ACS Publications最新文献

{"title":"[⁶⁸Ga]Ga-HM or [⁶⁸Ga]Ga-PM: Which Is Superior for PET/CT Imaging of HMGB1-Positive Tumors?","authors":"Kunyao Wang, Wenqi Zhao, Xiaozhang Xu, Ting Liang, Chao Zhang, Weijing Tao, Xin Li, Feng Gao","doi":"10.1021/acs.molpharmaceut.5c01012","DOIUrl":"https://doi.org/10.1021/acs.molpharmaceut.5c01012","url":null,"abstract":"<p><p>High mobility group box 1 (HMGB1) is highly expressed in various malignancies and has been considered as a promising molecular target for cancer diagnosis and therapy. In this study, two novel peptide-based radiotracers targeting HMGB1 were synthesized, each achieving high radiochemical purity (>95%). Of these tracers, [⁶⁸Ga]Ga-HM possessed superior characteristics with a high binding affinity for the PC3 cell line (<i>K</i>_d = 46.11 ± 0.97 nM). Micro-PET imaging and biodistribution investigation in PC3 tumor-bearing mice revealed significant tumor uptake (SUV_max = 1.52 ± 0.10) and an excellent tumor-to-muscle ratio (6.96 ± 0.64) at 30 min post-injection. Moreover, robust imaging performance and favorable biodistribution profiles were consistently observed for [⁶⁸Ga]Ga-HM across multiple distinct HMGB1-positive tumor models. These findings demonstrate that [⁶⁸Ga]Ga-HM could serve as a diagnostic tracer to identify tumors with high HMGB1 expression, enabling personalized cancer treatment through the selection and monitoring of targeted therapeutic approaches.</p>","PeriodicalId":52,"journal":{"name":"Molecular Pharmaceutics","volume":" ","pages":""},"PeriodicalIF":4.5,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032328","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Microscopic Insights into Hydrate Cage Decomposition and CO₂ Release of CO₂⁺ TBAB Double Hydrate in Cold Energy Discharge.","authors":"Kairan Yang, Zixu Han, Peng Zhang","doi":"10.1021/acs.jpcb.5c03829","DOIUrl":"10.1021/acs.jpcb.5c03829","url":null,"abstract":"<p><p>Semiclathrate tetrabutylammonium bromide (TBAB) hydrate can incorporate gas CO₂ to form CO₂ + TBAB double hydrate, which is an ideal gas and energy storage material due to its high energy density and favorable phase change conditions for refrigeration applications. In this study, the dissociation behaviors and underlying mechanism of this CO₂ + TBAB double hydrate at the microscale for energy release are studied through molecular dynamic simulations under thermal-driven conditions (283 K-301 K). The results indicate that two distinct hydrate cages (CO₂ 5¹² cages and TBAB semiclathrate cages) decompose in a stepwise manner during dissociation and exhibit distinct features. For the TBAB semiclathrate cage, the TBA⁺ ions initially adsorb on the hydrate surface as cages collapse and ultimately diffuse to the liquid phase. This phenomenon is attributed to the strong interaction between TBA⁺ ions and the hydrate cages strengthens the stability of the TBAB semiclathrate cage and empty the 5¹² cage after CO₂ release. For the CO₂ 5¹² cage, the cages deform and decompose upon the release of the encaged CO₂ molecules. The temperature dependence on the dissociation rate of the CO₂ + TBAB double hydrate could be described using the Arrhenius formula, with the activation energy determined to be 61.53 kJ mol^-1. A reduction in the 5¹² cage occupancy greatly diminishes hydrate stability and promotes the hydrate dissociation rate. Furthermore, the regulation of the CO₂ molecule on hydrate dissociation is realized through affecting the reformation of the 5¹² cage. The increase of the CO₂ molecule concentration in the liquid phase shows an inhibitory effect on the release of the CO₂ molecule from the hydrate cage because the possibility of reformation of the 5¹² cage at the hydrate surface increases, providing microscopic insights into the dissociation behavior of hydrate induced by depressurization at the macroscopic scale.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"9229-9239"},"PeriodicalIF":2.9,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936426","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":"Unraveling the Effects of Purine- and Pyrimidine-Based Ionic Liquids on G-Quadruplex.","authors":"Dipayan Sarder, Sanjoy Bandyopadhyay","doi":"10.1021/acs.jpcb.5c04379","DOIUrl":"10.1021/acs.jpcb.5c04379","url":null,"abstract":"<p><p>Formation of G-quadruplex (GQ) at the termini of the chromosomes found in cancer cells is known to inhibit telomere elongation and hence cell growth. As a consequence, GQ has been identified as a potential target for tumor-suppressing drugs. In recent times, aqueous ionic liquid (IL) solutions have been used as storage media for GQ samples. Hence, it is important and essential to obtain molecular-level