Front Chem
December 2022
The quantitative description of the supramolecular interaction occurring at the adhesion surfaces of different polymers has enabled elaborate dissections of contributions to cohesive and surface energies. An alternative analysis is proposed here based on solubility parameters and binding constants that traditionally describe the weakest and relatively larger association energies in polymer blends. The article emphasizes a feature of supramolecular polymers that has not received adequate consideration: The dynamic bond scrambling that allows a most efficient molecular recognition over significant areas of synthetic and biological surfaces.
View Article and Find Full Text PDFSoft Matter
October 2021
Chemical and shape recognition are the main assembling mechanisms of complex bio-structures. A refined assessment of relevant thermodynamic parameters includes the consideration of a variety of contributions from different molecular motions and electronic interactions. An additional refinement includes the analysis of recognition involving multiple distant partners.
View Article and Find Full Text PDFWhereas economists do not traditionally address social harmony, and sociologists or political scientists do not usually tackle economic development, the interaction of social harmony and economic development has recently become an object of intense concern. In their aim to foster evolved rather than uprooted cultural values, the authors of this research note suggest an educational approach to promote the concept and the implementation of what they refer to as . They propose interdisciplinary courses that include notions of history, sociology and economy.
View Article and Find Full Text PDFSelf-assembling may be defined as the spontaneous association of material units into structures that are often capable of cyclic reorganization and functional behavior. Various molecular recognition processes stabilize assemblies of polymers and biological structures. The present article analyzes cases in which chemical, shape and other recognition mechanisms are individually or cooperatively operative.
View Article and Find Full Text PDFWe compare steps observed during the fibrillogenesis of myofibrils with the sequence of steps predictable by a recent analysis of the structurization and functioning of striated muscles. The predicted assembly steps are based solely on fundamental equilibrium processes, particularly supramolecular interactions and liquid crystalline alignment of the rigid thick and thin filaments hosted within the sarcomer. Satisfactory agreement is obtained between several of the observed and the predicted fibrillogenesis steps.
View Article and Find Full Text PDFExtended linear structures self-assemble by the multi-stage-open-association mechanism of supramolecular polymerization (MSOA). Application of the model requires the identification of a repeating unit, the main-chain supramolecular bond, and the binding constant. The strength of the bond and the degree of polymerization become extremely large when multiple sites for non-covalent interactions occur.
View Article and Find Full Text PDFA novel approach to the description of the assembly mechanism of functional biological structures is presented. The approach is based on the identification of fundamental self-assembling processes to which an additional structurization "engineered" by Nature to optimize functions is superimposed. Application of the approach to the structure and contraction of the striated muscle evidences a key role of the residual liquid crystallinity of a constrained structure and the alteration of the compatibility between the thin and thick filaments driven by ionic interactions.
View Article and Find Full Text PDFPurely ionic interactions in natural and synthetic macromolecules involve the mutual interaction of fixed charges and their interaction with mobile ions. Such charge-dependent interactions lead to well-documented effects, including chain expansion of polyelectrolytes, globularization of polyampholytes, distributions of mobile ions according to charge screening, or ion condensation models. A variety of structural features, functions, and applications of these systems is amplified by the superimposition of charge-independent effects associated with the occurrence of less polar or hydrophobic groups, special salts, surfactants, or complementary protein assemblies.
View Article and Find Full Text PDFDynamic networks (DNs) recently reported in the literature are based on cross-linked supramolecular chains or on covalent chains with reversible bonds. As originally pointed out by Lehn, these networks should be regarded as dynamic materials exhibiting adaptive features due to continuous scrambling of their bonds and sequences. Results in the recent literature reveal that these networks undergo reversible long-range deformation resembling that of rubber networks.
View Article and Find Full Text PDFCohesion matters! The correlation between the conformational rigidity of the polyelectrolyte and the size and stability of the globular assembly is discussed in this review article. Some examples of models for the association of polyelectrolytes to globular assemblies are shown here.Supramolecular complexes of strong polyelectrolytes and oppositely charged ionic micelles or protein assemblies derive their main stabilization from electrostatic interactions that include the counterion condensation/release mechanism and from hydrophobic interactions distributed along apolar sections of the components.
View Article and Find Full Text PDFBiopolymers
August 2008
The thermodynamic framework and recent molecular descriptions of protein-salt interactions are critically reviewed. A reanalysis of earlier and recent data describing the role of salts on the thermal stability of collagen I over a wide range of concentration evidences the complex encroachment of charge-dependent and charge-independent interactions. Charge-independent interactions, operationally quantified by dilution parameters and association constants, are found to be the overriding factor for the large stabilization observed with nonbinding salts and for the large destabilization observed when strong salt binding occurs.
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