Mono- and bithiophene-substituted diarylethene photoswitches with emissive open or closed forms

• A. Lennart Schleper,
• Mariano L. Bossi,
• Vladimir N. Belov and
• Stefan W. Hell

Beilstein J. Org. Chem. 2019, 15, 2344–2354, doi:10.3762/bjoc.15.227

• oxidized DAEs. However, due to poor emission, SyTh1 was not considered as a fluorescence marker. Another promising compound for applications in super-resolution microscopy was DAE AsOTh1. A high emission efficiency and a relatively fast cycloreversion, makes it a good candidate for a photoswitch applicable

Azologization and repurposing of a hetero-stilbene-based kinase inhibitor: towards the design of photoswitchable sirtuin inhibitors

• Christoph W. Grathwol,
• Nathalie Wössner,
• Sören Swyter,
• Adam C. Smith,
• Enrico Tapavicza,
• Robert K. Hofstetter,
• Anja Bodtke,
• Manfred Jung and
• Andreas Link

Beilstein J. Org. Chem. 2019, 15, 2170–2183, doi:10.3762/bjoc.15.214

• ‐time photomodulation of sirtuins in vitro. Keywords: azo compounds; epigenetics; photoswitch; sirtuins; stilbenes; Introduction Sirtuins are protein deacylases that cleave off not only acetyl, but also other acyl groups from the ε-amino group of lysines in histones and many other substrate proteins

Insertion of [1.1.1]propellane into aromatic disulfides

• Robin M. Bär,
• Gregor Heinrich,
• Martin Nieger,
• Olaf Fuhr and
• Stefan Bräse

Beilstein J. Org. Chem. 2019, 15, 1172–1180, doi:10.3762/bjoc.15.114

• can lead to improved properties, e.g., increased water-solubility of drug candidates [2] or the electronical separation of a photoswitch and a chromophore [6]. Often used moieties for these kinds of applications are triptycenes, cubanes, bicyclo[2.2.2]octanes (BCOs) and bicyclo[1.1.1]pentanes (BCPs

Azologization of serotonin 5-HT₃ receptor antagonists

• Karin Rustler,
• Galyna Maleeva,
• Piotr Bregestovski and
• Burkhard König

Beilstein J. Org. Chem. 2019, 15, 780–788, doi:10.3762/bjoc.15.74

• photo-induced trans–cis isomerization representing the time of birth of the azobenzene photoswitch. Benefiting of their accessible synthesis, large change in polarity and geometry upon switching, excellent photochromic properties and tuneability, azobenzenes are amongst the most widely used photochromic

Oxidative and reductive cyclization in stiff dithienylethenes

• Michael Kleinwächter,
• Ellen Teichmann,
• Lutz Grubert,
• Martin Herder and
• Stefan Hecht

Beilstein J. Org. Chem. 2018, 14, 2812–2821, doi:10.3762/bjoc.14.259

• reduction wave is shifted to lower potentials compared to C2+ for all observed cases by up to >600 mV (see Table S1, Supporting Information File 1). 2) The amount of FP2+ formed depends on both the electronic structure of the photoswitch and the scan rate. While at slow scan rates (10 mV s−1) the conversion

Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules

• Hendrik V. Schröder and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190

• reported (Figure 16) [85]. However, the axle bears a central azobenzene photoswitch, who’s E/Z-transitions can be controlled by light. The redox-switchable shuttle works as previously described and the position of the wheel can be controlled by oxidation or reduction. However, the configuration of the

The role of alkyl substituents in deazaadenine-based diarylethene photoswitches

• Christopher Sarter,
• Michael Heimes and
• Andres Jäschke

Beilstein J. Org. Chem. 2016, 12, 1103–1110, doi:10.3762/bjoc.12.106

• DNA photoswitches for the application in bionanotechnology and synthetic biology. Keywords: diarylethene; nucleoside; electrocyclic rearrangement; photochromism; photoswitch; Introduction Most biomacromolecules are per se not responsive to light. Their conversion into photoresponsive molecules opens

• in which a purine nucleobase represented one of the aryl rings of the photoswitch (Figure 1B). Importantly and different from most other approaches towards photoswitchable nucleic acids, the nucleobase constituted an active part of the photoswitch (rather than an appendage), changing its bonding and

Photoswitchable precision glycooligomers and their lectin binding

• Daniela Ponader,
• Sinaida Igde,
• Marko Wehle,
• Katharina Märker,
• Mark Santer,
• David Bléger and
• Laura Hartmann

Beilstein J. Org. Chem. 2014, 10, 1603–1612, doi:10.3762/bjoc.10.166

• ; multivalent glycosystems; photoswitch; precision polymer; Introduction Carbohydrate ligand–receptor interactions underpin many important processes in biology, for example in host-pathogen interactions [1][2]. Although monosaccharides usually exhibit only low binding affinities, nature is able to obtain high

Amino-substituted diazocines as pincer-type photochromic switches

• Hanno Sell,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2013, 9, 1–7, doi:10.3762/bjoc.9.1

