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Towards photoswitchable quadruple hydrogen bonds via a reversible "photolocking" strategy for photocontrolled self-assembly.

ABSTRACT: Developing new photoswitchable noncovalent interaction motifs with controllable bonding affinity is crucial for the construction of photoresponsive supramolecular systems and materials. Here we describe a unique "photolocking" strategy for realizing photoswitchable control of quadruple hydrogen-bonding interactions on the basis of modifying the ureidopyrimidinone (UPy) module with an ortho-ester substituted azobenzene unit as the "photo-lock". Upon light irradiation, the obtained Azo-UPy motif is capable of unlocking/locking the partial H-bonding sites of the UPy unit, leading to photoswitching between homo- and heteroquadruple hydrogen-bonded dimers, which has been further applied for the fabrication of novel tunable hydrogen bonded supramolecular systems. This "photolocking" strategy appears to be broadly applicable in the rational design and construction of other H-bonding motifs with sufficiently photoswitchable noncovalent interactions.

SUBMITTER: Wei L

PROVIDER: S-EPMC8179285 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Photocontrolled reversible self-assembly of dodecamer nitrilase.

Project description:BackgroundNaturally photoswitchable proteins act as a powerful tool for the spatial and temporal control of biological processes by inducing the formation of a photodimerizer. In this study, a method for the precise and reversible inducible self-assembly of dodecamer nitrilase in vivo (in Escherichia coli) and in vitro (in a cell-free solution) was developed by means of the photoswitch-improved light-inducible dimer (iLID) system which could induce protein-protein dimerization.ResultsNitrilase was fused with the photoswitch protein AsLOV2-SsrA to achieve the photocontrolled self-assembly of dodecamer nitrilase. The fusion protein self-assembled into a supramolecular assembly when illuminated at 470 nm. Scanning electron microscopy showed that the assembly formed a circular sheet structure. Self-assembly was also induced by light in E. coli. Dynamic light scattering and turbidity assay experiments showed that the assemblies formed within a few seconds under 470-nm light and completely disassembled within 5 min in the dark. Assembly and disassembly could be maintained for at least five cycles. Both in vitro and in vivo, the assemblies retained 90% of the initial activity of nitrilase and could be reused at least four times in vitro with 90% activity.ConclusionsAn efficient method was developed for the photocontrolled assembly and disassembly of dodecamer nitrilase and for scaffold-free reversible self-assembly of multiple oligomeric enzymes in vivo and in vitro, providing new ideas and methods for immobilization of enzyme without carrier.

| S-EPMC5544783 | biostudies-literature

Reversible Photocontrolled Nanopore Assembly.

Project description:Self-assembly is a fundamental feature of biological systems, and control of such processes offers fascinating opportunities to regulate function. Fragaceatoxin C (FraC) is a toxin that upon binding to the surface of sphingomyelin-rich cells undergoes a structural metamorphosis, leading to the assembly of nanopores at the cell membrane and causing cell death. In this study we attached photoswitchable azobenzene pendants to various locations near the sphingomyelin binding pocket of FraC with the aim of remote controlling the nanopore assembly using light. We found several constructs in which the affinity of the toxin for biological membranes could be activated or deactivated by irradiation, thus enabling reversible photocontrol of pore formation. Notably, one construct was completely inactive in the thermally adapted state; it however induced full lysis of cultured cancer cells upon light irradiation. Selective irradiation also allowed isolation of individual nanopores in artificial lipid membranes. Photocontrolled FraC might find applications in photopharmacology for cancer therapeutics and has potential to be used for the fabrication of nanopore arrays in nanopore sensing devices, where the reconstitution, with high spatiotemporal precision, of single nanopores must be controlled.

| S-EPMC6743218 | biostudies-literature

How Robust Is the Reversible Steric Shielding Strategy for Photoswitchable Organocatalysts?

Project description:A highly appealing strategy to modulate a catalyst's activity and/or selectivity in a dynamic and noninvasive way is to incorporate a photoresponsive unit into a catalytically competent molecule. However, the description of the photoinduced conformational or structural changes that alter the catalyst's intrinsic reactivity is often reduced to a handful of intuitive static representations, which can struggle to capture the complexity of flexible organocatalysts. Here, we show how a comprehensive exploration of the free energy landscape of N-alkylated azobenzene-tethered piperidine catalysts is essential to unravel the conformational characteristics of each configurational state and explain the experimentally observed reactivity trends. Mapping the catalysts' conformational space highlights the existence of false ON or OFF states that lower their switching ability. Our findings expose the challenges associated with the realization of a reversible steric shielding for the photocontrol of Brønsted basicity of piperidine photoswitchable organocatalysts.

| S-EPMC9295146 | biostudies-literature

Axial chiral bisbenzophenazines: solid-state self-assembly via halide hydrogen bonds triggered by linear alkanes.

Project description:An axial chiral tetrachlorinated bisbenzo[a]phenazine has been discovered that undergoes an alkane-induced shift in the solid state from a disordered amorphous form to an ordered polycrystalline form. This phase transition is caused by the formation of pores that accommodate linear alkanes of varying lengths with a very strong affinity as judged by differential scanning calorimetry. Single crystal X-ray structure analysis revealed that a series of weak phenolic OH···Cl hydrogen bonds dictates the pore structure. These weak interactions can be disrupted mechanically, causing the material to revert to the amorphous form. Notably, the interchange between the amorphous and crystalline forms is readily reversible and is easily observed by characteristic colorimetric changes. Measurements via photoimage processing reveal that the degree of color change is dictated by the type of alkane employed.

| S-EPMC4353019 | biostudies-literature

Synthesis and Photocontrolled Supramolecular Self-Assembly of Azobenzene-Functionalized Perylene Bisimide Derivatives.

