Photochem最新文献_第3页

Metal Ion-Induced Formation of Metallogels by Visible-Light-Responsive Phenylalanine-Functionalized Arylazopyrazole Ligands 金属离子诱导形成可见光响应苯丙氨酸功能化芳唑配体的金属凝胶

Photochem Pub Date : 2023-10-24 DOI: 10.3390/photochem3040026

Mikayla Browning, Alexandra Jefferson, Jazz Geter, Kesete Ghebreyessus

{"title":"Metal Ion-Induced Formation of Metallogels by Visible-Light-Responsive Phenylalanine-Functionalized Arylazopyrazole Ligands","authors":"Mikayla Browning, Alexandra Jefferson, Jazz Geter, Kesete Ghebreyessus","doi":"10.3390/photochem3040026","DOIUrl":"https://doi.org/10.3390/photochem3040026","url":null,"abstract":"A visible-light-responsive arylazopyrazole-functionalized phenylalanine (4-MeS-AAP-NF) derived ligand was designed and synthesized, and it was found to form metallogels with reversible photo-responsive properties in mixed methanol/water (MeOH/H2O) solvents. The gelation behavior of the 4-MeS-AAP-NF ligand in the presence of different divalent metal ions in mixed methanol/water (MeOH/H2O) solvents at pH~11.60 was studied. It was found that the 4-MeS-AAP-NF ligand alone could not self-assemble to form any gels. However, in the presence of divalent metal ions, it readily formed the assembled metallogels in an alkaline aqueous/methanol solution with various morphologies. The results suggest that the gelation process was triggered by divalent metal ions. The presence of the AAP moiety in the gel matrix rendered the metallogel assemblies photo-responsive, and the reversible gel-to-sol phase transition was studied by UV-vis spectroscopy. The gels showed a slow, reversible visible-light-induced gel-to-sol phase transition under blue (λ = 405 nm) and then sol-to-gel transition by green light (λ = 530 nm) irradiation, resulting in the re-formation of the original gel state. The morphology and viscoelastic properties of the yellow–orange opaque metallogels were characterized by scanning electron microscopy (SEM) and rheological measurement, respectively.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":"C-18 8","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135316251","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

Photochemistry of β-γ-Unsaturated Spirolactones β-γ-不饱和螺内酯的光化学性质

Photochem Pub Date : 2023-10-17 DOI: 10.3390/photochem3040025

Werner Fudickar, Melanie Metz, Tobias Krüger-Braunert, Alexandra Kelling, Eric Sperlich, Pablo Wessig, Torsten Linker

{"title":"Photochemistry of β-γ-Unsaturated Spirolactones","authors":"Werner Fudickar, Melanie Metz, Tobias Krüger-Braunert, Alexandra Kelling, Eric Sperlich, Pablo Wessig, Torsten Linker","doi":"10.3390/photochem3040025","DOIUrl":"https://doi.org/10.3390/photochem3040025","url":null,"abstract":"β-γ-unsaturated spirolactones are easily available by Birch reduction. We describe their photochemistry in the presence of or without carbonyl compounds. The spirolactones show a distinct absorption band at 230 nm, which is not present in other cyclohexadienes. We explain this behavior by an interaction of the double bonds with the carbonyl group through space, further proven by TDDFT calculations. This allows their direct excitation with UV-C light. Interestingly, we obtain only products of an oxa-di-π-methane rearrangement, hitherto unknown for lactones. This speaks for a reaction pathway starting from singlet states, confirmed by calculated relative energies of biradical intermediates. Although polymerization is the main side reaction, we were able to isolate tricyclic lactones in moderate yields in a pure form. In the presence of benzaldehyde or benzophenone, excitation with UV-B light was possible, leading to H-atom abstraction in the allylic position and formation of alcohols. With an electron-rich double bond, the Paternó–Büchi products were isolated as well. The different diastereomers were separated by column chromatography or HPLC. Their relative configurations were determined using NOESY measurements or X-ray structure analysis. Overall, β-γ-unsaturated spirolactones show a remarkably different photochemistry compared to other cyclohexadienes, affording new products in only a few steps.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":"38 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135993835","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

