Chemical tuning of photoswitchable azobenzenes: a photopharmacological case study using nicotinic transmission

• Lorenzo Sansalone,
• Jun Zhao,
• Matthew T. Richers and
• Graham C. R. Ellis-Davies

Beilstein J. Org. Chem. 2019, 15, 2812–2821, doi:10.3762/bjoc.15.274

• glutathione. However, attempts to conjugate with a cysteine on a genetically modified nicotinic acetylcholine receptor did not afford the expected light-responsive channel. Our data indicate that the 4FAB photoswitch can be derivatized bifunctionally for genetically-targeted photopharmacology whilst

A chiral self-sorting photoresponsive coordination cage based on overcrowded alkenes

• Constantin Stuckhardt,
• Diederik Roke,
• Wojciech Danowski,
• Edwin Otten,
• Sander J. Wezenberg and
• Ben L. Feringa

Beilstein J. Org. Chem. 2019, 15, 2767–2773, doi:10.3762/bjoc.15.268

• , Germany Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC, Leiden, The Netherlands 10.3762/bjoc.15.268 Abstract In recent years, increasing efforts have been devoted to designing new functional stimuli-responsive supramolecular assemblies. Here, we present three isomeric

• is essential for the application of SCCs towards chiral recognition and sensing [34][35][36][37]. To the best of our knowledge no self-sorted responsive SCCs have been reported so far. Molecular motors based on overcrowded alkenes are unique photoswitches that are able to undergo unidirectional

• interesting strategy to form responsive coordination complexes, as they feature a large geometric change upon switching [47]. Herein, we report a photoresponsive coordination cage with ligands based on a first generation molecular motor (Figure 1). Cages with a Pd2L4 composition are formed from bidentate

A combinatorial approach to improving the performance of azoarene photoswitches

• Joaquin Calbo,
• Aditya R. Thawani,
• Rosina S. L. Gibson,
• Andrew J. P. White and
• Matthew J. Fuchter

Beilstein J. Org. Chem. 2019, 15, 2753–2764, doi:10.3762/bjoc.15.266

• including imaging applications [20], photopharmacology [21], supramolecular chemistry [22][23], responsive foams [24], coordination chemistry [25] and DNA nanotechnology [26][27]. Whilst the azopyrazoles have excellent properties for use in a variety of photo-addressable applications, it remains frustrating

In search of visible-light photoresponsive peptide nucleic acids (PNAs) for reversible control of DNA hybridization

• Lei Zhang,
• Greta Linden and
• Olalla Vázquez

Beilstein J. Org. Chem. 2019, 15, 2500–2508, doi:10.3762/bjoc.15.243

• melting temperatures (TM) by the analysis of the first derivative [50]. TM values are summarized in Table 2. The incorporation of the visible-light responsive azobenzene (PNA 3) stabilized the duplex in comparison with the Aeg(Ac)-modified analogue 5. However, the TM of 3 is 14 °C lower than the one

Ultrafast processes triggered by one- and two-photon excitation of a photochromic and luminescent hydrazone

• Alessandro Iagatti,
• Baihao Shao,
• Alberto Credi,
• Barbara Ventura,
• Ivan Aprahamian and
• Mariangela Di Donato

Beilstein J. Org. Chem. 2019, 15, 2438–2446, doi:10.3762/bjoc.15.236

• their conformational, chemical or physical properties [1]. The possibility to control their operation in a direct and specific manner paves the way for applications in many different fields, involving the production of responsive materials and surfaces [2][3], energy conversion [4][5][6], catalysis [7

Sugar-derived oxazolone pseudotetrapeptide as γ-turn inducer and anion-selective transporter

• Sachin S. Burade,
• Sushil V. Pawar,
• Tanmoy Saha,
• Navanath Kumbhar,
• Amol S. Kotmale,
• Manzoor Ahmad,
• Pinaki Talukdar and
• Dilip D. Dhavale

Beilstein J. Org. Chem. 2019, 15, 2419–2427, doi:10.3762/bjoc.15.234

• selective anion transport that occurs by an anion–anion antiport mechanism. The absence of the γ-turn conformation as well as ion transport activity in linear tetrapeptide 9 – the precursor of 2a, suggest that the oxazolone ring in 2a is a γ-turn inducer as well as responsive for selective anion transport

