Materials Science › Materials Chemistry

Photochromic and Fluorescence Chemistry

Works Count: 33027

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Description

This cluster of papers focuses on the development, properties, and applications of photochromic materials and molecular switches, including diarylethenes, azobenzenes, and spiropyrans. The research covers areas such as fluorescence modulation, optical control, nanoparticles, and their diverse biological applications.

Keywords

Photochromic; Molecular Switches; Diarylethenes; Azobenzene; Spiropyran; Fluorescence Modulation; Optical Control; Nanoparticles; Biological Applications; Light-Activated

Photochromism : molecules and systems

2003-01-01

Heinz Dürr , Henri Bouas‐Laurent

Visible‐Light‐Activated Molecular Switches

2015-06-19

David Bléger , Stefan Hecht

The ability to influence key properties of molecular systems by using light holds much promise for the fields of materials science and life sciences. The cornerstone of such systems is … The ability to influence key properties of molecular systems by using light holds much promise for the fields of materials science and life sciences. The cornerstone of such systems is molecules that are able to reversibly photoisomerize between two states, commonly referred to as photoswitches. One serious restriction to the development of functional photodynamic systems is the necessity to trigger switching in at least one direction by UV light, which is often damaging and penetrates only partially through most media. This review provides a summary of the different conceptual strategies for addressing molecular switches in the visible and near-infrared regions of the optical spectrum. Such visible-light-activated molecular switches tremendously extend the scope of photoswitchable systems for future applications and technologies.

Photochemistry of azobenzene-containing polymers

1989-12-01

G. Sudesh Kumar , D. C. Neckers

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPhotochemistry of azobenzene-containing polymersG. Sudesh Kumar and D. C. NeckersCite this: Chem. Rev. 1989, 89, 8, 1915–1925Publication Date (Print):December 1, 1989Publication History Published online1 May 2002Published inissue … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPhotochemistry of azobenzene-containing polymersG. Sudesh Kumar and D. C. NeckersCite this: Chem. Rev. 1989, 89, 8, 1915–1925Publication Date (Print):December 1, 1989Publication History Published online1 May 2002Published inissue 1 December 1989https://pubs.acs.org/doi/10.1021/cr00098a012https://doi.org/10.1021/cr00098a012research-articleACS PublicationsRequest reuse permissionsArticle Views9277Altmetric-Citations1233LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Photochromism: Memories and SwitchesIntroduction

2000-05-01

Masahiro Irie

ADVERTISEMENT RETURN TO ISSUEPREVEditorialNEXTPhotochromism: Memories and SwitchesIntroductionM. IrieCite this: Chem. Rev. 2000, 100, 5, 1683–1684Publication Date (Web):May 10, 2000Publication History Published online10 May 2000Published inissue 1 May 2000https://pubs.acs.org/doi/10.1021/cr980068lhttps://doi.org/10.1021/cr980068leditorialACS PublicationsCopyright © … ADVERTISEMENT RETURN TO ISSUEPREVEditorialNEXTPhotochromism: Memories and SwitchesIntroductionM. IrieCite this: Chem. Rev. 2000, 100, 5, 1683–1684Publication Date (Web):May 10, 2000Publication History Published online10 May 2000Published inissue 1 May 2000https://pubs.acs.org/doi/10.1021/cr980068lhttps://doi.org/10.1021/cr980068leditorialACS PublicationsCopyright © 2000 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views21486Altmetric-Citations764LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (14 KB) Get e-AlertscloseSUBJECTS:Analytical apparatus,Circuits,Optical properties,Organic compounds,Photochromism Get e-Alerts

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A digital fluorescent molecular photoswitch

2002-12-01

Masahiro Irie , Tuyoshi Fukaminato , Takatoshi Sasaki +2 more

Photoswitches: From Molecules to Materials

2010-04-28

Maria‐Melanie Russew , Stefan Hecht

Small organic molecules, capable of undergoing efficient and reversible photochemical reactions to switch them between (at least) two (meta)stable isomers associated with markedly different properties, continue to impact the materials … Small organic molecules, capable of undergoing efficient and reversible photochemical reactions to switch them between (at least) two (meta)stable isomers associated with markedly different properties, continue to impact the materials world. Such photoswitches are being implemented in a variety of materials for applications ranging from optical devices to "smart" polymers. All approaches exploit the photoswitching molecular entities as gates, which translate an incoming light stimulus to trigger macroscopic property changes of the materials. In this progress report, the most promising recent examples in this field are highlighted and put in perspective. Moving from supramolecular systems in solution to surfaces and finally to bulk materials, important design concepts are discussed, emphasizing both the challenges as well as the great promise of such truly advanced materials.

Reversible Surface Morphology Changes of a Photochromic Diarylethene Single Crystal by Photoirradiation

2001-03-02

Masahiro Irie , Seiya Kobatake , M. Horichi

The surface morphology of a diarylethene single crystal [1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene] determined by atomic force microscopy changed reversibly upon photoirradiation. The crystal underwent a thermally irreversible but photochemically reversible color change (colorless … The surface morphology of a diarylethene single crystal [1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene] determined by atomic force microscopy changed reversibly upon photoirradiation. The crystal underwent a thermally irreversible but photochemically reversible color change (colorless to blue) upon alternate irradiation with ultraviolet (wavelength lambda = 366 nm) and visible (lambda > 500 nm) light that drove reversible photocyclization reactions. Upon irradiation with 366-nm light, new steps appeared on the (100) single-crystalline surface that disappeared upon irradiation with visible light (lambda > 500 nm). The step height, about 1 nm, corresponds to one molecular layer. Irradiation with 366-nm light formed valleys on the (010) surface that also disappeared by bleaching upon irradiation with visible light (lambda > 500 nm). The surface morphological changes can be explained by the molecular structural changes of diarylethenes regularly packed in the single crystal. These crystals could potentially be used as photodriven nanometer-scale actuators.

Spiropyrans and Spirooxazines for Memories and Switches

2000-03-10

Garry Berkovic , Valeri Krongauz , Victor U. Weiss

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSpiropyrans and Spirooxazines for Memories and SwitchesGarry Berkovic, Valeri Krongauz, and Victor WeissView Author Information Soreq Nuclear Research Center, Yavne 81800, Israel Department of Organic Chemistry, The … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSpiropyrans and Spirooxazines for Memories and SwitchesGarry Berkovic, Valeri Krongauz, and Victor WeissView Author Information Soreq Nuclear Research Center, Yavne 81800, Israel Department of Organic Chemistry, The Weizmann Institute of Science, Rehovot 76100, Israel ELOP Electrooptic Ltd. Industries, Rehovot 76111, Israel Cite this: Chem. Rev. 2000, 100, 5, 1741–1754Publication Date (Web):March 10, 2000Publication History Received27 May 1999Revised30 December 1999Published online10 March 2000Published inissue 1 May 2000https://pubs.acs.org/doi/10.1021/cr9800715https://doi.org/10.1021/cr9800715research-articleACS PublicationsCopyright © 2000 American Chemical SocietyRequest reuse permissionsArticle Views13435Altmetric-Citations1397LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Absorption,Lasers,Molecules,Nonlinear optics,Polymers Get e-Alerts

Azobenzene photoswitches for biomolecules

2011-01-01

Andrew A. Beharry , G. Andrew Woolley

The photoisomerization of azobenzene has been known for almost 75 years but only recently has this process been widely applied to biological systems. The central challenge of how to productively … The photoisomerization of azobenzene has been known for almost 75 years but only recently has this process been widely applied to biological systems. The central challenge of how to productively couple the isomerization process to a large functional change in a biomolecule has been met in a number of instances and it appears that effective photocontrol of a large variety of biomolecules may be possible. This critical review summarizes key properties of azobenzene that enable its use as a photoswitch in biological systems and describes strategies for using azobenzene photoswitches to drive functional changes in peptides, proteins, nucleic acids, lipids, and carbohydrates (192 references).

Biologically Active Molecules with a “Light Switch”

2006-07-07

Günter Mayer , Alexander Heckel

Biologically active compounds which are light-responsive offer experimental possibilities which are otherwise very difficult to achieve. Since light can be manipulated very precisely, for example, with lasers and microscopes rapid … Biologically active compounds which are light-responsive offer experimental possibilities which are otherwise very difficult to achieve. Since light can be manipulated very precisely, for example, with lasers and microscopes rapid jumps in concentration of the active form of molecules are possible with exact control of the area, time, and dosage. The development of such strategies started in the 1970s. This review summarizes new developments of the last five years and deals with "small molecules", proteins, and nucleic acids which can either be irreversibly activated with light (these compounds are referred to as "caged compounds") or reversibly switched between an active and an inactive state.

Caged compounds: photorelease technology for control of cellular chemistry and physiology

2007-07-30

Graham C. R. Ellis‐Davies

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Allosteric control of an ionotropic glutamate receptor with an optical switch

2005-12-11

Matthew Volgraf , Pau Gorostiza , Rika Numano +3 more

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Photoremovable protecting groups: reaction mechanisms and applications

2002-06-06

Anna Paola Pelliccioli , Jakob Wirz

Regulated Fast Nucleocytoplasmic Shuttling Observed by Reversible Protein Highlighting

2004-11-18

Ryoko Ando , Hideaki Mizuno , Atsushi Miyawaki

The observation of the regulation of fast protein dynamics in a cellular context requires the development of reliable technologies. Here, a signal regulation cascade reliant on the stimulus-dependent acceleration of … The observation of the regulation of fast protein dynamics in a cellular context requires the development of reliable technologies. Here, a signal regulation cascade reliant on the stimulus-dependent acceleration of the bidirectional flow of mitogen-activated protein kinase (extracellular signal-regulated kinase) across the nuclear envelope was visualized by reversible protein highlighting. Light-induced conversion between the bright and dark states of a monomeric fluorescent protein engineered from a novel coral protein was employed. Because of its photochromic properties, the protein could be highlighted, erased, and highlighted again in a nondestructive manner, allowing direct observation of regulated fast nucleocytoplasmic shuttling of key signaling molecules.

