self-powered, spectrally resolved photodetectors incorporating multiple detection units within a single gradient NW are demonstrated. This work provides a feasible strategy for the realization of perovskite-based ultracompact optoelectronics, imaging sensors, and other miniaturized semiconductor devices.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"30978–30986 30978–30986"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tumor-Derived Extracellular Vesicles Enable Tumor Tropism Chemo-Genetherapy for Local Immune Activation in Triple-Negative Breast Cancer","authors":"Zaihui Peng,&nbsp;Tingting Zhao,&nbsp;Pingping Gao,&nbsp;Guozhi Zhang,&nbsp;Xiujuan Wu,&nbsp;Hao Tian,&nbsp;Man Qu,&nbsp;Xuanni Tan,&nbsp;Yi Zhang*,&nbsp;Xiang Zhao* and Xiaowei Qi*,&nbsp;","doi":"10.1021/acsnano.3c1296710.1021/acsnano.3c12967","DOIUrl":"https://doi.org/10.1021/acsnano.3c12967https://doi.org/10.1021/acsnano.3c12967","url":null,"abstract":"<p >Triple-negative breast cancer (TNBC) is highly heterogeneous, lacks accessible therapeutic targets, and features an immunosuppressive tumor microenvironment (TME). Anthracycline-based chemotherapy remains the primary treatment method for TNBC, while the current popular immune checkpoint inhibitors persistently encounter therapeutic resistance. Therefore, there is an urgent need to explore combined therapeutic strategies to remodel the TME and improve the treatment response. Considering the highly specific homing ability of tumor cell-derived vesicles and the key role of the signal transduction and activation of the transcription factor 3 (STAT3) pathway in TNBC, we propose a synergistic therapeutic strategy that integrates gene therapy, chemotherapy, and immunotherapy based on STAT3 short interfering RNA (siSTAT3) and doxorubicin (DOX)-functionalized tumor-derived extracellular vesicles (TEVs) (siSTAT3-DOX@TEV). The in vitro and in vivo results demonstrate that siSTAT3-DOX@TEV target tumor tissues precisely, downregulate STAT3 expression, and synergistically and efficiently induce immunogenic death, thereby reversing the immunosuppressive TME. Moreover, mass cytometry and immunohistochemistry reveal the local immune activation effect of siSTAT3-DOX@TEV, with a significant increase in M1 macrophages, CD4⁺ T cells, and CD8⁺ T cells in tumor tissues. These results provide strong hints for the development of TEV-based chemo-gene therapeutic agents for TNBC treatment at the clinical level.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"30943–30956 30943–30956"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnano.3c12967","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609268","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Directing Organometallic Ring–Chain Equilibrium by Electrostatic Interactions","authors":"Rujia Hou,&nbsp;Yuhong Gao,&nbsp;Yuan Guo,&nbsp;Chi Zhang* and Wei Xu*,&nbsp;","doi":"10.1021/acsnano.4c1204610.1021/acsnano.4c12046","DOIUrl":"https://doi.org/10.1021/acsnano.4c12046https://doi.org/10.1021/acsnano.4c12046","url":null,"abstract":"<p >Dynamic chemistry, which falls into the realm of both supramolecular and covalent chemistry, enables intriguing properties, such as structural diversity, self-healing, and adaptability. Due to robustness of covalent bonds compared to noncovalent ones, dynamic covalent chemistry has been exploited to synthesize complex molecular nanostructures at solid/liquid interfaces under ambient conditions, generally responsive to internal factors that directly regulate intermolecular covalent bonds. However, directing dynamics of covalent nanostructures, <i>e.g</i>., the typical ring–chain equilibria, on surface by extrinsic interactions remains elusive and challenging. Herein, we have controllably directed the ring–chain equilibrium of covalent organometallic structures by regulating intermolecular electrostatic interactions, thus achieving on-surface dynamic covalent chemistry under ultrahigh vacuum conditions. Our findings unravel the dynamic mechanism of covalent polymers governed by weak intermolecular interactions at the submolecular level, which not only bridges the gap between supramolecular and covalent chemistry but also offers great opportunities for the fabrication of adaptive polymeric nanostructures that respond to different conditions.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31478–31484 31478–31484"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609652","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recent Progress of Imaging Chemical Bonds by Scanning Probe Microscopy: A Review","authors":"Dingguan Wang*,&nbsp;Tobias Haposan,&nbsp;Jinwei Fan,&nbsp; Arramel* and Andrew T. S. Wee*,&nbsp;","doi":"10.1021/acsnano.4c1052210.1021/acsnano.4c10522","DOIUrl":"https://doi.org/10.1021/acsnano.4c10522https://doi.org/10.1021/acsnano.4c10522","url":null,"abstract":"<p >In the past decades, the invention of scanning probe microscopy (SPM) as the versatile surface-based characterization of organic molecules has triggered significant interest throughout multidisciplinary fields. In particular, the bond-resolved imaging acquired by SPM techniques has extended its fundamental function of not only unraveling the chemical structure but also allowing us to resolve the structure–property relationship. Here, we present a systematical review on the history of chemical bonds imaged by means of noncontact atomic force microscopy (nc-AFM) and bond-resolved scanning tunneling microscopy (BR-STM) techniques. We first summarize the advancement of real-space imaging of covalent bonds and the investigation of intermolecular noncovalent bonds. Beyond the bond imaging, we also highlight the applications of the bond-resolved SPM techniques such as on-surface synthesis, the determination of the reaction pathway, the identification of molecular configurations and unknown products, and the generation of artificial molecules created via tip manipulation. Lastly, we discuss the current status of SPM techniques and highlight several key technical challenges that must be solved in the coming years. In comparison to the existing reviews, this work invokes researchers from surface science, chemistry, condensed matter physics, and theoretical physics to uncover the bond-resolved SPM technique as an emerging tool in exploiting the molecule/surface system and their future applications.