ACS Physical Chemistry Au最新文献

{"title":"Molecular CO2 Storage: State of a Single-Molecule Gas","authors":"Yoshifumi Hashikawa*,&nbsp;Shumpei Sadai and Yasujiro Murata*,&nbsp;","doi":"10.1021/acsphyschemau.3c00068","DOIUrl":"10.1021/acsphyschemau.3c00068","url":null,"abstract":"<p >CO₂ evolution is one of the urgent global issues; meanwhile, understanding of sorptive/dynamic behavior is crucial to create next-generation encapsulant materials with stable sorbent processes. Herein, we showcase molecular CO₂ storage constructed by a [60]fullerenol nanopocket. The CO₂ density reaches 2.401 g/cm³ within the nanopore, showing strong intramolecular interactions, which induce nanoconfinement effects such as forbidden translation, restricted rotation, and perturbed vibration of CO₂. We also disclosed an equation of state for a molecular CO₂ gas, revealing a very low pressure of 3.14 rPa (1 rPa = 10^–27 Pa) generated by the rotation/vibration at 300 K. Curiously enough, the CO₂ capture enabled to modulate an external property of the encapulant material itself, i.e., association of the [60]fullerenol via intercage hydrogen-bonding.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00068","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139501241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Magnetoelectrocatalysis: Evidence from the Hydrogen Evolution Reaction","authors":"Krysti L. Knoche Gupta,&nbsp;Heung Chan Lee and Johna Leddy*,&nbsp;","doi":"10.1021/acsphyschemau.3c00039","DOIUrl":"10.1021/acsphyschemau.3c00039","url":null,"abstract":"<p >Hydrogen evolution reaction (HER) rates are higher where magnetic gradients are established at electrode surfaces. In comparison of literature data for metals with comparable work functions, we note 1000× higher rates for paramagnetic metals than diamagnetic metals. With unpaired electron spins, paramagnetic and ferromagnetic metals establish interfacial magnetic gradients. At diamagnetic electrodes, gradients are induced by addition of magnetized microparticles. Onset of hydrogen evolution for magnetized γ-Fe₂O₃ microparticles in Nafion on diamagnetic glassy carbon electrodes is lower by 190 mV (−18 kJ mol^–1) relative to demagnetized microparticles. Chemically the same as demagnetized particles, the physical distinction of magnetic field and gradient at magnetized microparticles increases electron transfer rate. For magnetized Fe₃O₄ microparticles, the onset is lower by 280 mV (−27 kJ mol^–1). Paramagnetic platinum electrodes are unaffected by addition of magnetized microparticles. Magnetoelectrocatalysis is established by magnetic gradients.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00039","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139082884","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electron Transfer at Molecule–Metal Interfaces under Floquet Engineering: Rate Constant and Floquet Marcus Theory","authors":"Yu Wang,&nbsp; and ,&nbsp;Wenjie Dou*,&nbsp;","doi":"10.1021/acsphyschemau.3c00049","DOIUrl":"10.1021/acsphyschemau.3c00049","url":null,"abstract":"<p >Electron transfer (ET) at molecule–metal or molecule–semiconductor interfaces is a fundamental reaction that underlies all electrochemical processes and substrate-mediated surface photochemistry. In this study, we show that ET rates near a metal surface can be significantly manipulated by periodic driving (e.g., Floquet engineering). We employ the Floquet surface hopping and Floquet electronic friction algorithms developed previously to calculate the ET rates near the metal surface as a function of driving amplitudes and driving frequencies. We find that ET rates have a turnover effect when the driving frequencies increase. A Floquet Marcus theory is further formulated to analyze such a turnover effect. We then benchmark the Floquet Marcus theory against Floquet surface hopping and Floquet electronic friction methods, indicating that the Floquet Marcus theory works in the strong nonadiabatic regimes but fails in the weak nonadiabatic regimes. We hope these theoretical tools will be useful to study ET rates in the plasmonic cavity and plasmon-assisted photocatalysis.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00049","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138823514","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Vision for the Future of Astrochemistry in the Interstellar Medium by 2050","authors":"Ryan C. Fortenberry*,&nbsp;","doi":"10.1021/acsphyschemau.3c00043","DOIUrl":"10.1021/acsphyschemau.3c00043","url":null,"abstract":"<p >By 2050, many, but not nearly all, unattributed astronomical spectral features will be conclusively linked to molecular carriers (as opposed to nearly none today in the visible and IR); amino acids will have been observed remotely beyond our solar system; the largest observatories ever constructed on the surface of the Earth or launched beyond it will be operational; high-throughput computation either from brute force or machine learning will provide unprecedented amounts of reference spectral and chemical reaction data; and the chemical fingerprints of the universe delivered by those of us who call ourselves astrochemists will provide astrophysicists with unprecedented resolution for determining how the stars evolve, planets form, and molecules that lead to life originate. Astrochemistry is a relatively young field, but with the entire