Reversible switching of arylazopyrazole within a metal–organic cage

• Anton I. Hanopolskyi,
• Soumen De,
• Michał J. Białek,
• Yael Diskin-Posner,
• Liat Avram,
• Moran Feller and
• Rafal Klajn

Beilstein J. Org. Chem. 2019, 15, 2398–2407, doi:10.3762/bjoc.15.232

• photochromism in the spiropyran switch [18]. Other recent studies of photochromic systems within macrocyclic and supramolecular hosts [19] include dihydroazulene switches [20] and red-shifted azobenzenes [21][22] inside cucurbiturils and cyclodextrins. The behavior of light-responsive compounds can also be

Targeted photoswitchable imaging of intracellular glutathione by a photochromic glycosheet sensor

• Xianzhi Chai,
• Hai-Hao Han,
• Yi Zang,
• Jia Li,
• Xiao-Peng He,
• Junji Zhang and
• He Tian

Beilstein J. Org. Chem. 2019, 15, 2380–2389, doi:10.3762/bjoc.15.230

• the photochromic fluorescence reporter into GSH-responsive MnO2 nanosheets, a highly efficient photoswitchable hybrid biosensor is successfully presented with the demanded functionality for precise cell imaging. Results and Discussion Synthesis of dithienylethene fluorescence reporter (Glyco-DTE) The

• surface of nanosheets. Apart from the quenched fluorescence, the photoswitchable emission was also prohibited (Figure S2, Supporting Information File 1), probably due to the significantly reduced emission operation window of Glyco-DTE. We then investigated the GSH-responsive performance of Glyco-DTE@MnO2

• fluorescent sensors for detecting intracellular GSH or discriminative sensing of GSH with other common biothiols (e.g., Cys and Hcy) [45][46]. In this work, the highly accessible 2D MnO2 nanosheet is used as the GSH responsive site instead of traditional functional groups that require elaborate design for

1,2,3-Triazolium macrocycles in supramolecular chemistry

• Mastaneh Safarnejad Shad,
• Pulikkal Veettil Santhini and
• Wim Dehaen

Beilstein J. Org. Chem. 2019, 15, 2142–2155, doi:10.3762/bjoc.15.211

• have led to applications in molecular recognition, sensing, molecular machines and devices, supramolecular polymers, stimuli-responsive materials, supramolecular catalysis and drug-delivery systems [4][5][6][7]. Inspired by the attractive role of various N-heterocyclic building blocks such as

Morphology-tunable and pH-responsive supramolecular self-assemblies based on AB₂-type host–guest-conjugated amphiphilic molecules for controlled drug delivery

• Yang Bai,
• Cai-ping Liu,
• Di Chen,
• Long-hai Zhuo,
• Huai-tian Bu and
• Wei Tian

Beilstein J. Org. Chem. 2019, 15, 1925–1932, doi:10.3762/bjoc.15.188

• -responsive supramolecular self-assemblies have been constructed, the controlled drug delivery induced by morphology transitions of these supramolecular self-assemblies on the basis of host–guest-conjugated monomers (HGCMs) are few reported. In this paper, the self-assembly behaviors of AB2-type HGCMs, e.g

• varied morphology could inhibit cancer cell proliferation, indicating their potential application in the field of drug delivery. Keywords: β-cyclodextrin; controlled drug delivery; host–guest interaction; stimuli-responsive; supramolecular self-assemblies; Introduction Supramolecular self-assemblies

• stimuli-responsive supramolecular self-assemblies with regulated self-assembly morphologies due to their response to various external stimuli, such as temperature [12], light [13][14][15], redox [16][17][18], and pH [19][20]. In addition, β-cyclodextrin (β-CD), pillararene and cucurbituril have been

Identification of optimal fluorescent probes for G-quadruplex nucleic acids through systematic exploration of mono- and distyryl dye libraries

• Xiao Xie,
• Michela Zuffo,
• Marie-Paule Teulade-Fichou and
• Anton Granzhan

Beilstein J. Org. Chem. 2019, 15, 1872–1889, doi:10.3762/bjoc.15.183

• (up to 150 nm) and, in certain cases, structural selectivity with respect to one or another G4 folding topology. These dyes can be considered as promising G4-responsive sensors for in vitro or imaging applications. As a possible application, we implemented a simple two-dye fluorimetric assay allowing

