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Thermodynamic Insights on the Structure-Property Relationships in Substituted Benzenes: Are the Pairwise Interactions in Tri-Substituted Methyl-Nitro-Benzoic Acids Still Valid?
IF 3 4区 化学
ChemPlusChem Pub Date : 2025-02-03 DOI: 10.1002/cplu.202400703
José M Silva Ferraz, Vladimir N Emel'yanenko, Dzmitry H Zaitsau, Artemiy A Samarov, Bruno Brunetti, Andrea Ciccioli, Stefano Vecchio Ciprioti, Sergey P Verevkin
{"title":"Thermodynamic Insights on the Structure-Property Relationships in Substituted Benzenes: Are the Pairwise Interactions in Tri-Substituted Methyl-Nitro-Benzoic Acids Still Valid?","authors":"José M Silva Ferraz, Vladimir N Emel'yanenko, Dzmitry H Zaitsau, Artemiy A Samarov, Bruno Brunetti, Andrea Ciccioli, Stefano Vecchio Ciprioti, Sergey P Verevkin","doi":"10.1002/cplu.202400703","DOIUrl":"10.1002/cplu.202400703","url":null,"abstract":"<p><p>A comprehensive experimental thermochemical study of nine methyl-substituted nitrobenzoic acids was carried out, leading to the final standard molar enthalpies of formation in the gas phase. The combustion energies were measured using high-precision combustion calorimetry, and the enthalpies of formation of the crystal phase were derived. The sublimation enthalpies were obtained from the vapor pressure-temperature dependencies measured using the classic Knudsen effusion mass loss and the transpiration methods. The standard molar enthalpies of vaporisation were derived from the temperature dependence of the mass-loss rates measured using the non-isothermal thermogravimetry. The thermal behaviour, including melting temperatures and standard molar enthalpies of fusion, was investigated by DSC. The high-level quantum chemical G* methods were used for the mutual validation of the experimental and theoretical gas phase enthalpies of formation of methyl-substituted nitrobenzoic acids. The consistent set of experimental properties at the reference temperature T=298 K was evaluated and recommended for thermochemical calculations. The pairwise interactions of the substituents on the benzene ring were derived from nitro-toluenes, methyl-benzoic acids and nitro-benzoic acids available in the literature, and the additivity of the contributions when three substituents are placed simultaneously in the benzene ring was discussed.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400703"},"PeriodicalIF":3.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143078079","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}
引用次数: 0
Automated Investigation of Metal-Ligand Interactions by a Newly Established Robotic Workflow for Titrations.
IF 3 4区 化学
ChemPlusChem Pub Date : 2025-02-03 DOI: 10.1002/cplu.202400686
Michael Ringleb, Lukas Klähn, Stefan Zechel, Ulrich S Schubert
{"title":"Automated Investigation of Metal-Ligand Interactions by a Newly Established Robotic Workflow for Titrations.","authors":"Michael Ringleb, Lukas Klähn, Stefan Zechel, Ulrich S Schubert","doi":"10.1002/cplu.202400686","DOIUrl":"10.1002/cplu.202400686","url":null,"abstract":"<p><p>In this work, we present a new workflow to set up an automated platform for the investigation of metal complex formation in solutions. With the utilization of this robot titration platform, the generation of an abundancy of solvated metal complexes in differing coordination number is possible in a simple manner. The generated complexes can subsequently be sampled into differing vessels to examine them in detail. We present sampling for UV/Vis and NMR spectroscopy at chosen model systems, however, the platform can easily be adapted to provide samples for other techniques, e. g., for infrared spectroscopy.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400686"},"PeriodicalIF":3.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143121789","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}
引用次数: 0
Heteroleptic (NHC/MIC) Biscarbene Ag(I) and Au(I) Complexes: Synthesis, Characterization and Catalytic Applications.
