化学•材料最新文献

{"title":"Weak Interactions Break Strong Bonds: Noncovalent Complexes of H-X with N-Heterocycles.","authors":"Jagadeesan Sreelakshmy, Kalarikkal B Indulekha, Eapen Thomas, Cherumuttathu H Suresh","doi":"10.1021/acs.jpca.4c06558","DOIUrl":"10.1021/acs.jpca.4c06558","url":null,"abstract":"<p><p>The phenomenon of positive cooperativity in noncovalent complexes, arising from electron donor-acceptor (eDA) interactions and subsequent electron reorganization, has been investigated by using density functional theory (DFT) at the ωB97XD/6-311 + G(3df,2pd) level. The study focuses on the interaction of various nitrogen- and oxygen-containing heterocycles with HF and HCl molecules. The formation of dimer complexes leads to electron flow from the nitrogen lone pair to the hydrogen halide, enhancing the electron density on the halogen atom, as made evident by molecular electrostatic potential (MESP) analysis. The introduction of additional HX molecules induces positive cooperativity, strengthening noncovalent N···H interaction and ultimately facilitating spontaneous H-X bond cleavage and formation of stable ion pairs. Substituent effects and positional isomerism in substituted pyridines reveal that electron-donating groups─especially at the ortho position─markedly enhance bond activation via neighboring group effects. Cooperative enhancement is also demonstrated in higher-order clusters (trimers to pentamers), particularly for the stronger H-F bond, which requires greater interaction synergy to cleave. The studies on O-heterocycles highlighted the impact of electronegativity on the extent of bond activation and the requirement for additional cooperative interactions to achieve H-X bond cleavage. The Δ<i>V</i>_n(Cl) MESP parameter shows a strong correlation with interaction energy, serving as a predictive descriptor of bond activation. These findings provide valuable insights into the remarkable ability of weak noncovalent interactions to facilitate the breaking of strong bonds, offering insights with broad implications for catalysis, molecular design, and noncovalent bond activation strategies.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4835-4843"},"PeriodicalIF":2.7,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144118344","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}

{"title":"¹H and ¹⁹F NMR Toolbox for Examining Interactions between Fluorinated Compounds and Polystyrene Nanoparticles.","authors":"Sekinah O Dauda, Rajan Rai, Emily G Cushman, Ashley Abel, Daphna Shimon, Leah B Casabianca","doi":"10.1021/acs.jpcb.5c02259","DOIUrl":"10.1021/acs.jpcb.5c02259","url":null,"abstract":"<p><p>Per- and polyfluoroalkyl substances (PFAS) and micro- and nanoplastic (MNP) are both emerging environmental pollutants, yet the interactions between the two are rarely studied on a fundamental level. Here we use a suite of NMR techniques to examine binding between polystyrene nanoparticles (PSNP) and fluorinated compounds or nonfluorinated analogues, with the aim of understanding how fluorination influences the strength of binding. In addition, we have compared the different NMR techniques in terms of reproducibility and ease of use. We find that fluorination does not have a significant effect on binding for aromatic compounds or aliphatic alcohols. However, we have established a toolbox of both quantitative and qualitative NMR techniques that can be used to examine binding between a large receptor and fluorinated compounds either with or without NMR-observable hydrogen atoms.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"5642-5651"},"PeriodicalIF":2.8,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144126228","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}

{"title":"Performance of Density Functional Approximations in Calculations of Electronic Two-Photon Transition Strengths of Fluorescent Dyes.","authors":"Marta Chołuj","doi":"10.1021/acs.jpca.5c01509","DOIUrl":"10.1021/acs.jpca.5c01509","url":null,"abstract":"<p><p>The performance of B3LYP, PBE0, and CAM-B3LYP functionals in the prediction of the two-photon transition strengths (for low-energy transitions) of 18 dipolar donor-acceptor systems containing a difluoroborate moiety was evaluated against results obtained using the resolution-of-identity implementation of the coupled-cluster CC2 model. The generalized few-state model approach, in which the two-photon transition strength is expressed in terms of electronic structure parameters, i.e., excitation energies, dipole moments, and transition dipole moments, was applied to gain deeper insight into the behavior of selected exchange-correlation functionals. The obtained results show that all three functionals provide two-photon transition strengths that differ significantly from the reference strengths, especially in the case of molecules exhibiting the highest 2PA strength.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4903-4910"},"PeriodicalIF":2.7,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144135899","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}

