Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Effect of ring rize on photoisomerization properties of stiff stilbene macrocycles.

ABSTRACT: A series of stiff stilbene macrocycles have been studied to investigate the possible impact of the macrocycle ring size on their photodynamic properties. The results show that reducing the ring size counteracts the photoisomerization ability of the macrocycles. However, even the smallest macrocycle studied (stiff stilbene subunits linked by a six carbon chain) showed some degree of isomerization when irradiated. DFT calculations of the energy differences between the E- and Z-isomers show the same trend as the experimental results. Interestingly the DFT study highlights that the energy difference between the E- and Z-isomers of even the largest macrocycle (linked by a twelve carbon chain) is significantly higher than that of the stiff stilbene unit itself. In general, it is indicated that addition of even a flexible chain to the stiff stilbene unit may significantly affect its photochemical properties and increase the photostability of the resulting macrocycle.

SUBMITTER: Olsson S

PROVIDER: S-EPMC6808211 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Effect of ring rize on photoisomerization properties of stiff stilbene macrocycles.

Olsson Sandra S Benito Pérez Óscar Ó Blom Magnus M Gogoll Adolf A

Beilstein journal of organic chemistry 20191011

A series of stiff stilbene macrocycles have been studied to investigate the possible impact of the macrocycle ring size on their photodynamic properties. The results show that reducing the ring size counteracts the photoisomerization ability of the macrocycles. However, even the smallest macrocycle studied (stiff stilbene subunits linked by a six carbon chain) showed some degree of isomerization when irradiated. DFT calculations of the energy differences between the <i>E</i>- and <i>Z</i>-isomer ...[more]

PMID: 31666875

Similar Datasets

Photoinduced Strain-Assisted Synthesis of a Stiff-Stilbene Polymer by Ring-Opening Metathesis Polymerization.

Project description:Developing a novel strategy to synthesize photoresponsive polymers is of significance owing to their potential applications. We report a photoinduced strain-assisted synthesis of main-chain stiff-stilbene polymers by using ring-opening metathesis polymerization (ROMP), activating a macrocyclic π-bond connected to a stiff-stilbene photoswitch through a linker. Since the linker acts as an external constraint, the photoisomerization to the E-form leads to the stiff-stilbene being strained and thus reactive to ROMP. The photoisomerization of Z-form to E-form was investigated using time-dependent NMR studies and UV/Vis spectroscopy. The DFT calculation showed that the E-form was less stable due to a lack of planarity. By the internal strain developed due to the linker constraint through photoisomerization, the E-form underwent ROMP by a second generation Grubbs catalyst. In contrast, Z-form did not undergo polymerization under similar conditions. The MALDI-TOF spectrum of E-form after polymerization showed the presence of oligomers of >5.2 kDa.

| S-EPMC7756494 | biostudies-literature

Photoinduced transformations of stiff-stilbene-based discrete metallacycles to metallosupramolecular polymers.

Project description:Control over structural transformations in supramolecular entities by external stimuli is critical for the development of adaptable and functional soft materials. Herein, we have designed and synthesized a dipyridyl donor containing a central Z-configured stiff-stilbene unit that self-assembles in the presence of two 180° di-Pt(II) acceptors to produce size-controllable discrete organoplatinum(II) metallacycles with high efficiency by means of the directional-bonding approach. These discrete metallacycles undergo transformation into extended metallosupramolecular polymers upon the conformational switching of the dipyridyl ligand from Z-configured (0°) to E-configured (180°) when photoirradiated. This transformation is accompanied by interesting morphological changes at nanoscopic length scales. The discrete metallacycles aggregate to spherical nanoparticles that evolve into long nanofibers upon polymer formation. These fibers can be reversibly converted to cyclic oligomers by changing the wavelength of irradiation, which reintroduces Z-configured building blocks owing to the reversible nature of stiff-stilbene photoisomerization. The design strategy defined here represents a novel self-assembly pathway to deliver advanced supramolecular assemblies by means of photocontrol.

| S-EPMC4066485 | biostudies-literature

Reversible Photoisomerization of Monolayers of π-Expanded Oligothiophene Macrocycles at Solid-Liquid Interfaces.

