Journal of Chemical Sciences最新文献

{"title":"One-dimensional titanium dioxide nanotube arrays for hydrogen generation","authors":"Swarna Lakshmi Rajendran,&nbsp;Viswanathan Alagan","doi":"10.1007/s12039-025-02420-8","DOIUrl":"10.1007/s12039-025-02420-8","url":null,"abstract":"<div><p>The ever-increasing global energy demand has necessitated alternate sources of energy. Photoelectrochemical water splitting proved to be a viable method of green hydrogen production. In the present study, four different one-dimensional titanium dioxide nanotube arrays (TNAs) were fabricated by varying the time duration of the second anodization. The highly ordered TNAs proved to be potential photoanodes for photoelectrochemical water splitting, for production of hydrogen. The fabricated TNAs were confirmed as stable anatase crystal structures using X-ray diffraction and Raman spectroscopy analysis. The TNAs showed an increase in length with an increase in anodization time. The morphological studies revealed the formation of the one-dimensional tube-like morphology of TNAs with lengths varying from 1.41 μm to 6.35 μm. The increased length and one-dimensional nanotube formation implied an increased number of active sites and an increased surface-to-volume ratio. The observed increase in photocurrent may be attributed to increased electrode–electrolyte interfacial area, where charge and mass transport occured. The band-gap of the TNAs showed a minimal progressive decrease with an increase in anodization time. The oxidation states of the constituent elements were confirmed using X-ray photoelectron spectroscopy. Contact angle measurement indicated a transition from slight hydrophobicity to slight hydrophilicity with an increase in the anodization time of the TNAs. Electrochemical studies of TNAs exhibited increased photo-response with an increase in anodization time. The influence of anodization time on the characteristics of TNAs is explored in this study.</p><h3>Graphical abstract</h3><p>TiO₂ Nanotube Arrays (TNAs) were synthesized by two – step anodization method, by varying second anodization time. The TNAs were tested for their efficacy as photo-anode, following exhaustive characterization techniques. The activity of the potential photoanodes for PEC water splitting was analyzed using LSV, CA, EIS and Tafel plots\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 4","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145037291","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":"Electron affinity, vertical detachment energies of nitromethane–water complexes: Dispersion–corrected density functional investigation","authors":"Sachin D Yeole,&nbsp;Saurabh Srivastava","doi":"10.1007/s12039-025-02409-3","DOIUrl":"10.1007/s12039-025-02409-3","url":null,"abstract":"<div><p>Microhydration of neutral and anionic nitromethane molecules was investigated up to <span>(n =10)</span> water molecules using dispersion-corrected density functional B2PLYPD with aug-cc-pVDZ basis sets. The calculated interaction energies of both anion and neutral nitromethane–water clusters were extrapolated to the complete basis set (CBS) limit. It was observed that the water molecules interact with the methyl group of the nitromethane in the case of a neutral molecule, whereas in anionic nitromethane hydration, water molecules build a hydrogen bond network strongly around the nitro group of the nitromethane. The SAPT analysis and MED critical point calculations have revealed that the anionic nitromethane–water cluster is more stable as compared to the neutral one. Further, the SAPT analysis showed that an increase in stability in case of the interaction in an anionic nitromethane–water complex is because of a higher attractive contribution from the electrostatic and dispersion components. The vertical detachment energy (VDE) and electron affinity (EA) values of nitromethane were also calculated, and the VDE values were found to be in good agreement with the experimental values.</p><h3>Graphical abstract</h3><p>Anionic Nitromethane-(H₂O)_n clusters investigated using Dispersion Corrected Density Functional Theory and compared with neutral counterparts. The calculated VDE values show good agreement with Experimental values.