{"title":"Single-Lipid Diffusion Behaviors in Cell Membranes Modulated by Cholesterol-Based Heterogeneity.","authors":"Xiao Xu, Cheng Xu, Wanting Zhang, Zhiheng Liu, Yushuang Wei, Kai Yang, Bing Yuan","doi":"10.1021/acs.jpcb.5c01625","DOIUrl":"10.1021/acs.jpcb.5c01625","url":null,"abstract":"<p><p>Over a century after the proposal of Fluid Mosaic Model, the relationship between functionally related multiple-scale spatial heterogeneity of the cell membrane and mobility of component molecules, both inherent features of cell membrane, remains elusive. Single-lipid tracking enables the analysis of structural heterogeneity at different spatial scales within the cell membrane from a lipid diffusion perspective. Herein, specifically designed cholesterol (Chol)-based membrane systems were utilized to investigate the distinct impacts of molecular-level interactions between diverse membrane components and micrometer-scale spatial confinement on lipid diffusion. The results demonstrate that the incorporation of Chol into 1,2-dioleoyl-<i>sn-glycero</i>-3-phosphocholine (DOPC) membranes decelerates lipid diffusion, with a positive correlation observed between the degree of deceleration and the mole ratio of Chol molecules. Across all these systems, lipid diffusion consistently adheres to the continuous time random walk (CTRW) model, indicating lipid entrapment resulting from specific molecular interactions. Conversely, micrometer-scale spatial confinement induced by phase separation not only reduces the diffusion rate of DOPC molecules but also triggers a transition from CTRW to fractional Brownian motion (fBM) or random walk on a fractal (RWF) mode within a confinement width range of 6.3-5.4 μm, suggesting a crowded microenvironment. In living cell membranes, this transformation in lipid diffusion is observed following Chol depletion, implying that lipid raft disruption leads to increased crowding within the lipid microenvironment. This study enhances our understanding of the relationship between lipid diffusion and membrane microenvironment across different spatial scales while providing insights into characterizing spatially heterogeneous structures within cell membranes from the perspective of lipid diffusion.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"5464-5476"},"PeriodicalIF":2.8,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148680","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}

{"title":"Assessment of Anticancer and Antibacterial Activities of Patchouli Essential Oil Nanoemulsion.","authors":"Irom Ragish Singh, Ajmal Koya Pulikkal, Malsawmdawngkima Hnamte, Laldingliani Tlau Bualchhuak, Awadhesh Kumar","doi":"10.1021/acs.jpcb.5c01654","DOIUrl":"10.1021/acs.jpcb.5c01654","url":null,"abstract":"<p><p>Patchouli essential oil (PEO) obtained from <i>Pogostemon cablin</i>, acclaimed for its therapeutic properties and aroma, has gained increased attention for its potential applications in the food, pharmaceutical, and cosmeceutical industries. However, the application of PEO is modest due to its hydrophobicity, poor solubility in aqueous media, and high volatility. Nanoemulsions (NEs) rescue these inconsistencies with their proficiency in encapsulating PEO as nanosized droplets, thus providing a new dimension to the modern-day drug delivery of PEO. The present work reports the preparation of patchouli essential oil-based nanoemulsions (PNEs) by ultrasonication using Tween 80 as an emulsifier and water as the continuous medium. Twelve PNEs were prepared with 1:1, 1:2, and 1:3 oil-to-surfactant ratios (OSRs) and sonication times of 5, 10, 15, and 20 min. An increase in the sonication time and a decrease in the level of the OSR reduced the average droplet diameter (<i>Z</i>_avg) of the PNEs. PNE with 1:3 OSR and 20 min sonication was optimized for biological studies as it displayed the minimum <i>Z</i>_avg (∼14 nm), maximum stability upon centrifugation (5000 rpm), thermal treatment (30, 60, and 90 °C), and storage (4 weeks), where it showed a slowest Ostwald ripening rate (ω) of ∼6.7 × 10^-6 nm³ s^-1. The optimized PNE showed <i>in vitro</i> anticancer activity against A549 lung cancer cells by showing cell cytotoxicity and inducing apoptosis. The observation of a lower IC₅₀ of the optimized PNE (0.71 μL mL^-1) than that of PEO (1.13 μL mL^-1) confirmed improved anticancer activity. The first evidence of anticancer activity of PNE against the A549 lung cancer cell line is presented. Moreover, the optimized PNE also showed antibacterial activity against <i><i>Vibrio cholerae</i></i>, <i>Bacillus cereus</i>, <i><i>Escherichia coli</i></i>, <i>Staphylococcus aureus</i>, and <i><i>Salmonella typhimurium</i></i> with minimum inhibitory concentration (MIC) values of 3.12, 3.12. 6.25, 6.25, and 3.12 μg mL^-1, respectively.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"5630-5641"},"PeriodicalIF":2.8,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144155246","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}