Rapid and reversible shape changes of molecular crystals on photoirradiation

2007-04-01

Seiya Kobatake , Shizuka Takami , Hiroaki Muto +2 more

Thermally irreversible photochromic systems. Reversible photocyclization of diarylethene derivatives

1988-02-01

Masahiro Irie , M. MOHRI

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThermally irreversible photochromic systems. Reversible photocyclization of diarylethene derivativesMasahiro Irie and Masaaki MohriCite this: J. Org. Chem. 1988, 53, 4, 803–808Publication Date (Print):February 1, 1988Publication History Published … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThermally irreversible photochromic systems. Reversible photocyclization of diarylethene derivativesMasahiro Irie and Masaaki MohriCite this: J. Org. Chem. 1988, 53, 4, 803–808Publication Date (Print):February 1, 1988Publication History Published online1 May 2002Published inissue 1 February 1988https://pubs.acs.org/doi/10.1021/jo00239a022https://doi.org/10.1021/jo00239a022research-articleACS PublicationsRequest reuse permissionsArticle Views5287Altmetric-Citations650LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Photochromic organic–inorganic hybrid materials

2011-01-01

Rosario Pardo , Marcos Zayat , David Lévy

Photochromic organic-inorganic hybrid materials have attracted considerable attention owing to their potential application in photoactive devices, such as optical memories, windows, photochromic decorations, optical switches, filters or non-linear optics materials. … Photochromic organic-inorganic hybrid materials have attracted considerable attention owing to their potential application in photoactive devices, such as optical memories, windows, photochromic decorations, optical switches, filters or non-linear optics materials. The growing interest in this field has largely expanded the use of photochromic materials for the purpose of improving existing materials and exploring new photochromic hybrid systems. This tutorial review summarizes the design and preparation of photochromic hybrid materials, and particularly those based on the incorporation of organic molecules in organic-inorganic matrices by the sol-gel method. This is the most commonly used method for the preparation of these materials as it allows vitreous hybrid materials to be obtained at low temperatures, and controls the interaction between the organic molecule and its embedding matrix, and hence allows tailoring of the performance of the resulting devices.

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Photo-, Thermo-, Solvato-, and Electrochromic Spiroheterocyclic Compounds

2004-03-04

Владимир И. Минкин

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPhoto-, Thermo-, Solvato-, and Electrochromic Spiroheterocyclic CompoundsVladimir I. MinkinView Author Information Institute of Physical and Organic Chemistry, Rostov State University, 194/2 Stachka Avenue, 344090 Rostov on Don, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPhoto-, Thermo-, Solvato-, and Electrochromic Spiroheterocyclic CompoundsVladimir I. MinkinView Author Information Institute of Physical and Organic Chemistry, Rostov State University, 194/2 Stachka Avenue, 344090 Rostov on Don, Russian Federation Cite this: Chem. Rev. 2004, 104, 5, 2751–2776Publication Date (Web):March 4, 2004Publication History Received28 July 2003Published online4 March 2004Published inissue 1 May 2004https://pubs.acs.org/doi/10.1021/cr020088uhttps://doi.org/10.1021/cr020088uresearch-articleACS PublicationsCopyright © 2004 American Chemical SocietyRequest reuse permissionsArticle Views10649Altmetric-Citations834LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Aromatic compounds,Irradiation,Molecular structure,Ring opening reactions,Solvents Get e-Alerts

Fulgides for Memories and Switches

2000-03-18

Yasushi Yokoyama

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTFulgides for Memories and SwitchesYasushi YokoyamaView Author Information Department of Materials Chemistry, Faculty of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan Cite this: Chem. … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTFulgides for Memories and SwitchesYasushi YokoyamaView Author Information Department of Materials Chemistry, Faculty of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan Cite this: Chem. Rev. 2000, 100, 5, 1717–1740Publication Date (Web):March 18, 2000Publication History Received16 June 1999Published online18 March 2000Published inissue 1 May 2000https://pubs.acs.org/doi/10.1021/cr980070chttps://doi.org/10.1021/cr980070cresearch-articleACS PublicationsCopyright © 2000 American Chemical SocietyRequest reuse permissionsArticle Views6170Altmetric-Citations743LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Absorption,Aromatic compounds,Irradiation,Photochromism,Vinyl Get e-Alerts

Rapid Quantification of Adult and Developing Mouse Spatial Vision Using a Virtual Optomotor System

2004-11-22

Glen T. Prusky , N. M. Alam , Steven Beekman +1 more

purpose. To develop a simple, rapid method of quantifying the spatial vision of mice. methods. A rotating cylinder covered with a vertical sine wave grating was calculated and drawn in … purpose. To develop a simple, rapid method of quantifying the spatial vision of mice. methods. A rotating cylinder covered with a vertical sine wave grating was calculated and drawn in virtual three-dimensional (3-D) space on four computer monitors facing to form a square. C57BL/6 mice standing unrestrained on a platform in the center of the square tracked the grating with reflexive head and neck movements. The spatial frequency of the grating was clamped at the viewing position by repeatedly recentering the cylinder on the head. Acuity was quantified by increasing the spatial frequency of the grating until an optomotor response could not be elicited. Contrast sensitivity was measured at spatial frequencies between 0.03 and 0.35 cyc/deg. results. Grating acuity was measurable on the day of eye opening (postnatal day [P]15: mean acuity, 0.031 cyc/deg) and reached a maximum (∼0.4 cyc/deg) by P24. A peak in the contrast sensitivity function emerged on P16 (4.7, or 21% contrast at 0.064 cyc/deg). The peak remained at 0.064 cyc/deg and climbed to a maximum sensitivity of 24.5, or 4% contrast, by P29. Acuity was obtained in each mouse in <10 minutes, and a detailed contrast sensitivity curve was generated in approximately 30 minutes. conclusions. The virtual optomotor system provides a simple and precise method for rapidly quantifying mouse vision. Behavioral measures of vision in mice are essential for interpreting the results of experiments designed to reveal the cellular and molecular mechanisms of vision and visual development and for evaluating potential treatments for visual diseases.

Multicolour photochromism of TiO2 films loaded with silver nanoparticles

2002-12-15

Yoshihisa Ohko , Tetsu Tatsuma , Tsuyoshi Fujii +4 more

Ultrafast Dynamics of Photochromic Systems

2000-03-07

Naoto Tamai , Hiroshi Miyasaka

ADVERTISEMENT RETURN TO ISSUEPREVArticleUltrafast Dynamics of Photochromic SystemsNaoto Tamai and Hiroshi MiyasakaView Author Information Department of Chemistry, Faculty of Science, Kwansei Gakuin University, Uegahara, Nishinomiya, Hyogo 660-8581, Japan, Department of … ADVERTISEMENT RETURN TO ISSUEPREVArticleUltrafast Dynamics of Photochromic SystemsNaoto Tamai and Hiroshi MiyasakaView Author Information Department of Chemistry, Faculty of Science, Kwansei Gakuin University, Uegahara, Nishinomiya, Hyogo 660-8581, Japan, Department of Polymer Science and Engineering, Kyoto Institute of Technology, and CREST, Japan Science and Technology Corporation, Matsugasaki, Sakyo, Kyoto 606-8585, Japan Cite this: Chem. Rev. 2000, 100, 5, 1875–1890Publication Date (Web):March 7, 2000Publication History Received6 July 1999Published online7 March 2000Published inissue 1 May 2000https://pubs.acs.org/doi/10.1021/cr9800816https://doi.org/10.1021/cr9800816research-articleACS PublicationsCopyright © 2000 American Chemical SocietyRequest reuse permissionsArticle Views9442Altmetric-Citations757LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Absorption,Fluorescence,Isomerization,Lasers,Light absorption Get e-Alerts

Photochromic Materials: More Than Meets The Eye

2012-08-22

Junji Zhang , Qi Zou , He Tian

Abstract Photochromic materials are a family of compounds which can undergo reversible photo‐switches between two different states or isomers with remarkably different properties. Inspired by their smart photo‐switchable characteristics, a … Abstract Photochromic materials are a family of compounds which can undergo reversible photo‐switches between two different states or isomers with remarkably different properties. Inspired by their smart photo‐switchable characteristics, a variety of light‐driven functional materials have been exploited, such as ultrahigh‐density optical data storage, molecular switches, logic gates, molecular wires, optic/electronic devices, sensors, bio‐imaging and so on. This review commences with a brief description of exciting progress in this field, from systems in solution to modified functional surfaces. Further development of these photo‐switchable systems into practical applications as well as existing challenges are also discussed and put in prospect.

Linear and Nonlinear Optical Properties of Photochromic Molecules and Materials

2000-03-10

Jacques A. Delaire , Keitaro Nakatani

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLinear and Nonlinear Optical Properties of Photochromic Molecules and MaterialsJacques A. Delaire and Keitaro NakataniView Author Information Laboratoire de Photophysique et de Photochimie Supramoléculaires et Macromoléculaires (PPSM, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLinear and Nonlinear Optical Properties of Photochromic Molecules and MaterialsJacques A. Delaire and Keitaro NakataniView Author Information Laboratoire de Photophysique et de Photochimie Supramoléculaires et Macromoléculaires (PPSM, UMR 8531 of CNRS), Ecole Normale Supérieure de Cachan, 94235 Cachan Cedex, France Cite this: Chem. Rev. 2000, 100, 5, 1817–1846Publication Date (Web):March 10, 2000Publication History Received2 September 1999Published online10 March 2000Published inissue 1 May 2000https://pubs.acs.org/doi/10.1021/cr980078mhttps://doi.org/10.1021/cr980078mresearch-articleACS PublicationsCopyright © 2000 American Chemical SocietyRequest reuse permissionsArticle Views9682Altmetric-Citations1074LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Molecules,Nonlinear optics,Optical properties,Polarization,Polymers Get e-Alerts

Light-triggered self-healing and shape-memory polymers

2013-01-01

Damien Habault , Hongji Zhang , Yue Zhao

In this review, we highlight the recent progress made in light-controlled self-healing and shape memory polymers. We analyse the materials design, underlying mechanisms and chemistries involved in the different methods … In this review, we highlight the recent progress made in light-controlled self-healing and shape memory polymers. We analyse the materials design, underlying mechanisms and chemistries involved in the different methods developed for these two types of emerging photoresponsive materials. We show that these two seemingly different groups of functional materials are linked by a number of common approaches enabling their optical control, particularly the approaches based on the photothermal effect and photochemical reactions of photoswitching groups incorporated in polymer structures. Possible future developments and perspectives of using light as a unique trigger for polymer self-healing and shape-memory are also discussed.

