Photoinduced reversible transmittance modulation was achieved with the self-assembled block copolymer micelles. A large conformational change of the well-defined rod-coil diblock copolymers containing azobenzene and ether groups in the main chain of the rod block induced a remarkable macroscopic change which can be observed with the naked eye.
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http://dx.doi.org/10.1039/c2cc17265h | DOI Listing |
Chem Asian J
January 2025
Keio University Faculty of Science and Technology Graduate School of Science and Technology: Keio Gijuku Daigaku Rikogakubu Daigakuin Rikogaku Kenkyuka, Department of Applied Chemistry, 3-14-1 Hiyoshi, Kohoku-ku, 2238522, Yokohama, JAPAN.
For the development of new functional materials for various applications, such as drug or gene delivery and environmental remediation, the relationship between function and morphology has been considered an important aspect for controlling affinity to the targets. However, there are only a few reports on this relationship because the molecular strategy for the precise control of vesicle shape has been restricted. Herein, we report the photocontrol of vesicle shape using azobenzene-containing amphiphilic switches.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry, College of Natural Sciences, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea.
Photoinduced excited-state processes have been platforms for understanding the molecular mechanisms of many chemical and biological reactions. To elucidate associated chemical kinetics, time-resolved spectroscopic experiments have been performed tracking how the populations of reactants and products change during the reactions while reaction conditions such as the concentration of a reactant, temperature, and solvent properties change. Here, we simulate the lifetimes of a reactant and a product, and construct their lifetime-associated spectra with the various combinations of rate constants based on the analytical solutions of differential rate equations.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
Department of Chemistry, Johns Hopkins University, 3400 N. Charles Street, Baltimore, Maryland 21218, United States.
Diaryl thieno-[3,4-]thiophenes (TT) are photoswitchable compounds that operate through reversible photoinduced cyclization/cycloreversion and have been designed specifically for integration within π-conjugated polymers to switchably manipulate polymer electronic properties. Here we report on how cross conjugating the central TT moiety impacts photocyclization dynamics as interrogated using transient absorption spectroscopy (TAS) for a series of switches built with electron-rich substituents that have various electronic interaction strengths with the TT core. For cross-conjugated structures exhibiting a propensity to switch in steady-state photoconversion experiments, ultrafast TAS reveals signatures of rapid dynamics (occurring within <1-10 ps) similar to those observed for unsubstituted switches and that are consistent with photocyclization.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Pharmacology Unit, Department of Pathology and Experimental Therapeutics, Faculty of Medicine and Health Sciences, Institute of Neurosciences, University of Barcelona, L'Hospitalet de Llobregat 08907, Spain.
Incorporating photoisomerizable moieties within drugs offers the possibility of rapid and reversible light-dependent switching between active and inactive configurations. Here, we developed a photoswitchable adenosine A receptor (AR) agonist that confers optical control on this G protein-coupled receptor through noninvasive topical skin irradiation in an animal model of psoriasis. This was achieved by covalently bonding an adenosine-5'-methyluronamide moiety to a diazocine photochrome, whose singular photoswitching properties facilitated repeated interconversion between a thermally stable, biologically inactive agonist form and a photoinduced, pharmacologically active configuration.
View Article and Find Full Text PDFChem Sci
January 2025
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal Academic Building - 2, Bhopal By-pass Road, Bhauri Bhopal-462066 India
Herein, we unveiled a regio- and diastereoselective synthesis of cyclobutylated phenothiazines, a unique class of structural congeners of phenothiazines visible-light-irradiated intermolecular [2 + 2]-cycloaddition reaction, from readily available naphthoquinones, 2-aminothiophenols, and styrenes, either in a two-step or three-component coupling process. By varying substitutions in all three coupling partners, a library of cyclobutylated phenothiazines, including late-stage derivatization with five commercial drugs, has been realized with up to 97% isolated yield. In contrast to the reported pathways, the developed [2 + 2]-photocycloaddition seems to proceed a 'photoinduced-electron-transfer' (PET) mechanism, which is well corroborated with the experimental observations, Rehm-Weller equation, and computation studies.
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