• single-stranded controls (pink and black dots), to which none of the two dyes proves responsive. A few G4 structures located relatively far from the areas occupied by the respective groups. This is the case of G4CT, Bcl2Mid and, at least partially, UpsB-Q3. In the case of G4CT, previous studies report

• varying content of guanine and a wealth of duplex structures, and (2) discriminating G4 structures based on their topology, with the exception of a few notable cases presenting structural peculiarities. Quantum yield and brightness of the probes Four highly responsive and G4-selective dyes, namely 1p, 1u

Reversible end-to-end assembly of selectively functionalized gold nanorods by light-responsive arylazopyrazole–cyclodextrin interaction

• Maximilian Niehues,
• Patricia Tegeder and
• Bart Jan Ravoo

Beilstein J. Org. Chem. 2019, 15, 1407–1415, doi:10.3762/bjoc.15.140

• of gold nanorods (AuNR) by thiolated cyclodextrin (CD) host molecules. As a result of the complete removal of the precursor capping agent cetyltrimethylammonium bromide (CTAB) by a tetraethylene glycol derivative, competitive binding to the host cavity was prevented, and reversible, light-responsive

• –organic hybrid nanomaterials. Keywords: cyclodextrins; gold nanorods; host–guest chemistry; light-responsive materials; molecular switches; self-assembly; Introduction Metallic nanomaterials have received intense and interdisciplinary interest due to their unique optical [1], electronic [2][3] and

• nanoparticle systems [18][19][20][21][22][23][24]. The host–guest interaction can be responsive to external stimuli such as redox, pH or light, with the latter being the most desirable for assembling nanoparticles by virtue of its noninvasive nature [25]. Prominent light-responsive guest molecules are

Photochemical generation of the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical from caged nitroxides by near-infrared two-photon irradiation and its cytocidal effect on lung cancer cells

• Ayato Yamada,
• Manabu Abe,
• Yoshinobu Nishimura,
• Shoji Ishizaka,
• Masashi Namba,
• Taku Nakashima,
• Kiyofumi Shimoji and
• Noboru Hattori

Beilstein J. Org. Chem. 2019, 15, 863–873, doi:10.3762/bjoc.15.84

• , Japan Department of Molecular and Internal Medicine, Graduate School of Biomedical & Health Sciences, Hiroshima University, 1-2-3 Kasumi, Minami-ku, Hiroshima, Hiroshima 734-8551, Japan 10.3762/bjoc.15.84 Abstract Novel caged nitroxides (nitroxide donors) with near-infrared two-photon (TP) responsive

• -responsive photo-labile protecting group [56][57][58] with simple cyclic stilbene structures such as 2-(4-nitrophenyl)benzofuran (NPBF) that absorb in the NIR region of 710–760 nm for the uncaging of bioactive substances such as glutamate and Ca2+ [59][60][61][62][63][64]. Herein, we report the synthesis of

• new caged nitroxides (nitroxide donors) 2a and 2b having the TP-responsive NPBF chromophore and the NIR TP-triggered generation of the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical under atmospheric conditions using these species (Scheme 1). Because free radicals are cytotoxic due to their

New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions

• Iveta Chena Tichá,
• Simona Hybelbauerová and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2019, 15, 830–839, doi:10.3762/bjoc.15.80

• organoselenium-bridged bis-β-CDs. Subsequently, the same research group [26] investigated the performance of inclusion complexes of native and permethylated β-CDs and cinchona alkaloids as pH-responsive binding systems. Nevertheless, to the best of our knowledge, CD derivatives with covalently bonded cinchona

Synthesis of functionalized diazocines for application as building blocks in photo- and mechanoresponsive materials

• Widukind Moormann,
• Daniel Langbehn and
• Rainer Herges

Beilstein J. Org. Chem. 2019, 15, 727–732, doi:10.3762/bjoc.15.68

• ’-diaminodiazocine 2 (center) and 4,4’-diaminodiazocine 3 (right). Continuous lines: 100% cis and dashed lines: PSS (385 nm) at 298.15 K in acetonitrile. Synthesized target diazocines 4–7 for applications in responsive materials. UV–vis spectra of 3,3’-diaminodiazocine 2 (left), 3,3’-di(aminomethyl)diazocine 6a

