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Solution and Solid-State Optical Properties of Trifluoromethylated 5-(Alkyl/aryl/heteroaryl)-2-methyl-pyrazolo[1,5-a]pyrimidine System 三氟甲基化5-(烷基/芳基/杂芳基)-2-甲基吡唑并[1,5-a]嘧啶体系的溶液和固态光学性质
Photochem Pub Date : 2022-05-19 DOI: 10.3390/photochem2020024
Felipe S. Stefanello, Jean C. B. Vieira, Juliane N. Araújo, Vitória B. Souza, C. Frizzo, M. Martins, N. Zanatta, B. Iglesias, H. Bonacorso
{"title":"Solution and Solid-State Optical Properties of Trifluoromethylated 5-(Alkyl/aryl/heteroaryl)-2-methyl-pyrazolo[1,5-a]pyrimidine System","authors":"Felipe S. Stefanello, Jean C. B. Vieira, Juliane N. Araújo, Vitória B. Souza, C. Frizzo, M. Martins, N. Zanatta, B. Iglesias, H. Bonacorso","doi":"10.3390/photochem2020024","DOIUrl":"https://doi.org/10.3390/photochem2020024","url":null,"abstract":"This paper describes the photophysical properties of a series of seven selected examples of 5-(alkyl/aryl/heteroaryl)-2-methyl-7-(trifluoromethyl)pyrazolo[1,5-a]pyrimidines (3), which contain alkyl, aryl, and heteroaryl substituents attached to the scaffolds of 3. Given the electron-donor groups and -withdrawing groups, the optical absorption and emission in the solid state and solution showed interesting results. Absorption UV–Vis and fluorescence properties in several solvents of a pyrazolo[1,5-a]pyrimidines series were investigated, and all derivatives were absorbed in the ultraviolet region despite presenting higher quantum emission fluorescence yields in solution and moderate emission in the solid state. Moreover, the solid-state thermal stability of compounds 3a–g was assessed using thermogravimetric analysis. The thermal decomposition profile showed a single step with almost 100% mass loss for all compounds 3. Additionally, the values of T0.05 are considerably low (72–187 °C), especially for compound 3a (72 °C), indicating low thermal stability for this series of pyrazolo[1,5-a]pyrimidines.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42242079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 3
Structure-Function-Environment Relationship of the Isomers Zeaxanthin and Lutein 玉米黄质和叶黄素异构体的结构-功能-环境关系
Photochem Pub Date : 2022-04-18 DOI: 10.3390/photochem2020022
B. Demmig-Adams, S. K. Polutchko, W. W. Adams
{"title":"Structure-Function-Environment Relationship of the Isomers Zeaxanthin and Lutein","authors":"B. Demmig-Adams, S. K. Polutchko, W. W. Adams","doi":"10.3390/photochem2020022","DOIUrl":"https://doi.org/10.3390/photochem2020022","url":null,"abstract":"A synthesis is provided of the roles of the carotenoids zeaxanthin and/or lutein in opposing (i) photodamage in plants, (ii) photodamage to the human eye as well as cognitive dysfunction and a host of human diseases and disorders, and (iii) damage to extremophile microorganisms in the most inhospitable environments on earth. Selected examples are used to examine microenvironments and basic biological structures with which these xanthophylls associate as well as the effect of the organisms’ external environment. An overview is presented of the multiple principal mechanisms through which these xanthophylls can directly or indirectly impact organisms’ internal redox (oxidant/antioxidant) balance that provides input into the orchestration of growth, development, and defense in prokaryotic microorganisms, plants, and humans. Gaps in the research are identified, specifically with respect to the need for further in vivo assessment of the mechanisms.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47313318","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 13
Energy Relaxation of Porphycene in Atomic and Molecular Cryogenic Matrices 卟啉在原子和分子低温基质中的能量弛豫
Photochem Pub Date : 2022-04-06 DOI: 10.3390/photochem2020021
J. Dobkowski, I. Sazanovich, A. Gorski, J. Waluk