Photoisomerization in different classes of azobenzene

2011-10-18

H. M. Dhammika Bandara , Shawn C. Burdette

Azobenzene undergoes trans→cis isomerization when irradiated with light tuned to an appropriate wavelength. The reverse cis→trans isomerization can be driven by light or occurs thermally in the dark. Azobenzene's photochromatic … Azobenzene undergoes trans→cis isomerization when irradiated with light tuned to an appropriate wavelength. The reverse cis→trans isomerization can be driven by light or occurs thermally in the dark. Azobenzene's photochromatic properties make it an ideal component of numerous molecular devices and functional materials. Despite the abundance of application-driven research, azobenzene photochemistry and the isomerization mechanism remain topics of investigation. Additional substituents on the azobenzene ring system change the spectroscopic properties and isomerization mechanism. This critical review details the studies completed to date on the 3 main classes of azobenzene derivatives. Understanding the differences in photochemistry, which originate from substitution, is imperative in exploiting azobenzene in the desired applications.

Diarylethenes for Memories and Switches

2000-04-21

Masahiro Irie

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDiarylethenes for Memories and SwitchesMasahiro IrieView Author Information Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, and CREST, Japan Science and Technology Corporation (JST), … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDiarylethenes for Memories and SwitchesMasahiro IrieView Author Information Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, and CREST, Japan Science and Technology Corporation (JST), Hakozaki 6-10-1, Higashi-ku, Fukuoka 812, Japan Cite this: Chem. Rev. 2000, 100, 5, 1685–1716Publication Date (Web):April 21, 2000Publication History Received15 June 1999Published online21 April 2000Published inissue 1 May 2000https://pubs.acs.org/doi/10.1021/cr980069dhttps://doi.org/10.1021/cr980069dresearch-articleACS PublicationsCopyright © 2000 American Chemical SocietyRequest reuse permissionsArticle Views26195Altmetric-Citations3683LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Absorption,Conformation,Cyclization,Irradiation,Molecular structure Get e-Alerts

Coumarins in Polymers: From Light Harvesting to Photo-Cross-Linkable Tissue Scaffolds

2004-05-06

Scott R. Trenor , Allan R. Shultz , Brian J. Love +1 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCoumarins in Polymers: From Light Harvesting to Photo-Cross-Linkable Tissue ScaffoldsScott R. Trenor, Allan R. Shultz, Brian J. Love, and Timothy E. LongView Author Information Polymeric Materials and … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCoumarins in Polymers: From Light Harvesting to Photo-Cross-Linkable Tissue ScaffoldsScott R. Trenor, Allan R. Shultz, Brian J. Love, and Timothy E. LongView Author Information Polymeric Materials and Interfaces Laboratory, Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061-0344 Cite this: Chem. Rev. 2004, 104, 6, 3059–3078Publication Date (Web):May 6, 2004Publication History Received20 October 2003Published online6 May 2004Published inissue 1 June 2004https://pubs.acs.org/doi/10.1021/cr030037chttps://doi.org/10.1021/cr030037cresearch-articleACS PublicationsCopyright © 2004 American Chemical SocietyRequest reuse permissionsArticle Views11453Altmetric-Citations697LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Aromatic compounds,Irradiation,Oligomers,Polymers,Reaction products Get e-Alerts

Brominated 7-hydroxycoumarin-4-ylmethyls: Photolabile protecting groups with biologically useful cross-sections for two photon photolysis

1999-02-16

Toshiaki Furuta , Samuel S.‐H. Wang , Jami L. Dantzker +5 more

Photochemical release (uncaging) of bioactive messengers with three-dimensional spatial resolution in light-scattering media would be greatly facilitated if the photolysis could be powered by pairs of IR photons rather than … Photochemical release (uncaging) of bioactive messengers with three-dimensional spatial resolution in light-scattering media would be greatly facilitated if the photolysis could be powered by pairs of IR photons rather than the customary single UV photons. The quadratic dependence on light intensity would confine the photolysis to the focus point of the laser, and the longer wavelengths would be much less affected by scattering. However, previous caged messengers have had very small cross sections for two-photon excitation in the IR region. We now show that brominated 7-hydroxycoumarin-4-ylmethyl esters and carbamates efficiently release carboxylates and amines on photolysis, with one- and two-photon cross sections up to one or two orders of magnitude better than previously available. These advantages are demonstrated on neurons in brain slices from rat cortex and hippocampus excited by glutamate uncaged from N-(6-bromo-7-hydroxycoumarin-4-ylmethoxycarbonyl)-L-glutamate (Bhc-glu). Conventional UV photolysis of Bhc-glu requires less than one-fifth the intensities needed by one of the best previous caged glutamates, gamma-(alpha-carboxy-2-nitrobenzyl)-L-glutamate (CNB-glu). Two-photon photolysis with raster-scanned femtosecond IR pulses gives the first three-dimensionally resolved maps of the glutamate sensitivity of neurons in intact slices. Bhc-glu and analogs should allow more efficient and three-dimensionally localized uncaging and photocleavage, not only in cell biology and neurobiology but also in many technological applications.

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Azobenzene Photoswitching without Ultraviolet Light

2011-11-14

Andrew A. Beharry , Oleg Sadovski , G. Andrew Woolley

Most azobenzene-based photoswitches use UV light for photoisomerization. This can limit their application in biological systems, where UV light can trigger unwanted responses, including cellular apoptosis. We have found that … Most azobenzene-based photoswitches use UV light for photoisomerization. This can limit their application in biological systems, where UV light can trigger unwanted responses, including cellular apoptosis. We have found that substitution of all four ortho positions with methoxy groups in an amidoazobenzene derivative leads to a substantial (∼35 nm) red shift of the n−π* band of the trans isomer, separating it from the cis n−π* transition. This red shift makes trans-to-cis photoswitching possible using green light (530–560 nm). The cis state is thermally stable with a half-life of ∼2.4 days in the dark in aqueous solution. Reverse (cis-to-trans) photoswitching can be accomplished with blue light (460 nm), so bidirectional photoswitching between thermally stable isomers is possible without using UV light at all.

Photoresponsive Host–Guest Functional Systems

2015-02-20

Da‐Hui Qu , Qiaochun Wang , Qi‐Wei Zhang +2 more

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPhotoresponsive Host–Guest Functional SystemsDa-Hui Qu, Qiao-Chun Wang, Qi-Wei Zhang, Xiang Ma, and He Tian*View Author Information Key Laboratory for Advanced Materials & Institute of Fine Chemicals, East … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPhotoresponsive Host–Guest Functional SystemsDa-Hui Qu, Qiao-Chun Wang, Qi-Wei Zhang, Xiang Ma, and He Tian*View Author Information Key Laboratory for Advanced Materials & Institute of Fine Chemicals, East China University of Science & Technology, Meilong Road 130, Shanghai 200237, P. R. China*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 15, 7543–7588Publication Date (Web):February 20, 2015Publication History Received4 November 2014Published online20 February 2015Published inissue 12 August 2015https://pubs.acs.org/doi/10.1021/cr5006342https://doi.org/10.1021/cr5006342review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views20774Altmetric-Citations730LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Azobenzene,Irradiation,Light,Polymers,Supramolecular chemistry Get e-Alerts

Gold nanocages covered by smart polymers for controlled release with near-infrared light

2009-11-01

Mustafa Selman Yavuz , Yiyun Cheng , Jingyi Chen +7 more

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Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

2012-12-21

Petr Klán , Tomáš Šolomek , Christian G. Bochet +6 more

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPhotoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and EfficacyPetr Klán*†‡, Tomáš Šolomek†‡, Christian G. Bochet§, Aurélien Blanc∥, Richard Givens⊥, Marina Rubina⊥, Vladimir Popik#, Alexey Kostikov#, … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPhotoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and EfficacyPetr Klán*†‡, Tomáš Šolomek†‡, Christian G. Bochet§, Aurélien Blanc∥, Richard Givens⊥, Marina Rubina⊥, Vladimir Popik#, Alexey Kostikov#, and Jakob Wirz∇View Author Information† Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, 625 00 Brno, Czech Republic‡ Research Centre for Toxic Compounds in the Environment, Faculty of Science, Masaryk University, Kamenice 3, 625 00 Brno, Czech Republic§ Department of Chemistry, University of Fribourg, Chemin du Musée 9, CH-1700 Fribourg, Switzerland∥ Institut de Chimie, University of Strasbourg, 4 rue Blaise Pascal, 67000 Strasbourg, France⊥ Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, 5010 Malott Hall, Lawrence, Kansas 66045, United States# Department of Chemistry, University of Georgia, Athens, Georgia 30602, United States∇ Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland*E-mail: [email protected]. Phone: +420-54949-4856. Fax: +420-54949-2443.Cite this: Chem. Rev. 2013, 113, 1, 119–191Publication Date (Web):December 21, 2012Publication History Received29 April 2012Published online21 December 2012Published inissue 9 January 2013https://doi.org/10.1021/cr300177kCopyright © 2012 American Chemical SocietyRIGHTS & PERMISSIONSACS AuthorChoiceArticle Views77851Altmetric-Citations1248LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (17 MB) Get e-AlertscloseSUBJECTS:Alcohols,Fluorescence,Irradiation,Organic compounds,Reaction products Get e-Alerts

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Synthesis of azobenzenes: the coloured pieces of molecular materials

2011-01-01

Estı́baliz Merino

Azobenzenes are ubiquitous motifs very important in many areas of science. Azo compounds display crucial properties for important applications, mainly for the chemical industry. Because of their discovery, the main … Azobenzenes are ubiquitous motifs very important in many areas of science. Azo compounds display crucial properties for important applications, mainly for the chemical industry. Because of their discovery, the main application of aromatic azo compounds has been their use as dyes. These compounds are excellent candidates to function as molecular switches because of their efficient cis–transisomerization in the presence of appropriate radiation. The classical methods for the synthesis of azo compounds are the azo coupling reaction (coupling of diazonium salts with activated aromatic compounds), the Mills reaction (reaction between aromatic nitroso derivatives and anilines) and the Wallach reaction (transformation of azoxybenzenes into 4-hydroxy substituted azoderivatives in acid media). More recently, other preparative methods have been reported. This critical review covers the various synthetic methods reported on azo compounds with special emphasis on the more recent ones and their mechanistic aspects (170 references).

o-Fluoroazobenzenes as Readily Synthesized Photoswitches Offering Nearly Quantitative Two-Way Isomerization with Visible Light

2012-12-13

David Bléger , Jutta Schwarz , Albert M. Brouwer +1 more

Azobenzene functionalized with ortho-fluorine atoms has a lower energy of the n-orbital of the Z-isomer, resulting in a separation of the E and Z isomers' n→π* absorption bands. Introducing para-substituents … Azobenzene functionalized with ortho-fluorine atoms has a lower energy of the n-orbital of the Z-isomer, resulting in a separation of the E and Z isomers' n→π* absorption bands. Introducing para-substituents allows for further tuning of the absorption spectra of o-fluoroazobenzenes. In particular, electron-withdrawing ester groups give rise to a 50 nm separation of the n→π* transitions. Green and blue light can therefore be used to induce E→Z and Z→E isomerizations, respectively. The o-fluoroazobenzene scaffold is readily synthesized and can be inserted into larger structures via its aryl termini. These new azobenzene derivatives can be switched in both ways with high photoconversions, and their Z-isomers display a remarkably long thermal half-life.

