A Supercharged Molecular Motor Operating by Constitutional Alteration and Hydrogen Bonding DOI Creative Commons
Henry Dube, Pronay Kumar Biswas,

Ani Ozcelik

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Feb. 14, 2024

Abstract Molecular rotary motors undergo directional motions upon input of external energy and represent archetypical molecular machines. Light driven variants stand out as particularly easy to fuel continuously potentially carrying a very high content during their action. So far, such function via light induced bond rotations where the directionality is dictated by fixed source asymmetry within structure. During operation cycle there no further structural change happening except for rotation itself. In this work we disclose hitherto unknown highly effective mechanism motor rotation, which makes use constitutional alteration This in turn allows be controlled actively an intramolecular hydrogen instead sterics. Associated with unusual that retains from incident light, great importance application working under load. With these findings unique possibilities emerge design unprecedented modes action power.

Language: Английский

Visible light-responsive materials: the (photo)chemistry and applications of donor–acceptor Stenhouse adducts in polymer science DOI Creative Commons
Michèle Clerc, Sara Sandlass, Omar Rifaie‐Graham

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(23), P. 8245 - 8294

Published: Jan. 1, 2023

Donor-acceptor Stenhouse adduct (DASA) photoswitches have gained a lot of attention since their discovery in 2014. Their negative photochromism, visible light absorbance, synthetic tunability, and the large property changes between photoisomers make them attractive candidates over other commonly used for use materials with responsive or adaptive properties. The development such translation into advanced technologies continues to widely impact forefront research, DASAs thus attracted considerable interest field visible-light molecular switches dynamic materials. Despite this interest, there been challenges understanding complex behavior context both small molecule studies Moreover, incorporation polymers can be challenging due incompatibility conditions most common polymerization techniques. In review, therefore, we examine critically discuss recent developments DASA-containing polymers, aiming at providing better interplay properties constituents (matrix photoswitch). first part summarizes current DASA design switching second section discusses strategies materials, methods studying We also emerging applications polymeric ranging from light-responsive drug delivery systems, photothermal actuators, sensors photoswitchable surfaces. Last, summarize venture on steps required explore novel systems expand functional application opportunities polymers.

Language: Английский

Citations

55
Rhodanine-Based Chromophores: Fast Access to Capable Photoswitches and Application in Light-Induced Apoptosis DOI

Laura Köttner,

Friederike Wolff,

P. Mayer

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 1894 - 1903

Published: Jan. 11, 2024

Molecular photoswitches are highly desirable in all chemistry-related areas of research. They provide effective outside control over geometric and electronic changes at the nanoscale using an easy to apply, waste-free stimulus. However, simple access such molecular tools is typically not granted, elaborate syntheses substitution schemes needed order obtain efficient photoswitching properties. Here we present a series rhodanine-based that can be prepared one synthetic step without requiring purification. Photoswitching induced by UV visible light both switching directions, thermal stabilities metastable states as well quantum yields very high. An additional benefit hydrogen-bonding capacity rhodanine fragment, which enables applications supramolecular or medicinal chemistry. We further show known inhibitor SMI-16a photoswitchable apoptosis inducer. The biological activity effectively switched ON OFF reversible photoisomerization between inactive E active Z isomer. Rhodanine-based therefore represent valuable toolbox for implementing responsiveness breadth functional systems.

Language: Английский

Citations

17
Preparation of imidazole acids grafted chitosan with enhanced antioxidant, antibacterial and antitumor activities DOI
Bing Ma, Jingjing Zhang,

Yingqi Mi

et al.

Carbohydrate Polymers, Journal Year: 2023, Volume and Issue: 315, P. 120978 - 120978

Published: May 5, 2023

Language: Английский

Citations

36
Diaryl-hemiindigos as visible light, pH, and heat responsive four-state switches and application in photochromic transparent polymers DOI Creative Commons

Maximilian Sacherer,

Frank Hampel, Henry Dube

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 20, 2023

Photoswitches are indispensable tools for responsive chemical nanosystems and used today in almost all areas of the natural sciences. Hemiindigo (HI) derivatives have recently been introduced as potent photoswitches, but their full applicability has hampered by limited possibilities functionalization structural modification. Here we report on a short easy to diversify synthesis yielding diaryl-HIs bearing one additional aromatic residue at central double bond. The resulting chromophores offer an advantageous property profile combining red-light responsiveness, high thermal bistability, strong isomer accumulations both switching directions, photochromism, tunable acid gating. With this progress, broader realm becomes accessible HI which can now be synthetically tailored advanced future applications, e.g., research molecular machines switches, studies photoisomerization mechanisms, or generation smart addressable materials. To showcase potential these distinct light-responsive tools, demonstrate four-state switching, fueling, reversible inscription into transparent polymers using green red light well acid/base stimuli, addition comprehensive photochemical study compounds.

