化学最新文献_第8页

Degradation of p-Toluene Sulfonic Acid–Choline Chloride Deep Eutectic Solvent

IF 1.9 4区化学

ChemistrySelect Pub Date : 2025-04-21 DOI: 10.1002/slct.202405130

Dr. Wonseok Yang, Dr. James T. M. Amphlett, Nayoung Kim, Dr. Richard I. Foster, Prof. Sungyeol Choi

{"title":"Degradation of p-Toluene Sulfonic Acid–Choline Chloride Deep Eutectic Solvent","authors":"Dr. Wonseok Yang, Dr. James T. M. Amphlett, Nayoung Kim, Dr. Richard I. Foster, Prof. Sungyeol Choi","doi":"10.1002/slct.202405130","DOIUrl":"https://doi.org/10.1002/slct.202405130","url":null,"abstract":"The deep eutectic solvent (DES) formed between choline chloride (ChCl) and para-toluenesulfonic acid monohydrate (pTSA) is considered to be a promising solvent for green solvometallurgical processes. However, concerns regarding the green credentials of this DES and potential degradation pathways releasing toxic hydrochloric acid (HCl) remain. Here we report on the degradation of the ChCl-pTSA DES via the liberation of HCl gas. Dynamic thermogravimetric analysis – quadrupole mass spectrometry (TGA-QMS)(RT – 200 °C) confirmed both the loss of moisture, through dehydration, and the release of HCl, which was confirmed due to the presence of two peaks at 36 (HCl35) and 38 (HCl37). Isothermal TGA-QMS confirmed the release of HCl occurred at as low as 40 °C, the typical synthesis temperature of this DES, implying that HCl will be released no matter the operational temperature. Degradation led to the ChCl:pTSA solidifying, rendering it unusable as a solvent. Both TGA-QMS and subsequent 1H NMR indicated no further degradation products were produced with the solid degradation product concluded to be choline tosylate. This degradation renders the classification of this mixture as a ‘green and sustainable solvent’ questionable, and further questions the use of acidic hydrogen bond donors as DES precursors.","PeriodicalId":146,"journal":{"name":"ChemistrySelect","volume":"10 16","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/slct.202405130","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853056","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Pore engineering in isoreticular titanium‐isophthalate coordination polymers

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-04-21 DOI: 10.1002/anie.202503618

Sujing WANG, Qingqing Yan, Chenyang Nie, Valentin Diez Cabanes, Fu-An Guo, Yafei Du, Hailun Xia, Hao Wang, Guillaume Maurin, Peng Guo

{"title":"Pore engineering in isoreticular titanium‐isophthalate coordination polymers","authors":"Sujing WANG, Qingqing Yan, Chenyang Nie, Valentin Diez Cabanes, Fu-An Guo, Yafei Du, Hailun Xia, Hao Wang, Guillaume Maurin, Peng Guo","doi":"10.1002/anie.202503618","DOIUrl":"https://doi.org/10.1002/anie.202503618","url":null,"abstract":"Pore engineering through chemical environment modification is vital for developing industrial porous materials. Understanding the effects of substitutions in isoreticular porous coordination‐polymers—such as steric hindrance, vibrational capabilities, electronic influences, and hydropathy—is key to elucidating structure‐property relationships. However, accurately assessing the impact of functional groups on properties remains challenging due to limitations in current methodologies. In this study, we designed a series of titanium‐isophthalate coordination‐polymers with various functional groups to regulate pore characteristics and structural dimensionality. The unique spatial arrangement and electronic distribution of isophthalate and its functional groups provide an ideal platform to address these challenges. We conducted extensive investigations combining experimental methods with computational simulations to explore how pore engineering affects adsorptive separation and photoresponsive behavior in these compounds. Our findings not only tackle the synthesis challenge of isostructural titanium‐coordination polymers but also offer new insights into understanding structure‐property relationships achieved through modulation of their chemical environments.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853293","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

Tuning 3-D Nanomaterial Architectures Using Atomic Layer Deposition to Direct Solution Synthesis

IF 18.3 1区化学

Accounts of Chemical Research Pub Date : 2025-04-21 DOI: 10.1021/acs.accounts.5c00076

Alondra M. Ortiz-Ortiz, Daniel O. Delgado Cornejo, Ashley R. Bielinski, Neil P. Dasgupta

引用次数: 0

Accelerated ReaxFF Simulations of Vitrimers with Dynamic Covalent Adaptive Networks