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"30919–30942 30919–30942"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dual-Mode Reactive Oxygen Species-Stimulated Carbon Monoxide Release for Synergistic Photodynamic and Gas Tumor Therapy","authors":"Yuewen Yu,&nbsp;Le Zhang,&nbsp;Hanyu Jia,&nbsp;Chao Ji,&nbsp;Yucheng Liu,&nbsp;Zexian Zhao,&nbsp;Chunhui Dai,&nbsp;Dan Ding*,&nbsp;Ben Zhong Tang and Guangxue Feng*,&nbsp;","doi":"10.1021/acsnano.4c1027710.1021/acsnano.4c10277","DOIUrl":"https://doi.org/10.1021/acsnano.4c10277https://doi.org/10.1021/acsnano.4c10277","url":null,"abstract":"<p >Controllable carbon monoxide (CO) release simulated by light-generated reactive oxygen species (ROS) represents a promising approach for cancer therapy but is hampered by low CO release rate and low ROS generation of conventional photosensitizers in hypoxia tumor microenvironments. In this study, we developed a highly efficient nanoplatform (TPyNO₂–FeCO NPs) through co-encapsulating organic AIE photosensitizers (PSs) and CO prodrug (Fe₃(CO)₁₂), which are capable of light-triggered robust ROS generation and CO release for synergistic photodynamic therapy (PDT) and CO gas therapy. The success of this nanoplatform leverages the design of a PS, TPyNO₂, with exceptional type I and type II ROS generation capabilities, achieved through the introduction of the α-photoinduced electron transfer (α-PET) process. With the incorporation of a 4-nitrobenzyl unit as a typical PET donor, the intramolecular α-PET process not only suppresses the radiative decay to redirect the excited-state energy to intersystem crossing for more triplet-state formation but also promotes electron separation and transfer processes for radical-type ROS generation. The resultant TPyNO₂ demonstrates superior singlet oxygen, superoxide anion, and hydroxyl radial generation capabilities in the aggregate state. Upon light irradiation, TPyNO₂–FeCO NPs release CO via the type I and type II dual-mode ROS-mediated processes in a controlled and targeted manner, overcoming the limitations of conventional CO release systems. TPyNO₂–FeCO NPs also demonstrate a self-accelerating ROS–CO–ROS loop as the released CO induces intracellular oxidative stress, depolarizes mitochondria membrane potentials, and inhibits ATP production, leading to further intracellular ROS generation. Both <i>in vitro</i> and <i>in vivo</i> experiments validated the excellent antitumor performance of the combined PDT and CO gas therapy. This study provides valuable insights into the development of advanced PSs and establishes TPyNO₂–FeCO NPs as promising nanoplatforms for safe and effective antitumor applications.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31286–31299 31286–31299"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609412","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Shedding Light on the Kinetics of the Carboxysulfitic Scenario","authors":"S. B. White*,&nbsp;P. B. Rimmer* and Z. Liu,&nbsp;","doi":"10.1021/acsearthspacechem.4c0008310.1021/acsearthspacechem.4c00083","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00083https://doi.org/10.1021/acsearthspacechem.4c00083","url":null,"abstract":"<p >One way in which we can attempt to relate chemical pathways to geochemical environments is by studying the kinetics of a given sequence of reactions and identifying the conditions under which this chemistry is the most productive. Many prebiotic reactions rely on a source of fixed carbon; therefore, chemical pathways that suggest prebiotically plausible ways of fixing carbon are of significant interest. One such pathway is the carboxysulfitic reaction network, which uses solvated electrons, produced as a result of electron photodetachment from sulfite, to reduce carbon. In this work, we explore carboxysulfitic chemistry at three different pH values: 6, 9, and 12. We utilize a new light source, that matches the broadband spectral shape of the young Sun, to irradiate a mixture of bicarbonate and sulfite. We determine the rate equation for the production of formate from these compounds and find the order to be 0.71 ± 0.12 with respect to bicarbonate and −0.60 ± 0.10 with respect to sulfite. Following this, we determine rate constants for the production of formate considering two different mechanisms. We find this chemistry to be feasible at all three of the pH values tested, with the magnitude of the rate constants being highly dependent on the assumed mechanism. We suggest that these results may have implications for Mars Sample Return owing to Jezero Crater having had lakes similar to those in which we propose carboxysulfitic chemistry to have been the most productive. Due to Mars’ relatively unaltered surface, we propose that Mars Sample Return missions could look for preserved tracers of this chemistry, shedding light on Mars’ past conditions and its potential for having hosted life.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 11","pages":"2133–2144 2133–2144"},"PeriodicalIF":2.9,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00083","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}