Science China Chemistry最新文献_第3页

Visualization of the protective role of estrogen against female liver fibrosis via an ER viscosity NIR fluorescent probe 雌激素对女性肝纤维化的保护作用通过内质网黏度近红外荧光探针可视化

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-10-23 DOI: 10.1007/s11426-024-2061-7

Zheng Liu, Changyu Zhang, Zipeng Li, Wanying Ma, Jia Liu, Xiang Xia, Ning Xu, Wen Sun, Jianjun Du, Jiangli Fan, Xiaojun Peng

{"title":"Visualization of the protective role of estrogen against female liver fibrosis via an ER viscosity NIR fluorescent probe","authors":"Zheng Liu, Changyu Zhang, Zipeng Li, Wanying Ma, Jia Liu, Xiang Xia, Ning Xu, Wen Sun, Jianjun Du, Jiangli Fan, Xiaojun Peng","doi":"10.1007/s11426-024-2061-7","DOIUrl":"10.1007/s11426-024-2061-7","url":null,"abstract":"<div><p>Endoplasmic reticulum (ER) viscosity has emerged as a new potential biomarker for hepatic fibrosis (HF). Herein, we report the first ER-targeting viscosity-responsive near-infrared (NIR) fluorescent probe HBT-PP for investigations of HF pathogenesis. The twisted intramolecular charge transfer (TICT) and the excited state intramolecular proton transfer (ESIPT) are combined to endow HBT-PP with the selective response towards viscosity (∼62-fold) and a super large stokes shift (∼320 nm). HBT-PP mainly targets organelle ER and is able to image the drug- or alcohol-induced viscosity elevation in living cells. Significantly, HBT-PP was successfully applied to visualize the gender difference in HF and the protective role of estrogen in restraining HF progression. Of note, after 10 min of stain with HBT-PP, HF lesions showed a stage-based response, indicating the potential of this probe in fast and early diagnosis of HF. These results clearly demonstrated the promising application of HBT-PP as a new tool for exploring ER viscosity-involved physiological and pathological processes.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 1","pages":"360 - 368"},"PeriodicalIF":10.4,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925605","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

Potassium ions and cyano group modified g-C3N4 for effective generation of H2O2 through two-electron oxygen reduction 钾离子和氰基修饰g-C3N4，通过双电子氧还原有效生成H2O2

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-10-22 DOI: 10.1007/s11426-024-2200-1

Dongying Wang, Shulan Pu, Yongmin Chen, Ke Lei, Yujie Duan, Linjiao Mao, Xuhui Zeng, Xi Luo, Yuntao Zhang, Yuqin Dong, Jin Zhong Zhang, Yan Sun

{"title":"Potassium ions and cyano group modified g-C3N4 for effective generation of H2O2 through two-electron oxygen reduction","authors":"Dongying Wang, Shulan Pu, Yongmin Chen, Ke Lei, Yujie Duan, Linjiao Mao, Xuhui Zeng, Xi Luo, Yuntao Zhang, Yuqin Dong, Jin Zhong Zhang, Yan Sun","doi":"10.1007/s11426-024-2200-1","DOIUrl":"10.1007/s11426-024-2200-1","url":null,"abstract":"<div><p>Potassium ions (K<sup>+</sup>) doped graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) was prepared by a thermal etching method using potassium hydroxide (KOH) as an ion source. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results showed that the generation of the cyano group was detected while introducing K<sup>+</sup>. Under simulated sunlight irradiation, the sample with a K<sup>+</sup> doping amount of 10% showed the highest hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) generation rate of 2,140.2 µmol h<sup>−1</sup> g<sup>−1</sup>. The apparent quantum yield (AQY) at 400 nm and the solar-to-chemical conversion (SCC) are 4.35% and 1.23%, respectively. K<sup>+</sup> acted as a bridge between g-C<sub>3</sub>N<sub>4</sub> layers, which enhanced charge transfer efficiency. Meanwhile, the cyano group enhanced the adsorption capacity of protons (H<sup>+</sup>) and promoted the yield of H<sub>2</sub>O<sub>2</sub>. The catalyst exhibited excellent photocatalytic stability based on four-cycle experiments. In addition, a mechanism study showed that superoxide radicals (·O<sub>2</sub><sup>−</sup>) were the most important active species in the reaction system. Photocatalytic production of H<sub>2</sub>O<sub>2</sub> was achieved through consecutive single-electron steps. This study deepens the understanding of the oxygen reduction reaction process and opens up a new venue for improving H<sub>2</sub>O<sub>2</sub> generation.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 1","pages":"192 - 200"},"PeriodicalIF":10.4,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925575","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

