Light Responsiveness and Assembly of Arylazopyrazole-Based Surfactants in Neat and Mixed CTAB Micelles

Tyagi, Gunjan; Greenfield, Jake L.; Jones, Beatrice E.; Sharratt, William N.; Khan, Kasim; Seddon, Dale; Malone, Lorna A.; Cowieson, Nathan; Evans, Rachel C.; Fuchter, Matthew J.; Cabral, João T.

doi:10.1021/jacsau.2c00453

Cited by 13 publications

(19 citation statements)

References 42 publications

(74 reference statements)

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“…A much more elegant and less disruptive approach is to use photoswitchable surfactants ,− or surfactants that are reactive to other stimuli, , which can yield responsive interfaces and trigger property changes on larger length scales through changes in surface tension and interfacial composition. , We note that responsive materials are the basis to develop adaptive materials or interfaces, which are able to provide feedback arising from the joint actione.g., of multiple responsive unitswith the possibility to precondition the system …”

Section: Introductionmentioning

confidence: 99%

Photo-Responsive Control of Adsorption and Structure Formation at the Air–Water Interface with Arylazopyrazoles

et al. 2023

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Smart interfaces that are responsive to external triggers such as light are of great interest for the development of responsive or adaptive materials and interfaces. Using alkyl-arylazopyrazole butyl sulfonate surfactants (alkyl-AAP) that can undergo E/Z photoisomerization when irradiated with green (E) and UV (Z) lights, we demonstrate through a combination of experiments and computer simulations that there can be surprisingly large changes in surface tension and in the molecular structure and order at air−water interfaces. Surface tensiometry, vibrational sumfrequency generation (SFG) spectroscopy, and neutron reflectometry (NR) are applied to the study of custom-synthesized AAP surfactants with octyland H-terminal groups at air−water interfaces as a function of their bulk concentration and E/Z configuration. Upon photoswitching, a drastic influence of the alkyl chain on both the surface activity and the responsiveness of interfacial surfactants is revealed from changes in the surface tension, γ, where the largest changes in γ are observed for octyl-AAP (Δγ ∼ 23 mN/m) in contrast to H-AAP with Δγ < 10 mN/m. Results from vibrational SFG spectroscopy and NR show that the interfacial composition and the molecular order of the surfactants drastically change with E/Z photoisomerization and surface coverage. Indeed, from analysis of the S−O (head group) and C−H vibrational bands (hydrophobic tail), a qualitative analysis of orientational and structural changes of interfacial AAP surfactants is provided. The experiments are complemented by resolution of thermodynamic parameters such as equilibrium constants from ultra-coarse-grained simulations, which also capture details like island formation and interaction parameters of interfacial molecules. Here, the interparticle interaction ("stickiness") and the interaction with the surface are adjusted, closely reflecting experimental conditions.

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Section: Introductionmentioning

confidence: 99%

Photo-Responsive Control of Adsorption and Structure Formation at the Air–Water Interface with Arylazopyrazoles

et al. 2023

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“…[48] Recently, Fuchter, Cabral and coworkers synthesized similar AAP-based photosurfactants and studied their self-assembly into micelles (Figure 1f). [49] [42] (c) Molecular structures of AAP carboxylic acid based low molecular weight gelators. [45] (d) AAP-based tripodal gelators for water and organic solvents.…”

Section: Self-assembly and Materials Applicationsmentioning

confidence: 99%

Azoheteroarene and Diazocine Molecular Photoswitches: Self‐Assembly, Responsive Materials and Photopharmacology