IF 5.5 1区化学

Macromolecules Pub Date : 2025-04-21 DOI: 10.1021/acs.macromol.5c00501

Yiwen Zheng, Vikas Varshney, Aniruddh Vashisth

{"title":"Accelerated ReaxFF Simulations of Vitrimers with Dynamic Covalent Adaptive Networks","authors":"Yiwen Zheng, Vikas Varshney, Aniruddh Vashisth","doi":"10.1021/acs.macromol.5c00501","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00501","url":null,"abstract":"Vitrimers are a novel class of sustainable polymers with dynamic covalent adaptive networks driven by bond-exchange reactions between different constituents, making vitrimers reprocessable and recyclable. Current modeling approaches of bond-exchange reactions fall short in realistically capturing the complete reaction pathways, which limits our understanding of the viscoelastic properties of vitrimers. This research addresses these limitations by extending and employing the Accelerated reactive molecular dynamics (ReaxFF) technique, thus enabling a more accurate representation of vitrimer viscoelastic behavior at the molecular level. Bayesian optimization is employed to select force field parameters within the Accelerated ReaxFF framework, and an empirical function is proposed to model temperature dependence, thereby controlling the reaction probabilities under varying temperatures. The extended framework is employed to simulate nonisothermal creep behavior of vitrimers under different applied stress levels, heating rates, and numbers of reactions. The simulation results agree with experimental findings in the literature, validating the robustness of the framework.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"268 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853350","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

Biobased Oleyl Glycidyl Ether: Copolymerization with Ethylene Oxide, Postmodification, Thermal Properties, and Micellization Behavior

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2025-04-21 DOI: 10.1039/d5py00159e

Gregor M. Linden, Sandra Schüttner, Nora Fribiczer, Sebastian Seiffert, Holger Frey

{"title":"Biobased Oleyl Glycidyl Ether: Copolymerization with Ethylene Oxide, Postmodification, Thermal Properties, and Micellization Behavior","authors":"Gregor M. Linden, Sandra Schüttner, Nora Fribiczer, Sebastian Seiffert, Holger Frey","doi":"10.1039/d5py00159e","DOIUrl":"https://doi.org/10.1039/d5py00159e","url":null,"abstract":"Oleyl glycidyl ether (OlGE) is a highly hydrophobic monomer synthesized from a biobased fatty alcohol and epichlorohydrin. When combined with hydrophilic monomethoxy poly(ethylene glycol) (mPEG) macroinitiators, well-defined, highly amphiphilic AB block copolymers are obtained via anionic ring-opening polymerization (Đ ≤ 1.08). Surprisingly, an investigation of the copolymerization kinetics of OlGE and ethylene oxide revealed an almost ideally random copolymerization (rEO = 1.27, rOlGE = 0.78) despite the significant structural differences. Both statistical and block copolymers were investigated regarding their behavior in aqueous solution. The block copolymers of the type mPEG-b-POlGE featured two distinct melting temperatures (Tms). Besides a melting transition of mPEG, a second Tm is attributed to the crystallization of the cis-alkenyl side chain of the OlGE units. Varying degrees of side chain hydrogenation of the POlGE homopolymer using potassium azodicarboxylate (PADA) allowed for tailoring of the Tm. The thiol-ene click reaction allowed subsequent functionalization. This work not merely highlights the prospect of novel polyether surfactants, it also suggests the potential of biobased long-chain polyethers for the development of drug delivery systems featuring temperature-controlled release.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853393","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

Surfactant Free Microemulsions as Fluid Scaffolds for Thermal Stabilization of Lysozyme

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-04-21 DOI: 10.1039/d5cp00678c

Manvir Kaur, Manpreet Singh, Rajwinder Kaur, Navdeep Kaur, Pratap Kumar Pati, Tejwant Singh Kang

