Florian Deißenbeck, Sudarsan Surendralal, Mira Todorova, Stefan Wippermann* and Jörg Neugebauer,
{"title":"Revealing the Reaction Pathway of Anodic Hydrogen Evolution at Magnesium Surfaces in Aqueous Electrolytes","authors":"Florian Deißenbeck, Sudarsan Surendralal, Mira Todorova, Stefan Wippermann* and Jörg Neugebauer, ","doi":"10.1021/jacs.4c1008610.1021/jacs.4c10086","DOIUrl":"https://doi.org/10.1021/jacs.4c10086https://doi.org/10.1021/jacs.4c10086","url":null,"abstract":"<p >Aqueous metal corrosion is a major economic concern in modern society. A phenomenon that has puzzled generations of scientists in this field is the so-called anomalous hydrogen evolution: the violent dissolution of magnesium under electron-deficient (anodic) conditions, accompanied by strong hydrogen evolution and a key mechanism hampering Mg technology. Experimental studies have indicated the presence of univalent Mg<sup>+</sup> in solution, but these findings have been largely ignored because they defy our common chemical understanding and evaded direct experimental observation. Using recent advances in the <i>ab initio</i> description of solid–liquid electrochemical interfaces under controlled potential conditions, we describe the full reaction path of Mg atom dissolution from a kinked Mg surface under anodic conditions. Our study reveals the formation of a solvated [Mg<sup>2+</sup>(OH)<sup>−</sup>]<sup>+</sup> ion complex, challenging the conventional assumption of Mg<sup>2+</sup> ion formation. This insight provides an intuitive explanation for the postulated presence of (Coulombically) univalent Mg<sup>+</sup> ions, and the absence of protective oxide/hydroxide layers normally formed under anodic/oxidizing conditions. The discovery of this unexpected and unconventional reaction mechanism is crucial for identifying new strategies for corrosion prevention and can be transferred to other metals.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30314–30319 30314–30319"},"PeriodicalIF":14.4,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacs.4c10086","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585590","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}
Hou-Ming Xu, Chao Gu, Gang Wang, Pengfei Nan, Jian-Ding Zhang, Lei Shi, Shi-Kui Han*, Binghui Ge, Yang-Gang Wang, Jun Li and Shu-Hong Yu*,
{"title":"Kirkendall Effect-Driven Reversible Chemical Transformation for Reconfigurable Nanocrystals","authors":"Hou-Ming Xu, Chao Gu, Gang Wang, Pengfei Nan, Jian-Ding Zhang, Lei Shi, Shi-Kui Han*, Binghui Ge, Yang-Gang Wang, Jun Li and Shu-Hong Yu*, ","doi":"10.1021/jacs.4c1025210.1021/jacs.4c10252","DOIUrl":"https://doi.org/10.1021/jacs.4c10252https://doi.org/10.1021/jacs.4c10252","url":null,"abstract":"<p >The potential universality of chemical transformation principles makes it a powerful tool for nanocrystal (NC) synthesis. An example is the nanoscale Kirkendall effect, which serves as a guideline for the construction of hollow structures with different properties compared to their solid counterparts. However, even this general process is still limited in material scope, structural complexity, and, in particular, transformations beyond the conventional solid-to-hollow process. We demonstrate in this work an extension of the Kirkendall effect that drives reversible structural and phase transformations between metastable metal chalcogenides (MCs) and metal phosphides (MPs). Starting from Ni<sub>3</sub>S<sub>4</sub>/Cu<sub>1.94</sub>S NCs as the initial frameworks, ligand-regulated sequential extractions and diffusion of host/guest (S<sup>2–</sup>/P<sup>3–</sup>) anions between Ni<sub>3</sub>S<sub>4</sub>/Cu<sub>1.94</sub>S and Ni<sub>2</sub>P/Cu<sub>3</sub>P phases enable solid-to-hollow-to-solid structural motif evolution while retaining the overall morphology of the NC. An in-depth mechanistic study reveals that the transformation between metastable MCs and MPs occurs through a combination of ligand-dependent kinetic control and anion mixing-induced thermodynamic control. This strategy provides a robust platform for creating a library of reconfigurable NCs with tunable compositions, structures, and interfaces.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30372–30379 30372–30379"},"PeriodicalIF":14.4,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585979","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}
