Ju-Yeon Seo, Bahar Mostafiz, Xiaomin Tu, Constantine Yuri Khripin, Ming Zheng, Han Li, Emilia Peltola
{"title":"Single-Chirality Single-Wall Carbon Nanotubes for Electrochemical Biosensing","authors":"Ju-Yeon Seo, Bahar Mostafiz, Xiaomin Tu, Constantine Yuri Khripin, Ming Zheng, Han Li, Emilia Peltola","doi":"10.1039/d4cp04206a","DOIUrl":"https://doi.org/10.1039/d4cp04206a","url":null,"abstract":"Single-wall carbon nanotubes (SWCNTs) exhibit versatile optoelectronic properties closely linked to their structural characteristics, such as chiral angles and diameters. Given this, they are promising materials for biosensors. However, in studies investigating SWCNT-based electrochemical biosensors, raw soot has been mostly used. Soot typically contains a mixture of different chiralities, metallic compounds, and various impurities from the synthesis process. As a result, this mixture significantly limits the reproducibility and precision of SWCNT-based sensors. To ensure consistent sensor performance, we employed an aqueous two-phase extraction technique to purify and sort single-chirality SWCNTs—specifically, semiconducting (6,5) SWCNTs and metallic (6,6) SWCNTs. In addition, we used multiple fabrication methods to ensure that only pure-chirality SWCNTs were deposited onto the electrodes. Our findings emphasise the importance of using surfactant-free systems when investigating the influence of chirality on the electrochemical behaviour of SWCNTs. By using monochiral SWCNTs, we achieved precise control over their concentration and density, allowing us to assess their electrochemical properties accurately. Our results reveal that the adsorption-controlled process of the inner sphere redox probe (ISR) occurs on (6,5) SWCNTs, while a diffusion-controlled process is observed on (6,6) SWCNTs. These findings provide valuable insights that will enhance the performance of SWCNTs-based electrochemical biosensors.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"60 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385604","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":"Proton Transport in Liquid Phosphoric Acid: The Role of Nuclear Quantum Effects Revealed by Neural Network Potential","authors":"Pei Liu, Wei Li, Shuhua Li","doi":"10.1039/d4cp04195j","DOIUrl":"https://doi.org/10.1039/d4cp04195j","url":null,"abstract":"Pure phosphoric acid exhibits high proton conductivity and is widely used in modern industry. However, its proton transport (PT) mechanism remains less understood compared to that of water, which presents a significant challenge for advancing technologies like phosphoric acid fuel cells. In this study, we utilize machine learning (ML) potentials and molecular dynamics (MD) simulations to investigate the proton diffusion mechanisms in liquid phosphoric acid systems. The neural network potentials (NNPs) we developed demonstrate quantum chemical accuracy and stability across a range of temperatures. Our simulations reveal continuous proton hopping between phosphoric acid anions. Moreover, the radial distribution functions (RDFs) and diffusion coefficients obtained from ring polymer MD (RPMD)—a variant of path-integral MD (PIMD)—exhibit improved alignment with experimental values compared to classical MD results, as RPMD inherently accounts for nuclear quantum effects (NQEs) on proton behavior. Additionally, we employed neural networks (NN) combined with the charge equilibration method to predict the charge distribution in liquid phosphoric acid, examining the PT mechanism through vibrational spectra analysis. These findings provide deeper insights into the high proton conductivity of liquid phosphoric acid.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385665","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}
Rafael Alessandro Lima Chioquetti, Raphael Prata Bacil, Silvia Serrano
{"title":"A new approach to a first order irreversible homogeneous chemical reaction followed by an electrochemical process: theory, simulation and application","authors":"Rafael Alessandro Lima Chioquetti, Raphael Prata Bacil, Silvia Serrano","doi":"10.1039/d4cp04092a","DOIUrl":"https://doi.org/10.1039/d4cp04092a","url":null,"abstract":"Chronoamperometric profiles were derived for systems in which an irreversible, homogeneous chemical reaction generates an electroactive species that readily reacts at the surface of a planar electrode. From the resulting current (i) equations, a convolution approach was proposed to extract the rate constant of the chemical reaction through non-linear fitting. These equations were validated using digital simulations, and the semi-derivative approach successfully recovered the simulated parameters. The proposed kinetic method was then applied experimentally to the chemical oxidation of iodide by hydrogen peroxide in acidic medium, followed by the electrochemical reduction of triiodide. The rate constants measured with this kinetic method were consistent with existing literature across various temperatures, and an Arrhenius plot led to a reasonable value for an activation energy of the process.