Chemical Science最新文献_第8页

Retro-forward synthesis design and experimental validation of potent structural analogs of known drugs

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-19 DOI: 10.1039/d5sc00070j

Ahmad Makkawi, Wiktor Beker, Agnieszka Wolos, Sabyasachi Manna, Rafal Roszak, Sara Szymkuc, Martyna Moskal, Aleksei Koshevarnikov, Karol Molga, Anna Zadlo, Bartosz Andrzej Grzybowski

{"title":"Retro-forward synthesis design and experimental validation of potent structural analogs of known drugs","authors":"Ahmad Makkawi, Wiktor Beker, Agnieszka Wolos, Sabyasachi Manna, Rafal Roszak, Sara Szymkuc, Martyna Moskal, Aleksei Koshevarnikov, Karol Molga, Anna Zadlo, Bartosz Andrzej Grzybowski","doi":"10.1039/d5sc00070j","DOIUrl":"https://doi.org/10.1039/d5sc00070j","url":null,"abstract":"Generation of structural analogs to “parent” molecule(s) of interest remains one of the important elements of drug development. Ideally, such analogs should be synthesizable by concise and robust synthetic routes. The current work illustrates how this process can be facilitated by a computational pipeline spanning (i) diversification of the parent via bioisosteric replacements, (ii) retrosynthesis of the thus generated “replicas” to identify substrates, (iii) forward syntheses originating from these substrates (and synthetically versatile “auxiliaries”) and guided “towards” the parent, and (iv) evaluation of the candidates for target binding and other medicinal-chemical properties. This pipeline proposes syntheses to thousands of readily makeable analogs in a matter of minutes, and is deployed here to validate by experiment seven structural analogs of Ketoprofen and six analogs of Donepezil. The concise, computer-designed syntheses are confirmed in 12 out of 13 cases, offering access to several potent inhibitors. While the synthesis-design component is robust, binding affinities are predicted less accurately although still to the order-of-magnitude, which may be valuable in discerning promising from inadequate binders.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654182","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

Understanding the factors governing the ammonia oxidation reaction by mononuclear ruthenium complex

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-19 DOI: 10.1039/d4sc02360a

Guo Chen, Xiao-Lv Ding, Piao He, Tao Cheng, Yang Chen, Jian Lin, Xi Zhang, Shan Zhao, Na Qiao, Xiao-Yi Yi

{"title":"Understanding the factors governing the ammonia oxidation reaction by mononuclear ruthenium complex","authors":"Guo Chen, Xiao-Lv Ding, Piao He, Tao Cheng, Yang Chen, Jian Lin, Xi Zhang, Shan Zhao, Na Qiao, Xiao-Yi Yi","doi":"10.1039/d4sc02360a","DOIUrl":"https://doi.org/10.1039/d4sc02360a","url":null,"abstract":"Precise regulation of the active site of molecular catalysts is appealing because it could catch a glimpse of the catalytic mechanism and possibly provide a new strategy for catalyst design. A ruthenium complex [Ru(dppMe, COMe)(bipy)(Cl)] (CSU-3) containing -Me and -COMe substituted dipyridylpyrrole as pincer ligand was designed and synthesized. Complex CSU-3 featured the Cl- ligand at axial position as active site for ammonia oxidation (AO), which is structurally analogous with AO catalyst [Ru(trpy)(dmabpy)(NH3)][PF6]2 (1) bearing terpyridine ligand, but is different from AO catalyst [Ru(dpp)(bipy)(NH3)] (CSU-2) containing unsubstituted dipyridylpyrrole as hemilabile ligand with active site at equatorial position. To insight into the role of active-site and ligand regulation in AO reaction, structure, electrochemical properties of CSU-3 and its catalytic performance and mechanism for AO reaction are comparably studied. Complex CSU-3 has good selective catalytic perforamnce for oxidation of ammonia to hydrazine with turnover frequency (TOF) of 258.8 h-1 and N2H4 formation selectivity of 84.7% at Eapp of 1.0 V . The DFT calculation reveal N2H4 as a dominant product is generated via an ammonia nucleophilic attack of Ruthenium(IV)-imide to form N2H4 followed by N2H4-by-NH3 substitution","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654181","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

High-affinity 1:2 recognition based on naphthyl-azocalix[4]arene and its application as a cleavable noncovalent connector in constructing responsive supramolecular polymeric materials

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-19 DOI: 10.1039/d5sc00075k

Shun-Yu Yao, An-Kang Ying, Wen-Chao Geng, Fang-Yuan Chen, Xin-Yue Hu, Kang Cai, Dong-Sheng Guo

引用次数: 0

Single-crystal chiral two-dimensional supramolecular organic frameworks for tunable circularly polarized luminescence.

