ACS Physical Chemistry Au最新文献

{"title":"","authors":"Clark Otey, Mukund Sharma, Jazmine Prana, Thomas M. Czyszczon-Burton, Alejandro Hernandez, María Camarasa-Gómez*, Daniel Hernangómez-Pérez* and Michael S. Inkpen*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 3","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":3.7,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsphyschemau.5c00021","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144448910","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 Highly Water-Soluble C60-Oligo-Lysine Conjugate as a Type I and Type II Photosensitizer with Enhanced ROS Generation and Photocytotoxicity","authors":"Yue Ma,&nbsp;Lorenzo Persi,&nbsp;Kateryna A. Tolmachova,&nbsp;Maxim Yulikov,&nbsp;Miroslav Peterek,&nbsp;Stephan Handschin,&nbsp;Nicola Armaroli,&nbsp;Barbara Ventura* and Yoko Yamakoshi*,&nbsp;","doi":"10.1021/acsphyschemau.5c00023","DOIUrl":"10.1021/acsphyschemau.5c00023","url":null,"abstract":"<p >C₆₀ has been regarded as a suitable photosensitizer for photodynamic therapy due to its excitation in the phototherapeutic window (650–900 nm), high quantum yields of ¹O₂ generation, and low dark toxicity. However, the use of this molecule in biomedical applications has been limited by its high aggregation tendency in polar solvents (e.g., water), resulting in quenching of its excited states. In this study, a C₆₀-peptide conjugate, C₆₀-oligo-Lys, with a lower aggregation tendency was investigated by chemical, physical, and photophysical methods in comparison to a previously reported water-soluble C₆₀-PEG conjugate. Photoinduced ¹O₂ generation was evaluated by both phosphorescence at 1274 nm and the electron spin resonance method in an aqueous solution, with comparison to the control C₆₀-PEG, revealing the superior capacity of the C₆₀-oligo-Lys conjugate. Importantly, the photoinduced type I electron transfer reaction is occurring in C60-oligo-Lys very efficiently, even in the absence of an e^– donor, presumably due to the partially unprotonated amines in the peptide, to form O₂^•– and ^•OH, which are generated in a further enhanced way by the addition of a physiological concentration of NADH. These species are more harmful to the target cells, including hypoxic tissues with limited oxygen concentration. Femtosecond transient absorption spectroscopy revealed different excited state dynamics for C₆₀-oligo-Lys and C₆₀-PEG at short time scales in water. By an in vitro cellular assay, significant cytotoxicity of C₆₀-oligo-Lys was observed (IC₅₀ &lt; 1 μM) on HeLa cells under visible light irradiation (527, 630, and 660 nm), while very limited cytotoxicity was observed for C₆₀-PEG (IC₅₀ &gt; 25 μM) under the same conditions. The strongly enhanced photocytotoxicity of C₆₀-oligo-Lys can be ascribed to the higher generation of both type I and type II ROS in addition to the potential affinity of the positively charged oligo-Lys moiety for the negatively charged cell membrane. The C₆₀-oligo-Lys conjugate reported in this study therefore shows high potential as a core photosensitizer for photodynamic therapy.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 4","pages":"398–409"},"PeriodicalIF":4.3,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12291136/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144733635","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":"Nonlinear Spectroscopy in Chlorophyll Dimers Embedded in an Asymmetric Phonon Bath","authors":"Mohamad Toutounji*,&nbsp;","doi":"10.1021/acsphyschemau.4c00085","DOIUrl":"10.1021/acsphyschemau.4c00085","url":null,"abstract":"<p >The electronic transition dipole moment 4-point time correlation function for a dimeric photosynthetic complex, from which nonlinear optical time-domain signals may be obtained. This 4-point time correlation function draws on an experimentally fit spectral density of the surrounding phonons of the photosynthetic protein. The spectral density of the photosynthetic phonons renders a phonon-sideband characterized by its <i>asymmetry</i>, caused by the unequal contribution from the photosynthetic phonons (bath) to the low- and high-energy sides of the optical signals. This spectral density manifests its asymmetry explicitly in the 1-phonon profile, due to the intimate spectral connection between them, which will in turn reflect in the entire phononic part of the absorption spectrum. The asymmetry plays an important role in characterizing the exciton–phonon coupling strength and the phonon relaxation mechanism, thereby providing flexibility in modeling the degree of symmetry needed for the bath and imparting the capability of fine-tuning the nature of electron–phonon coupling caused by pigment–protein interaction. To this end, the obtained nonlinear optical electronic transition dipole moment time correlation functions (Liouville space pathways) whereby both excitonic and exciton–phonon couplings are accounted for are deemed convenient, more tractable, and computationally expedient, a unique advantageous feature in the case of a multimode system, which is often the case in photosynthetic complexes. Linear spectra and photon echo signals to probe pigment–protein complexes, in which pure electronic dephasing, vibrational relaxation effects, 1-phonon profile asymmetry, exciton–exciton coupling, and exciton–phonon coupling in bacterial reaction centers and photosynthetic complexes are provided.