{"title":"[5]Helicene-Embedded Cycloparaphenylene Nanohoops with Möbius Topology: Synthesis, Photophysical Properties, and Aromaticity.","authors":"Huiji Yang, Shengzhu Guo, Weijie Guo, Lin Liu, Xiaoyu Liu, Jing He, Yanqing Fan, Zhe Lian, Xiaonan Li, Shu Huang, Xuebo Chen, Ying Wang, Hua Jiang","doi":"10.1002/asia.202500205","DOIUrl":"https://doi.org/10.1002/asia.202500205","url":null,"abstract":"<p><p>The relationship between Möbius topology and aromaticity still remains elusive, which is largely due to the related synthetic challenges and, further, the scarcity in both the quantity and the diversity of the constructed Möbius systems. In this work, we report the synthesis of [4n]Möbius conjugated all-carbon nanohoops ([5]H-[7,8]CPPs) by utilizing a [5]helicene unit as a hidden writhe and a masked aromatic unit to overcome the strain inherited from Möbius topology. X-ray analyses reveal that [5]H-[7,8]CPPs contain a [5]helicene moiety and an oligoparaphenylene unit, clearly exhibiting Möbius topology. Photophysical investigations demonstrated that [5]H-[7,8]CPPs exhibited moderately high fluorescence quantum yields, significantly higher than those of pristine [5]helicene and [7,8]CPPs. Chiroptical studies revealed that [5]H-[7,8]CPPs displayed an obvious Cotton effect in circular dichroism and bright circularly polarized luminescence, indicating efficient transfer of chirality from the [5]helicene to the overall carbon nanohoops. Importantly, theoretical investigations reveal that, though possessing a Möbius topology and a 4n π-electron array in the neutral state, [5]H-[7,8]CPPs fundamentally exhibit local Hückel aromaticity, while their dications, with a 4n + 2 π-electron in the conjugation circuits, show Hückel in-plane global aromaticity, deviating from the Heilbronner prediction. The results may help us to better understand the complicated relationship between Möbius topology and aromaticity.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00205"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223821","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}

{"title":"Unveiling the Pyridine Functionalized Dicyanostilbene/Reduced Graphene Oxide Electrode Materials for High Performance Symmetric Supercapacitors.","authors":"Sudhir D Jagadale, Sidhanath V Bhosale, Sheshanath V Bhosale","doi":"10.1002/asia.202500125","DOIUrl":"https://doi.org/10.1002/asia.202500125","url":null,"abstract":"<p><p>Pseudocapacitors (PSCs) are attractive alternatives with great potential in the next generation of electrical energy storage (EES) devices. So far, PSCs are mainly fabricated using inorganic transition metal oxides. To overcome the cost and stability issues of such PSCs, organic electrode materials available from renewable sources are attracting researchers' attention. In this study, to enhance the electrochemical performance of PSCs, we non-covalently functionalized reduced graphene oxide (rGO) substrate with a redox-active (2Z,2'Z)-2,2'-(1,4-phenylene)bis(3-(pyridin-4-yl)acrylonitrile) (DCBS), yielding the composite electrode systems. The presence of the pyridine ring system in combination with the nitrile (─C≡N) functional group provides an additional contribution of faradaic reversible redox reactions and stability of the DCBS/rGO electrode in PSC performance. Significantly, our DCBS/rGO composite electrode-based three-electrode supercapacitor (SC) device exhibited excellent specific capacitance of 318.98 F g^-1 at 0.5 A g^-1 current density. Moreover, in symmetric supercapacitor (SSC) cell configuration, the DCBS/rGO at 0.5 A g^-1 current density displayed C_sp as high as 135.10 F g^-1 and an energy density of 24.31 Wh kg^-1 at 1080 W kg^-1 power density. The SSC device showed great C_sp retention (98.3%) after 10000 galvanostatic charge-discharge (GCD) cycles at a current density of 3 A g^-1. The present investigation underscores the DCBS/rGO based electrode materials offer ideas to improve the charge storage capacity, device stability and energy density for supercapacitors.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00125"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223830","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}

