ChemPhotoChemPub Date : 2024-09-20DOI: 10.1002/cptc.202400225
Takahiro Watanabe, Priyanka Swaminathan, Linnea Björk, Ayaka Nakanishi, Hisako Sato, Tamotsu Zako, K. P. R. Nilsson, Mikael Lindgren
{"title":"Spectroscopic Response of Chiral Proteophenes Binding to Two Chiral Insulin Amyloids","authors":"Takahiro Watanabe, Priyanka Swaminathan, Linnea Björk, Ayaka Nakanishi, Hisako Sato, Tamotsu Zako, K. P. R. Nilsson, Mikael Lindgren","doi":"10.1002/cptc.202400225","DOIUrl":"10.1002/cptc.202400225","url":null,"abstract":"<p>We recently reported on 8 different pentameric oligothiophenes, denoted proteophenes, with different amino acid substitution patterns along the conjugated thiophene backbone. The proteophenes were forming chiral both molecular (solvent dissolved) and self-assembled nano-architectonic structures, the latter having approximately 5–6 times greater ICD responses. Herein, two proteophenes, HS-84-E−E and HS-84-K−K, were further investigated in terms of binding to two chiral variants of insulin amyloid fibrils. Binding curves based on fluorescence revealed strong primary binding sites for both proteophenes and more unspecific secondary binding for especially the latter. Interestingly, their induced circular dichroism (ICD) responses were similar to or stronger than for their solvent form and showed a complicated alteration upon binding suggesting that the microstructure at the binding site governs the helical structure of the ligand. Hyperspectral fluorescence microscopy and FLIM revealed more details on the molecular binding in terms of proteophene emission decay-times. Vibrational circular dichroism (VCD) analysis showed that VCD signal of amyloid fibrils was enhanced upon binding of proteophenes, suggesting changes in the amyloid microstructures.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"9 1","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cptc.202400225","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250296","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}
ChemPhotoChemPub Date : 2024-09-19DOI: 10.1002/cptc.202400206
Yuji Shibasaki, Junichi Sato
{"title":"Novel Photobase Generators Derived from Proazaphosphatrane–Aryl Borate for High-Pressure Mercury Lamp Lithography","authors":"Yuji Shibasaki, Junichi Sato","doi":"10.1002/cptc.202400206","DOIUrl":"10.1002/cptc.202400206","url":null,"abstract":"<p>Herein, novel borate-type photobase generators (PBGs) that generate a proazaphosphatrane known as Verkade's base (2,8,9-triisobuthyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane (TTP)) were developed for photopatterning using a high-pressure mercury lamp. Eight PBGs were synthesized, each featuring distinct borate substituents: phenyl, <i>p</i>-fluorophenyl, <i>p</i>-tolyl, <i>p</i>-methoxyphenyl, <i>m</i>-fluoro-<i>p</i>-methylphenyl, 4-biphenyl, 2-naphthyl, and 6-methoxy-2-naphthyl. The relation between these substituents and their light absorption characteristics was analyzed via ultraviolet–visible spectroscopy and time-dependent density functional theory calculations. The PBG with the 6-methoxy-2-naphthylborate group (TTP–tetrakis[2-(6-methoxynaphthyl)]borate (TTP–TMNB)) demonstrated substantial light absorption near 365 nm (the i-line of the high-pressure mercury lamp), generating approximately 60 % of the corresponding TTP in deuterated tetrahydrofuran (THF) upon exposure to 650 mJ/cm<sup>2</sup>, as confirmed via <sup>1</sup>H nuclear magnetic resonance spectroscopy. To evaluate its photolithographic potential, TTP–TMNB was mixed with epoxy resin (jER1001) and a poly(methacrylic acid)-<i>co</i>-poly(methyl methacrylate) copolymer (PMA<sub>1.6</sub>-<i>co</i>-PMMA<sub>100</sub>) in THF. The resulting mixture was spin-coated onto a silicon wafer and irradiated with the i-line through a photomask to create a negative-tone image. The sensitivity and contrast of this photopolymer system were measured to be 45 mJ/cm<sup>2</sup> and 1.0, respectively; moreover, a clear 10-μm negative-tone resolution was achieved.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cptc.202400206","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250297","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}