Photocatalytic Degradation of Methylene Blue by Magnetic Opal/Fe3O4 Colloidal Crystals under Visible Light Irradiation 可见光下磁性蛋白石/Fe3O4胶体晶体光催化降解亚甲基蓝的研究

Photochem Pub Date : 2023-10-08 DOI: 10.3390/photochem3040024

Abraham Jorge Carmona-Carmona, Enrique Sánchez Mora, Jesús Ivan Peña Flores, César Márquez-Beltrán, María Dolores Castañeda-Antonio, Marlén Alexis González-Reyna, María Concepción Barrera, Khashayar Misaghian, Jesús Eduardo Lugo, Miller Toledo-Solano

引用次数: 0

5-Chlorocoumaranone-Conjugates as Chemiluminescent Protecting Groups (CLPG) and Precursors to Fluorescent Protecting Groups (FPG) 5-氯香豆素偶联物作为化学发光保护基团(CLPG)和荧光保护基团(FPG)前体

Photochem Pub Date : 2023-09-07 DOI: 10.3390/photochem3030023

Tim Lippold, A. Griesbeck, Robert Herzhoff, Mathias S. Wickleder, Laura Straub, Niko T. Flosbach

{"title":"5-Chlorocoumaranone-Conjugates as Chemiluminescent Protecting Groups (CLPG) and Precursors to Fluorescent Protecting Groups (FPG)","authors":"Tim Lippold, A. Griesbeck, Robert Herzhoff, Mathias S. Wickleder, Laura Straub, Niko T. Flosbach","doi":"10.3390/photochem3030023","DOIUrl":"https://doi.org/10.3390/photochem3030023","url":null,"abstract":"The introduction and cleavage of protecting groups and the subsequent release of protected molecules is an important tool in synthetic organic chemistry. When polyfunctionalized substrates are involved, the reactivity of similar functional groups must be differentiated and selectively switched on and off. A very useful switching agent is visible or UV-light in photoremovable protecting groups (PRPG), allowing the PG release upon interaction with electromagnetic radiation. The reverse principle is the release of a protected molecule, which is accompanied by emission of light, i.e., chemiluminescent protecting groups (CLPG). This principle is proposed and investigated for phenylalanine (using ureido carboxylic acid 2 and its methyl ester derivative 3) and the carbamate derivatives of paracetamol 4 and L-menthol 7, protected as the corresponding urea-/carbamate-coumaranones 5A, 5E, 6 and 8, respectively. While the carbamate derivative 6 released the protected substrate with a short and strong emission of blue light when treated with a base under atmospheric oxygen, 8 had to be treated additionally with potassium hydroxide in boiling ethanol to completely cleave the PG. Both urea-coumaranone derivatives 5A/5E had a flash-like CL without release of the protected amino acid and, thus, were converted into a fluorescent protecting group (FPG).","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44619186","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

Enhanced Photocatalytic Dehalogenation Performance of RuDoped In2O3 Nanoparticles Induced by Oxygen Vacancy 氧空位诱导Ru掺杂In2O3纳米粒子光催化脱卤性能的增强

Photochem Pub Date : 2023-09-01 DOI: 10.3390/photochem3030022

Jingjing Xiang, Jinting Shang, Zhen Wan

{"title":"Enhanced Photocatalytic Dehalogenation Performance of RuDoped In2O3 Nanoparticles Induced by Oxygen Vacancy","authors":"Jingjing Xiang, Jinting Shang, Zhen Wan","doi":"10.3390/photochem3030022","DOIUrl":"https://doi.org/10.3390/photochem3030022","url":null,"abstract":"Due to its favorable excited-state physicochemical properties, indium oxide (In2O3) has widely captured attention as a potentially great photocatalyst. However, an inferior charge separation efficiency limits its application. Recently, an increasing amount of evidence has demonstrated that the construction of surface defects is an effective strategy to boost photocatalytic performances. In this work, a ruthenium (Ru) species was successfully introduced into the lattice of In2O3 nanoparticles through co-precipitation and thermal treatment. It was found that the content of surface oxygen vacancies was directly related to the amount of Ru3+ doping, which further determines the separation efficiency of photogenerated carriers. As a result, the 0.5% Ru-In2O3 samples enriched with oxygen vacancies exhibit dramatically enhanced photocatalytic dehalogenation performances of decabromodiphenyl ether and hexabromobenzene, about four times higher than that of the pure In2O3 nanoparticles. This study emphasized the significance of the surface defects of the photocatalyst and may provide a valuable strategy to prepare highly active photocatalysts for photocatalytic dehalogenation reactions.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44828679","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

