Chemistry - A European Journal最新文献_第7页

Catechol-functionalized Covalent Organic Framework: Synthesis, Characterization and Metal-free Organocatalyst for CO2 Fixation under Mild Conditions.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-04-07 DOI: 10.1002/chem.202500654

Minghao Liu, Guoxin Cui, Xue Cai, Guan Yun, Weiqi Zeng, Jing Li, Jinghan Zhang, Rongxin Tan, Zhenlu Wang, Jian Jiang

{"title":"Catechol-functionalized Covalent Organic Framework: Synthesis, Characterization and Metal-free Organocatalyst for CO2 Fixation under Mild Conditions.","authors":"Minghao Liu, Guoxin Cui, Xue Cai, Guan Yun, Weiqi Zeng, Jing Li, Jinghan Zhang, Rongxin Tan, Zhenlu Wang, Jian Jiang","doi":"10.1002/chem.202500654","DOIUrl":"https://doi.org/10.1002/chem.202500654","url":null,"abstract":"Covalent organic frameworks (COFs) incorporating hydrogen bond donor (HBD) moieties show great promise for heterogeneous catalyst for CO2 cycloaddition. In this work, a catechol-functionalized COF (BL-TF-COF) was constructed via Schiff-base condensation under solvothermal conditions, which was characterized using PXRD, FT-IR, solid-state 13C NMR, SEM, HR-TEM, DRS and CV. BL-TF-COF presents high crystallinity, large BET surface area (523 m2 g-1) and remarkable chemical stability, along with abundant hydroxyl functional groups distributed on the pore wall. This framework shows a CO2 adsorption capacity up to 88 mg g-1 at 273 K and 1 bar. The binding locations of the adsorption of CO2 over BL-TF-COF was studied by grand canonical Monte Carlo (GCMC) simulations. BL-TF-COF displays remarkable catalytic performance for the cycloaddition of CO2 with epoxides under mild conditions. Under the condition of the epichlorohydrin/tetrabutylammonium bromide/BL-TF-COF molar ratio of 10210:630:4, the system achieved 62.5% substrate conversion at 25°C under atmospheric CO2 pressure (1 bar) within 48 h. Mechanistic insights into epoxide adsorption and activation processes were investigated through density functional theory (DFT) calculations.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500654"},"PeriodicalIF":3.9,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Circularly Polarized Luminescence Inversion Induced by Achiral Dyes in Organogels.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-04-07 DOI: 10.1002/chem.202500908

Tianjing Xu, Fanjie Lin, Fengqing Hu, Fengyan Song, Siao Shi, Jiayan Zhao, Dou Liu, Xinyue Zhang, Jinsong Han, Fei Li

引用次数: 0

Photoinduced Stable Circularly Polarized Luminescent Radicals From a Triphenylamine-Attached Planar Chiral Pillar[5]arene.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-04-07 DOI: 10.1002/chem.202500771

Jin-Fa Chen, Qing-Xiu Gao, Yu Tian, Shao-Ping Tao, Bingbing Shi, Hong Yao, Tai-Bao Wei, Pangkuan Chen, Qi Lin

{"title":"Photoinduced Stable Circularly Polarized Luminescent Radicals From a Triphenylamine-Attached Planar Chiral Pillar[5]arene.","authors":"Jin-Fa Chen, Qing-Xiu Gao, Yu Tian, Shao-Ping Tao, Bingbing Shi, Hong Yao, Tai-Bao Wei, Pangkuan Chen, Qi Lin","doi":"10.1002/chem.202500771","DOIUrl":"https://doi.org/10.1002/chem.202500771","url":null,"abstract":"Photoinduced organic radicals with unique luminescent properties are highly sought-after due to their important prospects in synthetic chemistry and materials science. However, the current development of organic free radicals, including photoinduced ones, is significantly limited and faces challenges related to stability and poor luminescence behavior. Taking advantage of the photoelectric activity of triarylamine, we herein describe an unusual luminescent radical, which can be rapidly generated by UV-irradiation of a solid-state triarylamine-functionalized π-conjugated pillar[5]arene (EtP5NN) in air, accompanied by luminescent color switching from bluish-violet to sky-blue. The persistent radicals within EtP5NN with a half-life of 12.7 hours suggest that the pillar[5]arene-skeleton straightforwardly improves the stability of radicals. The sterically bulky triarylamine groups inhibits the racemization of planar chiral pillar[5]arene, and allows the optical resolution of this system. The enhancement of circularly polarized luminescence (CPL) is triggered by UV-irradiation of the enantiomers (pS/pR-EtP5NN) in the solid state.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500771"},"PeriodicalIF":3.9,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794253","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 Drug Loading Pillar[5]arene-Based Nanodrug Delivery System Enhances Anticancer Efficacy and Reduces Toxicity.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-04-03 DOI: 10.1002/chem.202500885