universe as its playground, the discipline promises to persist as long as telescopic observations are made that require reference data and complementary chemical modeling. While the recent commissionings of the <i>James Webb Space Telescope</i> and Atacama Large Millimeter Array are ushering in the second “golden age” of astrochemistry (with the first being the radio telescopic boom period of the 1970s), this current period of discovery should facilitate unprecedented advances within the next 25 years. Astrochemistry forces the asking of hard questions beyond the physical conditions of our “pale blue dot”, and such questions require creative solutions that are influential beyond astrophysics. By 2050, more creative solutions will have been provided, but even more will be needed to answer the continuing question of our astrochemical ignorance.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00043","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138589420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigation of Corrosion Inhibition of Mild Steel in 0.5 M H2SO4 with Lachancea fermentati Inhibitor Extracted from Rotten Grapefruits (Vitis vinifera): Adsorption, Thermodynamic, Electrochemical, and Quantum Chemical Studies","authors":"Baluchamy Tamilselvi,&nbsp;Durvas Seshian Bhuvaneshwari*,&nbsp;Periyakaruppan Karuppasamy*,&nbsp;Sethuramasamy Padmavathy,&nbsp;Santhosh Nikhil,&nbsp;Surendra Boppanahalli Siddegowda and H C Ananda Murthy*,&nbsp;","doi":"10.1021/acsphyschemau.3c00055","DOIUrl":"10.1021/acsphyschemau.3c00055","url":null,"abstract":"<p >Corrosion inhibition of mild steel (MS) was studied using <i>Lachancea fermentati</i> isolate in 0.5 M H₂SO₄, which was isolated from rotten grapes (<i>Vitis vinifera</i>) via biofilm formation. Biofilm over the MS surface was asserted by employing FT-IR and FE-SEM with EDXS, electrochemical impedance spectroscopy (EIS), AFM, and DFT-ESP techniques. The weight loss experiments and temperature studies supported the physical adsorption behavior of the corrosion inhibitors. The maximum inhibition efficiency (IE) value (90%) was observed at 293 K for 9 × 10⁶ cfu/mL of <i>Lachancea fermentati</i> isolate. The adsorption of <i>Lachancea fermentati</i> isolate on the surface of MS confirms Langmuir’s adsorption isotherm model, and the −Δ<i>G</i> values indicate the spontaneous adsorption of inhibitor over the MS surface. Electrochemical studies, such as potentiodynamic polarization (PDP) and EIS were carried out to investigate the charge transfer (CT) reaction of the <i>Lachancea fermentati</i> isolate. Tafel polarization curves reveal that the <i>Lachancea fermentati</i> isolate acts as a mixed type of inhibitor. The Nyquist plots (EIS) indicate the increase in charge transfer resistance (<i>R</i>_ct) and decrease of double-layer capacitance (<i>C</i>_dl) values when increasing the concentration of <i>Lachancea fermentati</i> isolate. The spectral studies, such as UV–vis and FT-IR, confirm the formation of a complex between MS and the <i>Lachancea fermentati</i> isolate inhibitor. The formation of biofilm on the MS surface was confirmed by FE-SEM, EDXS, and XPS analysis. The proposed bioinhibitor shows great potential for the corrosion inhibition of mild steel in acid media.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00055","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138581297","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Patterns Lead the Way to Far-from-Equilibrium Materials","authors":"Pamela Knoll*,&nbsp;Bin Ouyang* and Oliver Steinbock*,&nbsp;","doi":"10.1021/acsphyschemau.3c00050","DOIUrl":"10.1021/acsphyschemau.3c00050","url":null,"abstract":"<p >The universe is a complex fabric of repeating patterns that unfold their beauty in system-specific diversity. The periodic table, crystallography, and the genetic code are classic examples that illustrate how even a small number of rules generate a vast range of shapes and structures. Today, we are on the brink of an AI-driven revolution that will reveal an unprecedented number of novel patterns, many of which will escape human intuition and expertise. We suggest that in the second half of the 21st century, the challenge for Physical Chemistry will be to guide and interpret these advances in the broader context of physical sciences and materials-related engineering. If we succeed in this role, Physical Chemistry will be able to extend to new horizons. In this article, we will discuss examples that strike us as particularly promising, specifically the discovery of high-entropy and far-from-equilibrium materials as well as applications to origins-of-life research and the search for life on other planets.