Molecular switches as photocontrollable “smart” receptors

Natali, Manuel; Giordani, Silvia

doi:10.1039/c2cs35015g

Cited by 453 publications

(257 citation statements)

References 110 publications

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“…[29] associated lifetimes for the photo-isomerization and its quantum yield for compound 1-3 in different solvents. [29] of TRIR data for a) DASA 1 in DMSO and b) DASA 3 in [D 6 ]DMSO. The upper traces in these two panels display steady-stateFTIR spectra of the two compounds.Inpanels c) and d), acomparisoni sshown between the long-lived components in DMSO/ [D 6 ]DMSO and deuterated chloroform.…”

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confidence: 99%

“…Molecular photoswitches change structure and properties reversibly upon light-irradiation, [1] enabling successful applications in the dynamic control of functions in material sciences, [2][3][4] supramolecular chemistry, [5,6] and in the biological context. [7][8][9][10][11][12] Applications differ markedly in the environment the photoswitch is exposed to,b ei td ifferent solvents, [13,14] matrices or surfaces,a nd understanding how ag iven photoswitch behaves in various environments is crucial for its success in any applications.…”

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Solvent Effects on the Actinic Step of Donor–Acceptor Stenhouse Adduct Photoswitching

et al. 2018

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Donor–acceptor Stenhouse adducts (DASAs) are negative photochromes that switch with visible light and are highly promising for applications ranging from smart materials to biological systems. However, the strong solvent dependence of the photoswitching kinetics limits their application. The nature of the photoswitching mechanism in different solvents is key for addressing the solvatochromism of DASAs, but as yet has remained elusive. Here, we employ spectroscopic analyses and TD‐DFT calculations to reveal changing solvatochromic shifts and energies of the species involved in DASA photoswitching. Time‐resolved visible pump‐probe spectroscopy suggests that the primary photochemical step remains the same, irrespective of the polarity and protic nature of the solvent. Disentangling the different factors determining the solvent‐dependence of DASA photoswitching, presented here, is crucial for the rational development of applications in a wide range of different media.

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Solvent Effects on the Actinic Step of Donor–Acceptor Stenhouse Adduct Photoswitching

et al. 2018

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“…Они представляют значительный интерес при соз-дании материалов для молекулярной электроники, оптической записи информации, фотофармаколо-гии, биовизуализации, хемо-и биосенсорики [1][2][3][4][5]. В связи с этим широко исследуют спиропираны и спирооксазины [6][7][8], фульгиды и фульгимиды [9][10][11], фото-и ионохромные гетероциклические кетоенамины [12; 13].…”

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Synthesis of Novel Nonsymmetric Dihetarylethenes With 1,3-Thiazole Bridge

Тихомирова¹,

Podshibyakin²,

Шепеленко³

et al. 2017

Sc. South Russ.