insights into the interaction mechanism between GQ and IL components. In this work, we have performed molecular dynamics (MD) simulations of c-kit promoter GQ in aqueous solutions of nucleobase ionic liquids (NBILs) containing 1-ethyl-3-methylimidazolium (Emim⁺) cations in combination with purine-based adenine (Ade^-) and guanine (Gua^-) anions, and pyrimidine-based thymine (Thy^-) and uracil (Ura^-) anions. The calculations revealed contrasting effects of purine and pyrimidine-based ILs on the conformational flexibilities of the GQ. Importantly, greater influence of the pyrimidine-based ILs on the structural integrity of the GQ has been found to be associated with relatively higher propensity of the Emim⁺ cations to replace water molecules that are not directly bound at the GQ surface in the presence of Thy^- and Ura^- anions as compared to that in the presence of Ade^- and Gua^-. It is further observed that in addition to the negatively charged GQ backbone, the Emim⁺ cations also exhibit strong favorable interaction with the GQ nucleobases due to preferential parallel stacked arrangements between the cation imidazolium rings and the nucleobases. Our analyses suggest that aqueous IL solutions containing purine-based anions can act as good media for the preservation of GQs.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"9138-9150"},"PeriodicalIF":2.9,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936072","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":"Emergence of Polymer-Networked Nanoparticle Structures as Primitive Neuromorphic Computing States.","authors":"Yinong Zhao, Xingfei Wei, Rigoberto Hernandez","doi":"10.1021/acs.jpca.5c02941","DOIUrl":"10.1021/acs.jpca.5c02941","url":null,"abstract":"<p><p>Polymer-networked nanoparticles are a promising alternative to silicon semiconductors for the realization of neuromorphic computing platforms. Variations in the interaction between gold nanoparticles (AuNPs) and polyelectrolyte linkers lead to the controlled formation of engineered nanoparticle network (ENPN) structures exhibiting a broad range of topologies and dynamics. Using dissipative particle dynamics (DPD) simulations, we designed triblock copolymers with polyelectrolyte ends that can selectively attach to each of two AuNPs and bridged them together through a middle polymer segment (or block). We leverage our earlier finding that AuNPs have well-defined valencies─that is, an optimal number of polymers that can fit (or fill) their surface, for a specific choice of the outer blocks at a given polymer length. The precise selection of the AuNP valence allows for controlled binding between the polymers and AuNPs. Meanwhile, the choice of the middle block enables control over internanoparticle spacing and network topology. We found that ENPNs can achieve distinct and stable states, satisfying a necessary condition for primitive neuromorphic computing. By swapping the surface coating ligand from citrate to mercaptopropionic acid (MPA), the valence on a given nanoparticle is also increased. Thus, we found that the selection of the surface coating consequently affects the designed ENPN structures, allowing for more flexibility in searching for the optimal components.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"8432-8440"},"PeriodicalIF":2.8,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936193","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":"Correction to \"Protonated and Sodiated Cyclophosphamide Fragmentation Pathways Evaluation by Infrared Multiple Photon Dissociation Spectroscopy\".","authors":"André S Fernandes, Guilherme Obeid, Tiago J N Laureno, Thiago C Correra","doi":"10.1021/acs.jpca.5c05328","DOIUrl":"10.1021/acs.jpca.5c05328","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"8464"},"PeriodicalIF":2.8,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936197","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":"Competing Modes of Hydrogen Activation in Singlet Pyridinylidenes: π-Approach <i>vs</i> σ*-Approach Reaction Pathways.","authors":"Gurli A Schuster, Virinder Bhagat, J Philipp Wagner","doi":"10.1021/acs.jpca.5c04771","DOIUrl":"10.1021/acs.jpca.5c04771","url":null,"abstract":"<p><p>Carbenes are promising reagents for the transition metal-free activation of molecular hydrogen. Depending on their multiplicity and electron configuration, carbenes can access different hydrogenation reaction mechanisms, with singlet carbenes usually leading to geminal hydrogenation products <i>via</i> a π-approach trajectory. Our group has recently prepared 1-iodopyridine-2-ylidene, <b>1-I</b>, introducing a new class of singlet <i>N</i>-heterocyclic carbenes featuring σ/σ* instead