{"title":"Surfactant Free Microemulsions as Fluid Scaffolds for Thermal Stabilization of Lysozyme","authors":"Manvir Kaur, Manpreet Singh, Rajwinder Kaur, Navdeep Kaur, Pratap Kumar Pati, Tejwant Singh Kang","doi":"10.1039/d5cp00678c","DOIUrl":"https://doi.org/10.1039/d5cp00678c","url":null,"abstract":"The electrostatic forces supported by hydrogen-bonding (H-bonding) interactions in the presence of surfactants stabilizes the microemulsions in general. It would be quite surprising to have surfactant free microemulsions (SFMEs) predominantly stabilized by weak but large number of H-bonding interactions contrary to common wisdom. Herein, the formulation and characterization of SFMEs comprising a hydrophobic ionic liquid (IL) and a deep eutectic solvent (DES) exhibiting high thermal stability is reported. The constituents of DES namely ethylene glycol (EG) and choline chloride (ChCl) act as polar and amphiphile components, respectively and an IL, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide works as a hydrophobic entity to form SFME. The formation mechanism as well as high temperature thermal stability of SFMEs has been discussed in terms of relative changes in the thickness of interfacial film stabilizing the polar and non-polar pseudo-domains predominantly via alteration in H-bonding interactions, which is supported by computational studies. The sufficiently low interfacial energy in SFMEs has been exploited to thermally stabilize Lysozyme (LYZ) in SFMEs, which showed remarkable thermal stability (up to 150 oC) as revealed by comparative enzyme activity at room temperature after heating, which is quite higher than that observed in buffer. The present study not only adds to the existing knowledge about the formation and stability of SFMEs but is also expected to prompt other researchers for designing relatively greener IL or deep eutectic solvent (DES) based SFMEs for utilization in various biological and other applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"37 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853428","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}

引用次数: 0

The Mechanism of Ru-catalyzed Directed C–H Arylation of Arenes: the Key Role of Bis-Cyclometalated Intermediates.

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-04-21 DOI: 10.1002/anie.202506707

Stuart A. Macgregor, Pablo Domingo-Legarda, Samuel E. Neale, Ambre Carpentier, Claire L. McMullin, Michael Findlay, Igor Larrosa

{"title":"The Mechanism of Ru-catalyzed Directed C–H Arylation of Arenes: the Key Role of Bis-Cyclometalated Intermediates.","authors":"Stuart A. Macgregor, Pablo Domingo-Legarda, Samuel E. Neale, Ambre Carpentier, Claire L. McMullin, Michael Findlay, Igor Larrosa","doi":"10.1002/anie.202506707","DOIUrl":"https://doi.org/10.1002/anie.202506707","url":null,"abstract":"The mechanism of Ru-catalysed N-directed C-H ortho-arylation with haloarenes has been under intense scrutiny over the last decade, with conflicting proposals concerning the relevance of various catalytic intermediates and the nature of the key steps. This work presents experimental and computational studies that address these long-standing questions. Stoichiometric, catalytic and mechanistic kinetic studies, supported by DFT calculations, reveal that bis-cyclometallated ruthenium species are key intermediates in these reactions. These studies also show that oxidative addition with bromoarenes proceeds via a concerted oxidative addition pathway, as demonstrated by DFT and experimental kinetic orders. Bromoarene activation does not proceed at mono-cyclometalated species. In the catalytic process, zero order kinetics are observed on both reaction substrates, an observation that is rationalised by DFT calculations which predict a rate-limiting step within the product-release stage. These results showcase how detailed experimental and DFT studies can combine to probe mechanistic questions, as well as resolving opposing views around the mechanism of these Ru-catalysed arylations that form the basis of promising mild C-H functionalisations.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"23 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853656","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

Customizing Circularly Polarized Afterglow by Stepwise Chiral Amplification in BINAPs/BINAPOs

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-21 DOI: 10.1039/d4sc08710k

Bo Yang, Su-Qiong Yan, Shirong Ban, Hui Ma, Yuan Zhang, Fanda Feng, Wei Huang

{"title":"Customizing Circularly Polarized Afterglow by Stepwise Chiral Amplification in BINAPs/BINAPOs","authors":"Bo Yang, Su-Qiong Yan, Shirong Ban, Hui Ma, Yuan Zhang, Fanda Feng, Wei Huang","doi":"10.1039/d4sc08710k","DOIUrl":"https://doi.org/10.1039/d4sc08710k","url":null,"abstract":"Overcoming spin-forbidden radiation in chiral phosphors has attracted enormous attention because of their capacity in circularly polarized organic ultra-long room temperature phosphorescence (CP-OURTP). However, their developments have been hindered by the short lifetimes and low dissymmetry factors, which is attributed to the differing parity selection rules that govern the electric and magnetic dipole moments in chiral molecules, as well as poor triplet populations via intersystem crossing (ISC). Taking stepwise chiral amplification at molecular and supramolecular aspects, herein, we firstly reported the donor-decorative BINAPs/BINAPOs with tunable D–A character and triplet incubation, which could enable hybridized local and charge-transfer (HLCT) characteristics, heavy atoms, and p−π* effects. These emitters could serve as guests in the polymer matrix. The doped phosphorescent polymer exhibits unimolecular circularly polarized luminescence with high quantum efficiency, impressive CP-OURTP lifetimes (up to 1.02 s), and decent dissymmetry factors (10−3 level). Comprehensive studies unveil that the impressive CP-OURTP from monomer emission is ascribed to the 1HLCT-controlled ISC and long-lived 3LE-governing triplet radiation, as well as superior electric-magnetic dipole moment environments. Moreover, given the high RTP activity of rigid polymerization, we demonstrate the potential application in CP-OURTP amplification. Using in-situ chiral liquid crystal polymerization, RM257 liquid crystal doped with 0.1−1.0 wt% PO1 guests demonstrate a secondary helical assembly, showing an amplified gCP-RTP factor (±0.11) and a long lifetime (0.83 s) after photopolymerization. The current materials' excellent performance in CP-OURTP and structural dependence could function as afterglow patterns for multiple optical encryption.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853675","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