Light-induced shape-memory polymers

2005-04-01

Andreas Lendlein , Hongyan Jiang , Oliver Jünger +1 more

Spiropyran-based dynamic materials

2013-08-27

Rafał Klajn

In the past few years, spiropyran has emerged as the molecule-of-choice for the construction of novel dynamic materials. This unique molecular switch undergoes structural isomerisation in response to a variety … In the past few years, spiropyran has emerged as the molecule-of-choice for the construction of novel dynamic materials. This unique molecular switch undergoes structural isomerisation in response to a variety of orthogonal stimuli, e.g. light, temperature, metal ions, redox potential, and mechanical stress. Incorporation of this switch onto macromolecular supports or inorganic scaffolds allows for the creation of robust dynamic materials. This review discusses the synthesis, switching conditions, and use of dynamic materials in which spiropyran has been attached to the surfaces of polymers, biomacromolecules, inorganic nanoparticles, as well as solid surfaces. The resulting materials show fascinating properties whereby the state of the switch intimately affects a multitude of useful properties of the support. The utility of the spiropyran switch will undoubtedly endow these materials with far-reaching applications in the near future.

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Organic photochromism (IUPAC Technical Report)

2001-01-01

Henri Bouas‐Laurent , Heinz Dürr

Abstract This technical report is a general introduction to organic photochromism. The definition of photochromism (PC) is given together with that of words with the ending "chromism", such as thermo-, … Abstract This technical report is a general introduction to organic photochromism. The definition of photochromism (PC) is given together with that of words with the ending "chromism", such as thermo-, electro-, piezo-, and tribochromism. Important concepts such as two-photon, gated, dual-mode PC and chirochromism are illustrated. The concept of fatigue (chemical degradation) and the determination of the main photochromic parameters (number of cycles, cyclability, half-life), and the spectrokinetic and mechanistic aspects are discussed. The main families of PC (organic compounds and biological receptors) are illustrated with chemical formulae, and the different types of reactions involved in the photochromic processes (pericyclic reactions, E / Z isomerization, group transfer, etc.) are listed. Some examples of applications to "optical power limiting" substances, photoresponsive materials, and photoswitchable biomaterials are considered.

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Red-Shifting Azobenzene Photoswitches for in Vivo Use

2015-09-28

Mingxin Dong , Amirhossein Babalhavaeji , Subhas Samanta +2 more

Recently, there has been a great deal of interest in using the photoisomerization of azobenzene compounds to control specific biological targets in vivo. These azo compounds can be used as … Recently, there has been a great deal of interest in using the photoisomerization of azobenzene compounds to control specific biological targets in vivo. These azo compounds can be used as research tools or, in principle, could act as optically controlled drugs. Such "photopharmaceuticals" offer the prospect of targeted drug action and an unprecedented degree of temporal control. A key feature of azo compounds designed to photoswitch in vivo is the wavelength of light required to cause the photoisomerization. To pass through tissue such as the human hand, wavelengths in the red, far-red, or ideally near infrared region are required. This Account describes our attempts to produce such azo compounds. Introducing electron-donating or push/pull substituents at the para positions delocalizes the azobenzene chromophore and leads to long wavelength absorption but usually also lowers the thermal barrier to interconversion of the isomers. Fast thermal relaxation means it is difficult to produce a large steady state fraction of the cis isomer. Thus, specifically activating or inhibiting a biological process with the cis isomer would require an impractically bright light source. We have found that introducing substituents at all four ortho positions leads to azo compounds with a number of unusual properties that are useful for in vivo photoswitching. When the para substituents are amide groups, these tetra-ortho substituted azo compounds show unusually slow thermal relaxation rates and enhanced separation of n-π* transitions of cis and trans isomers compared to analogues without ortho substituents. When para positions are substituted with amino groups, ortho methoxy groups greatly stabilize the azonium form of the compounds, in which the azo group is protonated. Azonium ions absorb strongly in the red region of the spectrum and can reach into the near-IR. These azonium ions can exhibit robust cis-trans isomerization in aqueous solutions at neutral pH. By varying the nature of ortho substituents, together with the number and nature of meta and para substituents, long wavelength switching, stability to photobleaching, stability to hydrolysis, and stability to reduction by thiols can all be crafted into a photoswitch. Some of these newly developed photoswitches can be used in whole blood and show promise for effective use in vivo. It is hoped they can be combined with appropriate bioactive targets to realize the potential of photopharmacology.

Recent progresses on diarylethene based photochromic switches

2004-01-01

He Tian , Songjie Yang

Organic photochromic materials have received considerable attention because of their potential for photonic applications, especially for fast and high density data storage. In 2000, Chemical Reviews published a special issue … Organic photochromic materials have received considerable attention because of their potential for photonic applications, especially for fast and high density data storage. In 2000, Chemical Reviews published a special issue on photochromic materials including a review about the properties and applications of diarylethene photochromic compounds. Since then much impressive progress has been made in this area. Various new diarylethene derivatives have been prepared and examined. The tutorial review presented herein describes developments in diarylethene-based molecular switches made in the last three years. In addition, the synthetic aspects of diarylethene photochromic compounds, which are important issues and neglected in most previous reviews, have been included.

Photochromism of Diarylethene Molecules and Crystals: Memories, Switches, and Actuators

2014-12-16

Masahiro Irie , Tuyoshi Fukaminato , Kenji Matsuda +1 more

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPhotochromism of Diarylethene Molecules and Crystals: Memories, Switches, and ActuatorsMasahiro Irie*†, Tuyoshi Fukaminato‡, Kenji Matsuda§, and Seiya Kobatake∥View Author Information† Research Center for Smart Molecules, Rikkyo University, … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPhotochromism of Diarylethene Molecules and Crystals: Memories, Switches, and ActuatorsMasahiro Irie*†, Tuyoshi Fukaminato‡, Kenji Matsuda§, and Seiya Kobatake∥View Author Information† Research Center for Smart Molecules, Rikkyo University, Nishi-Ikebukuro 3-34-1, Toshima-ku, Tokyo 171-8501, Japan‡ Research Institute for Electronic Science, Hokkaido University, N20, W10, Kita-ku, Sapporo 001-0020, Japan§ Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan∥ Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, Sugimoto 3-3-138, Sumiyoshi-ku, Osaka 558-8585, Japan*E-mail: [email protected]Cite this: Chem. Rev. 2014, 114, 24, 12174–12277Publication Date (Web):December 16, 2014Publication History Received19 May 2014Published online16 December 2014Published inissue 24 December 2014https://pubs.acs.org/doi/10.1021/cr500249phttps://doi.org/10.1021/cr500249preview-articleACS PublicationsCopyright © 2014 American Chemical SocietyRequest reuse permissionsArticle Views43769Altmetric-Citations2136LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Crystals,Electromagnetic radiation,Fluorescence,Irradiation,Molecular structure Get e-Alerts

Reversible Photocontrol of Biological Systems by the Incorporation of Molecular Photoswitches

2013-04-25

Wiktor Szymański , John M. Beierle , Hans A. V. Kistemaker +2 more

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTReversible Photocontrol of Biological Systems by the Incorporation of Molecular PhotoswitchesWiktor Szymański, John M. Beierle†, Hans A. V. Kistemaker‡, Willem A. Velema, and Ben L. Feringa*View Author … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTReversible Photocontrol of Biological Systems by the Incorporation of Molecular PhotoswitchesWiktor Szymański, John M. Beierle†, Hans A. V. Kistemaker‡, Willem A. Velema, and Ben L. Feringa*View Author Information Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands*E-mail: [email protected]Cite this: Chem. Rev. 2013, 113, 8, 6114–6178Publication Date (Web):April 25, 2013Publication History Received3 May 2012Published online25 April 2013Published inissue 14 August 2013https://doi.org/10.1021/cr300179fCopyright © 2013 American Chemical SocietyRIGHTS & PERMISSIONSACS Editors' ChoiceArticle Views42184Altmetric-Citations905LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (36 MB) Get e-AlertscloseSUBJECTS:Azobenzene,Genetics,Irradiation,Monomers,Peptides and proteins Get e-Alerts

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Photopharmacology: Beyond Proof of Principle

2014-01-23

Willem A. Velema , Wiktor Szymański , Ben L. Feringa

Pharmacotherapy is often severely hindered by issues related to poor drug selectivity, including side effects, environmental toxicity, and the emergence of resistance. Lack of selectivity is caused by the inability … Pharmacotherapy is often severely hindered by issues related to poor drug selectivity, including side effects, environmental toxicity, and the emergence of resistance. Lack of selectivity is caused by the inability to control drug activity in time and space. Photopharmacology aims at solving this issue by incorporating photoswitchable groups into the molecular structure of bioactive compounds. These switching units allow for the use of light as an external control element for pharmacological activity, which can be delivered with very high spatiotemporal precision. This Perspective presents the reader with the current state and outlook on photopharmacology. In particular, the principles behind photoregulation of bioactivity, the challenges of molecular design, and the possible therapeutic scenarios are discussed.

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Emerging Targets in Photopharmacology

2016-07-04

Michael M. Lerch , Mickel J. Hansen , Gooitzen M. van Dam +2 more

Abstract The field of photopharmacology uses molecular photoswitches to establish control over the action of bioactive molecules. It aims to reduce systemic drug toxicity and the emergence of resistance, while … Abstract The field of photopharmacology uses molecular photoswitches to establish control over the action of bioactive molecules. It aims to reduce systemic drug toxicity and the emergence of resistance, while achieving unprecedented precision in treatment. By using small molecules, photopharmacology provides a viable alternative to optogenetics. We present here a critical overview of the different pharmacological targets in various organs and a survey of organ systems in the human body that can be addressed in a non‐invasive manner. We discuss the prospects for the selective delivery of light to these organs and the specific requirements for light‐activatable drugs. We also aim to illustrate the druggability of medicinal targets with recent findings and emphasize where conceptually new approaches have to be explored to provide photopharmacology with future opportunities to bring “smart” molecular design ultimately to the realm of clinical use.