Sha Tan, Oleg Borodin, Nan Wang, Dean Yen, Conan Weiland and Enyuan Hu*,
{"title":"Synergistic Anion and Solvent-Derived Interphases Enable Lithium-Ion Batteries under Extreme Conditions","authors":"Sha Tan, Oleg Borodin, Nan Wang, Dean Yen, Conan Weiland and Enyuan Hu*, ","doi":"10.1021/jacs.4c0780610.1021/jacs.4c07806","DOIUrl":"https://doi.org/10.1021/jacs.4c07806https://doi.org/10.1021/jacs.4c07806","url":null,"abstract":"<p >Lithium-ion batteries (LIBs) face increasingly stringent demands as their application expands into new areas, including extreme temperatures and fast charging. To meet these demands, the electrolyte should enable fast lithium-ion transport and form stable interphases on electrodes simultaneously. In practice, however, improving one aspect often compromises another. For instance, the trend toward electrolytes forming anion-derived interphases typically reduces transport efficiency due to weak-solvating solvents. We propose that instead of relying on anions to form the interphase, leveraging both solvents and anions to form interphases can potentially lead to a balancing point between robust interphase formation and effective ion transport. Guided by this design principle, 2,2-difluoroethyl ethyl carbonate (DFDEC) was identified as the promising solvent. With the new electrolyte using DFDEC as the major solvent and lithium bis(fluorosulfonyl) imide (LiFSI) as the salt, graphite||LiNi<sub>0.8</sub>Mn<sub>0.1</sub>Co<sub>0.1</sub>O<sub>2</sub> (NMC811) full cells are capable of fast charging and demonstrate long-term cycling stability with a cutoff voltage of 4.5 V. Notably, the battery shows a capacity retention of 84.3% after 500 cycles with an average Coulombic efficiency (CE) as high as 99.93%. This new electrolyte also enables stable battery cycling across a wide temperature range (−20 to 60 °C), with excellent capacity retention.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30104–30116 30104–30116"},"PeriodicalIF":14.4,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585556","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":"A Syndiotactic Polymer via Spontaneous Exoselective Single-Crystal-To-Single-Crystal Topochemical Diels–Alder Cycloaddition Reaction","authors":"Sourav Pathak, and , Kana M. Sureshan*, ","doi":"10.1021/jacs.4c1142610.1021/jacs.4c11426","DOIUrl":"https://doi.org/10.1021/jacs.4c11426https://doi.org/10.1021/jacs.4c11426","url":null,"abstract":"<p >We designed and synthesized an amide-based monomer decorated with furan as the diene unit and maleimide as the dienophile unit at its termini. Single-crystal X-ray diffraction (SCXRD) analysis of its crystal revealed a head-to-tail arrangement of molecules with furan and maleimide groups of neighboring molecules proximally placed in an arrangement suitable for their topochemical Diels–Alder cycloaddition (TDAC) to form a linear polymer. The monomer underwent a spontaneous single-crystal-to-single-crystal (SCSC) polymerization at room temperature, yielding a linear polymer with oxa-bicyclic linkage. SCXRD analysis revealed that the cycloaddition occurred in an exoselective manner, and the absolute stereochemistry of the oxa-bicyclic linkage alternated in successive repeat units, leading to a syndiotactic linear polymer. The polymerization can be accelerated by heating the powder at 120 °C; the topochemical nature of the high-temperature reaction was established by time dependent differential scanning calorimetry (DSC), time-dependent powder X-ray diffraction (PXRD), and UV–visible spectroscopic analysis; the polymer was characterized using solid-state NMR spectroscopy and MALDI-TOF mass spectrometry.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30495–30501 30495–30501"},"PeriodicalIF":14.4,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585563","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}
Jiangbo Wu, Zhaoyi Gu, Justin A. Modica, Sijia Chen, Milan Mrksich* and Gregory A. Voth*,
