Journal of Physical Organic Chemistry最新文献_第3页

Kinetic and Mechanistic Investigation of L-Phenylalanine Oxidation by Alkaline Cu(III) Periodate in CPC Micellar Medium 碱性高酸铜（III）在CPC胶束介质中氧化l -苯丙氨酸的动力学和机理研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-11-11 DOI: 10.1002/poc.4669

Abhishek Srivastava, Neetu Srivastava, Rajeev Kumar Dohare

{"title":"Kinetic and Mechanistic Investigation of L-Phenylalanine Oxidation by Alkaline Cu(III) Periodate in CPC Micellar Medium","authors":"Abhishek Srivastava, Neetu Srivastava, Rajeev Kumar Dohare","doi":"10.1002/poc.4669","DOIUrl":"https://doi.org/10.1002/poc.4669","url":null,"abstract":"<div>\u0000 \u0000 Amino acid oxidation is fascinating because different oxidants produce diverse compounds. No research has examined how metal catalysts affect amino acid oxidation by diperiodatocuprate (III) (DPC) in micellar environments. This research is crucial to understanding amino acids in redox processes and identifying active species of Ru(III) and DPC. The study will evaluate how cationic surfactant affects Ru(III)-facilitated L-phenylalanine (L-Pheala) oxidation utilizing DPC in an alkaline medium. The reaction's advancement has been assessed employing the pseudo-first-order condition as a gauge for [OH−], [DPC], ionic strength, [L-Pheala], [Ru(III)], [IO4−], [Surfactant], and temperature. L-Pheala and DPC interact stoichiometrically in a ratio of 1:4. Across the spectrum of concentrations examined, the reported reaction reflects less than unit order kinematics in relation to both [L-Pheala] (0.61 in the aqueous medium and 0.58 in the CPC micellar medium) and [OH−] (0.47 in the aqueous medium and 0.51 in the CPC micellar medium), first-order reliance on the [DPC] and [Ru(III)], and negative fractional-order for [IO4−] (−0.54 in the aqueous medium and −0.56 in the CPC micellar medium). A zero salt effect is suggested by the observed constancy in oxidation rate with the inclusion of electrolytes. The oxidation rate is significantly enhanced by Ru(III) solution (as a catalyst) at ppm concentration. Cetylpyridinium chloride (CPC) micellar media facilitate an additional enhancement (four times) in the rate of the reaction. CPC thus exhibits an excellent compatibility with Ru(III) for the L-Pheala oxidation using (DPC).\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142868157","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

On the Photosensitizer Activity From Psoralen in Lipid and Aqueous Media: A Theoretical Study 脂质和水介质中补骨脂素光敏剂活性的理论研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-11-04 DOI: 10.1002/poc.4672

Alan Couttolenc, Alberto V. Jerezano, César Espinoza, Manuel E. Medina

{"title":"On the Photosensitizer Activity From Psoralen in Lipid and Aqueous Media: A Theoretical Study","authors":"Alan Couttolenc, Alberto V. Jerezano, César Espinoza, Manuel E. Medina","doi":"10.1002/poc.4672","DOIUrl":"https://doi.org/10.1002/poc.4672","url":null,"abstract":"<div>\u0000 \u0000 The photosensitizer mechanism by the psoralen (PSO) reacts to produce reactive oxygen species has not been thoroughly studied; thus, this work was carried out a study of the reaction and mechanism involved in the photosensitizer activity of PSO, employing M06-2X/6-311++G(d,p) of the density functional theory. There is a competition between the generation of radical anion superoxide (type I mechanism) and the singlet oxygen molecule (type II mechanism) in lipid media; therefore, the ROS anion superoxide and singlet oxygen could be formed as products of the reaction involved in the photosensitizer activity of PSO in lipid media. In aqueous media, the reaction involved in the photosensitizer activity of PSO was only attributed to the type I mechanism; hence, in aqueous media, the photosensitizer activity of PSO yielded the anion superoxide. The present study supports the photosensitizer activity of the PSO in lipid and aqueous media. It enhances the knowledge of these reactions in different media and their application to reactivity, including the physiology media.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142868007","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Theoretical Perspective on the Sensing Mechanism of a Pyrazinium-Based Fluorescent Probe Towards 2,4,6-Trinitrophenol 吡嗪基荧光探针对2,4,6-三硝基苯酚传感机理的理论研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-30 DOI: 10.1002/poc.4670

Meiheng Lv, Tingting Wang, Yuhang Zhang, Zexu Cai, Yue Gao, Feng Yan, Yifan Zhang, Jiaqi Song, Jianyong Liu