{"title":"Energy Relaxation of Porphycene in Atomic and Molecular Cryogenic Matrices","authors":"J. Dobkowski, I. Sazanovich, A. Gorski, J. Waluk","doi":"10.3390/photochem2020021","DOIUrl":"https://doi.org/10.3390/photochem2020021","url":null,"abstract":"The kinetics of relaxation of high-lying electronic states of porphycene (porphyrin isomer) embedded in different cryogenic matrices were studied using picosecond time-resolved fluorescence (TRF) and transient absorption (TA) techniques. The molecule was excited into the Soret band, i.e., with a large energy excess compared to that of the lowest (Q) excited state. The TRF and TA time profiles obtained for porphycene embedded in argon and methane matrices were remarkably different: the overall relaxation in argon occurred in 64 ps, whereas the corresponding value for methane matrix was 18 ps. Analysis of the evolution over time of different spectral ranges of TRF spectra indicates the multidimensional character of relaxation kinetics.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47658208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Photoelectrochemical Energy Conversion over 2D Materials 二维材料上的光电化学能量转换
Photochem Pub Date : 2022-03-30 DOI: 10.3390/photochem2020020
A. Raza, Xinyu Zhang, Sarfraz Ali, Changhai Cao, Arslan Ahmed Rafi, Gao Li
{"title":"Photoelectrochemical Energy Conversion over 2D Materials","authors":"A. Raza, Xinyu Zhang, Sarfraz Ali, Changhai Cao, Arslan Ahmed Rafi, Gao Li","doi":"10.3390/photochem2020020","DOIUrl":"https://doi.org/10.3390/photochem2020020","url":null,"abstract":"The solar motivated photoelectrochemical (PEC), used in water splitting systems, shows superior talent in converting solar energy in the form of cleaning and in sustaining a chemical energy evolution. PEC systems present by integrating a photoelectrode, which involves light-harvesting to absorb solar energy, thereby introducing an interlayer for the transformation of photogenerated electrons and holes, along with a co-catalyst to trigger oxidation and reduce the chemical reactions. In this review, we describe a variety of two-dimensional (2D) layered photoanodes and photocathodes, such as graphitic carbon nitrides, transition metal dichalcogenides, layered double hydroxides, MXenes, and co-catalysts for the assembly of combined photoelectrodes belonging to oxygen evolution and/or hydrogen evolution chemical reactions. The basic principles of PEC water splitting associated with physicochemical possessions relating to photoelectrodes unified with catalytic chemical reactions have been investigated. Additionally, the mechanisms attributing to a relationship with 2D photoelectrodes have been incorporated as a supplementary discussion. The improvement strategies, which include the construction of heterostructures, surface functionalization, and formations of heterojunctions, have also been discussed. The issues and challenges relevant to the field have been acknowledged for facilitating future research, indicating optimized conversion activity corresponding to PEC water splitting.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46697079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 15
Phosphorescence of C5N− in Rare Gas Solids 稀有气体固体中C5N−的磷光
Photochem Pub Date : 2022-03-28 DOI: 10.3390/photochem2020019
U. Szczepaniak, R. Kołos, J. Guillemin, C. Crépin
{"title":"Phosphorescence of C5N− in Rare Gas Solids","authors":"U. Szczepaniak, R. Kołos, J. Guillemin, C. Crépin","doi":"10.3390/photochem2020019","DOIUrl":"https://doi.org/10.3390/photochem2020019","url":null,"abstract":"Phosphorescence of C5N− was discovered following the ArF-laser (193 nm) photolysis of cyanodiacetylene (HC5N) isolated in cryogenic argon, krypton, and xenon matrices. This visible emission, with an origin around 460 nm, is vibrationally resolved, permitting the measurement of frequencies for eight ground-state fundamental vibrational modes, including the three known from previous IR absorption studies. Phosphorescence lifetime amounts to tens or even hundreds of ms depending on the matrix host; it is five times longer than in the case of HC5N.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41830561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Water Clusters in Interaction with Corannulene in a Rare Gas Matrix: Structures, Stability and IR Spectra 稀有气体基质中水团簇与珊瑚烯相互作用的结构、稳定性和红外光谱
Photochem Pub Date : 2022-03-25 DOI: 10.3390/photochem2020018
H. Leboucher, J. Mascetti, Christian Aupetit, J. Noble, A. Simon