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Аннотация. Разработан пятистадийный метод синтеза новых дигетарилэтенов с 1,3-тиазольным мостиком, содержащих 2,5-диметилтиофеновый и замещенные 2H-хромен-2-оновые заместители. Вза-имодействием 5(3)-метоксизамещенных салициловых альдегидов с янтарным ангидридом в присут-ствии триэтиламина получают 6-метоксикумарин-и 8-метоксикумаринуксусные кислоты. Их обработ-ка тионилхлоридом приводит к соответствующим хлорангидридам, которые использовали для дальней-ших превращений без дополнительной очистки. Ацилирование 2,5-диметилтиофена хлорангидридами кумаринуксусных кислот по реакции Фриделя -Крафтса в присутствии хлорида алюминия приводит к 3-(2-(2,5-диметилтиофен-3-ил)-2-оксоэтил)-6-метокси-и -8-метокси-2H-хромен-2-онам, которые при действии сульфурилхлорида образуют соответствующие хлоркетоны. Строение всех промежуточных продуктов подтверждено методами ИК-Фурье, яМР 1 H спектроскопии, масс-спектрометрии и элемент-ного анализа. Полученые хлоркетоны легко циклизуются при помощи арилтиомочевин или тиоамидов различных кислот, что открывает перспективы синтеза широких серий новых фотохромных диарилэте-нов с замещенным кумариновым фрагментом.Ключевые слова: синтез, дигетарилэтены, 2H-хромен-2-он, 2,5-диметилтиофен, молекулярные переключатели. Abstract. Five-step method for the synthesis of novel dihetarylethenes with a 1,3-thiazole bridge containing 2,5-dimethylthiophene and substituted 2H-chromene-2-one substituents was developed. 6-Methoxycoumarinand 8-methoxycumarin acetic acids were prepared by interaction of 5(3)-methoxysubstituted salicylic aldehydes with succinic anhydride in the presence of triethylamine. Their treatment with thionyl chloride leads to the corresponding chloroanhydrides, which were used for further conversions without additional purification. Acylation of 2,5-dimethylthiophene with coumarinacetic acid chloroanhydrides via the FriedelCrafts reaction in the presence of aluminum chloride leads to 3-(2-(2,5-dimethylthiophen-3-yl)-2-oxoethyl)-6-methoxy-and -8-methoxy-2H-chromen-2-ones, which form the corresponding chloro ketones upon the action of sulfuryl chloride. The structure of all intermediate products was confirmed by FT-IR, 1 H NMR spectroscopy, mass spectrometry and elemental analysis. The obtained chloro ketones are easily cyclized by arylthioureas or thioamides of various acids, which gives the possibility for the synthesis of wide series of novel photochromic diarylethenes with substituted coumarin fragment. SYNTHESIS OF NOVEL NONSYMMETRIC

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“…A photoswitchable spiropyran presents as one such sensing moiety, where these structures form the basis of a chemosensor when functionalised with a suitable ionophore that is capable of complexing with a metal ion [33,34]. Photo-controlled switching between the weakly fluorescent spiropyran (SP) and highly fluorescent merocyanine (MC) isomers occurs on irradiation with UV light or in the presence of the target metal ion, while visible light reverses the isomerisation (see 1 and 2 Figure 1A) [35][36][37].…”

Section: Introductionmentioning

confidence: 99%

A Rationally Designed, Spiropyran-Based Chemosensor for Magnesium

et al. 2018

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Magnesium ions (Mg 2+ ) play an important role in mammalian cell function; however, relatively little is known about the mechanisms of Mg 2+ regulation in disease states. An advance in this field would come from the development of selective, reversible fluorescent chemosensors, capable of repeated measurements. To this end, the rational design and fluorescence-based photophysical characterisation of two spiropyran-based chemosensors for Mg 2+ are presented. The most promising analogue, chemosensor 1, exhibits 2-fold fluorescence enhancement factor and 3-fold higher binding affinity for Mg 2+ (K d 6.0 µM) over Ca 2+ (K d 18.7 µM). Incorporation of spiropyran-based sensors into optical fibre sensing platforms has been shown to yield significant signal-to-background changes with minimal sample volumes, a real advance in biological sensing that enables measurement on subcellular-scale samples. In order to demonstrate chemosensor compatibility within the light intense microenvironment of an optical fibre, photoswitching and photostability of 1 within a suspended core optical fibre (SCF) was subsequently explored, revealing reversible Mg 2+ binding with improved photostability compared to the non-photoswitchable Rhodamine B fluorophore. The spiropyran-based chemosensors reported here highlight untapped opportunities for a new class of photoswitchable Mg 2+ probe and present a first step in the development of a light-controlled, reversible dip-sensor for Mg 2+ .

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Molecular switches as photocontrollable “smart” receptors

Cited by 453 publications

References 110 publications

Solvent Effects on the Actinic Step of Donor–Acceptor Stenhouse Adduct Photoswitching

Solvent Effects on the Actinic Step of Donor–Acceptor Stenhouse Adduct Photoswitching

Synthesis of Novel Nonsymmetric Dihetarylethenes With 1,3-Thiazole Bridge

A Rationally Designed, Spiropyran-Based Chemosensor for Magnesium

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