{"title":"Organotin(IV) carboxylates-derivatives of bexarotene: synthesis, characterization, anti/prooxidant activity, and high cytotoxicity.","authors":"D A Burmistrova, N P Pomortseva, N T Berberova, N R Almyasheva, M A Kiskin, A I Poddel'sky, A S Vashurin, I V Smolyaninov","doi":"10.1007/s00775-025-02117-w","DOIUrl":"https://doi.org/10.1007/s00775-025-02117-w","url":null,"abstract":"<p><p>New organotin(IV) mono- and bis-carboxylate complexes derivatives of Bexarotene (bex), viz. R₃Sn(bex) (where R = Ph (1); Cy (2); nBu (3)), and R₂Sn(bex)₂ (where R = Et (4), tBu (5), Ph (6)) were synthesized. Compounds were fully characterized using spectroscopic techniques. The molecular structure for the Ph₃Sn(bex) (1) in crystalline form was established by single-crystal X-ray diffraction. Electrochemical properties of tin complexes and bexarotene were investigated by cyclic voltammetry. The target compounds are characterized by the high oxidation potentials in the mixture of aprotic solvents. The anti/prooxidant activity of the complexes and bexarotene in the lipid peroxidation process and in the reaction of the DNA oxidative damage was studied in vitro. Excellent cell growth inhibition against A549, HCT 116 and MCF-7 cancer cells was observed for triorganotin (IV) carboxylates with IC₅₀ values mostly under the submicromolar concentration range and there are more effective than bexarotene or cisplatin.</p>","PeriodicalId":603,"journal":{"name":"Journal of Biological Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144214578","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}

{"title":"<i>tert</i>-Butyl Carbonate as a Nucleophile in Epoxide Ring Opening: A Cascade Synthesis of 5-(Hydroxymethyl)oxazolidin-2-one.","authors":"Kelly Lee, Xsingyi Lee, Ci-Yi Zhou, Yung-Lan Chu, Cheng-Kun Lin","doi":"10.1021/acs.joc.5c00537","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00537","url":null,"abstract":"<p><p>We report an efficient and scalable synthesis of 5-(hydroxymethyl)oxazolidin-2-ones using <i>tert</i>-butyl carbonate as a nucleophile in a Boc₂O-mediated epoxide ring-opening cascade. Optimization identified Et₃N as key to high yields, with electron-withdrawing aryl groups further enhancing efficiency (up to 91%). Mechanistic studies support the nucleophilic role of <i>tert</i>-butyl carbonate. This versatile method enables access to pharmaceutically relevant compounds, including intermediates for Linezolid, highlighting its value in medicinal chemistry.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144214365","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}

{"title":"Fabrication of Flexible Nanoporous Platinum Films via One-Pot Liquid Crystal Templated Synthesis","authors":"Seren Demir, Pelin Polat, Necip Ayhan Tertemiz, Beyza Vural, Elian Melissa Babahan, Ozan Baran Orhan, Nahit Polat, Sinan Balci, Fadime Mert Balci","doi":"10.1021/acs.jpcc.5c01829","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01829","url":null,"abstract":"Nanoporous platinum (NPP) thin films are crucial for applications in electrocatalysis, fuel cells, nanophotonics, and gas sensing. Conventional fabrication methods, such as dealloying, often leave residual elements that degrade the performance of the NPP thin films in applications such as electrocatalysis. In this study, for the first time, we introduce a novel method to fabricate ultrapure, flexible, large-area NPP thin films through a one-pot, liquid crystal-templated synthesis. A hexagonal lyotropic liquid crystal (LLC) phase, composed of a strong acid, a nonionic surfactant, water, and hexachloroplatinic acid, serves as a template. The LLC films, prepared with hexachloroplatinic acid concentrations of 0.1–0.5 M, exhibit distinct optical textures under a polarizing optical microscope and display low-angle diffraction patterns when analyzed with an X-ray diffractometer. Calcination at 450 °C yields ultrapure, conductive, and black colored NPP films. Importantly, we fabricate freestanding NPP thin films and successfully transfer them onto both rigid and flexible substrates. Bending tests reveal that a four-layer flexible NPP film having a thickness of around ∼174 nm maintains a stable sheet resistance (∼30 ohm/sq) after several hundred bend cycles (1000 cycles). These findings highlight the potential of ultrapure NPP films with high nanopore and ligament density for applications in electrocatalysis, fuel cells, gas sensors, broadband absorbers, bioelectronics, and flexible electronics.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"12 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219417","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}