ACS Publications最新文献_第10页

Analytic Computation of Vibrational Circular Dichroism Spectra Using Second-Order Møller-Plesset Perturbation Theory.

IF 5.7 1区化学

Journal of Chemical Theory and Computation Pub Date : 2025-04-08 Epub Date: 2025-03-25 DOI: 10.1021/acs.jctc.5c00047

Brendan M Shumberger, Kirk C Pearce, T Daniel Crawford

引用次数: 0

Integrating Solvent Effects into the Prediction of Kinetic Constants Using a COSMO-Based Equation of State.

IF 5.7 1区化学

Journal of Chemical Theory and Computation Pub Date : 2025-04-08 Epub Date: 2025-03-25 DOI: 10.1021/acs.jctc.5c00133

Francisco Paes, Gabriel de Souza Batalha, Fabiola Citrangolo Destro, René Fournet, Romain Privat, Jean-Noël Jaubert, Baptiste Sirjean

{"title":"Integrating Solvent Effects into the Prediction of Kinetic Constants Using a COSMO-Based Equation of State.","authors":"Francisco Paes, Gabriel de Souza Batalha, Fabiola Citrangolo Destro, René Fournet, Romain Privat, Jean-Noël Jaubert, Baptiste Sirjean","doi":"10.1021/acs.jctc.5c00133","DOIUrl":"10.1021/acs.jctc.5c00133","url":null,"abstract":"While kinetic generators produce thermo-kinetic data for detailed gas-phase kinetic models, adapting these models for liquid-phase applications poses challenges due to the need for solvent-dependent thermodynamic properties. To bridge this gap, solvation energies are used to incorporate solvent effects into gas-phase thermo-kinetic data. However, such an adaptation depends on calculating liquid-phase data of unconventional solutes such as free radicals and transition states, which are not accessible with classical equations of states. To address this issue, this work proposes a flexible framework based on an equation of state that integrates all the latest advances of this model family and is called the tc-PR EoS. Combined with a quantum-based continuum solvation model (COSMO-RS) through an advanced mixing rule, the proposed model is made predictive by employing group contribution methods to estimate the pure compound input parameters required to perform thermodynamic calculations with the model. These parameters can be calculated for closed-shell molecules, free radicals, and transition states, with an average deviation of less than 10% with respect to the benchmark database containing experimental data as well as data obtained from quantum-based calculations and QSPR-type correlations. The tc-PR/COSMO-RS model is able to predict the solvation free energies of activation for H-abstraction reactions with an accuracy of approximately 0.2 kcal/mol, offering a high-throughput and accurate solution for integrating solvation effects into detailed kinetic models in the liquid phase.","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":" ","pages":"3625-3648"},"PeriodicalIF":5.7,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699103","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Gas Sensor Drift Compensation Using Semi-Supervised Ensemble Classifiers with Multi-Level Features and Center Loss.

IF 8.2 1区化学

ACS Sensors Pub Date : 2025-04-08 DOI: 10.1021/acssensors.4c03655

Kai Jiang, Min Zeng, Tao Wang, Yu Wu, Wangze Ni, Lechen Chen, Jianhua Yang, Nantao Hu, Bowei Zhang, Fuzhen Xuan, Siying Li, Anwei Shi, Zhi Yang

{"title":"Gas Sensor Drift Compensation Using Semi-Supervised Ensemble Classifiers with Multi-Level Features and Center Loss.","authors":"Kai Jiang, Min Zeng, Tao Wang, Yu Wu, Wangze Ni, Lechen Chen, Jianhua Yang, Nantao Hu, Bowei Zhang, Fuzhen Xuan, Siying Li, Anwei Shi, Zhi Yang","doi":"10.1021/acssensors.4c03655","DOIUrl":"https://doi.org/10.1021/acssensors.4c03655","url":null,"abstract":"The drift compensation of gas sensors is a significant and challenging issue in the field of electronic noses (E-nose). Compensating sensor drift has a great benefit in improving the performance of E-nose systems. However, conventional methods often perform poorly due to complex data relationships before and after drifting, or require label information for both nondrift (source data) and drift data (target data) to enhance performance, which is hard to achieve and even unrealistic. In this study, we propose a semisupervised domain adaptive convolutional neural network (CNN) based on ensemble classifiers of multilevel features, pretraining, and center loss to tackle the drift problem. The main idea is to make full use of multilevel features extracted from the network and apply Hilbert space's maximum mean discrepancy (MMD) to evaluate the domain similarity of the features at different levels. Then the corresponding MMD is used as a weight to achieve the weighted fusion of predictions in the classifier ensemble module, so as to obtain a more reliable result. Furthermore, to optimize training, MMD is used as a loss for pretraining to help feature extractors learn more robust and common features in two domains. Center loss is also applied to achieve more focused learning for features of the same class. The results on two data sets demonstrate the effectiveness of our method. The average classification accuracies under different settings reach 76.06% (long-drift) and 82.07% (short-drift), respectively, and the average R2 score reaches 0.804 in the regression task, which has significant improvements compared with several conventional methods. Our work provides an effective and reliable method at the algorithm level to solve the drift compensation problem of gas sensors.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802009","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

DirectMultiStep: Direct Route Generation for Multistep Retrosynthesis.