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00050","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138518807","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Follow Your Heart","authors":"Tianruo Shen*,&nbsp;","doi":"10.1021/acsphyschemau.3c00034","DOIUrl":"https://doi.org/10.1021/acsphyschemau.3c00034","url":null,"abstract":"","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00034","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138301467","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Screening 2D Materials for Their Nanotoxicity toward Nucleic Acids and Proteins: An In Silico Outlook","authors":"Titas Kumar Mukhopadhyay,&nbsp;Anupam Ghosh and Ayan Datta*,&nbsp;","doi":"10.1021/acsphyschemau.3c00053","DOIUrl":"10.1021/acsphyschemau.3c00053","url":null,"abstract":"<p >Since the discovery of graphene, two-dimensional (2D) materials have been anticipated to demonstrate enormous potential in bionanomedicine. Unfortunately, the majority of 2D materials induce nanotoxicity via disruption of the structure of biomolecules. Consequently, there has been an urge to synthesize and identify biocompatible 2D materials. Before the cytotoxicity of 2D nanomaterials is experimentally tested, computational studies can rapidly screen them. Additionally, computational analyses can provide invaluable insights into molecular-level interactions. Recently, various “<i>in silico</i>” techniques have identified these interactions and helped to develop a comprehensive understanding of nanotoxicity of 2D materials. In this article, we discuss the key recent advances in the application of computational methods for the screening of 2D materials for their nanotoxicity toward two important categories of abundant biomolecules, namely, nucleic acids and proteins. We believe the present article would help to develop newer computational protocols for the identification of novel biocompatible materials, thereby paving the way for next-generation biomedical and therapeutic applications based on 2D materials.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00053","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138494416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Simple and Efficient Detection Scheme of Two-Color Fluorescence Correlation Spectroscopy for Protein Dynamics Investigation from Nanoseconds to Milliseconds","authors":"Yutaka Sano,&nbsp;Yuji Itoh,&nbsp;Supawich Kamonprasertsuk,&nbsp;Leo Suzuki,&nbsp;Atsuhito Fukasawa,&nbsp;Hiroyuki Oikawa* and Satoshi Takahashi*,&nbsp;","doi":"10.1021/acsphyschemau.3c00040","DOIUrl":"10.1021/acsphyschemau.3c00040","url":null,"abstract":"<p >Nanosecond resolved fluorescence correlation spectroscopy (ns-FCS) based on two-color fluorescence detection is a powerful strategy for investigating the fast dynamics of biological macromolecules labeled with donor and acceptor fluorophores. The standard methods of ns-FCS use two single-photon avalanche diodes (SPADs) for the detection of single-color signals (four SPADs for two-color signals) to eliminate the afterpulse artifacts of SPAD at the expense of the efficiency of utilizing photon data in the calculation of correlograms. Herein, we demonstrated that hybrid photodetectors (HPDs) enable the recording of fluorescence photons in ns-FCS based on the minimal system using two HPDs for the detection of two-color signals. However, HPD exhibited afterpulses at a yield with respect to the rate of photodetection (&lt;10^–4) much lower than that of SPADs (∼10^–2), which could still hamper correlation measurements. We demonstrated that the simple subtraction procedure could eliminate afterpulse artifacts. While the quantum efficiency of photodetection for HPDs is lower than that for high-performance SPADs, the developed system can be practically used for two-color ns-FCS in a time domain longer than a few nanoseconds. The fast chain dynamics of the B domain of protein A in the unfolded state was observed using the new method.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00040","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135141298","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular Insights into Cu/Zn Metal Response to the Amyloid β-Peptide (1–42)","authors":"Anurag Prakash Sunda*,&nbsp; and ,&nbsp;Anuj Kumar Sharma*,&nbsp;","doi":"10.1021/acsphyschemau.3c00041","DOIUrl":"10.1021/acsphyschemau.3c00041","url":null,"abstract":"<p >Aβ1–40 peptide and Aβ1–42 peptide are the building units of beta-amyloid plaques present in Alzheimer’s disease (AD)-affected brain. The binding affinity of various divalent metal ions such as Cu and Zn present in AD-affected brain with different amino acids available in Aβ-peptide became the focus to explore their role in soluble neurotoxic oligomer formation. Cu²⁺ metal ions are known to enhance the neurotoxicity of the Aβ1–42 peptide by catalyzing the formation of soluble neurotoxic oligomers. The competitive preference of both Cu²⁺ and Zn²⁺ simultaneously to interact with the Aβ-peptide is unknown. The divalent Cu and Zn ions were inserted in explicit aqueous Aβ1–42 peptide configurations to get insights into the binding competence of these metal ions with peptides using classical molecular dynamics (MD) simulations. The metal-ion interactions reveal that competitive binding preferences of various peptide sites become metal-ion-specific and differ significantly. For Cu²⁺, interactions are found to be more significant with respect to those of Asp-7, His-6, Glu-11, and His-14. Asp-1, Glu-3, Asp-7, His-6, Glu-11, and His-13 amino acid residues show higher affinity toward Zn²⁺ ions. MD simulations show notable variation in the solvent-accessible surface area in the hydrophobic region of the peptide. Infinitesimal mobility was obtained for Zn²⁺ compared to Cu²⁺ in an aqueous solution and Cu²⁺ diffusivity deviated significantly at different time scales, proving its labile features in aqueous Aβ1–42 peptides.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00041","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135216593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}