IF 3 4区 化学
ChemPlusChem Pub Date : 2025-01-29 DOI: 10.1002/cplu.202400765
Francisco J Ruiz-Mendoza, Emmanuel Campos-Dominguez, M Guadalupe Torres-Salazar, Alejandro Álvarez-Hernández, Daniel Mendoza-Espinosa
{"title":"Heteroleptic (NHC/MIC) Biscarbene Ag(I) and Au(I) Complexes: Synthesis, Characterization and Catalytic Applications.","authors":"Francisco J Ruiz-Mendoza, Emmanuel Campos-Dominguez, M Guadalupe Torres-Salazar, Alejandro Álvarez-Hernández, Daniel Mendoza-Espinosa","doi":"10.1002/cplu.202400765","DOIUrl":"10.1002/cplu.202400765","url":null,"abstract":"<p><p>A series of hetero-biscarbene silver(I) and gold(I) complexes of the general formula [NHC-M-MIC]PF<sub>6</sub> (NHC=imidazol-2-ylidene, MIC=1,2,3-triazol-5-ylidene) have been prepared via the treatment of NHC-M-Cl precursors in reaction with an in situ generated mesoionic carbene (MIC). The new heteroleptic complexes have been fully characterized including NMR spectroscopy, elemental analysis, melting points and single crystal X-ray diffraction. The silver(I) derivatives were employed successfully in the solvent free KA<sup>2</sup> (ketone-alkyne-amine) coupling for the preparation of a series of quaternary carbon-containing propargyl amines while, the gold(I) biscarbenes, demonstrated a good performance in the A<sup>3</sup> (aldehyde, amine, alkyne) coupling and the benzylic oxidation processes under low catalyst loadings.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400765"},"PeriodicalIF":3.0,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062836","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}
引用次数: 0
Effect of UV Light Exposure Duration on the Removal of Exfoliation Agent Residues in Two-Dimensional Perovskite Nanosheets: An AFM Study
IF 3 4区 化学
ChemPlusChem Pub Date : 2025-01-29 DOI: 10.1002/cplu.202400678
Fatma Pinar Gordesli-Duatepe, Begümnur Küçükcan, Özge Sağlam
{"title":"Effect of UV Light Exposure Duration on the Removal of Exfoliation Agent Residues in Two-Dimensional Perovskite Nanosheets: An AFM Study","authors":"Fatma Pinar Gordesli-Duatepe,&nbsp;Begümnur Küçükcan,&nbsp;Özge Sağlam","doi":"10.1002/cplu.202400678","DOIUrl":"10.1002/cplu.202400678","url":null,"abstract":"<p>Accurate determination of dielectric properties and surface characteristics of two-dimensional (2D) perovskite nanosheets, produced by chemical exfoliation of layered perovskites, is often hindered by exfoliation agent residues such as tetrabutylammonium (TBA). This study investigated the effect of ultraviolet (UV) light exposure duration on the removal of TBA residues from 2D Ca<sub>2</sub>NaNb<sub>4</sub>O<sub>13</sub><sup>−</sup> nanosheets deposited on silicon substrates via Langmuir-Blodgett method using atomic force microscopy (AFM). Nanoscale adhesion forces between silicon AFM tips and nanofilms exposed to UV light for 3, 12, 18, and 24 hours were measured. Nanofilms exposed to UV for 12 hours showed significant heterogeneity in adhesion forces compared to control nanofilms not exposed to UV. This heterogeneity improved after 18 hours and reached maximum homogeneity at 24 hours. A noticeable decrease in adhesion forces indicated a reduction in TBA residues after 18 hours, with further reduction observed at 24 hours. The most probable adhesion forces for control nanofilms and those exposed to UV for 3 and 12 hours were 1.6-fold and 2.0-fold higher, respectively, compared to nanofilms exposed to UV for 18 and 24 hours. Similarly, surface roughness peaked at 12 hours and then decreased with longer exposure, resulting in a smoother surface at 24 hours.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"90 3","pages":""},"PeriodicalIF":3.0,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cplu.202400678","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057604","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
Solvent Effect on Antimicrobial Hydrophilic Xerogel Coating of Medicinal Leathers in Simulated Industrial Finishing Process.
