ChemPlusChem最新文献

{"title":"Bulky Ligands for Open Channels: Manganese (II) sql MOFs from Pyridyl-Functionalised [3]Polynorbornanes.","authors":"William Murrell, Pavel M Usov, Carol Hua, Fred Pfeffer","doi":"10.1002/cplu.202500065","DOIUrl":"10.1002/cplu.202500065","url":null,"abstract":"<p><p>Two, semi-linear, fused [n]polynorbornanes based aliphatic ligands (one a di-Methyl ester L_Me and the other a di-Ethyl ester L_Et) have been synthesised and used to form two isoreticular sql MOFs of the formula [Mn(L)₂(NO₃)₂]. Crystal structure analysis revealed large pores with a distinct lack of interpenetration with the nets neatly aligned to create extended 1D channels. Of interest, the ester moieties of these ligands orient into the channels highlighting the potential for creating customised, pore functionalised MOFs.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500065"},"PeriodicalIF":3.0,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143456353","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Novel DMAP@Mesoporous Silica Hybrid Heterogeneous Catalysts for the Knoevenagel Condensation: Greener Synthesis through Eco-friendly Solvents.","authors":"Julio C Fernandes P Brito, Fabio Travagin, Mauro Barbero, Cristina Esteban, Urbano Díaz, Alexandra Velty, Giovanni B Giovenzana, Ivana Miletto, Enrica Gianotti","doi":"10.1002/cplu.202400741","DOIUrl":"10.1002/cplu.202400741","url":null,"abstract":"<p><p>This article reports a sustainable synthesis of a novel organic-inorganic hybrid catalysts, featuring 4-(dimethylamino)pyridine (DMAP) immobilized onto mesoporous MCM-41 silica and amorphous Aerosil silica supports. Using (±)-2-methyltetrahydrofuran (MeTHF), a bio-based solvent, the covalent binding of DMAP to silica surfaces was achieved, reducing reliance on traditional petroleum-based solvents like toluene. The DMAP-functionalized hybrid catalysts, characterized through XRPD, TGA/DTA, FE-SEM, and FT-IR, demonstrated effective catalytic performance in the Knoevenagel condensation, a reaction relevant in producing fine chemicals and pharmaceuticals. The mesoporous MCM-41-supported catalyst exhibited superior activity due to its high surface area and ordered porous structure, with 97 % yield and 99 % selectivity. Stability and reusability were validated through leaching and recycling tests, confirming minimal DMAP leaching and robust catalytic performance over consecutive cycles. This green synthetic pathway underscores the potential of hybrid catalysts in advancing sustainable chemistry, promoting reduced energy consumption, and supporting a circular economy through recyclable, highly active catalysts in eco-friendly solvents. These findings demonstrate that MCM-41-supported DMAP hybrids are viable candidates for eco-friendly applications.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400741"},"PeriodicalIF":3.0,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447810","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multifluoro-Modification Enhancing Catalytic Activity and Thermal Stability of Bis(imino)pyridylcobalt Chlorides for Linear Polyethylene.","authors":"Zahra Hosseinzadeh, Qiuyue Zhang, Quanchao Wang, Ali Muhammad Ashfaq, Tongling Liang, Yanping Ma, Wen-Hua Sun","doi":"10.1002/cplu.202500007","DOIUrl":"10.1002/cplu.202500007","url":null,"abstract":"<p><p>The multifluoro aniline, 2,6-bis[bis(4-fluorophenyl)methyl]-4-trifluoromethoxy-phenylamine, is meticulously synthesized and utilized to form a series of bis(imino)pyridine derivatives. These derivatives react with cobalt chloride to give six bis(imino)pyridylcobalt (II) complexes (alkyl: 2,6-dimethyl Co1; 2,6-diethyl Co2; 2,6-diisopropyl Co3; 2,4,6-trimethyl Co4; 2,6-diethyl-4-methyl Co5; 2,6-bis[bis(4-fluorophenyl)methyl]-4-trifluoromethoxy Co6). High activity and good thermal stability in ethylene polymerization are achieved by these cobalt complexes in the presence of MAO or MMAO. Notably, superior polymerization results are observed in n-hexane compared to toluene with peak activity reaching 1.55×10⁷ g (PE) mol^-1 (Co) h^-1 at 70 °C in n-hexane. Moreover, the resulting polyethylenes are highly linear, featuring vinyl terminal group, and exhibit a wide range of molecular weights (M_w: 22.5-285 kg mol^-1) along with high melting points (T_m >127.3 °C).