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 4","pages":"327–337"},"PeriodicalIF":4.3,"publicationDate":"2025-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12291140/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144733642","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":"Coffee Silver Skin: A Useful Adsorbent Substrate for Norfloxacin Removal and Photodegradation","authors":"Domenico Cignolo,&nbsp;Vito Rizzi,&nbsp;Maria Teresa Bozzelli,&nbsp;Paola Fini,&nbsp;Andrea Petrella,&nbsp;Pinalysa Cosma and Jennifer Gubitosa*,&nbsp;","doi":"10.1021/acsphyschemau.5c00013","DOIUrl":"10.1021/acsphyschemau.5c00013","url":null,"abstract":"<p >This work proposes the use of Coffee Silver Skin, a by-product of coffee production, as an adsorbent substrate for the removal of the antibiotic Norfloxacin from water and assesses the possibility of regenerating it through advanced oxidation processes. In detail, the study was developed by showing the best conditions for the pollutant removal, in which the adsorption process occurred with the main involvement of electrostatic interactions. A preliminary desorption approach in the presence of salt-based solutions, i.e., NaCl and 0.1 M MgCl₂, was followed with the aim of desorbing the non-photodegraded Norfloxacin from the regenerated adsorbent. Therefore, indirectly, the quantitative evaluation of photodestroyed Norfloxacin was assessed according to selected working conditions: UV light, UV light/H₂O₂, UV light/TiO₂, and UV light/TiO₂/H₂O₂. Moreover, a comparison with the literature devoted to Norfloxacin photodegradation directly in water was accomplished. The use of UV light/TiO₂ occurred as the best approach for the purpose of obtaining the complete degradation of Norfloxacin in 6 h. On the other hand, the use of H₂O₂ did not improve the process. Thus, to reduce the irradiation time, Norfloxacin degradation was evaluated simultaneously during its release from the adsorbent, in a 0.1 M MgCl₂ solution, retrieving a similar and well-known behavior observed when the pollutant was degraded in water. In 3 h, the desorbed Norfloxacin was destroyed, enabling the recycling of Coffee Silver Skin for up to 3 cycles.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 4","pages":"375–386"},"PeriodicalIF":4.3,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12291120/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144733638","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 Dynamics Simulations of Self-Assembled E2(SW)6E2 Peptide Nanofibers: Implications for Drug Delivery and Biomimetic Material Design","authors":"Karinna Mendanha,&nbsp; and ,&nbsp;Guilherme Colherinhas*,&nbsp;","doi":"10.1021/acsphyschemau.5c0002810.1021/acsphyschemau.5c00028","DOIUrl":"https://doi.org/10.1021/acsphyschemau.5c00028https://doi.org/10.1021/acsphyschemau.5c00028","url":null,"abstract":"<p >This work investigates the molecular dynamics of the peptide nanofiber E₂(SW)₆E₂, a biomolecule/structure in an aqueous solution, characterized by hydrophilic and hydrophobic contrasts. Through classical molecular dynamics simulations, the study examines the energetic, structural, and dynamic properties of this nanofiber, with a focus on energetic and hydrogen bond (HB) interactions between peptides and peptide-water. Simulations of different fiber lengths indicate that larger models exhibit increased structural stability and longer HB lifetimes, contributing to enhanced fiber flexibility and integrity. Additionally, the analysis of the mass density profile along the nanofiber length reveals local decreases (but not zero) in mass density. The results further emphasize the potential of these structures for applications in ion and drug transport due to their hydrophobic core and hydrophilic surface. This work provides a comprehensive understanding of molecular interactions in self-assembled bionanomaterials in aqueous solutions.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 3","pages":"302–315 302–315"},"PeriodicalIF":3.7,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.5c00028","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146620","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 Dynamics Simulations of Self-Assembled E₂(SW)₆E₂ Peptide Nanofibers: Implications for Drug Delivery and Biomimetic Material Design.","authors":"Karinna Mendanha, Guilherme Colherinhas","doi":"10.1021/acsphyschemau.5c00028","DOIUrl":"10.1021/acsphyschemau.5c00028","url":null,"abstract":"<p><p>This work investigates the molecular dynamics of the peptide nanofiber E₂(SW)₆E₂, a biomolecule/structure in an aqueous solution, characterized by hydrophilic and hydrophobic contrasts. Through classical molecular dynamics simulations, the study examines the energetic, structural, and dynamic properties of this nanofiber, with a focus on energetic and hydrogen bond (HB) interactions between peptides and peptide-water. Simulations of different fiber lengths indicate that larger models exhibit increased structural stability and longer HB lifetimes, contributing to enhanced fiber flexibility and integrity. Additionally, the analysis of the mass density profile along the nanofiber length reveals local decreases (but not zero) in mass density. The results further emphasize the potential of these structures for applications in ion and drug transport due to their hydrophobic core and hydrophilic surface. This work provides a comprehensive understanding of molecular interactions in self-assembled bionanomaterials in aqueous solutions.