{"title":"Megamolecule Self-Assembly Networks: A Combined Computational and Experimental Design Strategy","authors":"Jiangbo Wu, Zhaoyi Gu, Justin A. Modica, Sijia Chen, Milan Mrksich* and Gregory A. Voth*, ","doi":"10.1021/jacs.4c1189210.1021/jacs.4c11892","DOIUrl":"https://doi.org/10.1021/jacs.4c11892https://doi.org/10.1021/jacs.4c11892","url":null,"abstract":"<p >This work describes the use of computational strategies to design megamolecule building blocks for the self-assembly of lattice networks. The megamolecules are prepared by attaching four Cutinase-SnapTag fusion proteins (CS fusions) to a four-armed linker, followed by functionalizing each fusion with a terpyridine linker. This functionality is designed to participate in a metal-mediated self-assembly process to give networks. This article describes a simulation-guided strategy for the design of megamolecules to optimize the peptide linker in the fusion protein to give conformations that are best suited for self-assembly and therefore streamlines the typically time-consuming and labor-intensive experimental process. We designed 11 candidate megamolecules and identified the most promising linker, (EAAAK)<sub>2</sub>, along with the optimal experimental conditions through a combination of all-atom molecular dynamics, enhanced sampling, and larger-scale coarse-grained molecular dynamics simulations. Our simulation findings were validated and found to be consistent with the experimental results. Significantly, this study offers valuable insight into the self-assembly of megamolecule networks and provides a novel and general strategy for large biomolecular material designs by using systematic bottom-up coarse-grained simulations.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30553–30564 30553–30564"},"PeriodicalIF":14.4,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585550","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}
Anustoop Das, Koyendrila Debnath, Ivy Maria, Subarna Das, Prabir Dutta, Diptikanta Swain, Umesh V. Waghmare and Kanishka Biswas*,
{"title":"Influence of Subvalent Twin-Rattler for High n-Type Thermoelectric Performance in Bi13S18Br2 Chalcohalide","authors":"Anustoop Das, Koyendrila Debnath, Ivy Maria, Subarna Das, Prabir Dutta, Diptikanta Swain, Umesh V. Waghmare and Kanishka Biswas*, ","doi":"10.1021/jacs.4c1173810.1021/jacs.4c11738","DOIUrl":"https://doi.org/10.1021/jacs.4c11738https://doi.org/10.1021/jacs.4c11738","url":null,"abstract":"<p >Metal chalcohalides, owing to their higher stability over halides and greater tunability of electronic features over chalcogenides, open new avenues for investigating properties of materials. Complex metal chalcohalides can be a good choice for thermoelectric studies for their halide-like low thermal conductivity and chalcogenide-like high electrical conductivity. Here, we have investigated the thermoelectric properties of <i>n</i>-type Bi<sub>13</sub>S<sub>18</sub>Br<sub>2</sub> and utilized the concept of Fajans’ polarization to describe the formation of a dimer <i></i><math><msubsup><mrow><mi>Bi</mi></mrow><mrow><mn>2</mn></mrow><mrow><mrow><mn>4</mn></mrow><mrow><mo>+</mo></mrow></mrow></msubsup></math> and explained how it can help achieve high thermoelectric figure of merit (zT) of ∼1.0 at 748 K. This zT value is so far the highest-reported value for pristine metal chalcohalides. The existence of <i></i><math><msubsup><mrow><mi>Bi</mi></mrow><mrow><mn>2</mn></mrow><mrow><mrow><mn>4</mn></mrow><mrow><mo>+</mo></mrow></mrow></msubsup></math> subunit in Bi<sub>13</sub>S<sub>18</sub>Br<sub>2</sub> is experimentally verified by synchrotron X-ray pair distribution function (X-PDF) analysis. The complex structure of Bi<sub>13</sub>S<sub>18</sub>Br<sub>2</sub> having a large unit cell exhibits simultaneous dimer-cation rattler (i.e., “twin-rattler”), which decreases the lattice thermal conductivity drastically. We observed evidence of such low-energy rattling vibrations from DFT-calculated eigen mode visualizations of the phonon dispersion. The subvalent nature of <i></i><math><msubsup><mrow><mi>Bi</mi></mrow><mrow><mn>2</mn></mrow><mrow><mrow><mn>4</mn></mrow><mrow><mo>+</mo></mrow></mrow></msubsup></math>accommodates an extra electron in <i>Bi</i>(<i>6p</i><sub><i>z</i></sub>) orbital, which helps form a weakly dispersed donor band just below the Fermi energy (<i>E</i><sub>F</sub>), leading to a significant reduction in band gap (0.77 eV), which is favorable for high thermoelectric performance. Consequently, we obtained a semiconducting nature of <i>n</i>-type Bi<sub>13</sub>S<sub>18</sub>Br<sub>2</sub> with moderate electrical conductivity, as well as a high Seebeck coefficient. Our investigation presents the importance of fundamental chemistry in thermoelectrics and demonstrates the influence of subvalent twin-rattler in triggering high thermoelectric performance in metal chalcohalides.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30518–30528 30518–30528"},"PeriodicalIF":14.4,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585596","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}