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Organic Photochromic and Thermochromic Compounds

2002-01-01

John C. Crano , Robert Guglielmetti

Photochromism into nanosystems: towards lighting up the future nanoworld

2017-12-18

Ling Wang , Quan Li

This review provides a state-of-the-art account of photochromism into diverse functional nanosystems such as nanomachines, nanoparticles, nanoelectronics, nanoassemblies and biological nanosystems. This review provides a state-of-the-art account of photochromism into diverse functional nanosystems such as nanomachines, nanoparticles, nanoelectronics, nanoassemblies and biological nanosystems.

In Vivo Photopharmacology

2018-07-09

Katharina Hüll , Johannes Morstein , Dirk Trauner

Synthetic photoswitches have been known for many years, but their usefulness in biology, pharmacology, and medicine has only recently been systematically explored. Over the past decade photopharmacology has grown into … Synthetic photoswitches have been known for many years, but their usefulness in biology, pharmacology, and medicine has only recently been systematically explored. Over the past decade photopharmacology has grown into a vibrant field. As the photophysical, pharmacodynamic, and pharmacokinetic properties of photoswitches, such as azobenzenes, have become established, they have been applied to a wide range of biological targets. These include transmembrane proteins (ion channels, transporters, G protein-coupled receptors, receptor-linked enzymes), soluble proteins (kinases, proteases, factors involved in epigenetic regulation), lipid membranes, and nucleic acids. In this review, we provide an overview of photopharmacology using synthetic switches that have been applied in vivo, i.e., in living cells and organisms. We discuss the scope and limitations of this approach to study biological function and the challenges it faces in translational medicine. The relationships between synthetic photoswitches, natural chromophores used in optogenetics, and caged ligands are addressed.

The evolution of spiropyran: fundamentals and progress of an extraordinarily versatile photochrome

2019-01-01

Luuk Kortekaas , Wesley R. Browne

Spiropyrans have played a pivotal role in the emergence of the field of chromism following their discovery in the early 20th century, with almost ubiquitous use in materials applications especially … Spiropyrans have played a pivotal role in the emergence of the field of chromism following their discovery in the early 20th century, with almost ubiquitous use in materials applications especially since their photochromism was discovered in 1952. Their versatility continues to lend them to application in increasingly diverse fields not least due to recent discoveries of properties that have expanded their utility extensively. This review provides an overview of their rich history and highlights the contemporary relevance of the spiropyrans.

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Photochromism, Molecules and Systems

1992-01-01

D. A.K.

Diarylethene as a photoswitching unit

2004-10-15

Kenji Matsuda , Masahiro Irie

Visible-light-induced I2-mediated cyclization of ortho-biarylchalcones of naphthofuran series towards oxa[5]helicenes

2025-06-25

Валерий З. Ширинян , A. V. Zakharov , Eva E. Evsikova +2 more | Synlett

This work presents a novel, eco-friendly, transition metal-free method for synthesizing oxa[5]helicenes via visible-light-induced photocyclization of ortho-biarylchalcones of naphthofuran series. It was found that the obtained compounds are highly stable … This work presents a novel, eco-friendly, transition metal-free method for synthesizing oxa[5]helicenes via visible-light-induced photocyclization of ortho-biarylchalcones of naphthofuran series. It was found that the obtained compounds are highly stable to both UV (365 nm) and visible light (LED420) irradiation in the presence of atmospheric oxygen or molecular iodine.

In vitro and in vivo evaluation of chemically synthesized, receptor-biased interleukin-4 and photocaged variants

2025-06-25

Mamiko Ninomiya , Cecilie Egholm , Daniel Breu +2 more | Science Advances

Interleukin-4 (IL-4) plays a central role in type 2 immune responses. Despite its potential use for allergic and autoimmune diseases, its pleiotropic receptor binding complicates selective targeting of IL-4 signaling … Interleukin-4 (IL-4) plays a central role in type 2 immune responses. Despite its potential use for allergic and autoimmune diseases, its pleiotropic receptor binding complicates selective targeting of IL-4 signaling pathways. We developed a chemical synthesis of (i) IL-4 variants with atomically tailored side-chain modifications that deter specific receptor interactions and (ii) conditionally activatable IL-4 variants uncaged with 365-nanometer light. In primary cell studies, different variants elicited selective STAT5 or STAT6 phosphorylation in lymphocytes or neutrophils. In murine studies, photocaged IL-4 suppressed inflammation only upon UV irradiation, demonstrating precise on demand control. We accomplished the synthesis and folding of IL-4, a hydrophobic cytokine with three disulfide bonds, using the alpha-ketoacid-hydroxylamine (KAHA) ligation to assemble three segments. We introduced further conjugations, including PEGylation for half-life extension, through orthogonal ligations enabled by functionalized amino acid building blocks. This work highlights the flexibility of chemical protein synthesis to produce therapeutically valuable cytokines, including receptor-biased and spatiotemporally activatable IL-4 variants.

Enhancing 365 nm Photoresist Performance Using 2-Isopropylthioxanthone as a Photosensitizer

2025-06-24

Litao Zhou , Zhaoxian Tang , Haoyuan Li +2 more | ACS Applied Materials & Interfaces

Chemical amplification resists (CARs) are critical for advanced lithography, yet nonionic photoacid generators (PAGs) often suffer from low sensitivity. This study investigates the use of 2-isopropylthioxanthone (2-ITX) as a photosensitizer … Chemical amplification resists (CARs) are critical for advanced lithography, yet nonionic photoacid generators (PAGs) often suffer from low sensitivity. This study investigates the use of 2-isopropylthioxanthone (2-ITX) as a photosensitizer to enhance the performance of i-line (365 nm) photoresist systems. Four PAGs were synthesized, including TFPSO, BrTFPSO, TFPVSO, and BrTFPVSO. TFPSO, BrTFPSO was mixed with copolymers of 2-Ethyl-2-adamantyl methacrylate (EAMA) and 2-Oxotetrahydrofuran-3-yl methacrylate (GBLMA) to obtain a PAG-blended photoresist system. TFPVSO, BrTFPVSO was copolymerized with EAMA and GBLMA to obtain the PAG-bound photoresist system. Photoresist formulations with 10-20 wt % 2-ITX were evaluated for sensitivity, contrast, and acid diffusion. The PAG-blended system with 10 wt % 2-ITX achieved a dose-to-clear (E0) of 38.4 mJ/cm2 with high contrast (γ = 18.5). Elevated postexposure bake (PEB) temperatures (110 °C) further improved sensitivity (E0 = 5.6 mJ/cm2). PAG-bound systems exhibited reduced acid diffusion (pattern error <1%) but lower sensitivity (E0 = 150.9-673.7 mJ/cm2). Characterization via ultraviolet-visible (UV-vis) and 1H NMR spectroscopy revealed that 2-ITX facilitates the transfer of energy to PAGs without participating in the photolytic decomposition process. These findings highlight the crucial importance of 2-ITX in enhancing photoresist performance and show that the inclusion of photosensitizers expands the applicability of photoresists.

Dynamic Regulation of Radical Photochromism and Photoluminescence via Polymer Polarity

2025-06-24

Quanchi Tian , Qiuyue Ding , Chao‐Nan Xu +4 more | Angewandte Chemie

While polymer matrices are widely used to protect excited‐state phosphors from oxygen and moisture quenching by providing a network that enables long‐lived room‐temperature phosphorescence (RTP), the influence of polymer polarity … While polymer matrices are widely used to protect excited‐state phosphors from oxygen and moisture quenching by providing a network that enables long‐lived room‐temperature phosphorescence (RTP), the influence of polymer polarity on phosphors for stable free radicals with radical luminescence (RL) has not been well studied. In this work, naphthalene diimide (NDI) derivatives, denoted as NDI‐XC‐OH (X = 2‐6), featuring different alkyl alcohol chains, exhibit multi‐responsive and tunable RTP and RL properties through polymer matrix polarity regulation. Experimental results reveal that NDI‐XC‐OH•− anion radicals are generated via not only photoinduction in the excited state but also intermolecular interactions of polar matrix in the ground state. Theoretical simulations demonstrate that polar polymers rich in hydrogen‐bonding donors (e.g., ‐NH2, ‐NH‐ and ‐OH), where electrostatic interactions dominate over dispersion (E/D > 1), more readily induce anion radicals compared to polar polymers rich in acceptors (e.g., ‐CN and ‐CO‐), where dispersion interactions outweigh electrostatic effects (E/D < 1). These derivatives exhibit potential applications in information encryption and volatile amine detection due to their chromic and luminescent properties. These findings offer perspectives on the role of polymer matrix polarity in modulating anion radical behavior, and mechanistic insights into the balance between RTP and RL properties.

From Triplet to Twist: The Photochemical E/Z‐Isomerization Pathway of the Near‐Infrared Photoswitch peri‐Anthracenethioindigo

2025-06-23

Martina Hartinger , Maximilian Herm , Christoph M. Schüßlbauer +4 more | Angewandte Chemie

In recent years, significant progress has been made in the effort to shift the absorption of photoresponsive molecules into the long‐wavelength region of the electromagnetic spectrum. A breakthrough in this … In recent years, significant progress has been made in the effort to shift the absorption of photoresponsive molecules into the long‐wavelength region of the electromagnetic spectrum. A breakthrough in this field was the recent development of π‐extended indigoid photoswitches, i.e., peri‐anthracenethioindigo (PAT), exhibiting all‐red to near‐infrared absorption. The excited‐state isomerization mechanisms of this very new addition to the realm of photoswitching are currently not understood at all, prohibiting a rational further development. In this study, we present a combined theoretical and experimental approach, including (TD‐)DFT and ADC(2) calculations as well as steady‐state and time‐resolved femtosecond spectroscopy, to explore the isomerization pathways of this photoswitch. Our findings show that E‐to‐Z photoisomerization on singlet potential energy surfaces (PESs) is highly unfavorable and instead shows that photoswitching proceeds on the T₁ PES. These insights enhance our understanding of thioindigoid photochemistry and demonstrate that extension of the π‐system and peri‐connectivity in the heterocycle unlock extremely favorable photoswitching properties along with the desirable red‐shift in absorption. Reliable photoswitching from the triplet is achieved because of its favorable energy, which evades undesirable interference from oxygen quenching. These results pave the way for advancing thioindigoid‐based photoswitches to improved performance and functionality in a rational way.