</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500007"},"PeriodicalIF":3.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439589","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stabilization of Verdigris Pigment on Paper: Evaluation of Antioxidants Under Mild Accelerated Degradation Conditions.","authors":"Jasna Malešič, Klara Retko, Matjaž Finšgar, Irena Kralj Cigić","doi":"10.1002/cplu.202400670","DOIUrl":"10.1002/cplu.202400670","url":null,"abstract":"<p><p>Copper-based pigments, such as verdigris, have caused severe damage to many important historical documents, and their preservation remains a significant concern for paper conservators and researchers. This study re-evaluates the efficacy of two promising antioxidants, tetrabutylammonium bromide (TBABr) and benzotriazole (BTA), as stabilization agents for paper documents containing verdigris pigment. The evaluation was conducted under mild accelerated degradation conditions using historically accurate mock-up paper samples. To assess the stability of the mock-up papers, various parameters were measured during accelerated degradation, including colour, molecular weight (Mw), and pH value. Size exclusion chromatography measurements of Mw confirmed that TBABr provided superior stabilization compared to BTA. Additionally, the total colour change was slightly more pronounced in the samples treated with BTA compared to those treated with TBABr. However, during degradation, some paper samples containing thicker application of pigment exhibited significant black and brown spots, regardless of treatment (untreated, treated with BTA, or TBABr). X-ray photoelectron spectroscopy confirmed the presence of both Cu(I) and Cu(II) oxidation states in all samples, with a higher Cu(II) content on the surface of TBABr treated samples compared to those treated with BTA. This may indicate differences in the mechanisms of degradation. Raman spectroscopy identified the spots on both untreated and TBABr-treated samples as copper(II) oxide.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400670"},"PeriodicalIF":3.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Triazole-Derived Ruthenium(II) Complexes as Novel Candidates for Cancer Therapy.","authors":"Oscar A Lenis-Rojas, Catarina Roma-Rodrigues, Beatriz Carvalho, Vasco Andrade, Sofia Friães, Pablo Cabezas-Sainz, Jhonathan Angel Araujo Fernández, Sabela Fernández Vila, Álvaro J Arana, Laura Sanchez, Pedro V Baptista, Clara S B Gomes, Alexandra R Fernandes, Beatriz Royo","doi":"10.1002/cplu.202400775","DOIUrl":"10.1002/cplu.202400775","url":null,"abstract":"<p><p>The first examples of Ru(II) η⁶-arene (benzene and p-cymene) complexes containing a bidentate triazolylidene-triazolide ligand have been prepared and fully characterized. Their antiproliferative effect has been investigated against tumour cells A2780 (ovarian carcinoma), HCT116 (colorectal carcinoma), and HCT116dox (colorectal carcinoma resistant to doxorubicin), and in human dermal fibroblasts. The Ru complex bearing the p-cymene arene group exhibited a stronger antiproliferative effect across all tested cell lines, while the benzene-containing complex displayed higher selectivity toward tumor cells. Both complexes induced apoptosis, likely through ROS production (in the benzene complex), and inhibited tumorigenic processes, including cell migration and angiogenesis. In zebrafish models, they showed strong selectivity for cancer cells with minimal toxicity to healthy cells, effectively reducing the proliferation of HCT116 colorectal cancer cells. This study provides the first in vivo evidence of the anticancer potential of Ru triazolylidenes in zebrafish models.