IF 5.6 2区化学

Journal of Chemical Information and Modeling Pub Date : 2025-04-08 DOI: 10.1021/acs.jcim.4c01982

Yu Shee, Anton Morgunov, Haote Li, Victor S Batista

{"title":"DirectMultiStep: Direct Route Generation for Multistep Retrosynthesis.","authors":"Yu Shee, Anton Morgunov, Haote Li, Victor S Batista","doi":"10.1021/acs.jcim.4c01982","DOIUrl":"https://doi.org/10.1021/acs.jcim.4c01982","url":null,"abstract":"Traditional computer-aided synthesis planning (CASP) methods rely on iterative single-step predictions, leading to exponential search space growth that limits efficiency and scalability. We introduce a series of transformer-based models that leverage a mixture of experts approach to directly generate multistep synthetic routes as a single string, conditionally predicting each transformation based on all preceding ones. Our DMS Explorer XL model, which requires only target compounds as input, outperforms state-of-the-art methods on the PaRoutes dataset with 1.9x and 3.1x improvements in Top-1 accuracy on the n1 and n5 test sets, respectively. Providing additional information, such as the desired number of steps and starting materials, enables both a reduction in model size and an increase in accuracy, highlighting the benefits of incorporating more constraints into the prediction process. The top-performing DMS-Flex (Duo) model scores 25-50% higher on Top-1 and Top-10 accuracies for both n1 and n5 sets. Additionally, our models successfully predict routes for the FDA-approved drugs not included in the training data, demonstrating strong generalization capabilities. While the limited diversity of the training set may affect performance on less common reaction types, our multistep-first approach presents a promising direction toward fully automated retrosynthetic planning.","PeriodicalId":44,"journal":{"name":"Journal of Chemical Information and Modeling ","volume":" ","pages":""},"PeriodicalIF":5.6,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802011","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}

引用次数: 0

Bridging the Gap between Transformer-Based Neural Networks and Tensor Networks for Quantum Chemistry.

IF 5.7 1区化学

Journal of Chemical Theory and Computation Pub Date : 2025-04-08 Epub Date: 2025-03-02 DOI: 10.1021/acs.jctc.4c01703

Bowen Kan, Yingqi Tian, Yangjun Wu, Yunquan Zhang, Honghui Shang

{"title":"Bridging the Gap between Transformer-Based Neural Networks and Tensor Networks for Quantum Chemistry.","authors":"Bowen Kan, Yingqi Tian, Yangjun Wu, Yunquan Zhang, Honghui Shang","doi":"10.1021/acs.jctc.4c01703","DOIUrl":"https://doi.org/10.1021/acs.jctc.4c01703","url":null,"abstract":"The neural network quantum state (NNQS) method has demonstrated promising results in ab initio quantum chemistry, achieving remarkable accuracy in molecular systems. However, efficient calculation of systems with large active spaces remains challenging. This study introduces a novel approach that bridges tensor network states with the transformer-based NNQS-Transformer (QiankunNet) to enhance accuracy and convergence for systems with relatively large active spaces. By transforming tensor network states into active space configuration interaction type wave functions, QiankunNet achieves accuracy surpassing both the pretraining density matrix renormalization group (DMRG) results and traditional coupled cluster methods, particularly in strongly correlated regimes. We investigate two configuration transformation methods: the sweep-based direct conversion (Conv.) method and the entanglement-driven genetic algorithm (EDGA) method, with Conv. showing superior efficiency. The effectiveness of this approach is validated on H2O with a large active space (10e, 24o) in the cc-pVDZ basis set, demonstrating an efficient routine between DMRG and QiankunNet and also offering a promising direction for advancing quantum state representation in complex molecular systems.","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":"21 7","pages":"3426-3439"},"PeriodicalIF":5.7,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802030","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Nanocomposite Hydrogels and Micro/Nanostructures for Printing Organoids.