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 4","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007806","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":"Structure and lowest excitation properties of the backbone-modified GC PNA dimers","authors":"K Indumathi,&nbsp;A Abiram,&nbsp;G Praveena","doi":"10.1007/s12039-025-02398-3","DOIUrl":"10.1007/s12039-025-02398-3","url":null,"abstract":"<div><p>The proposed research aims to investigate the structure and lowest excitation properties of GG-CC and GC-CG (G, guanine; C, cytosine) peptide nucleic acid (PNA) dimers, incorporating different amino acids such as serine, aspartic acid, and histidine using the density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The structures under consideration have been optimized at the Becke’s three-parameter hybrid density functional (B3) with correlation function of Lee, Yang and Parr (LYP)/6-31G* level of theory. The study involves calculating the backbone torsions and backbone-base linker torsions, correlating them with experimental data. The computed excitation energy for the GG-CC PNA system is compared with the natural GG-CC DNA system. The lowest excitation properties, such as excitation energy, wavelength, and oscillator strength, reveal their dependency on both the stacking arrangement and the molecular environment, irrespective of whether the PNA is modified or unmodified. Additionally, a highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) analyses were conducted. This study is intended to serve as a foundational tool for understanding the molecular behaviour of PNAs under light absorption, potentially leading to further exploitation in photo-related applications.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 3","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144920458","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":"Application of CDFT and IT-based descriptors in analyzing structure, properties, reactivity and toxicity","authors":"Arpita Poddar,&nbsp;Pratim Kumar Chattaraj","doi":"10.1007/s12039-025-02401-x","DOIUrl":"10.1007/s12039-025-02401-x","url":null,"abstract":"<div><p>This article explores the application of conceptual density functional theory (CDFT) and information-theoretic approach (ITA) to various chemical phenomena, demonstrating their predictive power in diverse molecular systems. IT descriptors have been employed to investigate conformational stability, molecular acidity, aromaticity, and electrophilicity/nucleophilicity, revealing strong correlations between information-theoretic measures and experimental observations. Moreover, CDFT-based QSAR and QSPR models have shown significant predictive capabilities in pharmacological toxicity and physicochemical properties, such as partition coefficient and enthalpy of vaporization. The integration of CDFT and IT descriptors has provided deeper insights into reactivity trends in pericyclic reactions, allowing for the classification of mechanisms based on electrophilicity indices. Additionally, periodic trends in CDFT and IT descriptors have been examined, reaffirming the fundamental chemical principles. The review article underscores the robustness of IT and CDFT methodologies in capturing electronic structure variations and predicting the chemical behavior of molecules. The integration of these descriptors offers a comprehensive approach to understanding chemical reactivity, stability, and molecular interactions, paving the way for future advancements in theoretical and computational chemistry. </p><h3>Graphical abstract</h3><p>The applications of Conceptual Density Functional Theory (CDFT) and the Information-Theoretic Approach (ITA) have been widely used in predicting the toxicity, activity, and reactivity of chemical systems. Moreover, Quantitative Structure–Activity Relationship (QSAR) studies are conducted using CDFT and ITA descriptors through regression equations.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 3","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144920457","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":"Innovative synthesis of ketopeptide from lysine and methyl-3-hydroxybutyrate","authors":"Jiawei Cao,&nbsp;Jinxia Fu,&nbsp;Jianhao Ke,&nbsp;Jiahui Cheng,&nbsp;Hongyi Ren,&nbsp;Xuejing Wang,&nbsp;Zhe Wang,&nbsp;Jiaqi Li,&nbsp;Ruiting Ma,&nbsp;Zijin Xu,&nbsp;Gang Zhang,&nbsp;Shimin Kang","doi":"10.1007/s12039-025-02397-4","DOIUrl":"10.1007/s12039-025-02397-4","url":null,"abstract":"<p>The synthesis of ketopeptides is garnering significant interest due to their potential in pharmaceutical and health applications. This study introduces an efficient method for synthesizing a novel ketopeptide, 2-amino-6-[(3-hydroxy-1-oxobutyl) amino] hexanoic acid, known as BHB-L, from lysine and methyl-3-hydroxybutyrate (MHB) through an amidation reaction. Conducted under mild conditions (100 °C for 12 hours), this process achieved a lysine conversion rate of 92.5% and resulted in a BHB-L purity of 94.8%. The synthesized BHB-L demonstrated substantial thermal stability and was capable of releasing 3-hydroxybutyric acid (BHB) effectively in simulated human gastrointestinal environments. This research not only provides a feasible pathway for producing BHB-derived ketopeptides but also highlights their potential utility in medical and health-related fields.