of the usually encountered σ/π frontier orbitals. Carbene <b>1-I</b> reacts with H₂ <i>via</i> a unique sideways σ*-approach, leading to pyridinium iodide formation with N-I bond cleavage. This study investigates how nitrogen substituents with varying bond strengths (I < Br < Cl < OCF₃ < OMe < NMe₂ < F < Me) influence the electronic structure of the carbene and its preference for σ*- or π-approach hydrogenation. Using high-accuracy DLPNO-CCSD(T) and NEVPT2 computations, we find that I-, Br-, Cl-, and OCF₃-substituted pyridinylidenes adopt a σ²σ^*0 configuration and favor σ*-approach hydrogenation. In contrast, OMe-, NMe₂-, and Me-substituted carbenes exhibit a σ²π⁰ configuration and lower barriers for the π-approach hydrogenation. Interestingly, the fluorine-substituted carbene assumes a σ²π⁰ electron configuration yet still preferentially undergoes σ*-approach hydrogenation.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"8380-8386"},"PeriodicalIF":2.8,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936264","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":"Interactions and Cold Collisions of AlF in the Ground and Excited Electronic States with He.","authors":"Sangami Ganesan-Santhi, Matthew D Frye, Marcin Gronowski, Michał Tomza","doi":"10.1021/acs.jpca.5c02533","DOIUrl":"10.1021/acs.jpca.5c02533","url":null,"abstract":"<p><p>Aluminum monofluoride (AlF) is a promising candidate for laser cooling and the production of dense ultracold molecular gases, thanks to its relatively high chemical stability and diagonal Franck-Condon factors. In this study, we examine the interactions and collisions of AlF in its <i>X</i>¹Σ⁺, <i>a</i>³Π, and <i>A</i>¹Π electronic states with ground-state He using state-of-the-art ab initio quantum chemistry techniques. We construct accurate potential energy surfaces (PESs) employing either the explicitly correlated coupled-cluster CCSD(T)-F12 method augmented by the CCSDT correction or the multireference configuration-interaction method for higher-excited electronic states. Subsequently, we employ these PESs in coupled-channel calculations to determine the scattering cross sections for AlF + He collisions and bound states of the complex. We estimate the uncertainty of the calculated PESs and apply it to assess the uncertainty of the scattering results. We find a relatively low sensitivity of the cross sections to the variation of the PESs, but the positions of shape resonances remain uncertain. The present results are relevant for further improvements and optimizations of buffer-gas cooling of AlF molecules.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"8239-8250"},"PeriodicalIF":2.8,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936283","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":"Disrupting Amyloid Filaments of Tau by Means of Electric Fields.","authors":"Pablo Andrés Vargas-Rosales, Giuseppe Giangreco, Amedeo Caflisch","doi":"10.1021/acs.jpcb.5c04393","DOIUrl":"10.1021/acs.jpcb.5c04393","url":null,"abstract":"<p><p>The tau protein is a major component of neurofibrillary tangles, one of the hallmarks of Alzheimer's disease, which is the most common neurodegenerative disorder in the elderly. Experimental and computational studies have shed light on the fibrillar morphologies of tau and the kinetics of self-assembly, but little is known about the structural stability of the fibrils in the presence of external electric fields. We investigated the behavior of cross-β filaments of tau under the effect of an oscillating external electric field by means of multiple molecular dynamics simulations. Two models of the aqueous solvent were used: explicit water and implicit solvent based on the continuum dielectric. The simulations started from tau filaments with two different topologies determined by cryogenic electron microscopy of patient samples: the so-called straight filament (SF) and paired helical filament (PHF). Two values of the electric field strength and oscillation frequencies of 0.1, 1, or 10 GHz were employed. In all simulations, tau segment 340-KSEKLDFKDRV-350, which includes seven charged side chains, showed pronounced flexibility, which was exacerbated at high field strength. A larger loss of β-strand content was observed for the SF than for the PHF topology. Moreover, the SF assembly dissociated into two protofilaments in the presence of the external field, which was not observed for the more stable PHF topology. The loss of β-sheet structure was highest at the frequency of 1 GHz and smallest at 10 GHz in the explicit water simulations, while mixed decays of β-sheet content were obtained with the implicit solvent.