ChemPhotoChemPub Date : 2024-09-19DOI: 10.1002/cptc.202400210
Lei Wu, Zhenlin Chen, Yuchao Zhang
{"title":"Modulating N−H Bond Cleavage in Catalytic Ammonia Oxidation Reaction","authors":"Lei Wu, Zhenlin Chen, Yuchao Zhang","doi":"10.1002/cptc.202400210","DOIUrl":"10.1002/cptc.202400210","url":null,"abstract":"<p>The ammonia oxidation reaction (AOR) exhibits significant potential for environmental remediation and energy utilization. Nevertheless, the complex reaction mechanism of the AOR poses numerous challenges to its application. To overcome these challenges and realize an efficient AOR process, a thorough understanding of every elementary reaction step, especially the cleavage of N−H bonds, is crucial. This review delves into the influence of N−H bond cleavage on the rate and selectivity of AOR, and summarizes the latest advancements in promoting this crucial step. Furthermore, we discuss the challenges faced by N−H bond cleavage and provide insights into the design of efficient catalytic AOR systems.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250298","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}
ChemPhotoChemPub Date : 2024-09-19DOI: 10.1002/cptc.202400188
Nisha Odedara, Niteen Borane, Rajamouli Boddula
{"title":"Design and Synthesis of Aggregation-Caused Quenching Hydroxy-Phenanthroimidazole Derivatives for Probing of Fe3+ Ions and as Potential Blue Light Emitters","authors":"Nisha Odedara, Niteen Borane, Rajamouli Boddula","doi":"10.1002/cptc.202400188","DOIUrl":"10.1002/cptc.202400188","url":null,"abstract":"<p>Fluorescence aggregated molecules tend to employ versatile opportunities in metal ion probe sensors and fluorescent lighting. To achieve this dual challenging task, currently synthesized three phenanthroimidazole-naphthalene-based compounds Pq-tBu-OH, Pq-mF-OH, and Pq-pF-OH are derived based on substitution at N<sub>1</sub> position for better photophysical and electrochemical properties. Compared experimental and theoretical calculations define the highest bandgap to be 2.75 eV of Pq-pF-OH, and the same molecule expressed a higher (348 °C) thermal decomposition. The calculated singlet and triplet energies found in the range of 3.24–3.67 and 2.70–2.72 eV indicate well energy transfer from S<sub>1</sub>→S<sub>0</sub> (quantum yield of 23.36 %, lifetime is 4.05 ns). Among the numerous morphologies, the solid form exhibited improved intensive deep blue emission (x=0.159, y=0.051), and its InGaN LED results demonstrated a strong deep blue emission at 418 nm. Moreover, the fluorophores were experimentally visualizing the aggregation-caused quenching (ACQ) which enables the probing of Fe<sup>3+</sup> ion. However, for the first time, the ACQ-assisted concept is applied through synthesized molecules for Fe<sup>3+</sup> ion probing via fluorescence spectra, Job's plot calculation, and <sup>1</sup>H NMR results. In addition, the probe works excellently at a detection limit of 10 μM and it could also act as a potential competitor for lighting applications.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142268675","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}
ChemPhotoChemPub Date : 2024-09-18DOI: 10.1002/cptc.202400203
Antonietta Mancuso, Rosaria Anna Picca, Margherita Izzi, Cinzia Di Franco, Olga Sacco, Vincenzo Vaiano, Vincenzo Venditto
{"title":"An Innovative Biphasic Reaction System for Highly Selective Benzene Hydroxylation based on Photocatalytic Polymer Composites","authors":"Antonietta Mancuso, Rosaria Anna Picca, Margherita Izzi, Cinzia Di Franco, Olga Sacco, Vincenzo Vaiano, Vincenzo Venditto","doi":"10.1002/cptc.202400203","DOIUrl":"10.1002/cptc.202400203","url":null,"abstract":"<p>The hydroxylation of benzene to phenol in presence of hydrogen peroxide was performed using a new biphasic system consisting of a solid phase, a photocatalytically active monolithic polymer composite, immersed in an aqueous phase in which H<sub>2</sub>O<sub>2</sub> is dissolved. In detail, ZnO photocatalytic particles were embedded into the hydrophobic syndiotactic polystyrene (sPS) polymer. Zinc oxide nanostructures (ZnO NSs) were synthesized by an electrochemical procedure. The surface morphology and structure of ZnO nanoparticles and ZnO-sPS monolithic aerogel composite (ZnO/sPS) were investigated by scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy analysis. Photocatalytic results evidenced that, under UV irradiation, both ZnO NSs and biphasic system water-photocatalytic composites had a high benzene oxidative property but with very low phenol yield (<2 %) at pH=7. To enhance the phenol selective formation, the pH of the aqueous solution surrounding the photocatalytic polymer composite was modified. A phenol yield of about 94 % and benzene conversion higher than 99 % was obtained in alkaline conditions (pH=11).</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142268629","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}
{"title":"Theoretical Insight into Fluorination on Low-Cost A-π-D-π-A Type Donor Materials for All-Small-Molecule Organic Photovoltaic Cells","authors":"Jia-Qian Nong, Jin-Hong Han, Jian Pan, Zhi-Wen Zhao, Yan-Ling Wang, Qing-Qing Pan, Su-Qin Liu, Hong-Hong Fan","doi":"10.1002/cptc.202400264","DOIUrl":"10.1002/cptc.202400264","url":null,"abstract":"<p>Low-cost organic photovoltaic (OPV) devices have shown enormous potential in large-scale industrial applications. And it has attracted widespread attention in the past few decades. However, the photophysical characteristics of these budget-friendly materials haven't been explored much. Here, low-cost small materials, including small molecule 1 (<b>asm1</b>) with ortho-fluorinated side chain and small molecule 2 (<b>asm2</b>) with meta-fluorinated side chain were selected to probe the fluorination effect on the absorption spectra, electrochemical energy levels, electrostatic potential (ESP), etc. The results show that the molecules <b>asm1</b> and <b>asm2</b> have good planarity of the backbone. And the meta-fluorinated side chain of <b>asm2</b> contributes more to the highest occupied molecular orbital and less to the lowest unoccupied molecular orbital than <b>asm1</b>. Moreover, differences in ESP are found between donor and acceptor materials. Furthermore, strong and broad light absorption in the visible region of these low-cost molecules is observed, resulting in a better short-circuit current density for the devices constructed by the donors <b>asm1</b>, <b>asm2</b>, and acceptor <b>Y6</b>. In addition, more charge transfer mechanisms are characterized for the <b>asm1/Y6</b> system. The introduction of ortho-fluorination in the conjugated side chain of the molecule is a favorable approach, which will provide theoretical guidance for further molecular design experiments.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250299","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}
ChemPhotoChemPub Date : 2024-09-17DOI: 10.1002/cptc.202400182
Shaina Dhamija, Arijit K. De
{"title":"Dielectric-Controlled Ultrafast Twisted Intramolecular Charge-Transfer VS trans to cis Isomerization Pathways in a Push-Pull Stilbene: Global Analysis Perspectives","authors":"Shaina Dhamija, Arijit K. De","doi":"10.1002/cptc.202400182","DOIUrl":"10.1002/cptc.202400182","url":null,"abstract":"<p>We explore excited-state dynamics of 4,4’-dimethylaminonitrostilbene (DNS), a push-pull stilbene, undergoing twisted intramolecular charge transfer and/or <i>trans</i> to <i>cis</i> isomerization, which is dependent on solvent polarity. We show how global analysis of femtosecond pump/broadband-probe data aids in elucidating the involvement of interconverting conformers and/or isomers, and the timescales associated with such interconversion, often unexplored in single-wavelength kinetic analysis.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142268679","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}
ChemPhotoChemPub Date : 2024-09-13DOI: 10.1002/cptc.202400009
Wenjun Lu, Yingyi Zhao, Prof. Baiwang Sun