</p><p> A novel ketopeptide is first time prepared from lysine and methyl-3-hydroxybutyrate through amidation reaction, which can release 3-hydroxybutyric acid in simulated human gastrointestinal environments.</p>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 3","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144905172","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":"Ancient ambidextrous protein defies the rule of molecular handedness","authors":"Dibyendu Das","doi":"10.1007/s12039-025-02419-1","DOIUrl":"10.1007/s12039-025-02419-1","url":null,"abstract":"<div><p>A recent study by Liam Longo and co-workers at the Earth-Life Science Institute, published in Angewandte Chemie, reports the discovery of an ancient helix-hairpin-helix protein motif capable of functioning in both left- and right-handed forms, thus challenging the concept that biomolecular interactions are strictly dependent on homochirality. This rather rare “ambidextrous” property suggests that such motifs may be molecular relics from a pre-LUCA era when mirror-image life forms coexisted, and offers new insights into the origins and evolution of molecular asymmetry seen in living matter.</p><h3>Graphical abstract</h3><p>The ‘helix-hairpin-helix’ motif allows the binding of a simple peptide to both DNA and its mirror image. Credit: Liam M S Longo.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 3","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144888130","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":"Synthesis and characterization of polymeric linoleic acid graft copolymers using atom transfer radical polymerization","authors":"Abdulkadir AllI,&nbsp;Meltem Gündüz,&nbsp;Hayat Çulcu","doi":"10.1007/s12039-025-02412-8","DOIUrl":"10.1007/s12039-025-02412-8","url":null,"abstract":"<div><p>Linoleic acid modified through autoxidation, hydroxylation, and bromination was utilized for the first time in controlled/living radical polymerization methods such as atom transfer radical polymerization (ATRP). A brominated polymeric linoleic acid macromonomer initiator (ATRP–MIM) was synthesized as a macromolecular initiator (MIM) based on polymeric linoleic acid for use in ATRP. Using this ATRP–MIM and styrene monomer, novel graft copolymers were successfully synthesized via ATRP. The effects of various reaction parameters, including monomer concentration, initiator concentration, and polymerization kinetics, were systematically investigated. Additionally, the impact of reaction conditions on molecular weight and polydispersity was studied. The percentage compositions of the structural contents of graft copolymers were determined using ¹H NMR. Detailed characterization, including structural analysis, thermal properties, and molecular weight determination, was performed using techniques such as Fourier-transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The obtained graft copolymers exhibited enhanced thermal stability and well-defined molecular structures, contributing to the development of bio-based polymeric materials with specialized properties for applications in coatings, biocompatible systems, and advanced functional materials.</p><h3>Graphical abstract</h3><p>This study introduces the use of modified linoleic acid, altered through autoxidation, hydroxylation, and bromination, in controlled radical polymerization methods such as atom transfer radical polymerization (ATRP) for the first time. The research focuses on the synthesis of graft copolymers by using a brominated polymeric linoleic acid initiator (ATRP-MIM) in copolymerization with styrene.</p>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 3","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144880722","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":"Rate coefficients and Arrhenius parameters for the isomerization of 15 selected C7H7+ cations: A computational study","authors":"Kiew S Kharnaior,&nbsp;Shemphang Hynniewta","doi":"10.1007/s12039-025-02391-w","DOIUrl":"10.1007/s12039-025-02391-w","url":null,"abstract":"<div><p>In a previous communication (<i>Comp. Theor. Chem.</i> <b>1091</b> (2016) 150), concerted isomerization reactions of 15 C₇H₇⁺ cations in the gas phase had been studied. The present study deals with the kinetics of these concerted isomerization reactions using the M06-2X functional. From the potential energy profiles of these reactions, the rate coefficients are estimated by using transition state theory along with the estimation of Wigner’s empirical transmission coefficient for quantum tunnelling. The rate coefficient values are calculated over a temperature range of 200–500 K, where the Arrhenius activation energies, along with the pre-exponential factors, are determined for each of these reactions.