Tuning Intermediate Binding Enables Selective Electroreduction of Carbon Dioxide to Carbon Monoxide on Copper-Indium Catalyst

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-21 DOI: 10.1039/d5sc01110h

Shengzhou Xu, Chenglong Wang, Chunjing Ran, Hexing Yang, Wangjiang Gao, Bitao Dong, Yuhang Liu, Dan Ren

{"title":"Tuning Intermediate Binding Enables Selective Electroreduction of Carbon Dioxide to Carbon Monoxide on Copper-Indium Catalyst","authors":"Shengzhou Xu, Chenglong Wang, Chunjing Ran, Hexing Yang, Wangjiang Gao, Bitao Dong, Yuhang Liu, Dan Ren","doi":"10.1039/d5sc01110h","DOIUrl":"https://doi.org/10.1039/d5sc01110h","url":null,"abstract":"Electrosynthesis of carbon monoxide (CO) from carbon dioxide (CO2) and water driven by renewable electricity represents a sustainable route to carbon upgrading, but the lack of cost-effective catalyst hinders its scaling-up. Here, we judiciously designed bimetallic Cu-In catalyst via in situ electroreduction of In-coated CuO nanowires. This facilely-prepared Cu-In catalyst delivers an excellent performance towards CO production in a flow cell, with a Faradaic efficiency of CO up to 91% at -69 mA cm-2. In contrast to the previous studies suggesting that In-modified Cu strengthens the adsorption of *COOH and/or weakens the binding of *H, we revealed otherwise that the modification of In on Cu weakens the adsorption of CO and facilitates a faster desorption of CO from Cu, thus inhibiting C-C coupling process and leading to the suppressed formation of multi-carbon products, through a rigorous analysis of electrochemical reduction of CO, electrochemical adsorption of *CO and in situ Raman spectroscopy. Finally, we wired our CuIn-based electrolyzer with an efficient triple-junction solar cell for the demonstration of solar-driven CO2 conversion and achieved a solar-to-chemical energy conversion efficiency of greater than 10% for CO.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"35 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853683","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

Controlling the cis/trans Content of Biobased Unsaturated Polyesters by Judicious Choice of a Biosourced Catalyst

IF 8.4 1区化学

ACS Sustainable Chemistry & Engineering Pub Date : 2025-04-21 DOI: 10.1021/acssuschemeng.4c10451

Claire Morand, Daniele Mantione, Andrew P. Dove, Haritz Sardón, Coralie Jehanno

{"title":"Controlling the cis/trans Content of Biobased Unsaturated Polyesters by Judicious Choice of a Biosourced Catalyst","authors":"Claire Morand, Daniele Mantione, Andrew P. Dove, Haritz Sardón, Coralie Jehanno","doi":"10.1021/acssuschemeng.4c10451","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10451","url":null,"abstract":"Replacing fossil-derived polymers with biobased alternatives is essential to reduce the environmental impact of plastics production, as it helps to decrease reliance on finite fossil resources and promotes sustainability by using renewable raw materials. However, biobased options remain scarce in the industry, as it is difficult to produce fully biobased polymers at a reasonable cost with the same functional properties. In this study, 100% biobased unsaturated polyesters are synthesized from maleic acid and 1,3-propanediol through bulk polycondensation mediated by biosourced catalysts. The resulting materials present different degrees of double bond isomerization depending on the catalyst employed, with higher trans content obtained using catalysts that exhibit greater nucleophilicity. With the objective of using these polyester resins for additive manufacturing, the reactivity of the double bonds was analyzed through FTIR and photo-DSC, while the cross-linking process was studied by photorheology, which highlighted the superior reactivity of the trans double bonds. This study opens avenues for the synthesis of 100% biosourced polyester resins with tunable cis/trans content.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"66 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853691","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