Language: Английский

Citations

27
All-visible-light-driven stiff-stilbene photoswitches DOI Creative Commons
Fan Xu, Jinyu Sheng, Charlotte N. Stindt

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(18), P. 6763 - 6769

Published: Jan. 1, 2024

This work outlines a simple synthetic strategy providing formylated stiff-stilbenes. The photoisomerization of stiff-stilbenes could be fully controlled using visible light and is accompanied by high photostationary state distribution.

Language: Английский

Citations

9
Heterocyclic Hemithioindigos: Highly Advantageous Properties as Molecular Photoswitches** DOI

Verena Josef,

Frank Hampel, Henry Dube

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(43)

Published: Aug. 30, 2022

A survey of heterocyclic hemithioindigo photoswitches is presented identifying a number structural motives with outstanding property profiles. The highly sought-after combination pronounced color change, quantitative switching in both directions, exceptional high quantum yields, and tunable thermal stability metastable states can be realized 4-imidazole, 2-pyrrole, 3-indole-based derivatives. In the former, an unusual preorganization using isomer selective chalcogen- hydrogen bonding allows to precisely control geometry changes tautomerism upon switching. Heterocyclic hemithioindigos thus represent promising advanced capabilities that will great value anyone interested establishing defined reversible at molecular level.

Language: Английский

Citations

31
Application of photopharmacology in agrochemicals DOI Creative Commons
Wen Fu, Zhong Li, Xusheng Shao

et al.

Advanced Agrochem, Journal Year: 2023, Volume and Issue: 2(2), P. 142 - 153

Published: April 17, 2023

Photopharmacology is a novel technology in drug design that aims at solving poor selectivity. This currently the proof-of-concept phase and relies on photoactivation or inactivation of photochromic ligands (PCLs) to regulate biological functions living organisms. As potential molecular tools future agriculture 4.0, pesticides are effective optical control receptors, ion channels, behaviors, enzymes, which displays an innovative way pesticide discovery. In this review, we highlight progresses photoisomerized insecticides fungicides. By integrating photoswitches, such as azobenzenes diarylethenes, into molecules, several PCLs were developed for regulation important insect fungi targets vivo, including GABARs, RyRs, nAChRs, SURs, sodium GluCls, SDH. The results highly significant revealing interactions agrochemicals with their targets, functions, provide powerful toolkits understanding ligand-receptor interactions. Moreover, there growing demand diverse range PCLs, particularly those sensitive red NIR light sunlight, actual field use agriculture. We envision particular mode discovery great promise overcoming challenges posed by improper agrochemicals.

Language: Английский

Citations

22
Thiazolylazopyrazoles as Nonsymmetric Bis‐Heteroaryl Azo Switches: High‐Yield Visible‐Light Photoisomerization and Increased Z‐Isomer Stability by o‐Carbonylation DOI
Tongtong Dang,

Dongfang Dong,

Jiabin Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: March 2, 2023

Following the progress on mono-heteroaryl azo switches (Het-N=N-Ph), a few bis-heteroaryl (Het-N=N-Het) have been studied recently, whereas nonsymmetric ones (Het1 -N=N-Het2 ) that can combine respective merits of each heterocycle, received little attention. Here we report thiazolylazopyrazoles as visible-light switching character thiazole ring and ease o-substitution pyrazole ring. Thiazolylazopyrazoles achieve (near-)quantitative isomerization in both directions long Z-isomer thermal half-lives several days. In contrast to drastically destabilizing effect o-methylation, o-carbonylation remarkably stabilize Z isomers by inducing attractive intramolecular interactions (dispersion, C-H⋅⋅⋅N bond, lone-pair⋅⋅⋅π interaction). Our work highlights importance rational combination two heterocycles suitable structural substitution developing switches.

Language: Английский

Citations

20
A cross-conjugation approach for high-performance diaryl-hemithioindigo photoswitches DOI Creative Commons

Max Zitzmann,

Frank Hampel, Henry Dube

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(21), P. 5734 - 5742

Published: Jan. 1, 2023

A new class of diaryl-hemithioindigo is presented as capable reversible photoswitches with enhanced structural elaboration and stimuli-responsive behavior. Multi-state multi-stimuli addressability enable advanced molecular logic operations.

Language: Английский

Citations

19
Visible‐ and Near‐Infrared Light‐Driven Molecular Photoswitches for Biological Applications DOI Open Access
Yang Xu, Yuqi Tang, Quan Li

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 19, 2024

Abstract Molecular photoswitches can undergo isomerization under light exposure, making them uniquely attractive for high spatiotemporal resolution remote control of biological functions. Visible and near‐infrared (NIR) light, with their low energy consumption, safety, strong tissue penetration, are particularly suitable applications. Therefore, developing visible‐ NIR light‐driven molecular use is great significance. This review introduces the most common presents state‐of‐art applications in bioimaging, biosensing, drug delivery, photocontrolled cancer phototherapy, photopharmacology. The opportunities challenges future development outlined.

Language: Английский

Citations

7