{"title":"Theoretical Perspective on the Sensing Mechanism of a Pyrazinium-Based Fluorescent Probe Towards 2,4,6-Trinitrophenol","authors":"Meiheng Lv, Tingting Wang, Yuhang Zhang, Zexu Cai, Yue Gao, Feng Yan, Yifan Zhang, Jiaqi Song, Jianyong Liu","doi":"10.1002/poc.4670","DOIUrl":"https://doi.org/10.1002/poc.4670","url":null,"abstract":"<div>\u0000 \u0000 Rapid detection of chemical explosives plays a critical role in national security and public safety. An in-depth study of the sensing mechanism is particularly urgent for the development of highly efficient, sensitive, and selective chemical sensors for the precise detection of chemical explosives. Density functional theory (DFT) and time-dependent DFT approaches were used in this work to examine the sensing mechanism of a novel fluorescent probe 1-benzyl-3,5-di (thiophen-2-yl)pyrazin-1-ium bromide (BTPyz) for the detection of 2,4,6-trinitrophenol (TNP). A comprehensive theoretical exploration was carried out, and a different interaction mode between the probe and TNP from that in the original experiment was proposed. The π–π stacking was established to be the recognition interaction between BTPyz and TNP anion, and the active site was determined from the three potential sizes according to the Gibbs free energy analysis results. The rationality of the reaction mode and the π–π stacking product between the BTPyz and TNP (BTN) was further confirmed by the fluorescence properties (absorption and emission spectra). According to the findings of frontier molecular orbitals (FMOs), photoinduced electron transfer (PET) is the intrinsic mechanism through which TNP quenches the probe's fluorescence.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142869224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Kinetic, Spectral and Mechanistic Regularities of New Reaction Systems With Chromogenic SN2-Type Reaction for Detection of Epoxy Compounds sn2型显色新反应体系检测环氧化合物的动力学、光谱和机理规律

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-28 DOI: 10.1002/poc.4668

Anton Charyarov, Stanislav Bakhtin

{"title":"Kinetic, Spectral and Mechanistic Regularities of New Reaction Systems With Chromogenic SN2-Type Reaction for Detection of Epoxy Compounds","authors":"Anton Charyarov, Stanislav Bakhtin","doi":"10.1002/poc.4668","DOIUrl":"https://doi.org/10.1002/poc.4668","url":null,"abstract":"<div>\u0000 \u0000 New reaction systems “oxirane – nucleophile X– – proton-donor reagent AH – solvent” have been proposed for the detection of epoxides in which nucleophilic opening of the oxirane ring occurs accompanied by the formation of a colored product. The kinetic and mechanistic regularities of reactions in the proposed systems were investigated. Reaction orders with respect to the components of the systems have been determined: close to 1 – for oxirane and X−, close to 0 – for AH. It was shown that the proposed chromogenic reactions represent nucleophilic substitution of SN2-type and allow the detection of epoxides containing both a terminal and internal epoxy group, which can be used to monitor processes in systems where epoxides are either the initial compounds or the synthesis products. Based on the conducted studies, it is possible to develop methods for the quantitative determination of epoxides using kinetic methods of analysis and UV–visible spectroscopy.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142869164","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Structural Modeling of Fluorinated Quinoxaline Core–Based Chromophores for Efficient Photovoltaic Materials: A DFT Study 用于高效光伏材料的氟化喹喔啉核基发色团的结构模型：DFT 研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-18 DOI: 10.1002/poc.4663

Iqra Shafiq, Sana Nasrullah, Maria Zafar, Iram Irshad, Syed Muddassir Ali Mashhadi, Saifullah Bullo, Muhammad Arshad, Rajeh Alotaibi

{"title":"Structural Modeling of Fluorinated Quinoxaline Core–Based Chromophores for Efficient Photovoltaic Materials: A DFT Study","authors":"Iqra Shafiq, Sana Nasrullah, Maria Zafar, Iram Irshad, Syed Muddassir Ali Mashhadi, Saifullah Bullo, Muhammad Arshad, Rajeh Alotaibi","doi":"10.1002/poc.4663","DOIUrl":"https://doi.org/10.1002/poc.4663","url":null,"abstract":"<div>\u0000 \u0000 Herein, a series of fluorinated quinoxaline core–based chromophores (MTH1-MTH6) with A1–π–A2–π–A1 configuration was designed by structural modulation of end-capped acceptors in MTHR. The quantum chemical calculations were accomplished at MPW1PW91/6-311G(d,p) functional to explore optoelectronic and photovoltaic properties of these designed compounds. The findings revealed that all the derivatives exhibited narrow band gap (Egap = 2.163–2.666 eV) with red shift spectra (610.24–766.944 eV in chloroform) as compared with MTHR. The designed compounds exhibited comparable open-circuit voltage (Voc) and higher power conversion efficiencies (PCEs) as compared with the MTHR. Among the entitled chromophores, MTH1 was found to be a promising chromophore for organic solar cells (OSCs) owning to its lowest Egap (2.163 eV) with highest absorption peak (766.944 nm in chloroform and 717.709 nm in gaseous phase). The aforementioned findings indicate that molecular engineering of chromophores with extended acceptors enhances photovoltaic response, and this motivates researchers to develop highly effective photovoltaic devices.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142868803","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

A 19F Solvatomagnetic Comparison Method for the Determination of the α1 Scale of Solvent Hydrogen-Bond Donation and Its Application to Deep Eutectic Solvents 19F溶剂磁比较法测定溶剂氢键给予α1尺度及其在深共晶溶剂中的应用