IF 15.8 1区材料科学

ACS Nano Pub Date : 2025-04-08 Epub Date: 2025-03-31 DOI: 10.1021/acsnano.4c17587

Daixi Xie, Bingda Chen, Wenqing Wang, Wenjing Guo, Zhiyuan Sun, Long Wang, Bin Shi, Yanlin Song, Meng Su

引用次数: 0

IF 4.5 2区医学

Molecular Pharmaceutics Pub Date : 2025-04-08 DOI: 10.1021/acs.molpharmaceut.5c00108

Soumya Ranjan Pujahari, Swpnil Engla, Rohit Soni, Subrata Patra, Manjesh Kumar Hanawal, Ashutosh Kumar

{"title":"Structural Similarity of Biological Drugs Using Statistical Signal Processing and Nuclear Magnetic Resonance Spectral Pattern Analysis.","authors":"Soumya Ranjan Pujahari, Swpnil Engla, Rohit Soni, Subrata Patra, Manjesh Kumar Hanawal, Ashutosh Kumar","doi":"10.1021/acs.molpharmaceut.5c00108","DOIUrl":"https://doi.org/10.1021/acs.molpharmaceut.5c00108","url":null,"abstract":"Biosimilar drugs are highly similar to the available marketed drugs and have no clinically meaningful differences in terms of safety, purity, and potency. As per stringent drug regulatory requirements, biosimilar drugs must match closely to all attributes of the listed marketed drug, including establishing high similarity of higher-order structures. Here, we have developed a combined approach using high-resolution two-dimensional nuclear magnetic resonance (NMR) spectra and image-based statistical signal processing algorithms to establish robust comparability of critical quality attributes of biological drugs. We have integrated a computational approach to 2D NMR data analysis, which could replace the traditional methods of manually extracting chemical shift values and intensities for each peak and performing a range of statistical analyses, which are laborious and prone to ambiguity. Our algorithm simplifies and streamlines this process, making it more accurate, less time-consuming, and avoiding personal biases. We have employed our methods with a diverse range of biotherapeutics and complex NMR data and shown a degree of similarity between reference and test drugs with our differentially assigned similarity scores.","PeriodicalId":52,"journal":{"name":"Molecular Pharmaceutics","volume":" ","pages":""},"PeriodicalIF":4.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143810127","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}

引用次数: 0

Endoscopic Delivery of a Double-Umbrella-Shaped Hydrogel Occluder with Instant Mechanical Interlock and Robust Wet Adhesion for Gastric Perforation Repair.

IF 8.3 2区材料科学

ACS Applied Materials & Interfaces Pub Date : 2025-04-08 DOI: 10.1021/acsami.5c00982

Haiyang Li, Ningli Chai, Yanyu Yang, Zhenyu Liu, Zhengyuan Liu, Xuemiao Liu, Shuang Liu, Lizhou Zhu, Haoqi Zhai, Wengang Zhang, Chen Du, Xing Wang, Longsong Li, Enqiang Linghu

{"title":"Endoscopic Delivery of a Double-Umbrella-Shaped Hydrogel Occluder with Instant Mechanical Interlock and Robust Wet Adhesion for Gastric Perforation Repair.","authors":"Haiyang Li, Ningli Chai, Yanyu Yang, Zhenyu Liu, Zhengyuan Liu, Xuemiao Liu, Shuang Liu, Lizhou Zhu, Haoqi Zhai, Wengang Zhang, Chen Du, Xing Wang, Longsong Li, Enqiang Linghu","doi":"10.1021/acsami.5c00982","DOIUrl":"https://doi.org/10.1021/acsami.5c00982","url":null,"abstract":"Achieving robust adhesion of bioadhesives on wet tissues to block gastric perforation remains a challenge due to the gradually deteriorated adhesive-tissue interactions by interfacial acidity and multienzyme gastric fluids, thus accompanying failure shedding and life-threatening risks. Here, we report a biocompatible double-umbrella-shaped endoscopy-deliverable hydrogel occluder (EHO) made of caffeic acid (CA)-grafted chitosan (CS) and polyacrylamide (PAM) by molding technique, which is capable of the customizable, rapid, robust, and long-term sealing of large gastric perforations. In addition to interfacial physiochemical interactions (e.g., H-bonding, chelation) between the tissues and polymers, efficient sealing also integrates the advantages of fast mechanical interlocking in space and gradual self-expansion over time to tolerant acidic and mechanically dynamic environments. The EHO exhibits favorable biodegradability due to the reducible disulfide cross-linkers and remarkable protective barrier functions to impede the infiltration of gastric acid and digestive pepsin into the wound. To validate EHO's therapeutic efficacy, we further demonstrate the robust in vivo sealing to large gastric tissues via endoscopic delivery to the porcine stomach and monitor of healing process with improved retention of endogenous growth factors. Besides, in views of simple hydrogel fabrication using molding technique, the biodegradable EHO can be facilely tailored with various topologies according to application scenarios in surgical and minimally invasive endoscopic delivery, thus offering a promising alternative for clinical repair of gastrointestinal perforations and other organs.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.3,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143810128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Localized Cancer Treatment Using Thiol-Ene Hydrogels for Dual Drug Delivery.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-04-08 DOI: 10.1021/acs.biomac.5c00387