Dual-functional additive of cesium ion for achieving ultrahigh efficiency of persistent phosphorescence in existing polymer-based materials 用于在现有聚合物基材料中实现超高效持久磷光的铯离子双功能添加剂

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-10-22 DOI: 10.1007/s11426-024-2247-4

Yao Liu, Jinzheng Chen, Yiling Miao, Kaimin Zhang, Faxu Lin, Huahua Huang, Lina Zhang, Zhan Yang, Yi Zhang, Zhenguo Chi, Zhiyong Yang

{"title":"Dual-functional additive of cesium ion for achieving ultrahigh efficiency of persistent phosphorescence in existing polymer-based materials","authors":"Yao Liu, Jinzheng Chen, Yiling Miao, Kaimin Zhang, Faxu Lin, Huahua Huang, Lina Zhang, Zhan Yang, Yi Zhang, Zhenguo Chi, Zhiyong Yang","doi":"10.1007/s11426-024-2247-4","DOIUrl":"10.1007/s11426-024-2247-4","url":null,"abstract":"<div><p>Despite great achievements obtained for polymer-based room-temperature phosphorescence (RTP) materials, the limited efficiencies of persistent RTP still hinder their development. Herein, a simple and universal strategy of using the dual-functional additive of Cs<sup>+</sup> was presented, which could simultaneously enhance the efficiency (<i>Φ</i><sub>p</sub>) and maintain the long lifetime (<i>τ</i><sub>p</sub>) of RTP in existing polymer-based systems with various phosphors and polymers. Among them, the commercial emitter (TpB)-doped polyvinyl alcohol (PVA)/Cs<sub>2</sub>CO<sub>3</sub> system possessed an extremely high <i>Φ</i><sub>p</sub> up to 75.5% and still maintained a long <i>τ</i><sub>p</sub> of 2.13 s, by introducing the heavy-atom effect and an extra network of ionic bonding through the Cs<sup>+</sup> additive. Additionally, the temperature resistance of RTP in TpB@PVA/Cs<sup>+</sup> film could also be improved to 85 °C. More satisfactorily, the efficiency of Förster resonance energy transfer (FRET) from RTP to near-infrared (NIR) was also remarkably enhanced in the multi-component systems. This work provides a simple and universal strategy for developing polymer systems with high RTP performance.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 2","pages":"754 - 762"},"PeriodicalIF":10.4,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11426-024-2247-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446555","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

Mechanically robust and dynamic supramolecular polymer networks enabled by [an]daisy chain backbones 由菊花链主干实现的机械鲁棒和动态超分子聚合物网络

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-10-21 DOI: 10.1007/s11426-024-2329-7

Yongming Wang, Yi Ding, Yuhang Liu, Shaolei Qu, Wenbin Wang, Wei Yu, Zhaoming Zhang, Feng Liu, Xuzhou Yan