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"4 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385667","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":"Ferrocene derivatives and aniline copolymers with tunable magnetoresistance and dielectric properties","authors":"Huiyan Ren, Hongbo Gu","doi":"10.1039/d4cp04612a","DOIUrl":"https://doi.org/10.1039/d4cp04612a","url":null,"abstract":"Inspired by the electron-rich characteristics of ferrocene (Fc), we have strategically integrated this compound into polyaniline (PANI), aiming to modulate the magnetoresistance (MR) and dielectric properties of PANI. The copolymers (P(ANI-co-FcA)) were synthesized by copolymerization of aniline and 1,1’-bis[(4-aminophenyl)amino]carbon]ferrocene (FcA). The resistivity and temperature-dependent resistivity are performed to unveil the charge carrier transport mechanism, aligning with the Efros-Shklovskii variable-range hopping (ES-VRH) model. Additionally, the MR and dielectric properties are tuned by alternating the FcA content in the main chain of copolymers. MR analysis reveals a positive effect, which is intensified with an increased FcA content. Notably, the MR effect of P(ANI-co-FcA)-3 attains 1.51% under a magnetic field of 3 T. The real permittivity of copolymers is changed from negative to positive values upon the incorporation of FcA. This research proffers an approach to manipulating the electrical performance of conducting polymer materials for potential applications in electronic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385605","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}
Esther del Pino Rosendo, Okan Yildiz, Wojciech Pisula, Tomasz Marszalek, Paul W. M. Blom, Charusheela Ramanan
{"title":"Correction: Symmetry-breaking charge transfer and intersystem crossing in copper phthalocyanine thin films","authors":"Esther del Pino Rosendo, Okan Yildiz, Wojciech Pisula, Tomasz Marszalek, Paul W. M. Blom, Charusheela Ramanan","doi":"10.1039/d5cp90033f","DOIUrl":"https://doi.org/10.1039/d5cp90033f","url":null,"abstract":"Correction for ‘Symmetry-breaking charge transfer and intersystem crossing in copper phthalocyanine thin films’ by Esther del Pino Rosendo <em>et al.</em>, <em>Phys. Chem. Chem. Phys.</em>, 2023, <strong>25</strong>, 6847–6856, https://doi.org/10.1039/D2CP05240G.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"17 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385666","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}
Mohammadhasan (Hadi) Dinpajooh, Greta L Hightower, Richard E Overstreet, Lori A Metz, Neil Henson, Niranjan Govind, Andrew Ritzmann, Nicolas E Uhnak
{"title":"On the Stability Constants of Metal-Nitrate Complexes in Aqueous Solutions","authors":"Mohammadhasan (Hadi) Dinpajooh, Greta L Hightower, Richard E Overstreet, Lori A Metz, Neil Henson, Niranjan Govind, Andrew Ritzmann, Nicolas E Uhnak","doi":"10.1039/d4cp04295f","DOIUrl":"https://doi.org/10.1039/d4cp04295f","url":null,"abstract":"Stability constants of simple reactions involving addition of the NO<small><sub>3</sub></small><small><sup>-</sup></small> ion to hydrated metal complexes, [M(H<small><sub>2</sub></small>O)<small><sub>x</sub></small>]<small><sup>n+</sup></small> are calculated with a computational workflow developed using cloud computing resources. The computational workflow performs conformational searches for metal complexes at both low and high levels of theories in conjunction with a continuum solvation model (CSM). The low-level theory is mainly used for the initial conformational searches, which are complemented with high-level density functional theory conformational searches in the CSM framework to determine the coordination chemistry relevant for stability constant calculations. In this regard, the lowest energy conformations are found to obtain the reaction free energies for the addition of one NO<small><sub>3</sub></small><small><sup>-</sup></small> to [M(H<small><sub>2</sub></small>O)<small><sub>x</sub></small>]<small><sup>n+</sup></small> complexes, where M represents Fe(II), Fe(III), Sr(II), Ce(III), Ce(IV), and U(VI), respectively. Structural analysis of hundreds of optimized geometries at high-level theory reveals that NO<small><sub>3</sub></small><small><sup>-</sup></small> coordinates with