New Fluorescent Porphyrins with High Two-Photon Absorption Cross-Sections Designed for Oxygen-Sensitization: Impact of Changing the Connectors in the Peripheral Arms 具有高双光子吸收截面的新型荧光卟啉设计用于氧敏化:改变外围臂中的连接器的影响

Photochem Pub Date : 2023-08-10 DOI: 10.3390/photochem3030021

Limiao Shi, Zhipeng Sun, N. Richy, O. Mongin, M. Blanchard‐Desce, F. Paul, Christine O. Paul-Roth

{"title":"New Fluorescent Porphyrins with High Two-Photon Absorption Cross-Sections Designed for Oxygen-Sensitization: Impact of Changing the Connectors in the Peripheral Arms","authors":"Limiao Shi, Zhipeng Sun, N. Richy, O. Mongin, M. Blanchard‐Desce, F. Paul, Christine O. Paul-Roth","doi":"10.3390/photochem3030021","DOIUrl":"https://doi.org/10.3390/photochem3030021","url":null,"abstract":"In the continuation of our sustained interest in porphyrin-based dendrimers and their use as luminescent photosensitizers for two-photon photodynamic therapy (2P-PDT), we wondered about the effect of changing the connectors in our macromolecular structures. We also wanted to initiate preliminary studies on meso-tetraarylporphyrins decorated with more electron-releasing arms. Thus, various meso-tetrafluorenylporphyrin-cored star-shaped and dendrimeric derivatives have been synthesized and characterized, as well as their zinc(II) complexes. In the new dendrimeric derivatives, the peripheral fluorenyl units of the dendrons are linked to the inner core either by N-phenylcarbazole (CCbz) or triphenylamine (CTpa) connectors instead of the more classic 1,3,5-phenylene (CPh) linkers previously used by us. Selected linear and non-linear optical (LO and NLO) properties were then determined for these compounds via absorption or emission studies and by two-photon excited fluorescence (TPEF) measurements. It was found that the CCbz-containing dendrimer, which has the most rigid structure, exhibits a significantly lower two-photon absorption (2PA) cross-section than its CTpa analog, presenting a more flexible structure while rather similar luminescence and singlet oxygen activation quantum yields are found for both. The origin of this unexpected discrepancy is briefly discussed based on our photophysical data. It is then demonstrated that the latter dendrimer also outperforms several closely related dendrimers in terms of 2PA action cross-section and 2PA-oxygen sensitization, making its molecular architecture quite appealing for developing new 2PA photosensitizers suited to theranostic uses.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48352427","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

Modeling the Unimolecular Decay Dynamics of the Fluorinated Criegee Intermediate, CF3CHOO 氟化Criegee中间体CF3CHOO的单分子衰变动力学建模

Photochem Pub Date : 2023-07-14 DOI: 10.3390/photochem3030020

Lily M. Guidry, Courtney A. Poirier, Jordyn M Ratliff, Ernest Antwi, Barbara Marchetti, Tolga N. V. Karsili