Homo- and hetero-difunctionalized β-cyclodextrins: Short direct synthesis in gram scale and analysis of regiochemistry

• Gábor Benkovics,
• Mihály Bálint,
• Éva Fenyvesi,
• Erzsébet Varga,
• Szabolcs Béni,
• Konstantina Yannakopoulou and
• Milo Malanga

Beilstein J. Org. Chem. 2019, 15, 710–720, doi:10.3762/bjoc.15.66

• selective functionalization of these cyclic oligosaccharides can remarkably improve their complexing ability and enables their application as artificial enzymes [2][3][4], chiral resolving agents [5], stimuli-responsive materials [6], molecular sensors [7] or bioactive hosts with significant emerging

Polyaminoazide mixtures for the synthesis of pH-responsive calixarene nanosponges

• Antonella Di Vincenzo,
• Antonio Palumbo Piccionello,
• Alberto Spinella,
• Delia Chillura Martino,
• Marco Russo and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2019, 15, 633–641, doi:10.3762/bjoc.15.59

• . The desired responsivity to pH variations of the nanosponges obtained was verified by means of absorption tests on a set of organic pollutant model molecules. Keywords: calixarenes; nanosponges; pH-responsive materials; pollutants; polyaminoazides; Introduction The ability to provide a response to

• presence of unreacted alkyne groups. Sequestration abilities of the CaNS nanosponges The possible pH-responsive sequestration abilities of materials CaNS-I and CaNS-II were verified by means of sequestration tests on a set of suitable guest, namely p-nitroaniline derivatives 6–10 and dyes 11–15 (Figure 4

• work we verified the feasibility of synthesizing new pH-responsive calixarene nanosponges by using two different polyaminoazide mixtures as the reticulating agent. Full characterization (HR-ESIMS, FTIR, 1D and 2D NMR) of the mixtures has been provided. It is particularly important to stress that the

LCST phase behavior of benzo-21-crown-7 with different alkyl chains

• Yan Deng,
• Xing Li,
• Qiao Zhang,
• Zheng Luo,
• Chengyou Han and
• Shengyi Dong

Beilstein J. Org. Chem. 2019, 15, 437–444, doi:10.3762/bjoc.15.38

• -crown-7, B21C7s) can effectively control the thermo-responsive properties. Keywords: crown ethers; hydrophobic units; lower critical solution temperature; LCST; thermo-responsiveness; supramolecular chemistry; Introduction The introduction of stimuli-responsiveness into artificial materials is vital

• molecules-containing systems has been developed exhibiting LCST behavior and adjustable thermo-responsive properties. These include ionic liquids [27][28][29][30], macrocycles [31][32][33][34], and supramolecular pairs [26][35][36][37][38]. For example, the combination of macrocycles and supramolecular

• interactions can realize controlled release and product separation in complex supramolecular systems [35]. More options of small molecules with LCST properties not only give rise to more flexibility for LCST systems and thermo-responsive materials, but would be a great advantage for functionalization. In our

Olefin metathesis in multiblock copolymer synthesis

• Maria L. Gringolts,
• Yulia I. Denisova,
• Eugene Sh. Finkelshtein and
• Yaroslav V. Kudryavtsev

Beilstein J. Org. Chem. 2019, 15, 218–235, doi:10.3762/bjoc.15.21

• multiblock copolymers with the possibility to introduce stimuli-responsive functionalities were obtained using a bimetallic ruthenium initiator [74]. The initiator allowed for the single-step fabrication of symmetrically end-functionalized telechelic polymers using ROMP and functional chain terminators

Lectins of Mycobacterium tuberculosis – rarely studied proteins

• Katharina Kolbe,
• Sri Kumar Veleti,
• Norbert Reiling and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2019, 15, 1–15, doi:10.3762/bjoc.15.1

• successful strategies to survive, replicate and persist within macrophages for days, months or even years, including highly-specialized metabolic pathways for nutrient acquisition and stress-responsive processes for protection against the immune system [7][8][9][10][11][12]. In this regard, invasion of