Project description:Azobenzene (Azo) units were successfully introduced into perylene bisimide (PBI) structures in order to realize the photocontrolling of the morphology of the supramolecular assembly of PBI by a photoisomerization process. A total of three Azo-functionalized perylene bisimide derivatives (PBI1, PBI2, and PBI3) with different alkyl chain lengths were designed and synthesized by imidization of 3,4,9,10-perylene tetracarboxylic dianhydride with the corresponding amines. The structures of these compounds were characterized by proton nuclear magnetic resonance (1H NMR) and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The photoisomerization behaviors of Azo units in PBIs were investigated using ultraviolet-visible (UV-VIS) absorption spectroscopy, which were obviously effected by solvents and the alkyl chain length. Furthermore, the photoisomerization of Azo units has the obviously regulatory effect on the morphology of supramolecular assembly of PBIs, especially for the medium-length alkyl chain-linked Azo-functionalized PBI derivative (PBI2). This research realized the photocontrolling of the morphology of the supramolecular assembly of PBI derivatives by photoisomerization of Azo units.

| S-EPMC6681406 | biostudies-literature

Reversible self-assembly of superstructured networks.

Project description:Soft structures in nature, such as protein assemblies, can organize reversibly into functional and often hierarchical architectures through noncovalent interactions. Molecularly encoding this dynamic capability in synthetic materials has remained an elusive goal. We report on hydrogels of peptide-DNA conjugates and peptides that organize into superstructures of intertwined filaments that disassemble upon the addition of molecules or changes in charge density. Experiments and simulations demonstrate that this response requires large-scale spatial redistribution of molecules directed by strong noncovalent interactions among them. Simulations also suggest that the chemically reversible structures can only occur within a limited range of supramolecular cohesive energies. Storage moduli of the hydrogels change reversibly as superstructures form and disappear, as does the phenotype of neural cells in contact with these materials.

| S-EPMC6420308 | biostudies-literature

Enhancement of beta-sheet assembly by cooperative hydrogen bonds potential.

Project description:MotivationThe roughness of energy landscapes is a major obstacle to protein structure prediction, since it forces conformational searches to spend much time struggling to escape numerous traps. Specifically, beta-sheet formation is prone to stray, since many possible combinations of hydrogen bonds are dead ends in terms of beta-sheet assembly. It has been shown that cooperative terms for backbone hydrogen bonds ease this problem by augmenting hydrogen bond patterns that are consistent with beta sheets. Here, we present a novel cooperative hydrogen-bond term that is both effective in promoting beta sheets and computationally efficient. In addition, the new term is differentiable and operates on all-atom protein models.ResultsEnergy optimization of poly-alanine chains under the new term led to significantly more beta-sheet content than optimization under a non-cooperative term. Furthermore, the optimized structure included very few non-native patterns.AvailabilityThe new term is implemented within the MESHI package and is freely available at http://cs.bgu.ac.il/ approximately meshi.

| S-EPMC3140807 | biostudies-literature

Two-dimensional crystal engineering using halogen and hydrogen bonds: towards structural landscapes.

Project description:Two-dimensional (2D) crystallization on solid surfaces is governed by a subtle balance of supramolecular and interfacial interactions. However, these subtle interactions often make the prediction of supramolecular structure from the molecular structure impossible. As a consequence, surface-based 2D crystallization has often been studied on a case-by-case basis, which hinders the identification of structure-determining relationships between different self-assembling systems. Here we begin the discussion on such structure-determining relationships by comparing the 2D crystallization of two identical building blocks based on a 1,3,5-tris(pyridine-4-ylethynyl)benzene unit at the solution-solid interface. The concepts of supramolecular synthons and structural landscapes are introduced in the context of 2D crystallization on surfaces to identify common structural elements. The systems are characterized using scanning tunneling microscopy (STM). This strategy involves carrying out minor structural modifications on the parent compound to access supramolecular patterns that are otherwise not obtained. We demonstrate that this chemical perturbation strategy translates equally well for 2D co-crystallization experiments with halogen bond donors yielding porous bi-component networks. The holistic approach described here represents a stepping stone towards gaining predictive power over the 2D crystallization of molecules on solid surfaces.

| S-EPMC5427994 | biostudies-literature

Reversible self-assembly of gels through metal-ligand interactions

Project description:Metal-ligand interactions with various proteins form in vivo metal assemblies. In recent years, metallosupramolecular approaches have been utilized to forge an assortment of fascinating two- and three-dimensional nano-architectures, and macroscopic materials, such as metal-ligand coordination polymeric materials, have promise in artificial systems. However to the best of our knowledge, the self-assembly of macroscopic materials through metal-ligand interactions has yet to be reported. Herein we demonstrate a gel assembly formed via metal-ligand interactions using polyacrylamide modified with Fe-porphyrin and L-histidine moieties. The stress values for the assembly increase as the concentration of Fe-porphyrin or L-histidine in the gels increases. Moreover, agitation of Fe-porphyrin gel, Zn-porphyrin gel, and L-histidine gel in an 80?mM Tris-acetate buffer (pH 9.0) results in selective adhesion of the Fe-porphyrin gel to the L-histidine gel based on the affinities of Fe-porphyrin and Zn-porphyrin with L-histidine.

| S-EPMC4071618 | biostudies-literature

Magnetic nanosensors optimized for rapid and reversible self-assembly.

Project description:Magnetic nanoparticle-based sensors for MRI have been accelerated to a timescale of seconds using densely-functionalized particles of small size. Parameters that increase response rates also result in large nuclear magnetic relaxation rate and light scattering changes, allowing signals to be detected almost immediately after changes in calcium concentration.

| S-EPMC5489245 | biostudies-literature

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