Project description:Self-assembled monolayers of a π-expanded oligothiophene macrocycle undergo photoisomerization between their Z,Z and E,E diastereomers at the interface between octanoic acid solutions and highly oriented pyrolytic graphite (HOPG). The switching process proceeds in situ at the solid-liquid interface and was followed by scanning tunneling microscopy (STM). Upon illumination with light at 365 nm (546 nm), a monolayer of Z,Z-8mer (E,E-8mer) photoisomerizes to the E,E-8mer (Z,Z-8mer) form with changes in 2D hexagonal packing. These findings provide insight towards the design of photoresponsive surfaces with desirable optoelectronic and structural (host-guest) properties.

| S-EPMC6582435 | biostudies-literature

Photomodulation of Transmembrane Transport and Potential by Stiff-Stilbene Based Bis(thio)ureas.

Project description:Membrane transport proteins fulfill important regulatory functions in biology with a common trait being their ability to respond to stimuli in the environment. Various small-molecule receptors, capable of mediating transmembrane transport, have been successfully developed. However, to confer stimuli-responsiveness on them poses a fundamental challenge. Here we demonstrate photocontrol of transmembrane transport and electric potential using bis(thio)ureas derived from stiff-stilbene. UV-vis and 1H NMR spectroscopy are used to monitor E-Z photoisomerization of these bis(thio)ureas and 1H NMR titrations reveal stronger binding of chloride to the (Z)-form than to the (E)-form. Additional insight into the binding properties is provided by single crystal X-ray crystallographic analysis and DFT geometry optimization. Importantly, the (Z)-isomers are much more active in transmembrane transport than the respective (E)-isomers as shown through various assays. As a result, both membrane transport and depolarization can be modulated upon irradiation, opening up new prospects toward light-based therapeutics as well as physiological and optopharmacological tools for studying anion transport-associated diseases and to stimulate neuronal activity, respectively.

| S-EPMC8759083 | biostudies-literature

Push-Pull Stiff-Stilbene: Proton-Gated Visible-Light Photoswitching and Acid-Catalyzed Isomerization.

Project description:Donor-acceptor substituted stiff-stilbene is shown to undergo isomerization induced by visible light avoiding the need for harmful UV light. This visible-light photoswitching is inhibited by protonation of the dimethylamino-donor unit, disrupting the push-pull character and thus, gating of the photochromic properties is allowed by acid/base addition. Remarkably, the addition of a mild acid also triggers fast thermal back-isomerization, which is unprecedented for stiff-stilbene photoswitches usually having a very high energy barrier for this process. These combined features offer unique orthogonal control over switching behavior by light and protonation, which is investigated in detail by 1 H NMR and UV/Vis spectroscopy. In addition, TD-DFT calculations are used to gain further insight into the absorption properties. Our results will help elevating the level of control over dynamic behavior in stiff-stilbene applications.

| S-EPMC9298359 | biostudies-literature

A Photoresponsive Stiff-Stilbene Ligand Fuels the Reversible Unfolding of G-Quadruplex DNA.

Project description:The polymorphic nature of G-quadruplex (G4) DNA structures points to a range of potential applications in nanodevices and an opportunity to control G4 in biological settings. Light is an attractive means for the regulation of oligonucleotide structure as it can be delivered with high spatiotemporal precision. However, surprisingly little attention has been devoted towards the development of ligands for G4 that allow photoregulation of G4 folding. We report a novel G4-binding chemotype derived from stiff-stilbene. Surprisingly however, whilst the ligand induces high stabilization in the potassium form of human telomeric DNA, it causes the unfolding of the same G4 sequence in sodium buffer. This effect can be reversed on demand by irradiation with 400 nm light through deactivation of the ligand by photo-oxidation. By fuelling the system with the photolabile ligand, the conformation of G4 DNA was switched five times.

| S-EPMC6563076 | biostudies-literature

Photocontrol of Anion Binding Affinity to a Bis-urea Receptor Derived from Stiff-Stilbene.