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"9124-9137"},"PeriodicalIF":2.9,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936397","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":"Optoelectronic Properties of Tetracyanoquinodimethane (TCNQ) Related Compounds for Applications to OSCs and OLEDs: A Theoretical Study.","authors":"Subhankar Sardar","doi":"10.1021/acs.jpca.5c03095","DOIUrl":"10.1021/acs.jpca.5c03095","url":null,"abstract":"<p><p>Tetracyanoquinodimethane (TCNQ) and related compounds are thoroughly investigated as potential innovative organic semiconductors and singlet fission (SF) materials. The TDDFT method with the PBE0/Def2-TZVP level is used to determine the geometrical structures, atomic dipole corrected Hirshfeld (ADCH) charge, population, dipole moment (μ), band gaps, different density of states (DOSs), excitation energies, hole-(λ_<i>H</i>) and electron-(λ_<i>E</i>) reorganization energies, SF properties, absorption-emission spectra, transition density matrix (TDM), electron localization function (ELF) of these molecules, and open circuit voltage (<i>V</i>_oc), fill factor (FF), and power conversion efficiency (PCE) of possible optoelectronic devices. At the CAM-B3LYP/6-311G** level, we examine the ground and excited state characteristics of 44 modeled TCNQ-related molecules. Two fundamental criteria, namely, the SF driving force (Δ = <i>E</i>(<i>S</i>₁) - <i>E</i>(<i>T</i>₁)) and the triplet-triplet annihilation (TTA) probability (Ω = <i>E</i>(<i>S</i>₁) - 2<i>E</i>(<i>T</i>₁)), have been analyzed to demonstrate the SF properties of these model materials. The current study reveals effective hole transport materials (HTMs) and electron transport materials (ETMs) in organic light-emitting diodes (OLEDs), and suitable SF materials in organic solar cells (OSCs) were chosen considering those multiple factors.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"8251-8277"},"PeriodicalIF":2.8,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936402","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":"Spectroscopic and Theoretical Insights into the Binding of Phenothiazinium Dye Methylene Blue with Triple- and Double-Helical Forms of RNA: A Comparative Study.","authors":"Rapti Goswami, Lopa Paul, Himal Das, Amar Ghosh, Susmita Chowdhury, Suman Das","doi":"10.1021/acs.jpcb.5c02810","DOIUrl":"10.1021/acs.jpcb.5c02810","url":null,"abstract":"<p><p>Higher-ordered nucleic acid structures like triplex and quadruplex forms have been the center of attention of the current research field of medicinal chemistry. The triplex is formed through the sequence-specific association of a single-stranded, triplex-forming oligonucleotide (TFO) with nucleic acid duplex structures. In our present study, we have focused on an RNA triplex (U.A*U) because of its various biological relevance including telomerase activity and movement of ribosomal template in mRNA coding regions. Methylene blue (MB), a cationic dye of phenothiazine families, has diverse pharmacological and clinical applications. Considering the wide range of medicinal uses of MB and the biological importance of higher-ordered structures of RNA, our present study has focused on the elucidation of the comparative binding interaction of methylene blue (MB) with RNA triplex (U.A*U) and duplex (A.U) structures employing various spectroscopic and theoretical tools. MB has been found to show a comparably higher binding affinity toward the triplex form (13.5 × 10⁵ M^-1) than the parent duplex form (2.36 × 10⁵ M^-1). The thermal melting profile revealed that MB substantially stabilized the Watson-Crick base-paired strands of both the RNA triplex and duplex structures; however, it destabilized the Hoogsteen base-paired strand of triple helical RNA. Fluorescence quenching, steady-state anisotropy, and circular dichroic studies all together supported the intercalative mode of binding. Thermodynamic data revealed that the interactions of MB with both RNA triplex and duplex forms were characterized by both negative enthalpy and entropy changes. Ionic strength-dependent study showed that the nonpolyelectrolytic forces are the predominating factors in the binding process, although a minor but certain extent of polyelectrolytic contribution is present. Moreover, theoretical calculations using DFT and TD-DFT methods were explored to validate the experimental spectrophotometric behavior (absorbance) of MB, assigning the energy levels involved in the electronic transition along with the vibrational modes.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"9068-9082"},"PeriodicalIF":2.9,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936414","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}