Tianyi Zhang, William G. Whitehurst, Matthew V. Pecoraro, Junho Kim, Stefan G. Koenig and Paul J. Chirik*,
{"title":"Redox-Neutral, Iron-Mediated Directed C–H Activation: General Principles and Mechanistic Insights","authors":"Tianyi Zhang, William G. Whitehurst, Matthew V. Pecoraro, Junho Kim, Stefan G. Koenig and Paul J. Chirik*, ","doi":"10.1021/jacs.4c1232910.1021/jacs.4c12329","DOIUrl":"https://doi.org/10.1021/jacs.4c12329https://doi.org/10.1021/jacs.4c12329","url":null,"abstract":"<p >Experimental and computational studies have been conducted and established the general principles for enabling redox-neutral C–H activation by iron(II) complexes. The idealized octahedral iron(II) dimethyl complex, (depe)<sub>2</sub>Fe(CH<sub>3</sub>)<sub>2</sub> (depe = 1,2-bis(diethylphosphino)ethane) promoted the directed, regioselective <i>ortho</i> C(sp<sup>2</sup>)–H methylation of pivalophenone. The rate of the iron(II)-mediated C(sp<sup>2</sup>)–H functionalization depended on the lability of L-type phosphine ligands, the spin state of the iron center, and the size of the X-type ligands (halide, hydrocarbyl) in P<sub>4</sub>Fe<sup>II</sup>X<sub>2</sub> complexes. The C(sp<sup>2</sup>)–H alkylation reaction proved general among multiple substrates with directing groups including carbonyl, imines and pyridines. Among these, ketones and aldehydes were identified as optimal and were compatible with various steric environments and presence of acidic α-hydrogens. With stronger nitrogen donors, higher barriers for product-forming reductive elimination were observed. The effect of orbital hybridization on the chemoselectivity of C–H activation through a σ-CAM pathway by <i>d</i><sup><i>n</i>>0</sup> transition metals was also established by studying the stoichiometric reactivity of the differentially substituted (depe)<sub>2</sub>Fe(Me)R complexes (R = alkyl, aryl), where the Fe–R bond with greater <i>s</i>-character preferentially promoted selective C–H activation. Deuterium labeling and kinetic studies, coupled with computational analysis, supported a pathway involving phosphine dissociation and rate-determining C–H bond activation, leading to the observed products.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30637–30652 30637–30652"},"PeriodicalIF":14.4,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585783","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":"Chemoselective Pd-Based Dyotropic Rearrangement: Fluorocyclization and Regioselective Wacker Reaction of Homoallylic Amides","authors":"Chen-Xu Liu, Qian Wang and Jieping Zhu*, ","doi":"10.1021/jacs.4c1335910.1021/jacs.4c13359","DOIUrl":"https://doi.org/10.1021/jacs.4c13359https://doi.org/10.1021/jacs.4c13359","url":null,"abstract":"<p >Fluorocyclization of alkenes tethered with a pronucleophile is an efficient transformation that converts easily accessible starting materials to fluorinated heterocycles in a single step. We report herein an unprecedented Pd(II)-catalyzed oxidative domino process that transforms homoallylic amides to 5,6-dihydro-4<i>H</i>-1,3-oxazines through a domino oxypalladation/Pd<sup>II</sup>–oxidation/dyotropic rearrangement/reductive elimination sequence. Three chemical bonds are created under these operationally simple conditions. Taking advantage of the facile hydrolysis of the α-fluoro tertiary alkyl ether under acidic conditions, a one-pot conversion of homoallylic amides to homologated ketones is subsequently developed, which represents a rare example of regioselective Wacker oxidation reaction of 1,1-disubstituted alkenes.