Project description:Toward the development of photoresponsive anion receptors, a stiff-stilbene photoswitch has been equipped with two urea anion-binding motifs. Photoinduced E/Z isomerization has been studied in detail by UV-vis and NMR spectroscopy. Titration experiments (1H NMR) reveal strong binding of acetate and phosphate to the (Z)-isomer, in which the urea groups are closely together. Isomerization to the (E)-form separates the urea motifs, resulting in much weaker binding. Additionally, geometry optimizations by density functional theory (DFT) illustrate that oxo-anion binding to the (Z)-form involves four hydrogen bonds.

| S-EPMC5330661 | biostudies-literature

Modulation of a Supramolecular Figure-of-Eight Strip Based on a Photoswitchable Stiff-Stilbene.

Project description:The preparation, assembly and dynamic properties of photoswitchable bisphosphine ligands based on the stiff-stilbene scaffold are reported. Directional bonding and coordination-induced assembly allow complexation of these ligands with palladium(II), resulting in the formation of discrete metallo-supramolecular entities. While the Z isomer forms a simple bidentate metallo-macrocycle, an intricate double helicate figure-of-eight dimer is observed with the E ligand. Topologically 3D complexes can thus be obtained from 2D ligands. Upon irradiation with UV light, isomerization of the ligands allows control of the architecture of the formed complexes, resulting in a light-triggered modulation of the supramolecular topology. Furthermore, a mechanistic investigation unveiled the dynamic nature of the helicate chirality, where a transmission of motion from the palladium centers yields an "eight-to-eight" inversion.

| S-EPMC7384132 | biostudies-literature

Stiff-Stilbene Ligands Target G-Quadruplex DNA and Exhibit Selective Anticancer and Antiparasitic Activity.

Project description:G-quadruplex nucleic acid structures have long been studied as anticancer targets whilst their potential in antiparasitic therapy has only recently been recognized and barely explored. Herein, we report the synthesis, biophysical characterization, and in vitro screening of a series of stiff-stilbene G4 binding ligands featuring different electronics, side-chain chemistries, and molecular geometries. The ligands display selectivity for G4 DNA over duplex DNA and exhibit nanomolar toxicity against Trypasanoma brucei and HeLa cancer cells whilst remaining up to two orders of magnitude less toxic to non-tumoral mammalian cell line MRC-5. Our study demonstrates that stiff-stilbenes show exciting potential as the basis of selective anticancer and antiparasitic therapies. To achieve the most efficient G4 recognition the scaffold must possess the optimal electronics, substitution pattern and correct molecular configuration.

| S-EPMC7318697 | biostudies-literature

Design, synthesis and bioactive properties of a class of macrocycles with tunable functional groups and ring size.

Project description:The design and synthesis of a versatile class of macrocycles with tunable functional groups and ring size are unfolded. Herein, a synthetic strategy is reported to furnish a new class of macrocycles in multi-gram scale in a two-step reaction. The total time taken for synthesizing a macrocycle is 1.5 h. Dithiocarbamates, an important functional group in biomedical and material sciences, is strategically incorporated in the macrocyclic backbone without metal for the first time. It is noteworthy that when state-of-the-art macrocycle synthesis is in millimolar concentration, this work employs the reaction in molar concentration (0.2-0.4 M). As proof-of-principle, a library of macrocycles was synthesized, varying the functional groups and ring size. The physicochemical properties of macrocycles revealed their druggable nature and are affirmed by protein (serum albumin) interaction study theoretically and experimentally. Diverse functional groups and ring sizes of macrocycles brought about twenty-five-fold difference in binding constant with the model protein.

| S-EPMC8938452 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data