{"title":"Mechanically robust and dynamic supramolecular polymer networks enabled by [an]daisy chain backbones","authors":"Yongming Wang, Yi Ding, Yuhang Liu, Shaolei Qu, Wenbin Wang, Wei Yu, Zhaoming Zhang, Feng Liu, Xuzhou Yan","doi":"10.1007/s11426-024-2329-7","DOIUrl":"10.1007/s11426-024-2329-7","url":null,"abstract":"<div><p>Supramolecular polymer networks (SPNs) have garnered significant research interest due to their dynamic properties. However, while current developments primarily focus on managing supramolecular crosslinks, the role of polymer backbones—equally crucial to SPN properties—has not yet been sufficiently explored. Herein, we utilize mechanically interlocked [<i>a</i>n]daisy chain as backbone to prepare a class of SPNs, where the force-induced motion of successive mechanical bonds toughens and reinforces the networks. In specific, the [<i>a</i>n]daisy chain backbones connect with polynorbornene chains through quadruple H-bonding in the SPN networks. Compared to the control with non-slidable backbone, The representative SPN-<b>2</b> exhibits a robust feature in tensile tests with high maximum stress (14.7 vs. 7.89 MPa) and toughness (83.8 vs. 48.6 MJ/m<sup>3</sup>). Moreover, it also has superior performance in energy dissipation benefitting from the [<i>a</i>n]daisy chain backbones as well as supramolecular crosslinks. Additionally, the SPN-<b>2</b> displayed exceptional self-healing and reprocessing capabilities due to their dynamic quadrable H-bonding crosslinkers. These findings demonstrate the untapped potential of [<i>a</i>n]daisy chain as a polymer skeleton to develop SPNs and open the door to design mechanically robust supramolecular materials with diverse smart functions.</p></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"67 12","pages":"4234 - 4241"},"PeriodicalIF":10.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142757929","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

Phase-transfer-shuttle generated in situ enables novel SN1-type fluorination of sulfonium ylide with hydrofluoric acid

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-10-21 DOI: 10.1007/s11426-024-2240-5

Yisa Xiao, Rui Wang, Zhaoxuan Xu, Qunchao Zhao, Renyi Pang, Tao Dong, Long Lu, Qilong Shen

{"title":"Phase-transfer-shuttle generated in situ enables novel SN1-type fluorination of sulfonium ylide with hydrofluoric acid","authors":"Yisa Xiao, Rui Wang, Zhaoxuan Xu, Qunchao Zhao, Renyi Pang, Tao Dong, Long Lu, Qilong Shen","doi":"10.1007/s11426-024-2240-5","DOIUrl":"10.1007/s11426-024-2240-5","url":null,"abstract":"<div><p>The development of a nucleophilic fluorination protocol using hydrofluoric acid as the fluoride source represents a long-sought goal in the field of organofluorine chemistry. We report herein the realization of such a reaction that employed alkyl-substituted sulfonium ylides as the substrates. The key to the success of the protocol was attributed to two factors: First, as a Brønsted base, the ylide was able to be protonated by HFaq, thus serving as a phase-transfer shuttle generated <i>in situ</i> to bring F<sup>−</sup> from aqueous phase to the organic phase promoting desolvation of fluoride ion. Second, after protonation, a sulfonium salt, a good leaving group, was generated and subsequent attacked by the fluoride to afford the alkyl fluoride. Mechanistic investigation indicates that the reaction occurs via an S<sub>N</sub>1 pathway. Because of the nature of the cationic intermediate in the reaction, two attractive rearrangement-fluorination approaches including 1,2-aryl migration fluorination and ring-expansion fluorination were disclosed.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 2","pages":"641 - 648"},"PeriodicalIF":10.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446553","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

ZIF-90-loaded DNAzyme-responsive PROTAC for the self-powered degradation of NF-κB

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-10-21 DOI: 10.1007/s11426-024-2246-0

Min Hou, Liang Sun, Tianyu Ren, Mingda Li, Chao Hu, Rong Liu, Shuang Gu, Mingyan Jiang, Jian-Hui Jiang, Jianjun He