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400775"},"PeriodicalIF":3.0,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143424626","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Greener Microplastics Removal: Progressive Replacement of Iron-Based Coagulants with Sodium Alginate and Chitosan to Enhance Sustainability.","authors":"Marco Facchino, Loris Pietrelli, Patrizia Menegoni, Mauro Capocelli, Emanuele Limiti, Marcella Trombetta, Francesco Basoli, Marcello De Falco","doi":"10.1002/cplu.202400736","DOIUrl":"10.1002/cplu.202400736","url":null,"abstract":"<p><p>Wastewater treatment plants (WWTPs) currently represent one of the main sources for microplastics (MPs) and other emerging contaminants entering the environment. Coagulation is a longstanding and cost-effective process designed to enhance the removal of colloidal particles and proved to be efficient in the abatement of MPs. The present study investigates the feasibility of a progressive replacement of ferric chloride (FeCl₃) with chitosan (CT) and sodium alginate (SA), starting from their use as coagulant aids. Coagulations tests were carried out to assess the performance of FeCl₃-CT and FeCl₃-SA systems in the removal of polystyrene (PS) microbeads, polyethylene (PE) and polyethylene terephthalate (PET) fragments with sizes lower than 500 μm. Results from experiments have shown that both CT and SA are useful to enhance the removal performance of conventional coagulation by improving the settling characteristics of flocs. The use of CT allows a reduction of coagulant dosage for removing PS and PE particles, while it turned out to be detrimental for the removal of PET fragments. Instead, SA at a concentration of 0.2 mg L^-1 proved to be useful both to achieve higher removal rate at a medium dosage of coagulant and to improve the efficiency of the process at lower dosages.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400736"},"PeriodicalIF":3.0,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143412607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cover Feature: Piercing the Shadows: Exploring the Influence of Signal Preprocessing on Interpreting Ultrasensitive Bioelectronic Sensor Data (ChemPlusChem 2/2025)","authors":"Mariapia Caputo,&nbsp;Lucia Sarcina,&nbsp;Cecilia Scandurra,&nbsp;Michele Catacchio,&nbsp;Matteo Piscitelli,&nbsp;Cinzia Di Franco,&nbsp;Paolo Bollella,&nbsp;Gaetano Scamarcio,&nbsp;Luisa Torsi,&nbsp;Eleonora Macchia","doi":"10.1002/cplu.202580202","DOIUrl":"https://doi.org/10.1002/cplu.202580202","url":null,"abstract":"<p><b>A single-molecule with a large transistor</b> (SiMoT) array is used to explore the impact of data preprocessing on electronic biosensor outcomes. Cyst fluid and plasma samples from 37 patients with pancreatic precursor cyst lesions are analyzed. New strategies to mitigate these effects are provided, ensuring that data interpretation remains accurate and reflective of the underlying biochemical information in the samples. More details can be found in the Research Article by Luisa Torsi, Eleonora Macchia, and co-workers (DOI: 10.1002/cplu.202400520).<figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"90 2","pages":""},"PeriodicalIF":3.0,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cplu.202580202","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143404334","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}

{"title":"Front Cover: Artificial Compartments Encapsulating Enzymatic Reactions: Towards the Construction of Artificial Organelles (ChemPlusChem 2/2025)","authors":"Peng Lin,&nbsp;Shiwei Zhang,&nbsp;Futa Komatsubara,&nbsp;Hiroaki Konishi,&nbsp;Eiji Nakata,&nbsp;Takashi Morii","doi":"10.1002/cplu.202580201","DOIUrl":"https://doi.org/10.1002/cplu.202580201","url":null,"abstract":"<p><b>The front cover shows</b> the artificial compartments constructed using liposomes, polymersomes, proteins, DNA nanostructures, and hybrid materials. Enzymes have been incorporated, assembled, or spatially organized into the membrane or membraneless compartments to efficiently carry out the enzymatic reactions or metabolic pathways and to understand the chemistry behind the compartment function. These compartments can be the building blocks to construct the artificial organelles with the target functions. More details can be found in the Review by Takashi Morii and co-workers (DOI: 10.1002/cplu.202400483).<figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"90 2","pages":""},"PeriodicalIF":3.0,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cplu.202580201","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143404714","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}