{"title":"Water Clusters in Interaction with Corannulene in a Rare Gas Matrix: Structures, Stability and IR Spectra","authors":"H. Leboucher, J. Mascetti, Christian Aupetit, J. Noble, A. Simon","doi":"10.3390/photochem2020018","DOIUrl":"https://doi.org/10.3390/photochem2020018","url":null,"abstract":"The interaction of polycyclic aromatic hydrocarbons (PAHs) with water is of paramount importance in atmospheric and astrophysical contexts. We report here a combined theoretical and experimental study of corannulene-water interactions in low temperature matrices and of the matrix’s influence on the photoreactivity of corannulene with water. The theoretical study was performed using a mixed density functional based tight binding/force field approach to describe the corannulene-water clusters trapped in an argon matrix, together with Born-Oppenheimer molecular dynamics to determine finite-temperature IR spectra. The results are discussed in the light of experimental matrix isolation FTIR spectroscopic data. We show that in the solid phase, π isomers of (C20H10)(H2O)n, with n = 2 or 3, are energetically favored. These π complexes are characterized by small shifts in corannulene vibrational modes and large shifts in water bands. These π structures, particularly stable in the case of the water trimer where the water cluster is trapped “inside” the corannulene bowl, may account for the difference in photoreactivity of non-planar–compared to planar–PAHs with water. Indeed, planar PAHs such as pyrene and coronene embedded in H2O:Ar matrices form σ isomers and react with water to form alcohols and quinones under low energy UV irradiation, whereas no photoreactivity was observed for corannulene under the same experimental conditions.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48236278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 2
Study of the Response Surface in the Photocatalytic Degradation of Acetaminophen Using TiO2 TiO2光催化降解对乙酰氨基酚响应面研究
Photochem Pub Date : 2022-03-10 DOI: 10.3390/photochem2010017
Adriana Marizcal-Barba, J. Sánchez-Burgos, V. Zamora-Gasga, A. Pérez Larios
{"title":"Study of the Response Surface in the Photocatalytic Degradation of Acetaminophen Using TiO2","authors":"Adriana Marizcal-Barba, J. Sánchez-Burgos, V. Zamora-Gasga, A. Pérez Larios","doi":"10.3390/photochem2010017","DOIUrl":"https://doi.org/10.3390/photochem2010017","url":null,"abstract":"An effective way to obtain the optimal parameters of a process or experiment is the response surface method. Using the Box–Behnken design further decreases the number of experiments needed to obtain sufficient data to obtain a reliable equation. From the equation, it is possible to predict the behavior of the response with respect to the combination of variables involved. In this study we evaluated the photocatalytic activity of the synthesized TiO2 for the degradation of acetaminophen, a frequently used and uncontrolled drug that has been detected with increasing frequency in wastewater effluents. The variables used for this study were pH, contaminant concentration (acetaminophen) and catalyst dose. We found, with a 95% confidence level, that 99% of the contaminant can be degraded to pH 10, contaminant to 35 mg/L and a catalyst dose of 0.15 g TiO2.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44788647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 4
Phosphorescence and Photophysical Parameters of Porphycene in Cryogenic Matrices 低温基质中卟啉的磷光和光物理参数
Photochem Pub Date : 2022-03-09 DOI: 10.3390/photochem2010016
Barbara Golec, A. Gorski, J. Waluk
{"title":"Phosphorescence and Photophysical Parameters of Porphycene in Cryogenic Matrices","authors":"Barbara Golec, A. Gorski, J. Waluk","doi":"10.3390/photochem2010016","DOIUrl":"https://doi.org/10.3390/photochem2010016","url":null,"abstract":"Matrix isolation studies were carried out for porphycene, an isomer of porphyrin, embedded in solid nitrogen and xenon. The external heavy atom effect resulted in nearly a 100% population of the triplet state and in the appearance of phosphorescence, with the origin located at 10163 cm−1. This energy is much lower than that corresponding to the T1 position in porphyrin. This difference could be explained by postulating that the orbital origin corresponds in both isomers to the second excited singlet state, which lies much closer to S1 in porphycene. Most of the vibrational frequencies observed in the phosphorescence spectrum correspond to totally symmetric modes, but several ones were assigned to the out-of-plane Bg vibrations. These bands are not observed in fluorescence, which suggests their possible role in vibronic-spin-orbit coupling.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49452196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Theoretical Modeling of Absorption and Fluorescent Characteristics of Cyanine Dyes 菁染料吸收和荧光特性的理论建模