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-17 DOI: 10.1002/poc.4665

Christian Laurence, Sergui Mansour, Daniela Vuluga, Julien Legros

引用次数: 0

The Study on Synthesis and Characterization of Insensitive Energetic Materials Based on 5-(5-Nitro-1H-1,2,4-Triazol-3-yl)-1H-Tetrazole 基于5-（5-硝基- 1h -1,2,4-三唑-3-基）- 1h -四唑的不敏感含能材料的合成与表征研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-15 DOI: 10.1002/poc.4667

Chenchen Lin, Pingping Yi, Xiaoyi Yi, Tingwei Wang, Jianguo Zhang, Piao He

引用次数: 0

The Cleavage of RNA Model Compounds: The Interplay Between the Nucleophile and the Leaving Group RNA 模型化合物的裂解：亲核剂与离去基团之间的相互作用

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-09 DOI: 10.1002/poc.4664

Jasmin I. Koski, Emilia Poijärvi, Anne Tulisalo, Heidi Korhonen, Satu Mikkola

{"title":"The Cleavage of RNA Model Compounds: The Interplay Between the Nucleophile and the Leaving Group","authors":"Jasmin I. Koski, Emilia Poijärvi, Anne Tulisalo, Heidi Korhonen, Satu Mikkola","doi":"10.1002/poc.4664","DOIUrl":"https://doi.org/10.1002/poc.4664","url":null,"abstract":"Hydrolytic reactions of phosphodiester bonds of RNA have been extensively studied over several decades. Information on the factors that affect the reactivity of phosphodiester bonds in biomolecules is important for the development of new nucleic acid-related therapeutics. Furthermore, the development of artificial nucleases requires efficient catalytic entities, and rational design of catalysts requires detailed understanding of the catalytic mechanisms. In the present article, we concentrate on the interplay between the nucleophile and leaving group both in the absence and in the presence of metal ion catalysts. The effect of the nucleophile on the reactivity of RNA model compounds has been studied with 2-hydroxypropyl and uridine 3′-aryl phosphates as well as with bis-(p-nitrophenyl)phosphate as substrates. pH-rate profiles for three different 2-hydroxypropyl arylphosphates were compared with those obtained with a uridine 3′-alkyl and aryl phosphates. The observations are discussed in terms of the relative goodness/poorness of the nucleophile and the leaving group. Metal complex-dependent reactions were studied in the presence of well-known and robust CuTerPy and CuBiPy complexes. The results show that CuTerPy and CuBiPy favour different types of phosphodiesters as substrates, depending on the properties of the nucleophile and leaving group, and suggest that the complexes utilize different catalysis mechanisms, which may depend also on the structure of the substrate. The results obtained further the understanding on the basic principles of metal complex-promoted cleavage of RNA and model compounds, help to assess the relevance of data obtained with model compounds and support the design of artificial enzymes for phosphodiester cleavage.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4664","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142868334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Computational Justification Towards Detection of Dual Anions on a Single Molecular Platform: The Role of Solvent in Decoration of Dual Channels 单分子平台上双阴离子检测的计算论证：溶剂在双通道修饰中的作用

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-06 DOI: 10.1002/poc.4666

Suvendu Paul

{"title":"Computational Justification Towards Detection of Dual Anions on a Single Molecular Platform: The Role of Solvent in Decoration of Dual Channels","authors":"Suvendu Paul","doi":"10.1002/poc.4666","DOIUrl":"https://doi.org/10.1002/poc.4666","url":null,"abstract":"<div>\u0000 \u0000 Ratiometric optical detection of analytes is a convenient strategy as the technique is devoid of relative error and background correction. Herein, solvent-guided ratiometric optical recognition of fluoride and bisulfate anions by a low-cost, “off-the-shelf” bioactive molecule, harmane (HRH) is thoroughly explored. Interestingly, solvent plays a dynamic role in the selective recognition of the dual anions via the dual channels of HRH in an intelligent manner. The probe displays high-fidelity recognition behavior towards fluoride ion in an aprotic solvent (acetonitrile) and towards bisulfate ion in a protic environment (acetonitrile/water; 5:1; v/v). Both the channels of HRH are very selective for a particular anion (F−/HSO4−) in a specific solvent. Organized and comprehensive theoretical calculation denotes that hydrogen bonding between the acidic pyrrolic proton of HRH and fluoride for the first channel and the acidic proton of bisulfate and the pyridinic nitrogen for the second channel of HRH led to the formation of a hydrogen-bonded ion pair (HBIP). Consequently, significant optical changes are observed in the visible region, which is convenient for real-life detection of F− and HSO4− independently. The essential role of solvent in tuning the dual channels of HRH is an important artifact in the literature of fundamental photochemistry.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867908","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Theoretical Investigation of Energetic Materials Based on Imidazole Framework Featuring Azido/Nitro/Nitrato/Fluoro Groups 基于叠氮基/硝基/硝基/氟基咪唑骨架的含能材料理论研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-01 DOI: 10.1002/poc.4661

Anjali Sharma, Kshetrimayum Dhruba Singh, Mridula Guin

引用次数: 0