Photochromic Properties of Thiophene and Thiazole-Substituted Bicyclic Aziridine in Solution and Solid State

2025-06-23

C. Castillo , Jagan Nath , Fernando Videgaray Ortega +7 more | ACS Omega

Tracking photophysical relaxation in spiropyran with simulated time-resolved X-ray absorption spectroscopy

2025-06-23

Lina Fransén , Brice Le Roux , Sonia Coriani +2 more | Communications Physics

From Triplet to Twist: The Photochemical E/Z‐Isomerization Pathway of the Near‐Infrared Photoswitch peri‐Anthracenethioindigo

2025-06-23

Martina Hartinger , Maximilian Herm , Christoph M. Schüßlbauer +4 more | Angewandte Chemie International Edition

In recent years, significant progress has been made in the effort to shift the absorption of photoresponsive molecules into the long-wavelength region of the electromagnetic spectrum. A breakthrough in this … In recent years, significant progress has been made in the effort to shift the absorption of photoresponsive molecules into the long-wavelength region of the electromagnetic spectrum. A breakthrough in this field was the recent development of π-extended indigoid photoswitches, i.e., peri-anthracenethioindigo (PAT), exhibiting all-red to near-infrared absorption. The excited-state isomerization mechanisms of this very new addition to the realm of photoswitching are currently not understood at all, prohibiting a rational further development. In this study, we present a combined theoretical and experimental approach, including (TD-)DFT and ADC(2) calculations as well as steady-state and time-resolved femtosecond spectroscopy, to explore the isomerization pathways of this photoswitch. Our findings show that E-to-Z photoisomerization on singlet potential energy surfaces (PESs) is highly unfavorable and instead shows that photoswitching proceeds on the T₁ PES. These insights enhance our understanding of thioindigoid photochemistry and demonstrate that extension of the π-system and peri-connectivity in the heterocycle unlock extremely favorable photoswitching properties along with the desirable red-shift in absorption. Reliable photoswitching from the triplet is achieved because of its favorable energy, which evades undesirable interference from oxygen quenching. These results pave the way for advancing thioindigoid-based photoswitches to improved performance and functionality in a rational way.

Manipulating Spatial Charge Transfer of Donor-Acceptor Type Phenothiazine Frameworks with Unprecedented Topologies for Switchable Photoredox Catalysis

2025-06-22

Huihui He , Zong‐Jie Guan , Jiangpei Yuan +6 more | CCS Chemistry

Efficient Solution‐Phase Synthesis of Sequence‐Defined Oligourethanes with Precise Chirality Control

2025-06-22

Anuj Sharma , Tapendu Samanta , Joanna Cybińska | Macromolecular Rapid Communications

ABSTRACT Nature relies on precisely defined macromolecules for complex biochemical processes with exceptional specificity and efficiency. To replicate these properties in synthetic systems, chemists have developed sequence‐defined macromolecules—polymers with absolute … ABSTRACT Nature relies on precisely defined macromolecules for complex biochemical processes with exceptional specificity and efficiency. To replicate these properties in synthetic systems, chemists have developed sequence‐defined macromolecules—polymers with absolute control over monomer sequence and structure, enabling tailored functions. However, their exploration in material science remains limited due to the challenges of synthesis, which is often low‐yielding and time‐consuming. To address this, we designed and synthesized Fmoc‐assisted stereo‐controlled sequence‐defined oligourethanes (SDOUs) in the solution phase. Our step‐economical synthesis employs a two‐step, one‐pot strategy, eliminating intermediate purification and achieving an average yield of >85% per step. The optimized protocol, using six modified chiral monomers, enables precise stereochemical and sequence control. Thermal analysis revealed that stereochemistry significantly influences thermal transitions, including glass transition, crystallization, and melting behaviors. Tandem mass spectrometry provided in‐depth sequencing analysis. We also demonstrated the post‐synthetic modification of the SDOUs with dansyl chloride and explored their photophysical properties, such as solvatochromism and aggregation. Circular dichroism analysis highlighted their unique structural and conformational features. This approach establishes scalable, efficient synthetic routes for stereochemically controlled sequence‐defined oligourethanes with diverse functional groups.

Light-Regulating Olefin Polymerization Featuring Dithienylethene Switches

2025-06-21

Nan Nie , Fan Yu , Menghe Xu +2 more | Macromolecules

Conditional Stabilization of the Hypoxia‐Inducible Factor HIF1α — Photoswitchable Stapled Peptides Prevent Elongin BC Mediated Degradation

2025-06-20

Van Tuan Trinh , Sabrina Fischer , Lei Zhang +5 more | Angewandte Chemie International Edition

Oxygen levels and its distribution are tightly regulated due to their critical impact on health. Hypoxia‐inducible factors (HIFs) are traditionally recognized as key regulators of the transcriptional response to low … Oxygen levels and its distribution are tightly regulated due to their critical impact on health. Hypoxia‐inducible factors (HIFs) are traditionally recognized as key regulators of the transcriptional response to low oxygen (hypoxia). Recent research expanded their functions, highlighting their potential as therapeutic targets. Despite these advances, there is still a need for chemical biology tools that offer precise spatiotemporal control within the HIF network and output. Here, we introduce an optochemical approach that enables significant differences in expression of HIF1α‐target genes depending on the photostationary state (PSS). Our photoswitchable stapled peptide PSB‐BCB‐04 stabilized HIF1α under normoxic conditions by targeting EloBC (ki = 7.9 ± 1.3 nM) and preventing VHL‐mediated degradation. Visible light allowed reversible regulation of peptide conformation, which entailed a 7‐fold difference in its EloBC‐binding capacity. In a proof‐of‐concept study, we demonstrated that inhibition of HIF1α degradation enabled isomer‐specific expression of the vascular endothelial growth factor (VEGFA) in prostate cancer cells. Our results validated the potential of photopharmacological stabilization of HIF1α and provided a new toolbox for on‐demand photocontrol over the HIF‐signalling pathway as well as VHL‐mediated degradation.

Demonstration of an All‐Optical AND Gate Mediated by Photochromic Molecules

2025-06-20

Heyou Zhang , Max Gießübel , Pankaj D. Dharpure +5 more | Advanced Functional Materials

Abstract The realization of a photonic logic AND gate, i.e. a logic AND gate that runs on photons rather than electrons, and where all steps are controlled by light, is … Abstract The realization of a photonic logic AND gate, i.e. a logic AND gate that runs on photons rather than electrons, and where all steps are controlled by light, is demonstrated. In a proof‐of‐principle experiment, this is accomplished by exploiting photochromic molecules for monitoring the presence or absence of photons of particular wavelengths that represent the logic variables.

Conditional Stabilization of the Hypoxia‐Inducible Factor HIF1α — Photoswitchable Stapled Peptides Prevent Elongin BC Mediated Degradation

2025-06-20

Van Tuan Trinh , Sabrina Fischer , Lei Zhang +5 more | Angewandte Chemie

Linear-light regulated bidirectional electron transfer of a pyromellitic diimide-based photochromic coordination polymer for inkless and erasable printing and information anticounterfeiting

2025-06-20

Jingfang Wang , Pengfei Hao , Shimin Zhang +4 more | Chemical Engineering Journal

Molecular Design for Luminescent Azobenzene‐Containing Conjugated Polymers and Their Application to Film Sensors for Recording Acid Exposure History

2025-06-19

Taichi Kato , Masayuki Gon , Kazuo Tanaka | Macromolecular Rapid Communications

ABSTRACT It has been found that azobenzene structures show luminescence by suppressing their photoisomerization and alternating electronic states through molecular modification and metal complexation. Herein, we propose a three‐step design … ABSTRACT It has been found that azobenzene structures show luminescence by suppressing their photoisomerization and alternating electronic states through molecular modification and metal complexation. Herein, we propose a three‐step design strategy for creating luminescent azobenzene derivatives from quantum chemical calculations. First, we introduced intramolecular hydrogen bonding between o ‐hydroxy groups and the azobenzene moiety, not only for stabilizing the n‐orbital of azobenzene but also for suppressing photoisomerization. Second, the expansion of the π‐conjugation was employed to convert the S 0– S 1 transition to the allowed π–π * transition. Third, we derived the fast excited‐state intramolecular proton transfer (ESIPT) process, which is suitable for observing emission from azobenzene. Through these steps, we designed and synthesized azobenzene derivatives and succeeded in observing intense deep‐red to NIR emission from conjugated polymers including azobenzene moieties in the main chain. Furthermore, we applied the synthesized polymers to film‐type acid vapor sensors. In addition to the real‐time detection ability toward acid vapor observed in our previous work, we found that the current material can discriminate whether the film was once exposed to acid vapor from the changes in luminescence and film colors. Our findings reveal that azobenzene is a potential platform for creating luminescent materials with stimuli‐responsiveness according to rational molecular design.

Design, Synthesis, and In Vitro Characterization of a Tryptamine-Based Visible-Light Photoswitchable 5-HT2AR Ligand Showing Efficacy Preference for β-Arrestin over Mini-Gq

2025-06-18

Alexandra Sink , Eline Pottie , Samuel J. Carter +7 more | Journal of Medicinal Chemistry

The serotonin 2A receptor (5-HT2AR) modulates various neurotransmitter systems and is implicated in psychiatric disorders, including depression and schizophrenia. Despite progress, the detailed mechanisms of signaling at the 5-HT2AR and … The serotonin 2A receptor (5-HT2AR) modulates various neurotransmitter systems and is implicated in psychiatric disorders, including depression and schizophrenia. Despite progress, the detailed mechanisms of signaling at the 5-HT2AR and its therapeutic implications remain unclear, warranting further exploration. Overcoming the limitations of conventional pharmacology, photopharmacology addresses issues such as spatial selectivity and spatiotemporal resolution by incorporating light as an additional external control element. To study the roles of G protein- and β-arrestin2-dependent signaling pathways independently, we designed a photoswitchable, pathway-selective 5-HT2AR ligand. In radioligand binding studies, the cis-photoisomer has a greater affinity than the trans-isomer at the 5-HT2AR and binds at nanomolar concentrations. In two highly analogous functional assays, the photoswitchable ligand showed a preference for β-arrestin2 recruitment over mini-Gαq recruitment relative to LSD, providing a compelling tool for investigating the role of β-arrestin2 recruitment in 5-HT2AR signaling and elucidating its potential role in psychedelic effects.

Orthogonal Thiol Addition Chemistry Based on Ether Acrylates

2025-06-18

Linh Duy Thai , Marco Neumaier , Christopher Barner‐Kowollik | Journal of the American Chemical Society

The thiol-Michael and radical thiol-ene addition chemistries are extremely powerful tools for the construction of advanced soft matter materials. However, a critical challenge of these chemistries lies in their nonideal … The thiol-Michael and radical thiol-ene addition chemistries are extremely powerful tools for the construction of advanced soft matter materials. However, a critical challenge of these chemistries lies in their nonideal orthogonality in which both acrylates (Michael acceptors) and electron-rich olefins are active in a radical thiol-ene reaction. Herein, we show that by employing an ether acrylate (β-alkoxyacrylate), readily accessible via the efficient hydroxyl-yne click reaction, true orthogonality between activated double bonds can be achieved. Critically, we exploit the radical inactive property of the ether acrylate for the efficient synthesis of difficult-to-prepare sequence-defined main-chain macromolecular photoswitches and brush-like polymers. The results reported open a straightforward opportunity to synthetically access advanced materials with controllable properties.