Fe(II) and Fe(III) in either a monodentate or bidentate manner. Interestingly, the lowest-energy conformations of Fe(II) metal-nitrate complexes exhibit monodentate or bidentate coordination with a coordination number of 6 while the bidentate seven-coordinated Fe(II) metal-nitrate complexes are approximately 2 kcal/mol higher in energy. Notably, for Fe(III) metal-nitrate complexes, the bidentate seven-coordinated configuration is more stable than the six-coordinated Fe(II) complexes (monodentate or bidentate) by a few thermal energy units. In contrast, Sr(II), Ce(III), Ce(IV), and U(VI) metal ions predominantly coordinate with NO<small><sub>3</sub></small><small><sup>-</sup></small> in a bidentate manner, exhibiting typical coordination numbers of 7, 9, 9, and 5, respectively. Stability constants are accordingly calculated using linear free energy approaches to account for the systematic errors and good agreements are obtained between the calculated stability constants and the available experimental data.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"17 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385670","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}
Guoqing Zhang, Zhen Cui, Aming Song, Shuang Zhang, Lu Wang
{"title":"Self-powered photodetector of GaN/Sc2CCl2 heterojunction with high carrier mobility and polarization sensitivity","authors":"Guoqing Zhang, Zhen Cui, Aming Song, Shuang Zhang, Lu Wang","doi":"10.1039/d4cp04162c","DOIUrl":"https://doi.org/10.1039/d4cp04162c","url":null,"abstract":"This study is based on first-principles calculations to investigate the GaN/Sc<small><sub>2</sub></small>CCl<small><sub>2</sub></small> heterojunction, and its electrical properties, optical properties, and photogalvanic effect under linearly polarized light are calculated. The GaN/Sc<small><sub>2</sub></small>CCl<small><sub>2</sub></small> heterojunction is a narrow-bandgap semiconductor (1.15 eV) with excellent dynamic and thermal stability, featuring electron transfer from the GaN layer to the Sc<small><sub>2</sub></small>CCl<small><sub>2</sub></small> layer. The heterojunction exhibits high carrier mobility (5670 cm<small><sup>2</sup></small> V<small><sup>−1</sup></small> s<small><sup>−1</sup></small>) and significantly enhanced light absorption in the visible spectrum compared to its monolayer counterparts. For the GaN/Sc<small><sub>2</sub></small>CCl<small><sub>2</sub></small> self-powered photodetector, the photocurrent shows little variation between linearly and elliptically polarized light, indicating low sensitivity to polarization type. Notably, at a photon energy of 1.2 eV, the photocurrent and extinction ratio reach maximum values of 12.78 <em>a</em><small><sub>0</sub></small><small><sup>2</sup></small> per photon and 326.1, respectively, demonstrating excellent photoresponse and high polarization sensitivity. The GaN/Sc<small><sub>2</sub></small>CCl<small><sub>2</sub></small> heterojunction can be used as an efficient photodetector material in fields such as photodetection. This research provides an effective strategy for designing high-performance heterojunction photodetectors.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"47 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375233","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}
N. Setti, A. Barrahi, M. Maatallah, Y. Kaddouri, R. Touzani, Abdelkader Zarrouk, A. Dafali, Burak Dikici, Khalid Karrouchi, Hatem A. Abuelizz
{"title":"Structure effect of the bipyrazol derivatives on corrosion inhibition of mild steel in 1M HCl: Weight loss, electrochemical measurements, XPS/SEM surface analysis, DFT and MC simulation","authors":"N. Setti, A. Barrahi, M. Maatallah, Y. Kaddouri, R. Touzani, Abdelkader Zarrouk, A. Dafali, Burak Dikici, Khalid Karrouchi, Hatem A. Abuelizz","doi":"10.1039/d4cp02946a","DOIUrl":"https://doi.org/10.1039/d4cp02946a","url":null,"abstract":"The inhibitory study of 4-(bis((1H-pyrazol-1-yl) methyl) amino) phenol (2PzH) and 4-(bis(3,5-dimethyl-1H-pyrazol-3-ylmethyl)amino] phenol (2PzMe) on mild steel (M-S) corrosion in 1M HClaggressive medium was conducted via, electrochemical techniques, thermodynamic parameters, XPS and SEM analysis. In fact, dissolution thermodynamic parameters and adsorption processes were worked out using the temperature change in gravimetric measurements. Obviously, the inhibition efficacy rises with the rise in 2PzH concentration to get to 95.7% and 2PzMe to get to 95.9% at 10-3M. The polarization measurement (PDP) also argued that these compounds are the mixed inhibitors. EIS measurements have divulged that the charge transfer resistance increased with the increase in inhibitor concentration. The