Photochem Pub Date : 2022-03-04 DOI: 10.3390/photochem2010015
S. Ilieva, M. Kandinska, A. Vasilev, D. Cheshmedzhieva
{"title":"Theoretical Modeling of Absorption and Fluorescent Characteristics of Cyanine Dyes","authors":"S. Ilieva, M. Kandinska, A. Vasilev, D. Cheshmedzhieva","doi":"10.3390/photochem2010015","DOIUrl":"https://doi.org/10.3390/photochem2010015","url":null,"abstract":"The rational design of cyanine dyes for the fine-tuning of their photophysical properties undoubtedly requires theoretical considerations for understanding and predicting their absorption and fluorescence characteristics. The present study aims to assess the applicability and accuracy of several DFT functionals for calculating the absorption and fluorescence maxima of monomethine cyanine dyes. Ten DFT functionals and different basis sets were examined to select the proper theoretical model for calculating the electronic transitions of eight representative molecules from this class of compounds. The self-aggregation of the dyes was also considered. The pure exchange functionals (M06L, HFS, HFB, B97D) combined with the triple-zeta basis set 6-311+G(2d,p) showed the best performance during the theoretical estimation of the absorption and fluorescent characteristics of cyanine dyes.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46384400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 3
Photophysics and Electrochemistry of Biomimetic Pyranoflavyliums: What Can Bioinspiration from Red Wines Offer? 仿生pyranoflavylium的光物理和电化学:从红酒中能得到什么生物启示?
Photochem Pub Date : 2022-03-01 DOI: 10.3390/photochem2010003
Eli Misael Espinoza, John Anthony Clark, Mimi Karen Billones, Gustavo Thalmer de Medeiros Silva, Cassio Pacheco da Silva, Frank Herbert Quina, Valentine Ivanov Vullev
{"title":"Photophysics and Electrochemistry of Biomimetic Pyranoflavyliums: What Can Bioinspiration from Red Wines Offer?","authors":"Eli Misael Espinoza,&nbsp;John Anthony Clark,&nbsp;Mimi Karen Billones,&nbsp;Gustavo Thalmer de Medeiros Silva,&nbsp;Cassio Pacheco da Silva,&nbsp;Frank Herbert Quina,&nbsp;Valentine Ivanov Vullev","doi":"10.3390/photochem2010003","DOIUrl":"https://doi.org/10.3390/photochem2010003","url":null,"abstract":"<p><p>Natural dyes and pigments offer incomparable diversity of structures and functionalities, making them an excellent source of inspiration for the design and development of synthetic chromophores with a myriad of emerging properties. Formed during maturation of red wines, pyranoanthocyanins are electron-deficient cationic pyranoflavylium dyes with broad absorption in the visible spectral region and pronounced chemical and photostability. Herein, we survey the optical and electrochemical properties of synthetic pyranoflavylium dyes functionalized with different electron-donating and electron-withdrawing groups, which vary their reduction potentials over a range of about 400 mV. Despite their highly electron-deficient cores, the exploration of pyranoflavyliums as photosensitizers has been limited to the \"classical\" <i>n</i>-type dye-sensitized solar cells (DSSCs) where they act as electron donors. In light of their electrochemical and spectroscopic properties, however, these biomimetic synthetic dyes should prove to be immensely beneficial as chromophores in <i>p</i>-type DSSCs, where their ability to act as photooxidants, along with their pronounced photostability, can benefit key advances in solar-energy science and engineering.</p>","PeriodicalId":74440,"journal":{"name":"Photochem","volume":"2 1","pages":"9-31"},"PeriodicalIF":0.0,"publicationDate":"2022-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8783599/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10264878","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}
引用次数: 3
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