Fabrication of photochromic spiropyran-based coatings for smart color-tunable textiles

2025-06-18

Shaorong Yang , Janesse Wing-Sze Hui , Tong Xue +2 more | Journal of Photochemistry and Photobiology A Chemistry

Unimolecular multi-color photoswitching via imidazole-fused tetraarylethylene: photochromism, ion sensing and applications

2025-06-18

Renjie Wang , Shunyang Liu , Lili Chen +3 more | Dyes and Pigments

Optical control of calcium‐permeable AMPA receptors by azobenzene–spermines

2025-06-18

Maxim V. Nikolaev , E. D. Gataulina , I. M. Fedorova +4 more | British Journal of Pharmacology

Background and Purpose Photo‐switchable compounds acting on ion channels are valuable tools for neuroscience. Specific ligands have been developed for many channels, but selective compounds providing effective optical control for … Background and Purpose Photo‐switchable compounds acting on ion channels are valuable tools for neuroscience. Specific ligands have been developed for many channels, but selective compounds providing effective optical control for calcium‐permeable α‐amino‐3‐hydroxy‐5‐methyl‐4‐isoxazolepropionic acid (AMPA) receptors are still lacking. Because the difference between calcium‐permeable and impermeable receptors is localised in the channel selectivity filter, the only feasible approach to discriminate between them is to design photo‐switchable pore blockers. We have, here, synthesised azobenzene derivatives of spermine and investigated their actions. Experimental Approach The biological activity of azobenzene–spermines was studied in electrophysiological experiments using isolated rat brain neurons, synaptic transmission in slices, fly larvae neuromuscular junction and recombinant AMPA receptors expressed in CHO cells. The experimental results were rationalised using computer modelling. Key Results The most active compound, azobenzene–spermine‐6 (ABSP‐6), selectively blocked calcium‐permeable AMPA receptors in low nanomolar concentrations under ambient light, with an IC 50 under illumination, three orders of magnitude higher. Using rat brain slices, ABSP‐6 provided optical control of excitatory postsynaptic current (EPSC) mediated by AMPA receptors in giant interneurons of striatum, while EPSCs in cortical pyramidal neurons were unaffected. Computer modelling suggests that in the light‐induced cis configuration, formation of an intramolecular H bond reduces the effective length of polyamine chain, resulting in marked loss of activity. Conclusions and Implications Our work provides the first effective optical control of calcium‐permeable AMPA receptors, suited to neurophysiological studies. It will be crucial in elucidating the localisation of glutamate receptor subtypes and clarifying their role in various processes.

A Sensitive Naked Eye Probe Based on Spiropyran for Exactness Sensing of F− Ions in Aqueous

2025-06-18

Xin Guo , P. H. Chen , Rui Wang +5 more | Canadian Journal of Chemistry

Most areas have long been affected by endemic fluorosis, which can lead to fluorosis bone disease and cardiovascular damage. The detection and treatment of fluoridated water has been of great … Most areas have long been affected by endemic fluorosis, which can lead to fluorosis bone disease and cardiovascular damage. The detection and treatment of fluoridated water has been of great concern. In this work, the sensors SP-1 and SP-2 were synthesized from naphthylamine and pyreneamine with carboxy-modified spiropyran via amidation reaction. The photoisomerization of spiropyran molecules under alternating ultraviolet/visible light irradiation resulted in changes in the conjugation system, which amplifies the combination between F- and the amide bonds of SP-1 and SP-2 molecules, enabling rapid and naked-eye detection of F-. Simultaneously, the impact of two distinct conjugated rings, pyridineamine and naphthaleneamine, on spiropyran detection of F- was investigated. Based on results from the UV spectrum, 1HNMR, and DFT theoretical calculation, it was determined that both sensor SP-1 and SP-2 can detect F- with a binding ratio of 1:1. The detection limits for sensor SP-1 are 0.978 uM for F-, and SP-2 are 0.173 µM for F-. The detection limit of SP-2, with a larger chromophore than SP-1, is lower and exhibits a more pronounced phenomenon. This study holds significant practical implications for rapid anion detection in aqueous environments, visual recognition without the need for specialized equipment, and energy conservation.

Photoswitchable Catalytic Divergent Synthesis by a Viologen‐Functionalized Lanthanide‐Organic Tetrahedral Cage

2025-06-17

Qing‐Fu Sun , Kea‐Tiong Tang , Yuxi Tian +5 more | Angewandte Chemie International Edition

Photoswitchable catalysis presents a significant challenge, particularly in the modulation of reaction pathways. In this study, we describe a redox‐active lanthanide‐organic tetrahedral cage 1, self‐assembled from a viologen‐functionalised ditopic tridentate … Photoswitchable catalysis presents a significant challenge, particularly in the modulation of reaction pathways. In this study, we describe a redox‐active lanthanide‐organic tetrahedral cage 1, self‐assembled from a viologen‐functionalised ditopic tridentate ligand and Eu(III) ions. Complexation‐induced charge redistribution and spatial rearrangement of ligands in the assembly endow 1 with distinct photochromic properties and redox activities compared to free ligand L. 1 can serve as a photoswitchable catalyst for divergent chemical transformations of various tetraarylborates, giving biaryls and phenols via photo‐oxidative coupling reaction under 365 nm light irradiation, or producing mono‐arene products through catalytic de‐composition process in the absence of light. This work represents the first example of photoswitchable divergent synthesis by a single self‐assembled coordination cage, paving the way for the design and construction of novel supramolecular edifices with switchable functions.

Merocyanine and Spiropyran Adsorption on Graphene

2025-06-17

Olivia Bushman , Andreas Riemann | ACS Omega

Photoswitchable Catalytic Divergent Synthesis by a Viologen‐Functionalized Lanthanide‐Organic Tetrahedral Cage

2025-06-17

Qing‐Fu Sun , Kea‐Tiong Tang , Yuxi Tian +5 more | Angewandte Chemie

SYNTHESIS AND PHOTOCHROMIC PROPERTIES OF A NEW FUNCTIONALLY SUBSTITUTED MOLECULE BASED ON SPIROPYRAN

2025-06-16

Artur A. Khuzin , Liliya L. Khuzina | Izvestia Ufimskogo Nauchnogo Tsentra RAN

In this work, we report the synthesis of a new salt of photochromic spiropyran containing various functional groups and capable of reversibly reacting to external influences. It is shown that … In this work, we report the synthesis of a new salt of photochromic spiropyran containing various functional groups and capable of reversibly reacting to external influences. It is shown that the synthesized spiropyran containing –CHO, –NO2, –OCH3, –(CH2)5PPh3 groups in its structure exhibits positive photochromism, as evi denced by its reversible photoinduced transformations under the action of ultraviolet and visible radiation. It is established that the presence of functional groups in the spirophotochrome molecule contributes to an increase in resistance to photodegradation.

Apo‐state structure of the metabotropic glutamate receptor 5 transmembrane domain obtained using a photoswitchable ligand

2025-06-16

Yasushi Kondo , Caitlin Hatton , R.K. Cheng +7 more | PubMed

Abstract Metabotropic glutamate receptor 5 (mGlu5) is implicated in various neurodegenerative disorders, making it an attractive drug target. Although several ligand‐bound crystal structures of mGlu5 exist, their apo‐state crystal structure … Abstract Metabotropic glutamate receptor 5 (mGlu5) is implicated in various neurodegenerative disorders, making it an attractive drug target. Although several ligand‐bound crystal structures of mGlu5 exist, their apo‐state crystal structure remains unknown. Here, we study mGlu5 structural changes using the photochemical affinity switch, alloswitch‐1, in combination with time‐resolved freeze‐trapping methods. By X‐ray crystallography, we demonstrated that isomerizing alloswitch‐1 leads to its release from the binding pocket within a few seconds. The apo structure, determined at a resolution of 2.9 Å, is more comparable to the inactive state than to the active state. Our approach presents an accessible alternative to time‐resolved serial crystallography for capturing thermodynamically stable transient intermediates. The mGlu5 apo‐structure provides molecular insights into the ligand‐free allosteric pocket, which can guide the design of new allosteric modulators.

Structure-Dependent Photochemical Dynamics of Modified ortho-Terphenyls Studied with One and Two-Photon Probes

2025-06-16

Ryan P. Brady , Luke R. O’Connor , Rachel A. Dziatko +2 more | The Journal of Physical Chemistry A

We report on structure-dependent one- and two-photon induced photochemical dynamics of modified ortho-terphenyls (OTPs), model 6π electrocyclizing photoreactants that exhibit distinct branching between reactive and nonreactive nonradiative excited-state deactivation channels. … We report on structure-dependent one- and two-photon induced photochemical dynamics of modified ortho-terphenyls (OTPs), model 6π electrocyclizing photoreactants that exhibit distinct branching between reactive and nonreactive nonradiative excited-state deactivation channels. Using both pump-probe transient absorption spectroscopy (TAS) and pump-repump-probe (PRP) TAS, we find an enhanced efficiency for cyclization over nonreactive deactivation with the addition of 4,4″ alkyl substitution on pendant rings. The nonreactive deactivation rate is largely unaffected by structural modifications, whereas the cyclization rate to form trans-4a,4b-dihydrotriphenylene (trans-DHT) decreases with increasing substituent size. Based on these observations, we conclude that the reactive and nonreactive deactivation channels involve distinctly different structural dynamics within low-lying electronic excited states to reach critical geometries (i.e., conical intersections). We show that the cis-DHT photoproduct yield obtained by resonant 1 + 1' excitation is sensitive to dynamics in the low-lying excited-states of OTP that are in turn sensitive to structural modifications. Within the sub-ps time regime, PRP and TAS signals evolve on significantly different timescales, highlighting that these methods have different contrasts for probing dynamics on low-lying potential energy surfaces.

