Search results for "Supramolecular"

Enhancement of metallo-supramolecular dissociation kinetics in telechelic terpyridine-capped poly(ethylene glycol) assemblies in the semi-dilute regi…

2019

The dynamics of supramolecular polymer assemblies is governed by that of their polymeric building blocks and that of the transient bonds between them. Entrapment of such bonds by topological crowding often causes renormalization of the bond lifetimes towards prolonging. In the present study, by contrast, we show that this effect can also be inverse in the case of telechelic metallo-supramolecular polymers in semi-dilute solution. We focus on linear poly(ethylene glycols) capped by terpyridine binding motifs at both ends that can form metal–ligand coordinative bonds with various transition metal ions, thereby creating transient metallo-supramolecular assemblies of varying length and binding …

Emergence, evidence, and effect of junction clustering in supramolecular polymer materials

2021

A significant fraction of biomaterials consists of supramolecular polymers and networks formed by non-covalent interactions between associative motifs. They typically contain complex structures in which on top of binary associations, phase-separation and aggregation of associative junctions occur. Such hierarchical assemblies have significant influences on the dynamics as well as the physical and mechanical properties of the materials. Similar to supramolecular biomaterials, aggregation of associative junctions has also been frequently reported to occur in synthetic supramolecular polymers and networks. Engineering of such secondary structures in a sense to create and control the extent of …

Tuneable Transient Thermogels Mediated by a pH- and Redox-Regulated Supramolecular Polymerization.

2017

A multistimuli-responsive transient supramolecular polymerization of β-sheet-encoded dendritic peptide monomers in water is presented. The amphiphiles, which contain glutamic acid and methionine, undergo a glucose oxidase catalyzed, glucose-fueled transient hydrogelation in response to an interplay of pH and oxidation stimuli, promoted by the production of reactive oxygen species (ROS). Adjusting the enzyme and glucose concentration allows tuning of the assembly and the disassembly rates of the supramolecular polymers, which dictate the stiffness and transient stability of the hydrogels. The incorporation of triethylene glycol chains introduces thermoresponsive properties to the materials. …

Electrospray ion mobility mass spectrometry of positively charged sodium bis[2-ethythexyl)sulfosuccinate aggregates.

2014

Collision cross-sections (CCS) of positively singly and multiply charged aggregates of the surfactant sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) in the gas phase have been measured by quadrupole ion mobility time-of-flight mass spectrometry. Calibration of the observed drift times to the CCS of the AOTNa non-covalent aggregates was achieved by collecting, under the same experimental conditions, the drift times of a range of singly and multiply charged polyalanine peptides whose CCS had been obtained by conventional ion mobility spectrometry. Together with an obvious increase of the aggregate cross-section with the aggregation number, it was found that the aggregate cross-section increa…

The dynamic orientation of membrane-bound peptides: bridging simulations and experiments.

2007

AbstractThe structural organization in a peptide/membrane supramolecular complex is best described by knowledge of the peptide orientation plus its time-dependent and spatial fluctuations. The static orientation, defined by the peptide tilt and a rotation about its molecular axis, is accessible through a number of spectroscopic methods. However, peptide dynamics, although relevant to understand the functionality of these systems, remains largely unexplored. Here, we describe the orientation and dynamics of Trp-flanked and Lys-flanked hydrophobic peptides in a lipid bilayer from molecular dynamics simulations. A novel view is revealed, where collective nontrivial distributions of time-evolvi…

Cooperative supramolecular polymerization and amplification of chirality in C3-symmetrical OPE-based trisamides.

2011

Sergeants-and-soldiers experiments demonstrate the amplification of chirality that transforms the racemic mixture of helical columns formed from OPE-based trisamides into enantiomerically enriched helical structures (see scheme).The cooperative supramolecular polymerization of the trisamides is investigated by theoretical calculations and temperature-dependent UV/Vis and CD experiments. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dominance of Chain Entanglement over Transient Sticking on Chain Dynamics in Hydrogen-Bonded Supramolecular Polymer Networks in the Melt

2018

The chain dynamics in supramolecular polymer networks is determined by the interplay of the kinetics of transient interchain association and relaxation of the network chains themselves. This interplay can be addressed by studying model supramolecular polymer networks in which the number of associative side groups and the molar mass of the covalently jointed backbone polymers are both varied systematically. To realize this idea, we use precursor chains with three different molar masses, which comes along with different extents of entanglement in the melt state. For each molar mass, the precursor polymers are functionalized with three different relative contents of associative side groups, gi…

1995

Supramolecular structures based on 4-(3,5-dioxo-1,2,4-triazolidin-4-yl) benzoic acid (U4A) units act as effective junction zones in functionalized polybutadienes, resulting in the formation of thermoplastic elastomers. The dynamics on a molecular scale of the phenyl rings have been probed by 2H-NMR. In the polymeric system, there are three spatially separated environments, which are reflected in the mobility of the polar units. Phenyl rings which are incorporated in the structures are either rigid or undergo 180° phenyl flips. The small fraction of free functional groups move isotropically and their mobility is coupled to the dynamics of the polybutadiene matrix. In two model compounds, whe…

Indanedione based binary chromophore supramolecular systems as a NLO active polymer composites

2010

Novel route to obtain EO material is proposed by supramolecular assembly of neutral-ground-state (NGS) and zwitterionic (ZWI) NLO chromophores in binary chromophore organic glass (BCOG) host–guest system. On a basis of our Langeven Dynamics (LD) molecular modeling combined with quantum chemical calculations, we have shown that anticipated enhancement NLO efficiency of BCOG material is possible via electrostatic supramolecular assembly of NGS with ZWI chromophore in antiparallel manner. Binding energy of such complex could be more dependent on molecular compatibility of components and local (atomic) charge distribution, then overall molecular dipole moments. According to our LD simulations t…

Polymeric gegenions induced variability and mobility of amphiphilic supramolecular structures on solid substrates

1992

Abstract The micromorphological variations of amphiphilic L -glutamate derivatives at air-substrate interfaces due to an adjacent mobile polymer matrix have been investigated via fluorescence microscopy. Adjusted monolayers of the L -glutamate derivatives have been transferred by LB technique out of different aggregation states onto various substrates. The substrates have been prepared by successive polymer preadsorption to the solid support. The influence of the adjacent polymer layers on the domain morphology as a function of water content and temperature has been examined intensively. Moreover, reversible domain changes induced by temperature variation of the transferred films have been …