IF 7.6 1区化学

Chemical Science Pub Date : 2025-03-19 DOI: 10.1039/d4sc08811e

Jialin Cui, Hui Wang, Hui Liu, Hailong Yu, Wei Wang, Yu Wang, Yingjie Zhao

{"title":"Single-crystal chiral two-dimensional supramolecular organic frameworks for tunable circularly polarized luminescence.","authors":"Jialin Cui, Hui Wang, Hui Liu, Hailong Yu, Wei Wang, Yu Wang, Yingjie Zhao","doi":"10.1039/d4sc08811e","DOIUrl":"https://doi.org/10.1039/d4sc08811e","url":null,"abstract":"Chiral supramolecular organic frameworks (SOFs) and hydrogen-bonded organic frameworks (HOFs) remain an unexplored field, with very few reported examples. Here, three chiral SOFs with perfect two-dimensional (2D) framework structures are constructed by self-assembly between the chiral macrocyclic host molecule and different guest molecules through host-guest and hydrogen-bonding interactions. Variations in the guest structures lead to different host-guest interactions. The formation of the 2D frameworks of the chiral host and the guest molecules realizes chirality transfer and enhances the performance of circularly polarized luminescence (CPL) through strong charge transfer (CT) mechanisms, leading to the successful regulation of the CPL of the obtained SOF series. Chiral SOFs are significant enough due to their ability to combine chirality with versatile porous frameworks, leading to innovative solutions in optical devices, separations, catalysis, and beyond. Their tunability and eco-friendly synthesis further enhance their importance in chiral materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11951166/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143751349","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mn-Rh Dual Single-Atom Catalyst for Inducing C−C Cleavage: Relay Catalysis Reversing Chemoselectivity in C-H Oxidation

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-18 DOI: 10.1039/d4sc08658a

Chang-Jie Yang, Yu-Da Huang, Yu-Yuan Zhang, Yong-Zhou Pan, Jiarui Yang, Ying-Ming Pan, Tao Gan, Hai-Tao Tang, Xia Zhang, Wen-Hao Li, Dingsheng Wang

{"title":"Mn-Rh Dual Single-Atom Catalyst for Inducing C−C Cleavage: Relay Catalysis Reversing Chemoselectivity in C-H Oxidation","authors":"Chang-Jie Yang, Yu-Da Huang, Yu-Yuan Zhang, Yong-Zhou Pan, Jiarui Yang, Ying-Ming Pan, Tao Gan, Hai-Tao Tang, Xia Zhang, Wen-Hao Li, Dingsheng Wang","doi":"10.1039/d4sc08658a","DOIUrl":"https://doi.org/10.1039/d4sc08658a","url":null,"abstract":"The integration of two entirely unrelated organic reactions into a novel reaction poses a formidable challenge. While diatomic catalysts (DACs) have exhibited promise as a framework for realizing this concept, the fusion of disparate organic reactions using DACs remains exceptionally uncommon. The reason for this is that there are often interactions between the two metal sites in DACs, which creates new difficulties in catalyst design for already complex reaction systems. Based on this situation, the incorporation of two completely isolated single-atom catalytic systems into the same reaction is a promising resolution. Herein, we synthesized a Mn-Rh dual single-atom catalyst (DSAC, Mn1-Rh1@O-TiC) and this DSAC demonstrates remarkable selectivity and conversion efficiency in the oxidation reaction of cumene, facilitating the highly efficient production of acetophenone (AP) in an almost quantitative form. The two completely isolated metal catalytic centers, Mn and Rh, each playing a distinct role in the reaction, synergistically propel the directed conversion of cumene to AP in a well-defined manner. This investigation not only illustrate a rare instance of dual single-atomic catalyst-mediated relay catalysis in organic synthesis but also imparts valuable insights into the systematic design of catalytic systems for organic tandem reactions, approached from the vantage point in atomic scale.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"61 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640034","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

Reticular chemistry guided function customization: a case study of constructing low-polarity channel for efficient C3H6/C2H4 separation

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-18 DOI: 10.1039/d4sc07959k

Jiantang Li, Zitong Song, Xia Zhou, Xue Wang, Meng Feng, Dongmei Wang, Banglin Chen

{"title":"Reticular chemistry guided function customization: a case study of constructing low-polarity channel for efficient C3H6/C2H4 separation","authors":"Jiantang Li, Zitong Song, Xia Zhou, Xue Wang, Meng Feng, Dongmei Wang, Banglin Chen","doi":"10.1039/d4sc07959k","DOIUrl":"https://doi.org/10.1039/d4sc07959k","url":null,"abstract":"Guided by principles of reticular chemistry, we have successfully presented the \"bending-bridge\" strategy, achieving an extraordinary function-targeted assembly by ingeniously redirecting the coordination direction of traditional SBUs. This led to the synthesis of a novel metal-organic framework (MOF), {[CH3NH3][InTPCA]·2H2O·NMF·DMF} (ZJNU-401). The smart design of bending branch within the ligand effectively transformed the tetrahedrally coordinated mononuclear In(III) into a square-planar configuration, thereby avoiding the introduction of open metal sites (OMSs) commonly associated with traditional ssb networks and creating a low-polarity pore surface environment. ZJNU-401 exhibits an optimal pore system that enhances its efficacy for high uptake of C3H6 and C2H6 over C2H4. The remarkable selectivity ratio of C3H6 to C2H4 reaches up to 15.45, alongside efficient one-step purification of C2H4 (> 99.95%) from the mixture of C3H6/C2H4. DFT calculations revealed that multiple O active sites within nonpolar pores provide stronger interactions with both C3H6 and C2H6 compared to those with C2H4.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640103","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