Zhilian Su, Jiakai Zhang, Shubin Wei, Wengui Duan, Yan Huang, Luzhi Liu

{"title":"High Drug Loading Pillar[5]arene-Based Nanodrug Delivery System Enhances Anticancer Efficacy and Reduces Toxicity.","authors":"Zhilian Su, Jiakai Zhang, Shubin Wei, Wengui Duan, Yan Huang, Luzhi Liu","doi":"10.1002/chem.202500885","DOIUrl":"https://doi.org/10.1002/chem.202500885","url":null,"abstract":"Nanodrug delivery is a critical approach in cancer therapy; however, the deposition of excipients often exacerbates the toxic burden of drugs. Herein, a pillar[5]arene-based supramolecular nanodrug delivery system (WP5⊃C6Py@DOX) has been developed to enhance cancer therapy efficacy while minimizing side effects. This system, constructed through host-guest interactions between a thioether-modified pillar[5]arene derivative (WP5) and a pyridinium salt derivative (C6Py), exhibited a remarkable 97% drug loading capacity for doxorubicin (DOX). It showed remarkable stability in both aqueous solutions and bovine serum, effectively minimizing premature drug leakage and reducing associated toxicity. The thioether modification of WP5 reacted with H2O2 to generate derivatives with improved water solubility, significantly enhancing biocompatibility while minimizing excipient deposition within endosomes. Cellular experiments revealed that the system not only reduced the toxicity of DOX to normal cells (BEAS-2B) but also significantly enhanced its antitumor activity against cancer cells (HepG2), with an IC50 of 1.2 μM, markedly outperforming free DOX (IC50: 6.3 μM). Furthermore, laser confocal imaging confirmed that the supramolecular drug delivery system effectively enters and accumulates in cancer cells, demonstrating promising therapeutic potential.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500885"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143778798","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Multifunctional Gold Super-Nanoparticle-Based Nanosystem for SERS-Guided Oxygen-Independent Phototherapy.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-04-03 DOI: 10.1002/chem.202500537

Jiamin Guo, Na Feng, Yuanzhu Liu, Liyan Liu, Yawen Zhang, Xinjian Yang, Enjun Wang

{"title":"Multifunctional Gold Super-Nanoparticle-Based Nanosystem for SERS-Guided Oxygen-Independent Phototherapy.","authors":"Jiamin Guo, Na Feng, Yuanzhu Liu, Liyan Liu, Yawen Zhang, Xinjian Yang, Enjun Wang","doi":"10.1002/chem.202500537","DOIUrl":"https://doi.org/10.1002/chem.202500537","url":null,"abstract":"Cancer treatment remains a formidable challenge due to the complex and hypoxic microenvironment of tumors, which often compromises therapeutic efficacy. To address this issue, a multifunctional gold super-nanoparticle-based nanosystem (GSPs1,4-BDT@PDA-AIPH-cRGD) was developed for surface-enhanced Raman scattering (SERS)-guided oxygen-independent phototherapy. This nanosystem integrates diagnostic and therapeutic functionalities through a gold superlattice-nanoparticle (GSP) core self-assembled from 5.8 nm gold nanoparticles (GNPs), functionalized with 1,4-benzenedithiol (1,4-BDT) as a Raman reporter. The GSPs are encapsulated with a polydopamine (PDA) shell for enhancing their structural stability, Raman signal amplification, and serving as a photothermal agent. The PDA coating is further loaded with 2,2'-azobis[2-(2-imidazolin-2-yl) propane] dihydrochloride (AIPH), a oxygen independent photosensitizer that releases cytotoxic free radicals, and cyclic arginine-glycine-aspartic acid (cRGD) peptide for tumor targeting. Under near-infrared (NIR) light irradiation, the nanosystem generates hyperthermia and releases free radicals, achieving oxygen-independent tumor ablation. Real-time SERS imaging ensures precise tumor monitoring, addressing key challenges in cancer management. This novel approach combines the benefits of highly sensitive SERS imaging, targeted drug delivery, and oxygen independent phototherapy, providing a robust platform for synergistic cancer diagnosis and treatment with significant therapeutic potential.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500537"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770734","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Integrating Electrochemical Electrodes into Mass Spectrometry Ionization Sources for Detection of Transient Intermediates.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-04-03 DOI: 10.1002/chem.202404646