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

• topologically complex TTF catenanes and cage compounds [52][74][102][103][104]. 6.1. Stimuli-responsive circumrotation The TTF-based catenane 26 allows implementing a stimuli-responsive circumrotation motion (Figure 24) [105]. Similar to the corresponding donor–acceptor rotaxanes, the macrocycle preferentially

• organosulfur compound TTF developed from a molecular switch with multiple electronic and material applications to one of the most widely used building blocks for the construction of stimuli-responsive MIMs and functional molecular devices. The development of straightforward organic reactions to implement TTFs

A switchable [2]rotaxane with two active alkenyl groups

• Xiu-Li Zheng,
• Rong-Rong Tao,
• Rui-Rui Gu,
• Wen-Zhi Wang and
• Da-Hui Qu

Beilstein J. Org. Chem. 2018, 14, 2074–2081, doi:10.3762/bjoc.14.181

• and thiol functional groups. The reversible shuttling movement of the macrocycle between two different recognition sites on the molecular thread can be driven by external acid and base. This kind of rotaxane bearing functional groups provides a powerful platform for preparing stimuli-responsive

• ][5][6][7]. During the past years, a large number of different MIMs has been constructed, such as handcuff catenane [8], molecular elevators [9][10], molecular muscles [11][12], trefoil necklace [13][14][15], molecular walkers [16][17][18] and molecular pumps [19][20]. Combining the stimuli-responsive

• , which act as important precursors for constructing stimuli-responsive supramolecular materials [21][22]. Rotaxanes [23][24][25][26][27][28][29][30][31], as one of the most important MIMs, have been deeply investigated because of their excellent properties and convenient synthesis. By introducing various

Synthesis and supramolecular self-assembly of glutamic acid-based squaramides

• Juan V. Alegre-Requena,
• Marleen Häring,
• Isaac G. Sonsona,
• Alex Abramov,
• Eugenia Marqués-López,
• Raquel P. Herrera and
• David Díaz Díaz

Beilstein J. Org. Chem. 2018, 14, 2065–2073, doi:10.3762/bjoc.14.180

• gels are typically made of low-molecular-weight (LMW) compounds self-assembled in different solvents via non-covalent interactions. In most cases, this feature enables reversible stimuli-responsive gel-to-sol transitions [31]. Usually, the entanglement of 1D nanofibers of gelator molecules generates a

An amphiphilic pseudo[1]catenane: neutral guest-induced clouding point change

• Tomoki Ogoshi,
• Tomohiro Akutsu and
• Tada-aki Yamagishi

Beilstein J. Org. Chem. 2018, 14, 1937–1943, doi:10.3762/bjoc.14.167

• ; Introduction Thermo-responsive molecules exhibiting a lower critical solution temperature (LCST) are very important for applications such as controlled drug release [1], molecular separation [2], and tissue culture substrates [3]. Poly(N-isopropylacrylamide) (pNIPAAm) is a widely used thermo-responsive polymer

• , which exhibits a clouding point around 32 °C [1][2][3][4]. Recently, thermo-responsive molecules with additional functions have been developed to replace pNIPAAm [5][6][7][8][9][10]. For example, we have developed thermo-responsive macrocyclic molecules which exhibit LCST behavior regulated by host

• -responsive LCST changes are very rare, while there have been some examples of LCST control using ionic chemical stimuli [5][6]. Results and Discussion Supramolecular structure and clouding point of bicyclic compound 3 The bicyclic compound 3 was prepared using a copper(I)-catalyzed alkyne–azide cycloaddition

Graphitic carbon nitride prepared from urea as a photocatalyst for visible-light carbon dioxide reduction with the aid of a mononuclear ruthenium(II) complex

• Kazuhiko Maeda,
• Daehyeon An,
• Ryo Kuriki,
• Daling Lu and
• Osamu Ishitani

Beilstein J. Org. Chem. 2018, 14, 1806–1812, doi:10.3762/bjoc.14.153

• -responsive photocatalyst mostly for H2 evolution from aqueous triethanolamine (TEOA) solution [2][3][5]. The present work also compares the activities for CO2 reduction with those for H2 evolution in order to obtain a better understanding on photocatalytic activities of g-C3N4 for different kinds of