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 3","pages":"302-315"},"PeriodicalIF":3.7,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12123548/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144200233","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":"Conductance Measurements of Polar Molecules in a Nonconducting Solvent.","authors":"Clark Otey, Mukund Sharma, Jazmine Prana, Thomas M Czyszczon-Burton, Alejandro Hernandez, María Camarasa-Gómez, Daniel Hernangómez-Pérez, Michael S Inkpen","doi":"10.1021/acsphyschemau.5c00021","DOIUrl":"10.1021/acsphyschemau.5c00021","url":null,"abstract":"<p><p>Solution-based single-molecule conductance measurements of α,ω-bis-(carboxylic acids) are conveniently performed using a high-boiling-point nonconducting ethereal solvent. First-principles calculations support experimental observations that linear oligoalkanes exhibit the expected exponential decay of conductance with length, whereas junctions comprising cyclic bridge hydrocarbons of different lengths and/or structures exhibit a similar conductance.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 3","pages":"249-253"},"PeriodicalIF":3.7,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12123542/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144200230","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":"Conductance Measurements of Polar Molecules in a Nonconducting Solvent","authors":"Clark Otey,&nbsp;Mukund Sharma,&nbsp;Jazmine Prana,&nbsp;Thomas M. Czyszczon-Burton,&nbsp;Alejandro Hernandez,&nbsp;María Camarasa-Gómez*,&nbsp;Daniel Hernangómez-Pérez* and Michael S. Inkpen*,&nbsp;","doi":"10.1021/acsphyschemau.5c0002110.1021/acsphyschemau.5c00021","DOIUrl":"https://doi.org/10.1021/acsphyschemau.5c00021https://doi.org/10.1021/acsphyschemau.5c00021","url":null,"abstract":"<p >Solution-based single-molecule conductance measurements of α,ω-bis(carboxylic acids) are conveniently performed using a high-boiling-point nonconducting ethereal solvent. First-principles calculations support experimental observations that linear oligoalkanes exhibit the expected exponential decay of conductance with length, whereas junctions comprising cyclic bridge hydrocarbons of different lengths and/or structures exhibit a similar conductance.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 3","pages":"249–253 249–253"},"PeriodicalIF":3.7,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.5c00021","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146504","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":"Anion-Driven Influence of Tetrabutylammonium-Based Ionic Liquids on DNA Stability and Interaction Mechanisms","authors":"K. K. Athira,&nbsp; and ,&nbsp;Ramesh L. Gardas*,&nbsp;","doi":"10.1021/acsphyschemau.5c00015","DOIUrl":"10.1021/acsphyschemau.5c00015","url":null,"abstract":"<p >Ionic liquids (ILs) have been widely used as alternative solvents for the stabilization, storage, and extraction of DNA. However, studies on the interaction between ammonium-based ILs and DNA, particularly focusing on the effect of anions, remain limited. Tetrabutylammonium (TBA) cation-based ILs with propanoate, bromide, glutamate, and threoninate anions were used to analyze IL–DNA interactions through UV–vis titrations, steady-state and time-resolved fluorescence, and molecular docking. The conformational stability and thermal stability of DNA in IL solutions were analyzed through circular dichroism spectroscopy and UV thermal studies, respectively. Viscosity measurements of the IL solutions were carried out to support the data obtained from UV thermal studies. The TBA cation displays multiple modes of interaction at the groove through electrostatic, hydrophobic, and hydrogen bonding. Among the studied anions, the propanoate anion exhibits significant hydrophobic interactions in addition to hydrogen bonding, whereas glutamate and threoninate primarily engage in hydrogen bonding. The difference in the effect of the ILs on DNA underscores the significant influence of the anions on IL–DNA interactions.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 4","pages":"387–397"},"PeriodicalIF":4.3,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12291139/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144733637","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":"Structural and Functional Relevance of Charge-Based Transient Interactions inside Intrinsically Disordered Proteins","authors":"Samuel Wohl*,&nbsp;Yishai Gilron and Wenwei Zheng*,&nbsp;","doi":"10.1021/acsphyschemau.5c00005","DOIUrl":"10.1021/acsphyschemau.5c00005","url":null,"abstract":"<p >Intrinsically disordered proteins (IDPs) perform diverse biological functions without adopting stable folded structures, instead existing as dynamic ensembles of flexible conformations. While these conformations were traditionally attributed to weak, nonspecific interactions, emerging evidence emphasizes the role of transient, specific interactions. Here, we investigate how charged amino acids within IDP sequences influence the prevalence of these interactions. Using model peptides, we establish an empirical relationship between the fraction of transient interactions and a novel sequence metric, the effective charge patch length. Extending this analysis to IDP ensembles with varying levels of transient interactions, we uncover heteropolymeric structural behaviors, including network formation in phase-separated condensates. A large-scale analysis reveals that approximately 20% of disordered regions in the human proteome exhibit charge-driven transient interactions, contributing to heteropolymeric conformational ensembles. Finally, we explore the functional enrichment of these interactions, underscoring their potential role in mediating diverse biological processes.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 4","pages":"356–366"},"PeriodicalIF":4.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12291128/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144733643","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}