Yun Li, Meng Su, Yu Hou, Yajun Zheng, Zhiping Zhang

{"title":"Integrating Electrochemical Electrodes into Mass Spectrometry Ionization Sources for Detection of Transient Intermediates.","authors":"Yun Li, Meng Su, Yu Hou, Yajun Zheng, Zhiping Zhang","doi":"10.1002/chem.202404646","DOIUrl":"https://doi.org/10.1002/chem.202404646","url":null,"abstract":"Identifying short-lived transient intermediates is challenging due to their brief lifetimes (as short as nanoseconds, and even picoseconds) and therefore low concentrations in many chemical processes. Conducting electrochemical reactions within mass spectrometry ion sources (i.e., insource or in situ EC-MS) offers the advantage of minimizing the distance between the electrodes and the mass spectrometer, thereby improving the detection of transient intermediates. However, a key challenge for in-source EC-MS is the effective integration of the electrodes into the MS ion sources. This mini-review highlights three main integration strategies: exploiting inherent electrochemical properties, incorporating a two- or three-electrode system, and implementing bipolar electrodes, focusing on the underlying mechanisms, experimental setups, and applications of these approaches. Future perspectives emphasize the directions of designing and modifying ionization sources, integrating electrocatalysis, enhancing transfer efficiency, developing automated screening platforms, as well as expanding practical applications.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404646"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770703","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Thermally Activated On-Surface Self-Metalation of Pd-Phthalocyanines.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-04-03 DOI: 10.1002/chem.202500944

Mattia Bassotti, Stefania Baronio, Luca Floreano, Luca Schio, Erik Vesselli, Alberto Verdini

{"title":"Thermally Activated On-Surface Self-Metalation of Pd-Phthalocyanines.","authors":"Mattia Bassotti, Stefania Baronio, Luca Floreano, Luca Schio, Erik Vesselli, Alberto Verdini","doi":"10.1002/chem.202500944","DOIUrl":"https://doi.org/10.1002/chem.202500944","url":null,"abstract":"Phthalocyanines (Pcs) are essential organic molecules with wide-ranging applications in fields such as catalysis and optoelectronics, owing to their stable aromatic structure and exceptional thermal stability. Equally important is their versatility, which can be achieved by modifying the central metal atom. In this context, metalation-the process by which a central metal atom is incorporated into the macrocycle-plays a critical role in tailoring both the electronic and structural properties of Pcs. In this work, we investigate the thermally activated on-surface synthesis of palladium phthalocyanine (PdPc) by depositing metal-free phthalocyanine (H2Pc) onto a Pd(001) surface in Ultra-High Vacuum (UHV) conditions. Using temperature-dependent X-Ray Photoemission Spectroscopy (XPS), we analyze the evolution of the N 1s core level signal, confirming the successful formation of PdPc. The appearance of a secondary peak in the Pd 3d core level, attributed to Pd atoms coordinated within the phthalocyanine molecule after metalation, provides further evidence for the PdPc synthesis. Additionally, Near-Edge X-Ray Absorption Fine Structure (NEXAFS) reveals that no desorption or chemical degradation occurs during the process. We believe this study represents a significant step forward in the scalable synthesis of PdPc, which, like other Pd-containing organic molecules, holds great potential for applications in catalysis and cancer therapy.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500944"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143778799","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

In Situ Generation by Cyclisation of an Organic Structure Directing Agent for the Synthesis of High Silica Zeolite ERS-7.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-04-03 DOI: 10.1002/chem.202500327

Magdalena Malgorzata Lozinska, Ruxandra Georgiana Chitac, Elliott Bruce, Malavika Manoj, Yuanyuan Du, Daniel Dawson, Sharon Ashbrook, Paul Cox, Paul Anthony Wright