bipyrazolic compounds were adsorbed on the steel surface as stated by the Langmuir adsorption model which was presented by chemisorption. These results were further strengthened by elemental characterization of the metal/solution contact employing XPS, for the two molecules tested. SEM technique disclosed the passive film forming on the metallic surface. The computational approach was computed utilizing the DFT method and Monte Carlo/Molecular dynamic (MC/MD) analysis to treat both the structure of 2PzH and 2PzMe in order to link the electron properties to the both compounds’ adsorption and inhibitory actions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375237","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":"In2F2 monolayer: a new class of two-dimensional materials with negative Poisson's ratio and topological phase","authors":"Shahram Yalameha, Javad Zahmatkesh, Fatemeh Zamanian, Zahra Nourbakhsh","doi":"10.1039/d4cp04871g","DOIUrl":"https://doi.org/10.1039/d4cp04871g","url":null,"abstract":"Two-dimensional (2D) materials have garnered significant attention for their exceptional potential in electronic, optical, and flexible nanodevices. In this study, we introduce a novel 2D In<small><sub>2</sub></small>F<small><sub>2</sub></small> monolayer, revealed through first-principles calculations, and demonstrate its thermal, dynamic, and mechanical stability. Our findings show that the In<small><sub>2</sub></small>F<small><sub>2</sub></small> monolayer exhibits notable anisotropic mechanical behavior, including auxetic properties characterized by a negative Poisson's ratio. Electronic band structure calculations, using both PBE–GGA and HSE06 functionals, indicate that this monolayer is a semiconductor with a small, nontrivial topological bandgap of approximately 1.58 meV. The observed s–p band inversion and calculated <img align=\"middle\" alt=\"Image ID:d4cp04871g-t1.gif\" src=\"https://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2025/CP/D4CP04871G/d4cp04871g-t1.gif\"/> invariant, confirm the presence of a nontrivial topological phase in this material. Furthermore, the optical absorption spectrum reveals strong anisotropy, with significant absorption in the visible to near-infrared range along the <em>y</em>-axis, suggesting potential applications in polarized photodetectors and anisotropic optoelectronic devices. The relatively low work function (3.86 eV) further increases its suitability for electron-emission applications, such as thermionic devices. These mechanical, electronic, and optical properties position the In<small><sub>2</sub></small>F<small><sub>2</sub></small> monolayer as a promising candidate for next-generation electronics, flexible electronics, and anisotropic optoelectronics.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"17 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375181","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":"Aromatic Trails. Persistence and Interplay Between Linked Spherical Aromatic Dicarboranes in Dimer to Hexamer Linear Arrays","authors":"Alvaro Muñoz-Castro","doi":"10.1039/d4cp03930k","DOIUrl":"https://doi.org/10.1039/d4cp03930k","url":null,"abstract":"The consecutive crack-link between well-defined building blocks is a plausible strategy in developing molecularly conceived materials. Here, we evaluate the resulting behavior of dimer to hexamer linear arrays based on linking spherical aromatic para-[C2B10H10] clusters (1) as relevant motifs toward understanding the characteristics of extended linear materials. Our results exhibit the persistence of spherical aromatic properties from the parent building block as isolated spherical aromatic states within the overall structure. Under different orientations of the applied field, the multiple enabled shielding cones at each linked cluster can evolve from a perfectly parallel disposition to an enhanced overlap under rotation. In addition, large values of NICS isosurfaces serve to locate the independent spherical aromatic states, whereas the use of anisotropy (NICSaniso) recovers the resulting isotropic regions at such states within the overall linear structure. Such behavior is expected to be envisaged in extended linear arrays and non-covalently interacting scenarios, such as self-assembled monolayers. Our results encourage further quests for understanding the interplay between different linked aromatic states, envisaging and unraveling the overall behavior of extended architectures designed by connecting aromatic building units.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"32 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375309","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}