2023

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Aromatic units tethered with an azo (−N=N−) functionality comprise a unique class of compounds, known as molecular photoswitches, exhibiting a reversible transformation between their E‐ and Z‐isomers in response to photo‐irradiation. Photoswitches have been explored extensively in the recent past to prepare dynamic self‐assembled materials, optoelectronic devices, responsive biomaterials, and more. Most of such materials involve azobenzenes as the molecular photoswitch and to date, SciFinder lists more than 7000 articles and 1000 patents. Subsequently, a great deal of effort has been invested to improve the photo‐isomerization efficiency and related mesoscopic properties of azobenzenes. Recently, azoheteroarenes and cyclic azobenzenes, such as arylazopyrazoles, arylazoisoxazoles, arylazopyridines, and diazocines, have emerged as second generation molecular photoswitches beyond conventional azobenzenes. These photoswitches offer distinct photoswitching behavior and responsive properties which make them highly promising candidates for multifaceted applications ranging from photoresponsive materials to photopharmacophores. In this minireview, we introduce the structural refinement and photoresponsive properties of azoheteroarenes and diazocines and summarize the state‐of‐the‐art on utilizing these photoswitches as responsive building blocks in supramolecular assembly, material science and photopharmacology, highlighting their versatile photochemical behavior, enhanced functionality, and latest applications.

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“…[48] Kürzlich synthetisierten Fuchter, Cabral und Mitarbeiter ähnliche AAPbasierte Phototenside und untersuchten deren Selbstorganisation zu Mizellen (Abbildung 1f). [49] Hier konnten ursprünglich gebildete abgeflachte ellipsoide Mizellen durch Bestrahlung reversibel in sphärische Mizellen mit kleineren Größen und dickeren Schalen umgewandelt werden. Außerdem wurde die Bildung gemischter Mizellen mit dem konventionellen Tensid CTAB untersucht, wodurch eine Veränderung der Mizellendimensionen bei Bestrahlung erreicht werden konnte.…”

Section: Selbstassemblierung Und Materialanwendungenunclassified

Azoheteroarene und Diazocine als Molekulare Photoschalter: Selbstassemblierung, Responsive Materialien und Photopharmakologie

2023

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Aromatische Einheiten, die mit einer Azofunktionalität (−N=N−) verknüpft sind, bilden eine einzigartige Klasse von Verbindungen, bekannt als molekulare Photoschalter, die bei Bestrahlung eine reversible Umwandlung zwischen ihren E‐ und Z‐Isomeren zeigen. Photoschalter wurden in näherer Vergangenheit umfassend untersucht, um dynamische, selbstassemblierende Materialien, optoelektronische Geräte, steuerbare Biomaterialien und vieles mehr, herzustellen. Die meisten dieser Materialien beinhalten Azobenzole als molekulare Photoschalter. Hierfür zeigt SciFinder bereits mehr als 7000 Artikel und 1000 Patente. Dementsprechend wurde viel Aufwand investiert, um die Effizienz der Photoisomerisierung und die damit verbundenen mesoskopischen Eigenschaften von Azobenzolen zu verbessern. Seit kurzer Zeit haben Azoheteroarene und zyklische Azobenzole wie Arylazopyrazole, Arylazoisoxazole, Arylazopyridine und Diazocine als Photoschalter der zweiten Generation an Bedeutung gewonnen. Diese Photoschalter bieten einzigartiges Schaltverhalten und responsive Eigenschaften, die sie zu vielversprechenden Kandidaten für die Entwicklung von photoresponsiven Materialien bis hin zu Photopharmakophoren machen. In diesem Kurzaufsatz stellen wir die strukturellen Unterschiede und photoresponsiven Eigenschaften von Azohezeroarenen und Diazocinen vor und fassen den aktuellen Stand der Anwendung dieser Photoschalter als responsive Bausteine in der supramolekularen Assemblierung, Materialwissenschaften und Photopharmakologie zusammen. Dabei soll ihr vielseitiges photochemisches Verhalten, ihre verbesserten Funktionalitäten und die neusten Anwendungen hervorgehoben werden.

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Light Responsiveness and Assembly of Arylazopyrazole-Based Surfactants in Neat and Mixed CTAB Micelles

Cited by 13 publications

References 42 publications

Photo-Responsive Control of Adsorption and Structure Formation at the Air–Water Interface with Arylazopyrazoles

Photo-Responsive Control of Adsorption and Structure Formation at the Air–Water Interface with Arylazopyrazoles

Azoheteroarene and Diazocine Molecular Photoswitches: Self‐Assembly, Responsive Materials and Photopharmacology

Azoheteroarene und Diazocine als Molekulare Photoschalter: Selbstassemblierung, Responsive Materialien und Photopharmakologie

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