Rigorous Treatment of Polytopal Rearrangements Reveal Surprising Complexity of Stereoisomerism Configuration Landscapes

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-18 DOI: 10.1039/d4sc08628g

Peter Canfield, Maxwell J Crossley

{"title":"Rigorous Treatment of Polytopal Rearrangements Reveal Surprising Complexity of Stereoisomerism Configuration Landscapes","authors":"Peter Canfield, Maxwell J Crossley","doi":"10.1039/d4sc08628g","DOIUrl":"https://doi.org/10.1039/d4sc08628g","url":null,"abstract":"Previously we posited that a systematic and general description of stereoisomerism could be based upon the principles of the polytopal rearrangement model. The most daunting challenge to this end is to comprehensively describe all possible geometries for arbitrary n-coordinate centres, ABn, and for this we have developed a physically-inspired rigorous approach. Here we demonstrate the detailed application of this approach to the AB4 system focussing on e-symmetric distortions of tetrahedral geometry to generate an angular configuration space (the AB4 T-4 E-mode space). Analytic expressions for the A–Bi unit vector configurations are presented and the resulting spherical (2D) configuration space is shown to exhibit the symmetries of a disdyakis dodecahedron. Detailed inspection and analysis of the angular configuration space reveals that, in addition to the expected (T-4-R) ⇌ (T-4-S) pseudorotation, it features numerous “orientation permutations” that are also pseudorotations. Through the worked examples of SiF4, XeF4, and a chiral silane, we generate the corresponding potential energy surfaces and examine the wider implications. We also outline experimental opportunities for investigating the unexpected configuration space complexity that this work has revealed. This rigorous and mathematically comprehensive approach and framework we name the Polytope Formalism.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"197 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640093","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

Vacuum Infiltration for Priming of Soybean Seeds: Optimization and Particle Tracking Using Fluorescent Silica Nanoparticles

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-18 DOI: 10.1039/d4sc08566c

Tana O'Keefe, Beza Tuga, Chaoyi Deng, Sharmaka Mohamud, Rima Jamous, Mark Sanders, Wade H Elmer, Jason C. White, Christy Haynes

{"title":"Vacuum Infiltration for Priming of Soybean Seeds: Optimization and Particle Tracking Using Fluorescent Silica Nanoparticles","authors":"Tana O'Keefe, Beza Tuga, Chaoyi Deng, Sharmaka Mohamud, Rima Jamous, Mark Sanders, Wade H Elmer, Jason C. White, Christy Haynes","doi":"10.1039/d4sc08566c","DOIUrl":"https://doi.org/10.1039/d4sc08566c","url":null,"abstract":"Agrochemical delivery is highly inefficient, and novel application methods are necessary to promote crop health and yields while reducing environmental impact. In this work, a vacuum infiltration seed priming strategy was developed to incorporate silica nanoparticles into soybeans. Although successful in initial greenhouse and field studies, little is known about the amount of nutrient being delivered and the conditions for optimum accumulation. Herein, various infiltration conditions were evaluated using fluorescent silica nanoparticles and confocal microscopy, including nanoparticle surface charge and concentration, infiltration time, infiltrate ionic strength and pH, and seed presoaking. Negative nanoparticle surface charge, higher nanoparticle concentration, shorter infiltration time, and potassium-based salts resulted in greater nanoparticle infiltration. Seed coat elemental analysis complemented fluorescence data and highlight the co-delivery of beneficial macronutrients like potassium and magnesium under ionic salt infiltration conditions. Overall, these findings illustrate a new strategy to biofortify nanoscale nutrients into soybean seeds that can be expanded into other agrochemical targets and crop species to promote sustainable agriculture.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"183 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640031","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 combined experimental and computational study reveals a crossover between conventional cross-coupling and carbene insertion pathways in a Pd catalyzed C(sp2)–H insertion

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-18 DOI: 10.1039/d5sc00777a

Arushi Tyagi, Kritika Gaur, Anubhav Goswami, Arko Seal, Mayuk Joddar, Garima Jindal

引用次数: 0

Palladium/Norbornenes-Catalyzed C−H Bond Activation and Annulation to Construct Polycyclic Aromatic Hydrocarbons-based Fluorescent Materials

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-18 DOI: 10.1039/d5sc00617a

Chunlin Zhou, Xianhui Yang, Lian Gou, Bijin Li

引用次数: 0