{"title":"ZIF-90-loaded DNAzyme-responsive PROTAC for the self-powered degradation of NF-κB","authors":"Min Hou, Liang Sun, Tianyu Ren, Mingda Li, Chao Hu, Rong Liu, Shuang Gu, Mingyan Jiang, Jian-Hui Jiang, Jianjun He","doi":"10.1007/s11426-024-2246-0","DOIUrl":"10.1007/s11426-024-2246-0","url":null,"abstract":"<div><p>Transcription factors (TFs) play vital roles in regulating gene expressions. Dysregulated or mutated TFs are implicated in a wide array of diseases, highlighting their potential as drug targets. However, TFs are considered undruggable by conventional inhibitor-based modalities. The recently emerged proteolysis targeting chimeras (PROTACs) have exhibited great potential in tackling TFs. In particular, DNA-ligand chimeras that arm E3 ligase-recruiting ligands to TF-binding double-strand DNA represent a promising strategy for the targeted proteolysis of TFs. Here, we report a DNAzyme-inducible PROTAC (DzTAC) that selectively degrades NF-κB in a zinc ion-dependent manner. We further applied zinc-imidazolate metal-organic framework-90 (ZIF-90) to encapsulate DzTAC (ZIF-90@DzTAC), facilitating its delivery into cancer cells while self-supplying Zn<sup>2+</sup> via adenosine triphosphate (ATP)-triggered ZIF-90 dissociation. Moreover, ZIF-90@DzTAC can enhance the treatment efficacy of doxorubicin-based chemotherapy in tumor-bearing mice. The developed DzTAC provides specific modulation over TF activity and opens an avenue for more functional nucleic acid-based control over targeted protein degradation.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 2","pages":"687 - 693"},"PeriodicalIF":10.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11426-024-2246-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446554","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

Emerging trends in the selective production of value-added aromatics 选择性生产增值芳烃的新趋势

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-10-17 DOI: 10.1007/s11426-024-2354-3

Yuchao Wu, Houliang Dai, Weisheng Yang, Yaxing Li, Lichen Liu

引用次数: 0

A low-cost wide bandgap polymer based on carboxylate substituted thiazole enables efficient organic solar cells with remarkable batch-to-batch reproducibility

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-10-17 DOI: 10.1007/s11426-024-2243-8

Xiaodong Zhu, Yuchen Lei, Jianhong Gao, Yanjun He, Jinsicheng Liu, Qian Guo, Xiang Gao, Liwei Xiong, Xunchang Wang, Renqiang Yang, Zhitian Liu

{"title":"A low-cost wide bandgap polymer based on carboxylate substituted thiazole enables efficient organic solar cells with remarkable batch-to-batch reproducibility","authors":"Xiaodong Zhu, Yuchen Lei, Jianhong Gao, Yanjun He, Jinsicheng Liu, Qian Guo, Xiang Gao, Liwei Xiong, Xunchang Wang, Renqiang Yang, Zhitian Liu","doi":"10.1007/s11426-024-2243-8","DOIUrl":"10.1007/s11426-024-2243-8","url":null,"abstract":"<div><p>Constructing the low-cost, high-efficiency, and good batch-to-batch reproducibility polymer donor is vitally important for the application of organic solar cells. Herein, we develop a structurally simple carboxylate-substituted thiazole as an electron-withdrawing building block to construct a low-cost polymer, PBTTzE, containing a facilely prepared chlorinated benzo[1,2-b:4,5-b′]dithiophene (BDTCl) donor unit. Benefiting from synergistic electron deficient effects of chlorination and ester group and C=N, as well as the noncovalent interaction of S⋯O and S⋯N, PBTTzE exhibits a deep HOMO energy level (−5.59 eV), and a planar skeleton structure. When combined with the IT-4F acceptor, the polymer (54 kDa) demonstrated a champion PCE of 15.87%, which is the highest value in the IT-4F-based binary devices to date. Moreover, PBTTzE exhibits excellent batch-to-batch reproducibility due to its very similar PCEs within a range of 43–76 kDa. In addition, an alloyed state and complementary absorption can be formed between PM6 and PBTTzE. Therefore, in a ternary device with PBTTzE added to the PM6:BTP-eC9 blend, a top PCE of 18.76% is achieved due to the suppressed energy loss, prolonged exciton diffusion distance, and improved charge transport. Our work demonstrates that the carboxylate-substituted thiazole is a highly promising acceptor unit for constructing low-cost and high-performance polymers.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 2","pages":"733 - 744"},"PeriodicalIF":10.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11426-024-2243-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446564","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

Lattice-mismatch-induced formation of defect-rich Pd–Cu alloy nanocages for enhanced formic acid oxidation activity

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-10-17 DOI: 10.1007/s11426-024-2347-y

Zhaojun Liu, Zhengyan Wang, Zhaoyu Wang, Hao Yuan, Yuke Bai, Xiaoxiao Wang, Zerui Mu, Chunxia Wu, Kai Liu, Zhun Hu, Chuanbo Gao