• isomer is more stable than the trans form. Compared to the parent EBAB, which is a very efficient photoswitch, the conversion from the cis to the trans isomer upon irradiation with 405 nm is reduced to 34% (diamino derivative 4) and 54% (diacetamido derivative 5, cf. 92% in the parent compound). The

A bisazobenzene crosslinker that isomerizes with visible light

• Subhas Samanta,
• Harris I. Qureshi and
• G. Andrew Woolley

Beilstein J. Org. Chem. 2012, 8, 2184–2190, doi:10.3762/bjoc.8.246

• crosslinker BPDBS, (4,4'-bis(4-(2-chloroacetamido)phenyl)diazenylbiphenyl-2,2'-disulfonate) (1, Scheme 1) [24]. This photoswitch can produce a minimum ~5 Å and a maximum ~23 Å end-to-end distance change upon trans–cis isomerization. It has a high absorption coefficient (45–60,000 M−1cm−1) and can produce up

• to ~80% trans–cis isomerization under favorable conditions. The suitability of this photoswitch for biological systems would be enhanced if the wavelengths required for photoisomerization were longer, so that UV light was not required. UV light is highly scattered by biological samples and can be a

• red-shifted compared to BPDBS with a maximum near 420 nm. The molar extinction coefficient for 2 was determined by 1H NMR coupled with UV–vis absorption spectra, to be 66,400 in DMSO at 428 nm, such that on a molar basis, the photoswitch is intensely colored. The spectra in aqueous solutions are pH

Control over molecular motion using the cis–trans photoisomerization of the azo group

• Estíbaliz Merino and
• María Ribagorda

Beilstein J. Org. Chem. 2012, 8, 1071–1090, doi:10.3762/bjoc.8.119

• photoswitch is a part of a macromolecular structure. A variety of photosensitive devices, such as smart polymers [36][37], liquid crystals [38][39], intelligent enzymes [40], and various switches and molecular machines [41][42][43][44][45][46][47][48], have been developed by using the photochromic properties

• fluorescent dye close to the photoswitch giving rise to a fluorescence change upon isomerization. The introduction of azobenzene-modified biomolecules in zebrafish proved that the photochemistry of azobenzenes was similar in vivo and in vitro, and that appropriate azobenzenes could be stable in vivo for days

• results in a collective structural change in a certain direction. This cooperative molecular motion of SAMazo acts as a molecular lift capable of lifting one Hg drop deposited on the monolayer of azobenzenes. Furthermore, this device acts as a photoswitch of the current between the Au(111) layer and the

On the bromination of the dihydroazulene/vinylheptafulvene photo-/thermoswitch

• Virginia Mazzanti,
• Martina Cacciarini,
• Søren L. Broman,
• Christian R. Parker,
• Magnus Schau-Magnussen,
• Andrew D. Bond and
• Mogens B. Nielsen

Beilstein J. Org. Chem. 2012, 8, 958–966, doi:10.3762/bjoc.8.108

• ; photoswitch; vinylheptafulvene; Introduction 1,8a-Dihydroazulene-1,1-dicarbonitrile (DHA, 1) is a yellow photochromic compound, which undergoes a light-induced 10-electron retro-electrocyclization to a red-colored vinylheptafulvene (VHF) (Scheme 1) [1][2][3]. The VHF compound is formed as the s-cis conformer

Diarylethene-modified nucleotides for switching optical properties in DNA

• Sebastian Barrois and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2012, 8, 905–914, doi:10.3762/bjoc.8.103

• applied for switching the binding affinities of proteins and peptides [32] but are still rather unexplored with respect to nucleic acids. The advantage of this type of photoswitch is that back reaction (reopening of the central ring) requires light and cannot be achieved in a thermally induced way

Building photoswitchable 3,4'-AMPB peptides: Probing chemical ligation methods with reducible azobenzene thioesters

• Gehad Zeyat and
• Karola Rück-Braun

Beilstein J. Org. Chem. 2012, 8, 890–896, doi:10.3762/bjoc.8.101

• binding motif is associated with H5N1 influenza infections. We reasoned that the attachment of a photoswitch next to SXV PDZ-binding motifs would be a powerful strategy for exploring the function of these PDZ-binding peptide ligands in vitro and in vivo. For the synthetic ligation studies presented herein

• synthesis and evaluation of photoswitchable protein analogues, for example receptors with the photoswitch placed in the direct neighborhood of the specific C-terminal binding motif. Results and Discussion The azobenzene ω-amino-acid thioesters 1b and 2b were prepared by following and applying literature

A perfluorocyclopentene based diarylethene bearing two terpyridine moieties – synthesis, photochemical properties and influence of transition metal ions

• Falk Wehmeier and
• Jochen Mattay

Beilstein J. Org. Chem. 2010, 6, No. 53, doi:10.3762/bjoc.6.53

• diarylethene unit (3) can be obtained by lithiation of 3-bromo-2-methylbenzo[b]thiophene (1) followed by quenching with perfluorocyclopentene (2), according to the method described by Irie [12]. Electrophilic iodination leads to the diiodo photoswitch 4 (Scheme 1) [13][14]. We decided to use the diiodo switch