IF 3 4区 化学
ChemPlusChem Pub Date : 2025-01-29 DOI: 10.1002/cplu.202400648
Theofanis Bompotis, Eirini Karastergiou, Konstantinos Giannakopoulos, Evangelos P Favvas, Marina Arvanitopoulou, Konstantinos Arvanitopoulos, Labros Arvanitopoulos, Georgia Kytherioti, Michail Vardavoulias, Dimitrios A Giannakoudakis, Laura Castellsagués, Sara Maria Soto González, Michael Arkas
{"title":"Solvent Effect on Antimicrobial Hydrophilic Xerogel Coating of Medicinal Leathers in Simulated Industrial Finishing Process.","authors":"Theofanis Bompotis, Eirini Karastergiou, Konstantinos Giannakopoulos, Evangelos P Favvas, Marina Arvanitopoulou, Konstantinos Arvanitopoulos, Labros Arvanitopoulos, Georgia Kytherioti, Michail Vardavoulias, Dimitrios A Giannakoudakis, Laura Castellsagués, Sara Maria Soto González, Michael Arkas","doi":"10.1002/cplu.202400648","DOIUrl":"10.1002/cplu.202400648","url":null,"abstract":"<p><p>The hydrophilic character and the protection against pathogen proliferation are the most pivotal characteristics of leathers intended for medical purposes. To achieve these goals, dispersions of TiO<sub>2</sub> particles incorporating three different formulations of biomimetically synthesized silica xerogels were tested. Emphasis has been given to the role of single and dual solvents employed. Microbiocide capability was induced by benzalkonium chloride along with silver nanoparticles. Particular emphasis should be given to hyperbranched poly(ethylene imine) multifunctional roles. Spontaneous mineralization of silver ions is realized in the dendritic cavities. The same polymer acts as a matrix that interacts with the hydrogen bonding network of orthosilicic acid directing and facilitating gel formation. Furthermore, it contributes to both hydrophilicity and antimicrobial properties. Gel formation and subsequent drying occur in the pores of the impregnated TiO<sub>2</sub> substrate. The resistance of the leathers to fungal and bacterial infections and biofilm formation was assessed against Klebsiella Pneumoniae, Escherichia coli, Pseudomonas aeruginosa, Enterococcus faecalis, Staphylococcus aureus, and Candida albicans. The affinity to water was proved by the contact angle method. The proposed treatment is a prospective environmentally friendly replacement to the standard finishing process of medical leathers.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400648"},"PeriodicalIF":3.0,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062838","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}
引用次数: 0
Exploring Supramolecular Frustrated Lewis Pairs.
IF 3 4区 化学
ChemPlusChem Pub Date : 2025-01-29 DOI: 10.1002/cplu.202400725
Paige R Hawkins, Chris S Hawes, Peter D Matthews
{"title":"Exploring Supramolecular Frustrated Lewis Pairs.","authors":"Paige R Hawkins, Chris S Hawes, Peter D Matthews","doi":"10.1002/cplu.202400725","DOIUrl":"10.1002/cplu.202400725","url":null,"abstract":"<p><p>Frustrated Lewis pairs (FLPs) have rapidly become one of the key metal-free catalysts for a variety of chemical transformations. Embedding these catalysts within a supramolecular assembly can offer improvements to factors such as recyclability and selectivity. In this review we discuss advances in this area, covering key supramolecular assemblies such as metal organic frameworks (MOFs), covalent organic frameworks (COFs), polymers and macrocycles.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400725"},"PeriodicalIF":3.0,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057605","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}
引用次数: 0
Half-Sandwich Organometallic Ir(III) and Ru(II) Compounds and their Interactions with Biomolecules.
IF 3 4区 化学
ChemPlusChem Pub Date : 2025-01-29 DOI: 10.1002/cplu.202400621
Sandra Kozieł, Daria Wojtala, Magdalena Szmitka, Monika Lesiów, Aleksandra Ziółkowska, Jacek Sawka, Edgar Del Carpio, Debbie C Crans, Urszula K Komarnicka
{"title":"Half-Sandwich Organometallic Ir(III) and Ru(II) Compounds and their Interactions with Biomolecules.","authors":"Sandra Kozieł, Daria Wojtala, Magdalena Szmitka, Monika Lesiów, Aleksandra Ziółkowska, Jacek Sawka, Edgar Del Carpio, Debbie C Crans, Urszula K Komarnicka","doi":"10.1002/cplu.202400621","DOIUrl":"https://doi.org/10.1002/cplu.202400621","url":null,"abstract":"<p><p>This review highlights how a Ir(III) and Ru(II) coordination complexes can change theirs cytotoxic activity by interacting with a biomolecules such as deoxyribonucleic acid (DNA), human albumins (HSA), nicotinamide adenine dinucleotide (NADH), and glutathione (GSH). We have selected biomolecules (DNA, NADH, GSH, and HSA) based on their significant biological roles and importance in cellular processes. Moreover, this review may provide useful information for the development of new half-sandwich Ir(III) and Ru(II) complexes with desired properties and relevant biological activities. Additionally, the examples discussed here may help us better understand what happens to a metal-based drug once it enters the body.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400621"},"PeriodicalIF":3.0,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057606","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}
引用次数: 0
PtAu-Carbon Nanotube/Glassy Carbon Electrode Composite Based Electrochemical Sensor for High-Precision Detection of Tetracycline.