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30014–30019 30014–30019"},"PeriodicalIF":14.4,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585559","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":"All Roads Lead to Rome: Isomers with Divergent Cathode Modification Mechanisms toward Ohmic Contact","authors":"Huanxiang Jiang*, Qi Liang, Haishuo Guo, Andong Zhang*, Xuewen Wang, Zheng Tang and Zhishan Bo*, ","doi":"10.1021/jacs.4c0956710.1021/jacs.4c09567","DOIUrl":"https://doi.org/10.1021/jacs.4c09567https://doi.org/10.1021/jacs.4c09567","url":null,"abstract":"<p >Cathode interfacial layers (CILs) hold utmost importance for achieving ohmic contact at the organic semiconductor–cathode interface of organic photovoltaic devices. Delving deep into diverse design principles and working mechanisms is of great significance for designing novel CILs with high performance. Herein, two novel nonamine-based CILs are designed: one featuring a cyclopentadiene unit, designated as CIL-cp; while the other, lacking cyclopentadiene, is referred to as CIL-ph, which is an isomer of CIL-cp. The subtle changes in chemical structures result in distinct modification mechanisms toward ohmic contact. On one hand, the robust electron-withdrawing characteristic of cyclopentadiene endows CIL-cp with lower energy levels, resulting in an interfacial dipole at the active layer–CIL-cp interface due to electron transfer from D18 to CIL-cp. On the other hand, CIL-ph exhibits a strong interfacial dipole at the CIL–Ag interface, which significantly reduces the work function (W<sub>F</sub>) of the silver electrode. Both CIL-cp and CIL-ph demonstrate excellent interfacial modification capability, whereas CIL-cp possesses a stronger electron extraction ability, thus leading to a high power conversion efficiency of 19.31% in the D18:L8-BO system. Our results reveal the distinctive operational mechanism of cyclopentadiene-based CILs, thus offering innovative design ideas for CIL materials.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30262–30271 30262–30271"},"PeriodicalIF":14.4,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585562","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}
Biswajit Roy, Meg Shieh, Tsuyoshi Takata, Minkyung Jung, Eshani Das, Shi Xu, Takaaki Akaike and Ming Xian*,
{"title":"Phototriggered Hydrogen Persulfide Donors via Hydrosulfide Radical Formation Enhancing the Reactive Sulfur Metabolome in Cells","authors":"Biswajit Roy, Meg Shieh, Tsuyoshi Takata, Minkyung Jung, Eshani Das, Shi Xu, Takaaki Akaike and Ming Xian*, ","doi":"10.1021/jacs.4c1154010.1021/jacs.4c11540","DOIUrl":"https://doi.org/10.1021/jacs.4c11540https://doi.org/10.1021/jacs.4c11540","url":null,"abstract":"<p >Hydrogen persulfide (H<sub>2</sub>S<sub>2</sub>) is an important sulfur-containing signaling molecule that plays a crucial role in the homeostasis of various organ systems, such as the renal, cardiovascular, liver, and gastrointestinal systems. However, research on H<sub>2</sub>S<sub>2</sub> in biological settings is still challenging due to its instability and high reactivity. Compounds that can controllably release H<sub>2</sub>S<sub>2</sub> (also known as donors) are thus crucial research tools. Currently, available H<sub>2</sub>S<sub>2</sub> donors are still very limited, with most of them relying on modified disulfide templates. These templates possess an unavoidable limitation of being susceptible to cellular disulfide exchange which can compromise their efficacy. In this work, we explored nondisulfide-based and nonoxidation-dependent templates for the design of H<sub>2</sub>S<sub>2</sub> donors. We found that tertiary naphthacyl thiols could undergo phototriggered C–S homolytic cleavage to form H<sub>2</sub>S<sub>2</sub> via hydrosulfide (HS) radicals. In addition, the release of H<sub>2</sub>S<sub>2</sub> was associated with the formation of a product with strong blue fluorescence, which allowed for real-time monitoring of the release process. This reaction was demonstrated to proceed effectively in both buffers and cells, with the ability to enhance intracellular production of persulfides, including GSSH, CysSSH, H<sub>2</sub>S<sub>2</sub>, H<sub>2</sub>S<sub>3</sub>, etc. It provides a unique photocontrolled H<sub>2</sub>S<sub>2</sub> donor system with distinct advantages compared to known H<sub>2</sub>S<sub>2</sub> donors due to its good stability and spatiotemporal control ability.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30502–30509 30502–30509"},"PeriodicalIF":14.4,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585553","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}