{"title":"In Situ Generation by Cyclisation of an Organic Structure Directing Agent for the Synthesis of High Silica Zeolite ERS-7.","authors":"Magdalena Malgorzata Lozinska, Ruxandra Georgiana Chitac, Elliott Bruce, Malavika Manoj, Yuanyuan Du, Daniel Dawson, Sharon Ashbrook, Paul Cox, Paul Anthony Wright","doi":"10.1002/chem.202500327","DOIUrl":"https://doi.org/10.1002/chem.202500327","url":null,"abstract":"Zeolites with high framework Si/Al ratios are of interest for industrial applications due to their hydrothermal stability. They are usually synthesised in the presence of pre-prepared organic structure directing agents (OSDAs). The high silica ERS-7 zeolite (topology type ESV) can be crystallised using N,N'-dimethylpyrrolidinium (dmpyrr) that is formed in situ via cyclisation of N,N,N',N'-tetramethyldiaminobutane (tmdab) when a cationic polymer is also present. The in situ generation of dmpyrr is demonstrated by solid-state 13C NMR spectroscopy and supported by both chemical analyses and comparative syntheses using pre-prepared dmpyrr. The cationic polymer inhibits the crystallisation of mordenite, which is otherwise observed to be the favoured product. The ERS-7 prepared via in situ dmpyrr synthesis (Si/Al = 14) is characterised by PXRD and solid-state NMR spectroscopy. The CO2 adsorption seen for the H- and Na-forms indicate interactions with accessible Na+ cations. The synthetic studies indicate the potential for in situ generation of OSDAs to reduce the need for extended OSDA syntheses.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500327"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770779","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Making and Breaking Supramolecular Synthons for Modular Protein Frameworks.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-04-03 DOI: 10.1002/chem.202500732

Niamh Mockler, Colin Raston, Peter B Crowley

{"title":"Making and Breaking Supramolecular Synthons for Modular Protein Frameworks.","authors":"Niamh Mockler, Colin Raston, Peter B Crowley","doi":"10.1002/chem.202500732","DOIUrl":"https://doi.org/10.1002/chem.202500732","url":null,"abstract":"Anionic calixarenes are useful mediators of protein assembly. In some cases, protein - calixarene cocrystallization yields multiple polymorphs. Ralstonia solanacearum lectin (RSL) cocrystallizes with p-sulfonato-calix[8]arene (sclx8) in at least four distinct pH-dependent arrangements. One of these polymorphs, occurring at pH ≤4, is a cubic framework in which RSL nodes are connected by sclx8 dimers. These dimers are supramolecular synthons, occurring in distinct crystal structures. Now, we show that the discus-shaped dimer of p-phosphonato-calix[6]arene (pclx6), can replace the sclx8 dimer yielding a new assembly of RSL. Remarkably, just one type of RSL - pclx6 cocrystal was formed, irrespective of pH or crystallization condition. These results with pclx6 contrast starkly with sclx8 and suggest that the calixarene type (e.g. phosphonate versus sulfonate) dictates the synthon durability, which in turn exerts control over protein assembly and polymorph selection. Breaking the pclx6 dimer required a mutant of RSL with an affinity tag for macrocycle binding. This highly accessible, dicationic site resulted in a significantly altered and porous framework with pclx6 (but not with sclx8). Experiments with ternary mixtures of RSL, pclx6 and sclx8 provide evidence of pH-driven self-sorting. Thus, the 'mix-and-match' of protein and supramolecular synthons is a promising approach to protein crystal engineering.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500732"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Anisotropic Thermal Expansion of an Adaptive Ni Metal-Organic Framework with One-Dimensional Helical Chains.

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-04-03 DOI: 10.1002/chem.202500341

Huichen Liu, Kangshuai Geng, Yupei Sun, Yi Wei, Hongwei Hou

{"title":"Anisotropic Thermal Expansion of an Adaptive Ni Metal-Organic Framework with One-Dimensional Helical Chains.","authors":"Huichen Liu, Kangshuai Geng, Yupei Sun, Yi Wei, Hongwei Hou","doi":"10.1002/chem.202500341","DOIUrl":"https://doi.org/10.1002/chem.202500341","url":null,"abstract":"Metal-organic frameworks (MOFs) are gradually becoming an ideal platform for investigating negative thermal expansion (NTE) owing to their designability and framework flexibility. In this work, we studied the thermal expansion phenomenon of the orthorhombic [Ni(L-cam)(4,4'-bpe)]n (L-cam = L-camphoric acid and 4,4'-bpe = 4,4'-vinylenedipyridine) with one-dimensional helical chains through thermogravimetric analysis, differential scanning calorimetry, variable temperature powder X-ray diffraction, and variable temperature single-crystal X-ray diffraction. The synergistic effect of the lateral thermal vibrations of bpe and the spring-like stretching thermal motion elucidated the mechanism of NTE along the c-axis. The positive thermal expansion (PTE) along the b-axis can be attributed to the spring-like stretching thermal motion of the helical chains. The a-axis was nearly unchanged exhibiting zero thermal expansion. The PTE happened in the unit cell volume due to the larger deformation along the b-axis compared to the c-axis. This study deepens our comprehension to the NTE of three-dimensional MOFs and provides a point of view for the design and synthesis in the development and investigation of other NTE materials.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500341"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143778788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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