IF 3 4区 化学
ChemPlusChem Pub Date : 2025-01-27 DOI: 10.1002/cplu.202400525
Ying Wang, Tianpeng Liu, Yanghai Feng, Lei Zhu, Jiping Jia, Hui Zhang, Yukou Du
{"title":"PtAu-Carbon Nanotube/Glassy Carbon Electrode Composite Based Electrochemical Sensor for High-Precision Detection of Tetracycline.","authors":"Ying Wang, Tianpeng Liu, Yanghai Feng, Lei Zhu, Jiping Jia, Hui Zhang, Yukou Du","doi":"10.1002/cplu.202400525","DOIUrl":"10.1002/cplu.202400525","url":null,"abstract":"<p><p>With enrichment of tetracycline (TC) in ecosystems, its accurate detection has become a major concern. Noble-metal nano-particles have attracted great interest as potential materials for sensing applications because of their remarkable electrical properties and adaptability. Herein, a novel electro-chemical detection technique based on carbon nano-tubes (CNTs) as the support material is developed to detect TC with high precision. To achieve a characteristic response to TC, a composite electrode for detection electrode is prepared by loading platinum-gold (PtAu) nano-particles on CNTs surface via electro-deposition. The oxidation peak at 0.38 V is used as the signal probe to draw a standard curve by comparing the intensities of the oxidation peaks at various TC concentrations. The PtAu-CNTs/GCE sensor exhibits remarkable sensitivity (LOD=1.05×10<sup>-8</sup> mol/L) and anti-interference properties. This study demonstrates the potential for TC detection in complex environments.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400525"},"PeriodicalIF":3.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143051094","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}
引用次数: 0
Open Rotaxane Surgery: What Molecular Editing Can Offer to Supramolecular Chemistry?
IF 3 4区 化学
ChemPlusChem Pub Date : 2025-01-27 DOI: 10.1002/cplu.202500038
Jędrzej P Perdek, Rafał A Grzelczak, Bartosz Szyszko
{"title":"Open Rotaxane Surgery: What Molecular Editing Can Offer to Supramolecular Chemistry?","authors":"Jędrzej P Perdek, Rafał A Grzelczak, Bartosz Szyszko","doi":"10.1002/cplu.202500038","DOIUrl":"10.1002/cplu.202500038","url":null,"abstract":"<p><p>The skeletal editing approach represents a paradigm shift in organic synthesis by directly targeting the molecular skeleton instead of relying on often long and complicated series of organic transformations. Recent advancements in nitrogen atom deletion reactions have enabled unprecedented late-stage, precise modifications of bioactive compounds and complex natural products, influencing a seemingly distant field such as supramolecular chemistry. In a recent contribution, the Leigh group demonstrated the extrusion of a nitrogen atom from an axle of a [2]rotaxane, extending the applicability of molecular editing to complex, mechanically interlocked architectures. This highlight seeks to examine the significance of the skeletal editing method in supramolecular chemistry, address its challenges, and offer an outlook on future directions in this emerging field.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500038"},"PeriodicalIF":3.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143045085","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}
引用次数: 0
Computational Insights into the Mechanism of Lewis Acid-Catalyzed Alkene-Aldehyde Coupling.
IF 3 4区 化学
ChemPlusChem Pub Date : 2025-01-24 DOI: 10.1002/cplu.202400751
Ricardo Meyrelles, Bogdan R Brutiu, Boris Maryasin
{"title":"Computational Insights into the Mechanism of Lewis Acid-Catalyzed Alkene-Aldehyde Coupling.","authors":"Ricardo Meyrelles, Bogdan R Brutiu, Boris Maryasin","doi":"10.1002/cplu.202400751","DOIUrl":"10.1002/cplu.202400751","url":null,"abstract":"<p><p>The Lewis acid-catalyzed coupling of alkenes and aldehydes presents a modern, versatile synthetic alternative to classical carbonyl addition chemistry, offering exceptional regio- and stereoselectivity. In this work, we present a comprehensive computational investigation into the reaction mechanism of this transformation. Our findings confirm the occurrence of an enantioselective transannular [1,5]-hydride shift step and demonstrate that the enantioselectivity of the reaction arises predominantly from steric clashes between functional groups in the cyclization step. Combining computational and experimental results, we establish that the Lewis acid catalyst facilitates the initial C-O coupling step between the alkene and the activated aldehyde. Investigations into systems with longer alkyl chains reveal that while they follow a similar mechanistic pathway, cyclization becomes kinetically hindered, preventing the reaction from proceeding. These insights illuminate the factors governing reaction outcomes and limitations, paving the way for future developments in this area.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400751"},"PeriodicalIF":3.0,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143031562","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}
引用次数: 0
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