</p><h3>Graphical abstract</h3><p>The graphical abstract highlight the two representative isomerisation reactions of bicyclo[3.2.0]heptadienyl cation <b>4</b> to tropyl cation <b>1</b> (global minimum) by C-C σ-bond collapse to π-bond via transition state <b>TS1</b> and <i>o</i>-tolyl cation <b>5</b> to benzyl cation <b>2</b> by 1,3-hydride shift via <b>TS4</b>.</p>\u0000<div><figure><div><div><picture><img></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 3","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144880864","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":"Conformational changes and domain motion of active site loops of apo and holo forms of serine hydroxymethyltransferase enzyme in aqueous medium","authors":"Shreya Rastogi,&nbsp;Kumari Soniya,&nbsp;Amalendu Chandra","doi":"10.1007/s12039-025-02400-y","DOIUrl":"10.1007/s12039-025-02400-y","url":null,"abstract":"<p>We have studied conformational changes in a pyridoxal <span>(5^prime)</span>-phosphate (PLP) dependent enzyme, namely serine hydroxymethyltransferase (SHMT), which plays an essential role in catalyzing the reversible simultaneous conversion of L-serine to glycine and tetrahydrofolate (THF) to 5,10-methylenetetrahydrofolate (folinic acid). When the substrate and PLP bind to SHMT, it undergoes a conformational change, transitioning from an open to a closed state. This closed state is achieved through subtle yet crucial movements in various loops within the enzyme, which are stabilized by interactions between active site residues, substrate and cofactor. In absence of interactions with the substrate and cofactor, the active site residues in the apo form of the enzyme are found to exhibit significant fluctuations. The current work reveals that three vital active site loops undergo conformational changes during the transition from the closed to open state. It may be noted that experimental studies comparing the crystal structures of apo and holo forms of SHMT have revealed domain movement upon substrate binding. Our study not only verifies the presence of this domain movement but also provides an in-depth analysis of the microenvironmental changes during the conformational transition.</p><p>We studied the conformational changes of serine hydroxymethyltransferase in apo and holo states. Three key active site loops, loop 1 (128–142), loop 2 (356–369), and loop 3 (48–68) play a crucial role in these transitions. In the holo form, Ser34 and Arg371 form hydrogen bonds with the PLP-SER complex, stabilizing these loops. In the apo form, the absence of these interactions induces chain movements, that affects distant structural regions. Specifically, Arg371 influences loop2 (356–369), while Ser34 affects loop3 (48–68). Hydrogen bonds and salt bridges are depicted as red and blue dashed lines. </p>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 3","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144880725","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":"Can carbene be used for a metal free reduction of carbon dioxide?","authors":"Priyanka Yadav,&nbsp;Pradeep Kumar","doi":"10.1007/s12039-025-02378-7","DOIUrl":"10.1007/s12039-025-02378-7","url":null,"abstract":"<p>Reduction of <span>(hbox {CO}_2)</span> to <span>(hbox {CO}_2)</span><span>(^-)</span> is a bottleneck in the conversion of <span>(hbox {CO}_2)</span> into various value-added chemicals. Here, based on quantum chemical calculations, we propose that the complexation of <span>(hbox {CO}_2)</span> with a carbene drastically reduces the electron affinity of <span>(hbox {CO}_2)</span> and thus makes the reduction of <span>(hbox {CO}_2)</span> spontaneous. Using various carbenes of different nucleophilicity, we have shown that the facile reduction of <span>(hbox {CO}_2)</span> in the presence of a carbene can be achieved for a variety of carbenes, and hence, offers an attractive route for converting <span>(hbox {CO}_2)</span> into various useful chemicals.</p><p> the reduction of CO<span>(_2)</span> to CO<span>(_2)</span> <span>(^-)</span> is a bottleneck in the conversion of CO<span>(_2)</span> into various value-added chemicals. There are two main challenges in converting CO<span>(_2)</span> to CO<span>(_2)</span> <span>(^-)</span>. First, the high energy barrier associated with CO<span>(_2)</span> to CO<span>(_2^-)</span> reduction, and a low solubility of CO<span>(_2)</span> in water. We have shown that by using a carbene-CO<span>(_2)</span> complex rather a bare CO<span>(_2)</span>, both of these limitations can be circumvented. </p>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 3","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144880724","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}