Reversible Antagonism of Dopamine D1 Receptor using a Photoswitchable Remotely Tethered Ligand

2025-06-15

Belinda E. Hetzler , Prashant Donthamsetti , Robert M. Wolesensky +3 more | bioRxiv (Cold Spring Harbor Laboratory)

Dopamine D1 receptor (D1R) plays key roles in health and disease. D1R is broadly expressed throughout the brain and body and is dynamically activated in response to endogenous dopamine, making … Dopamine D1 receptor (D1R) plays key roles in health and disease. D1R is broadly expressed throughout the brain and body and is dynamically activated in response to endogenous dopamine, making it difficult to target this receptor with sufficient precision. We previously developed a robust light-activatable, tetherable agonist for D1R, wherein a temporally precise photo-switch (the P compound) binds to a genetically-encoded membrane anchoring protein (the M protein) in specific brain locations and cell types. Here we extended our approach by developing a complementary antagonist P compound that could be used to block specific populations of D1R in the brain with precise timing. Together, we have generated a robust toolkit for interrogating D1R function in the brain with unprecedented precision.

Design and synthesis of dual stimuli-responsive Azo-bis(spiropyran) based advanced chromic materials for sensing applications

2025-06-14

Deepika Sharma , Sachin Goyal , Kamlesh Kumar | Materials Today Chemistry

Light‐Mediated Modification and Manipulation of Nucleic Acids

2025-06-14

Yujie Jiang , Yutong Zhou , Ruoqian Xie +3 more | ChemPhotoChem

Chemical modification of nucleic acids (oligonucleotide, DNA, and RNA) is a powerful tool, widely used in chemical biology. There is a growing interest in light‐mediated nucleic acid modification within biological … Chemical modification of nucleic acids (oligonucleotide, DNA, and RNA) is a powerful tool, widely used in chemical biology. There is a growing interest in light‐mediated nucleic acid modification within biological systems, driven by the exceptional spatiotemporal precision that light offers. Moreover, light‐induced chemical modification of nucleic acids, utilizing light as an external energy source, offers a powerful and efficient alternative to conventional labor‐intensive de novo synthesis. In this regard, visible light exhibits a highly efficient and selective approach, enabling precise labeling of target sites without compromising their structural integrity, while high‐energy UV light triggers detrimental photochemical reactions, causing DNA/RNA damage. Light‐mediated selective labeling and interstrand crosslinking of DNA/RNA duplexes hold great potential for applications in DNA repair, gene regulation, and nanotechnology. Photouncaging and photoswitching enable precise control over biological processes like transcription, RNA interference, and translation. Moreover, light‐mediated DNA‐encoded libraries provide a sustainable and efficient method for generating vast small‐molecule libraries, valuable for pharmaceutical discovery. This review highlights recent advancements in light‐mediated nucleic acid modifications, including labeling, crosslinking, photouncaging, photoswitching, and DNA‐encoded library synthesis, accompanied by comprehensive discussion and analysis.

Designing Reversible Photoswitching Azobenzene-Modified Nucleotide for Controlling Biological Function

2025-06-13

Juncheng Li , Jinxi Du , Weiwei He +7 more | Journal of the American Chemical Society

RNA plays vital roles in numerous normal and diseased cellular functions and processes. Reversible photoregulation of oligonucleotide's structure and function is a powerful strategy for both regulating biological processes and … RNA plays vital roles in numerous normal and diseased cellular functions and processes. Reversible photoregulation of oligonucleotide's structure and function is a powerful strategy for both regulating biological processes and developing novel RNA-based therapeutics. Herein, we designed an azobenzene-modified cytidine phosphoramidite and synthesized a series of oligoribonucleotides containing this photoswitchable residue. We validated the reversible photoisomerization in both ribonucleoside and oligoribonucleotide contexts and studied the overall impact of this cytidine modification through all-atom molecular dynamics (MD) simulations and UV melting experiments. We also showed that the modified oligoribonucleotide can switch the reverse transcription (RT) process upon light irradiation in the presence of various RT enzymes. In addition, the optical control mechanism of the HIV reverse transcriptase-mediated RT process was elucidated by MD simulation. This new chemical biology toolset enables reversible optical control of RNA structures and functions for gene regulation and novel drug development.

A Photoisomerizable Chiral Dopant for Fast and Precise Controlling the Reflection Band of the CLCN Film

2025-06-13

Xingchen Liu , Limin Wu , Yi Li +2 more | Chemistry - An Asian Journal

Abstract Colorful cholesteric liquid crystal polymer network (CLCN) patterns have been applied for decoration and anti‐counterfeiting. Generally, the handedness of the reflected lights is the same. In this paper, a … Abstract Colorful cholesteric liquid crystal polymer network (CLCN) patterns have been applied for decoration and anti‐counterfeiting. Generally, the handedness of the reflected lights is the same. In this paper, a chiral dopant derived from cyanostilbene is synthesized. Due to the isomerization and [2 + 2] photocycloaddition under the irradiation of the 365‐nm UV light, it exhibits a great change in the helical twisting power. The cholesteric liquid crystal mixture prepared using this chiral dopant can be applied for rapid optical recording. Colorful CLCN patterns are also prepared, which can reflect both left‐ and right‐handed circularly polarized lights. Namely, different patterns are observed through left‐ and right‐handed circular polarizers. Due to the luminescent property of the chiral dopant and its isomers, circularly polarized luminescence is emitted from the CLCN films.

The Essence of Nature Can be the Simplest (4)–Adenine: Powerful Reserve for Extracellular Fenton Chemistry

2025-06-13

Qunfu Wu , Jiao Zhou , Donglou Wang +1 more | Chemistry & Biodiversity

ABSTRACT Adenine has long been recognized for its critical roles in cellular metabolism and the storage of genetic information. However, the mechanism by which ATP, derived from adenine, outperforms nucleotides … ABSTRACT Adenine has long been recognized for its critical roles in cellular metabolism and the storage of genetic information. However, the mechanism by which ATP, derived from adenine, outperforms nucleotides formed from other nucleobases as the primary energy currency remains unclear. In this study, we demonstrate that metabolism of all nucleobases produces hydrogen peroxide (H 2 O 2 ), which serves as a key substrate for extracellular Fenton chemistry, a cellular energy mechanism that facilitates the increase of environmental temperature and the degradation of organic matter. Among the nucleobases, adenine metabolism generates the highest H 2 O 2 levels, followed by guanine. Using thermophilic fungi as a model, we found that compared with the mutant without the extracellular Fenton reactions, wild‐type strains with the extracellular Fenton chemistry showed downregulation of NTP synthesis and upregulation of nucleoside triphosphate degradation, resulting in H 2 O 2 production. The function of nucleosides as crucial reserves for the extracellular Fenton reactions of organisms may offer insights into potential and natural functions of stop codons, poly(A) tails in RNA biosynthesis, junk DNA in the genome, tumor recurrence after chemotherapy or radiotherapy, shortening of telomerase genes with each cell division and the differentiation of long‐lived keratinocyte stem cells with a high nucleus‐to‐cytoplasm ratio into short‐lived enucleated keratinocytes.

An ultraviolet-writable and infrared-erasable anti-counterfeiting strategy based on the combination of photochromic Zn2GeO4: Na+ phosphor and photothermal converter NaYb0.5Sm0.5(MoO4)2 agent

2025-06-13

Xin Chen , Xuezhu Sha , Li Wang +7 more | Journal of Colloid and Interface Science

Semicrystalline Poly(azobenzene) with Negative Photochromism for Photochemical Melting of Thick Samples

2025-06-13

Hantao Zhou , Jesus Guillen Campos , Rishabh Tennankore +4 more | ACS Macro Letters

Photomechanical effects based on photochemical transformations often suffer from challenges of restricted light penetration due to strong light attenuation, limiting their operation to micrometer-scale materials with relatively inefficient bending deformation … Photomechanical effects based on photochemical transformations often suffer from challenges of restricted light penetration due to strong light attenuation, limiting their operation to micrometer-scale materials with relatively inefficient bending deformation modes. While recent reports have established semicrystalline poly(azobenzene)s as a promising class of photochemically responsive materials, strong absorption of UV light required to drive trans to cis isomerization has limited switching to within several micrometers of the surface. Negative photochromism offers a possible route to circumvent this limitation, as reversible photobleaching of the ground state absorption upon switching extends the light penetration. Herein, we report the synthesis and characterization of P(Cx-dFdC-azo), a negative photochromic semicrystalline poly(azobenzene) incorporating ortho-difluoro, dichloro-substituted azo photoswitches. These polymers exhibit near-quantitative bidirectional photoisomerization─92% conversion to cis under 617 nm irradiation and 96% conversion to trans under 405 nm irradiation, along with reversible photomelting and crystallization. Photorheological studies demonstrate a significant increase over which photomelting can be achieved, from <10 μm for conventional poly(azobenzene) to at least 300 μm for P(Cx-dFdC-azo), highlighting the potential of these materials for photochemically responsive materials with macroscopic dimensions.

Intrinsically Adaptive Salicylaldimine: Mechanically and Thermally Induced Switching between Photochromism and Photoluminescence

2025-06-12

Zhiyuan Han , Meixia He , Jean‐Maríe Lehn +1 more | Journal of the American Chemical Society

Dynamically adaptive materials that respond to varying environmental stimuli have garnered significant attention due to their potential applications. Nevertheless, developing single-molecule-based intrinsically adaptive materials capable of responding to multiple stimuli … Dynamically adaptive materials that respond to varying environmental stimuli have garnered significant attention due to their potential applications. Nevertheless, developing single-molecule-based intrinsically adaptive materials capable of responding to multiple stimuli remains a challenge. Herein, we present an intrinsically adaptive salicylaldimine 1 featuring a urea group, demonstrating versatile adaptations across three different stacking states in response to light, mechanical, and thermal stimuli, thus facilitating controllable switching between photochromism and photoluminescence. Such adaptations are enabled by intermolecular hydrogen bonds between urea groups, which play a crucial role in modulating molecular stacking configurations. Specifically, the pristine imine 1 in crystal I state exhibits fluorescence quenching but demonstrates visible-light-driven reversible photochromism. Mechanical grinding disrupts the robust intermolecular hydrogen bond, deactivating photochromism while activating photoluminescence. The resulting imine 1 powder in amorphous state displays bright fluorescence and can be reverted to the initial crystal I state either through exposure to ethanol vapor or thermal annealing of imine 1 at 60 °C. Remarkably, a new stable crystalline state, crystal II, emerges after the thermal annealing of imine 1 at an exceptionally high temperature of 240 °C with 21.5-fold fluorescence enhancement compared to imine 1 in crystal I state. These versatile adaptations underscore its potential for applications in anticounterfeiting, information encryption, and high-temperature recording. Overall, these findings provide valuable insights into strategies for the development of intrinsically adaptive systems and materials.