{"title":"Lattice-mismatch-induced formation of defect-rich Pd–Cu alloy nanocages for enhanced formic acid oxidation activity","authors":"Zhaojun Liu, Zhengyan Wang, Zhaoyu Wang, Hao Yuan, Yuke Bai, Xiaoxiao Wang, Zerui Mu, Chunxia Wu, Kai Liu, Zhun Hu, Chuanbo Gao","doi":"10.1007/s11426-024-2347-y","DOIUrl":"10.1007/s11426-024-2347-y","url":null,"abstract":"<div><p>Crystallographic defects in noble metal nanocrystals are recognized as highly active catalytic sites, significantly enhancing activities in many important reactions. Despite their importance, synthesizing noble metal nanocrystals with a high density of defects poses a considerable synthetic challenge. Here, we present a novel lattice mismatch-induced formation mechanism to create high-density defects in noble metal nanocrystals. This approach takes advantage of lattice mismatch to enable non-epitaxial nucleation and growth of a noble metal on a foreign metal substrate, forming abundant noble metal crystallites with random lattice orientations not dictated by the substrate lattice. As these crystallites grow extensively, they merge, forming numerous grain boundaries and yielding defect-rich noble metal nanocrystals. Defect-rich alloy nanocrystals can also be synthesized through a subsequent vacancy-diffusion alloying process. We take defective PdCu alloy nanocages as an example and demonstrate the effectiveness of crystallographic defects in enhancing catalytic performance of noble metal nanocrystals. The nanocages exhibit superior activity in the electrocatalytic formic acid oxidation reaction, which is 1.6 times greater than their defect-free counterparts. Our strategy offers a new avenue for creating defect-rich noble metal nanocrystals as highly efficient catalysts for a wide array of catalytic applications.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 2","pages":"481 - 491"},"PeriodicalIF":10.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446563","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

Versatile chiroptical induction/manipulation through specific solvation of ion pairs by alcohols

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-10-16 DOI: 10.1007/s11426-024-2190-5

Chunhong Liu, Xin Chen, Yanling Shen, Ting Zhao, Dayang Zhou, Kun Li, Jiecheng Ji, Wanhua Wu, Xuemei Pu, Cheng Yang

{"title":"Versatile chiroptical induction/manipulation through specific solvation of ion pairs by alcohols","authors":"Chunhong Liu, Xin Chen, Yanling Shen, Ting Zhao, Dayang Zhou, Kun Li, Jiecheng Ji, Wanhua Wu, Xuemei Pu, Cheng Yang","doi":"10.1007/s11426-024-2190-5","DOIUrl":"10.1007/s11426-024-2190-5","url":null,"abstract":"<div><p>While extensive research has explored manipulating supramolecular chirality through internal and external factors, the specific solvation effect remains uncharted territory. This study synthesized <i>ortho</i>-functionalized pillar[5]arene (P[5]) derivatives <b>M</b><b><i>n</i></b> and <b>D</b><b><i>n</i></b> <i>via</i> thiol-Michael addition, characterizing them through spectroscopic and X-ray single-crystal analyses. <b>M</b><b><i>n</i></b> and <b>D</b><b><i>n</i></b> interacted with chiral amines, yielding significant circular dichroism (CD) responses. Intriguingly, the chiral induction exhibited pronounced specific solvation effects, where achiral alcohols either enhanced, attenuated, or reversed CD signals. Testing over 40 alcohols revealed correlations between the specific solvation effects and alcohol polarity and acidity. Molecular dynamics simulations unveiled that the alcohol interacted distinctly through hydrogen bonding, with one ion pair bonding up to four alcohol molecules. The <i>R</i><sub><i>p</i></sub>- and <i>S</i><sub><i>p</i></sub>-preference of the P[5] core could be altered by the number of bonded alcohols. This work uncovers the critical role of alcohol-specific solvation in ion pair-involved chiral assembly, pertinent for asymmetric ion-pairing catalysis and the use of alcohol additives in organic solvents.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 2","pages":"610 - 621"},"PeriodicalIF":10.4,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446540","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