{"title":"Modeling the Unimolecular Decay Dynamics of the Fluorinated Criegee Intermediate, CF3CHOO","authors":"Lily M. Guidry, Courtney A. Poirier, Jordyn M Ratliff, Ernest Antwi, Barbara Marchetti, Tolga N. V. Karsili","doi":"10.3390/photochem3030020","DOIUrl":"https://doi.org/10.3390/photochem3030020","url":null,"abstract":"When volatile alkenes are emitted into the atmosphere, they are rapidly removed by oxidizing agents such as hydroxyl radicals and ozone. The latter reaction is termed ozonolysis and is an important source of Criegee intermediates (CIs), i.e., carbonyl oxides, that are implicated in enhancing the oxidizing capacity of the troposphere. These CIs aid in the formation of lower volatility compounds that typically condense to form secondary organic aerosols. CIs have attracted vast attention over the past two decades. Despite this, the effect of their substitution on the ground and excited state chemistries of CIs is not well studied. Here, we extend our knowledge obtained from prior studies on CIs by CF3 substitution. The resulting CF3CHOO molecule is a CI that can be formed from the ozonolysis of hydrofluoroolefins (HFOs). Our results show that the ground state unimolecular decay should be less reactive and thus more persistent in the atmosphere than the non-fluorinated analog. The excited state dynamics, however, are predicted to occur on an ultrafast timescale. The results are discussed in the context of the ways in which our study could advance synthetic chemistry, as well as processes relevant to the atmosphere.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45711804","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

Photodynamic Anticancer and Antibacterial Activities of Sn(IV) N-Confused Meso-tetra(methylthiophenyl)porphyrin Sn（IV）N-混叠Meso-四（甲硫基苯基）卟啉的光动力抗癌和抗菌活性

Photochem Pub Date : 2023-06-30 DOI: 10.3390/photochem3030019

Somila Dingiswayo, Balaji Babu, Kristen Burgess, J. Mack, T. Nyokong

引用次数: 1

E–Z Photoisomerization in Proton-Modulated Photoswitchable Merocyanine Based on Benzothiazolium and o-Hydroxynaphthalene Platform 基于苯并噻唑鎓和邻羟基萘平台的质子调制光开关酞菁的E–Z光异构化

Photochem Pub Date : 2023-06-19 DOI: 10.3390/photochem3020018

Aleksey A. Vasilev, S. Baluschev, S. Ilieva, D. Cheshmedzhieva

引用次数: 0

Effect of Benzophenone Type UV Filters on Photodegradation of Co-existing Sulfamethoxazole in Water 二苯甲酮型紫外滤光剂对水中共存磺胺甲恶唑光降解的影响

Photochem Pub Date : 2023-06-01 DOI: 10.3390/photochem3020017

D. Kodikara, Zhongyu Guo, C. Yoshimura

{"title":"Effect of Benzophenone Type UV Filters on Photodegradation of Co-existing Sulfamethoxazole in Water","authors":"D. Kodikara, Zhongyu Guo, C. Yoshimura","doi":"10.3390/photochem3020017","DOIUrl":"https://doi.org/10.3390/photochem3020017","url":null,"abstract":"Benzophenones (BPs) frequently occur in water environments, and they are able to both screen UV light and to sensitize reactive intermediate (RI) production. However, BPs have largely been overlooked as a background water component when studying photodegradation of co-existing organic micropollutants (OMPs). Therefore, in this study, we investigated the influence of BP and its derivative oxybenzone (BP3) on the degradation of the co-existing model OMP sulfamethoxazole (SMX). A series of photodegradation experiments were conducted covering a range of BPs concentrations in μg/L levels, and the degradation of 1.00 μM of SMX was studied. The addition of BP at 0.10 μM, 0.25 μM, and 0.30 μM, and BP3 at 0.10 μM and 0.25 μM, significantly increased the first order degradation rate constant of 1.00 μM of SMX (kobs(BP)) by 36.2%, 50.0%, 7.3%, 31.5%, and 36.2% respectively, compared to that in the absence of any BPs. The maximum indirect photodegradation induced by BP and BP3 reached 33.8% and 27.7%, respectively, as a percentage of the observed SMX degradation rate at the [BPs]/[SMX] ratio of 0.25. In general, triplet excited dissolved organic matter (3SMX*, 3BP*, and 3BP3*) played the major role in the photosensitizing ability of BPs. The results further implied that the increase of SMX degradation at the molar ratio of 0.25 was possibly due to 3BP* for the mixture of SMX and BP. Overall, this study revealed the sensitizing ability of BP and BP3 on the co-existing OMP, SMX, in water for the first time. Our findings can be applied to other BP type UV filters which are similar to BP and PB3 in molecular structure.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43182551","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