Lakshmi Sathi Devi, Maria Rosa Gigliobianco, Serena Gabrielli, Dimitrios Agas, Maria Giovanna Sabbieti, Maria Beatrice Morelli, Consuelo Amantini, Cristina Casadidio, Piera Di Martino, Roberta Censi

{"title":"Localized Cancer Treatment Using Thiol-Ene Hydrogels for Dual Drug Delivery.","authors":"Lakshmi Sathi Devi, Maria Rosa Gigliobianco, Serena Gabrielli, Dimitrios Agas, Maria Giovanna Sabbieti, Maria Beatrice Morelli, Consuelo Amantini, Cristina Casadidio, Piera Di Martino, Roberta Censi","doi":"10.1021/acs.biomac.5c00387","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00387","url":null,"abstract":"Combinatorial cancer therapy benefits from injectable hydrogels for localized, controlled drug delivery. This study presents a thiol-ene conjugated hydrogel formed by cross-linking thiol-modified hyaluronic acid (HASH) with vinyl sulfone-modified β-cyclodextrin (CDVS). Four formulations (23Gel-16, 23Gel-33, 99Gel-16, 99Gel-33) were synthesized by varying HASH molecular weight (23 or 99 kDa) and CDVS modification (16% or 33%). Rheological analysis confirmed enhanced viscoelasticity with increasing molecular weight and modification (99Gel-33 > 99Gel-16 > 23Gel-33 > 23Gel-16). The system enabled combinatorial delivery of doxorubicin (DOX) and carvacrol (CRV), exhibiting tumor-responsive degradation and tunable release. DOX release accelerated under tumor-mimicking conditions (100% in 46 h vs 58.7% in PBS), while CRV showed an initial burst followed by sustained release. The hydrogel promoted mesenchymal stem cell proliferation and effectively inhibited triple-negative breast cancer cells. This injectable, tumor-responsive hydrogel system offers a promising platform for minimally invasive, personalized cancer therapy.","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143810200","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}

引用次数: 0

Switchable Nanophotosensitizers as Pyroptosis Inducers for Targeted Boosting of Antitumor Photoimmunotherapy.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-04-08 DOI: 10.1021/acs.biomac.5c00140

Xiaoxi Zhao, Qinjie Zhong, Naibijiang Abudouaini, Yan Zhao, Jibin Zhang, Guozhu Tan, Guifeng Miao, Xiaowu Wang, Jianqiang Liu, Ying Pan, Xiaorui Wang

{"title":"Switchable Nanophotosensitizers as Pyroptosis Inducers for Targeted Boosting of Antitumor Photoimmunotherapy.","authors":"Xiaoxi Zhao, Qinjie Zhong, Naibijiang Abudouaini, Yan Zhao, Jibin Zhang, Guozhu Tan, Guifeng Miao, Xiaowu Wang, Jianqiang Liu, Ying Pan, Xiaorui Wang","doi":"10.1021/acs.biomac.5c00140","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00140","url":null,"abstract":"Photodynamic therapy (PDT) has emerged as a promising modality for cancer treatment, but its clinical application is constrained by unexpected phototoxicity arising from nonspecific photosensitizer activation and their \"always-on\" nature. Herein, we developed a switchable nanophotosensitizer, poly(cation-π) nanoparticles (NP), which achieves supramolecular assembly through cation-π interactions. By coupling choline cationic moieties with aromatic photosensitizers (ZnPc), the polymer facilitates self-assembly driven by cation-π interactions for NP engineering. Surprisingly, the photoactivity of ZnPc was completely quenched upon complexation via cation-π interactions, thereby significantly avoiding skin phototoxicity. Upon targeting tumor cells, NP undergoes a GSH-responsive degradation process that weakens cation-π interactions, leading to spontaneous restoration of photoactivity and amplifying tumor immunogenic pyroptosis. In vivo studies demonstrated that NP achieved a high tumor inhibition rate of 84% while effectively avoiding skin phototoxicity. This work provides a novel perspective for enhancing the safety and efficacy of PDT-based tumor treatment.","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143810220","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}

引用次数: 0