{"title":"A Novel Approach to the Structural Design of Dual-State Emission Luminogens by Combining Tetraphenylethylene with Anthracene via Dihydroisoxazole","authors":"Wenjun Lu, Yingyi Zhao, Prof. Baiwang Sun","doi":"10.1002/cptc.202400009","DOIUrl":"10.1002/cptc.202400009","url":null,"abstract":"<p>Dual-state emission luminescent materials (DSEgens), which exhibit bright emissions in boththe solid state and solution, have been attracting research interest in the design of multifunctional materials.The delicate manipulation of molecular structures remains challenging in the synthesis of DSEgens. In this article, two novel molecules with dual-state emission were synthesized by combining tetraphenylethylene with anthracene via dihydroisoxazole. Tetraphenylethylene acts as a solid-state emitter, while the anthracene core functions as an emitter in the solution state to achieve DSE fluorescence properties. The THF/DCM mixture resulted in successfully obtaining the crystal structures of TPE−An−H and TPE−An−Cl. The quantum yields (QYs) of TPE−An−H were 31 % and 42 % in EA and the solid state, respectively, while TPE−An−Cl exhibited QYs of 32 % and 34 %. The novel synthesis method in this paper combines AIE with ACQ via dihydroisoxazole to achieve dual-state emission, offering a new and concise approach.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 11","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250300","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}
ChemPhotoChemPub Date : 2024-09-12DOI: 10.1002/cptc.202400235
Tim Silies, Nikos L. Doltsinis, Constantin G. Daniliuc, Fabio Rizzo
{"title":"Fluorene vs. Spirobifluorene: Effect of the π-System on TADF Properties","authors":"Tim Silies, Nikos L. Doltsinis, Constantin G. Daniliuc, Fabio Rizzo","doi":"10.1002/cptc.202400235","DOIUrl":"10.1002/cptc.202400235","url":null,"abstract":"<p>There are many options to design a molecular structure that could result in thermally activated delayed fluorescence (TADF). One promising strategy is to use the donor-π-acceptor motive where an electron-donating unit is linked to an electron-acceptor via an aryl moiety like phenyl. While this approach is widely used and well understood, the performance of the chromophores can be limited by different energy loss pathways, e. g. internal conversion, or by π-stacking. To circumvent these problems rigid structures with sterically demanding substituents are applied. In this work, we designed two TADF emitters based on phenothiazine and nitrile linked via spiro-9,9’-bi[fluorene] or 9,9-dimethylfluorene and compared the effect of the linker on the physical properties of the dyes. This work emphasizes the importance of careful design of conjugated spacer for efficient TADF emitters.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cptc.202400235","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217781","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}
ChemPhotoChemPub Date : 2024-09-10DOI: 10.1002/cptc.202480901
Grazia M. L. Consoli, Giuseppe Forte, Ludovica Maugeri, Salvatore Petralia
{"title":"Front Cover: Photo-Responsive TiO2-Gold Nanoparticle-Polymer Nanohybrid Exhibits Photothermal, Thermo-Release, and Photocatalytic Effects (ChemPhotoChem 9/2024)","authors":"Grazia M. L. Consoli, Giuseppe Forte, Ludovica Maugeri, Salvatore Petralia","doi":"10.1002/cptc.202480901","DOIUrl":"https://doi.org/10.1002/cptc.202480901","url":null,"abstract":"<p><b>The Front Cover</b> presents a nanohybrid system consisting of the photocatalyst TiO<sub>2</sub>, photothermal gold nanoparticles, and thermo-responsive poly-<i>N</i>-isopropylacrylamide (TiO<sub>2</sub>-Au-PNM). This system combines the photothermal-controlled cargo release, triggered by visible-light irradiation, mediated by lower critical solution temperature (LCST) and by photothermal conversion effect, with the excellent photocatalytic effect prompted by UVB-light excitation. More information can be found in the Research Article by Salvatore Petralia and co-workers (DOI 10.1002/cptc.202400088).<figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 9","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cptc.202480901","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142170084","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}