{"title":"Phenoxazinone Synthase-Like Catalytic Activity of Bi- and Trinuclear Copper(II) Complexes with 2-Benzylethanolamine: Experimental and Theoretical Investigations.","authors":"Oksana V Nesterova, Olena E Bondarenko, Armando J L Pombeiro, Dmytro S Nesterov","doi":"10.1002/cplu.202400613","DOIUrl":"10.1002/cplu.202400613","url":null,"abstract":"<p><p>The self-assembly reaction of 2-benzylaminoethanol (Hbae) with CuCl₂ or Cu(NO₃)₂ leads to the formation of binuclear [Cu₂(bae)₂(Cl)₂] (1) and [Cu₂(Hbae)₂(bae)₂](NO₃)₂ (2) complexes, while the trinuclear [Cu₃(Hbae)₂(bae)₂(dmba)₂](NO₃)₂ (3) compound was obtained using the auxiliar bulky substituted 2,2-dimethylbutyric acid (Hdmba). Crystallographic studies reveal the molecular structures of 1 and 2 based on the similar {Cu₂(μ-O)₂} core, while the structure of 3 features the {Cu₃(μ-O)₂} core with consecutive arranement of the metal centres, supported by the additional carboxylate bridges. The strong intermolecular hydrogen bonds join the molecular structures into 1D (for 1 and 3) or 2D (for 2) architectures. All three compounds act as catalysts for the aerobic oxidation of 2-aminophenol to the phenoxazinone chromophore (phenoxazinone synthase-like activity) with the maximum reaction rates up to 2.3×10^-8 M s^-1. The substrate scope involves methyl-, nitro- and chloro-substituted 2-aminophenols, disclosing the negligible activity of nitro-derivatives, while the 6-amino-m-cresol substrate shows the highest activity with the initial reaction rate of 5.8×10^-8 M s^-1. The mechanism of the rate-limiting reaction step (copper-catalysed formation of 2-aminophenoxyl radicals) was investigated at the DFT level. The combined DFT and CASSCF studies of the copper superoxo Cu^II-OO⋅ radical species as possible unconventional reaction intermediates resulted in a rational mechanism of H-atom abstraction, where the activation energies follow the experimental reactivity of substituted 2-aminophenols. The TDDFT and STEOM-DLPNO-CCSD theoretical calculations of the absorption spectra of substrates, phenoxazinone chromophores and putative polynuclear species containing 2-aminophenoxo ligand are reported.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400613"},"PeriodicalIF":3.0,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143389483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Computational Design of Covalently Bonded Mixed Stacking Cocrystals.","authors":"Lam H Nguyen, Thanh N Truong","doi":"10.1002/cplu.202500028","DOIUrl":"10.1002/cplu.202500028","url":null,"abstract":"<p><p>In this study, a computational design of a new type of donor-acceptor mixed stacking cocrystals is introduced. Our approach involves functionalizing trisilasumanene frameworks with electron-donating groups (-CH₃, -OH, -NH₂) and electron-withdrawing groups (-F, -CN), and then stacking donors and acceptors alternatively while connecting them either by sp³- and sp-carbon chains. Using the B3LYP-D3/6-31+G(d) level of theory, we demonstrate that these covalently bonded cocrystals can overcome the issue of thermal and mechanical instabilities observed in the non-covalently mixed stacking. Furthermore, modifying donor and acceptor groups can vary the bandgaps, approximated by the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) gaps, from 1.50 to 3.50 eV. The results also predict the covalently bonded mixed stacking cocrystals having much larger conductance via Yoshizawa model. In addition, variations in bridge lengths were found to have a small effect on the HOMO-LUMO gaps but allow for a new control parameter regarding the porosity of the materials. These results encourage experimental explorations.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500028"},"PeriodicalIF":3.0,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143381332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}