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Intermolecular Aggregation (intermolecular + aggregation)
Selected AbstractsThermoresponsive brush copolymers with poly(propylene oxide- ran -ethylene oxide) side chains via metal-free anionic polymerization "grafting from" techniqueJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2010Junpeng Zhao Abstract Thermoresponsive brush copolymers with poly(propylene oxide- ran -ethylene oxide) side chains were synthesized via a "grafting from" technique. Poly(p -hydroxystyrene) was used as the backbone, and the brush copolymers were prepared by random copolymerization of mixtures of oxyalkylene monomers, using metal-free anionic ring-opening polymerization, with the phosphazene base (t -BuP4) being the polymerization promoter. By controlling the monomer feed ratios in the graft copolymerization, two samples with the same side-chain length and different compositions were prepared, both of which possessed high molecular weights and low molecular weight distributions. The results from light scattering and fluorescence spectroscopy indicated that the brush copolymers in their dilute aqueous solutions were near completely solvated at low temperature and underwent slight intramolecular chain contraction/association and much more profound intermolecular aggregation at different stages of the step-by-step heating process. Above 50 °C, very turbid solutions, followed by macrophase separation, were observed for both of the samples, which implied that it was difficult for the brush copolymers to form stable nanoscopic aggregates at high temperature. All these observations were attributed, at least partly, to the distribution of the oxyalkylene monomers along the side chains and the overall brush-like molecular architecture. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2320,2328, 2010 [source] Solution Behavior of Temperature-Responsive Molecular Brushes Prepared by ATRPMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 1 2007Joanna Pietrasik Abstract Molecular brushes, with side chains consisting of two copolymers: 2-(dimethylamino)ethyl methacrylate with methyl methacrylate, and N,N -dimethylacrylamide with butyl acrylate were prepared by grafting-from via atom transfer radical polymerization (ATRP). Poly(2-(2-bromoisobutyryloxy)ethyl methacrylate) and poly(2-(2-bromopropionyloxy)ethyl methacrylate) were used as macroinitiators. Dynamic light scattering (DLS) studies were performed for aqueous solutions of molecular brushes below and above the lower critical solution temperature (LCST), and an unusual concentration-dependent LCST was observed. Due to the compact structure of molecular brushes, intramolecular collapse can occur when the average distance between molecules is much larger than the hydrodynamic dimensions of the individual macromolecules. However, if the concentration of the solution of molecular brushes is increased to the level in which the separation distance is comparable with the brush hydrodynamic dimensions, intermolecular aggregation occurs, as typically observed for solutions of linear polymers. [source] Kinetics of Demixing and Remixing Transitions in Aqueous Solutions of Poly(N -isopropylacrylamide): A Temperature-Jump 1H NMR StudyMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 21 2006Pavel V. Yushmanov Abstract Summary: The time course of the coil-to-globule collapse and intermolecular aggregation of poly(N -isopropylacrylamide) in aqueous solution upon exceeding the lower critical solution temperature (LCST) are investigated by temperature-jump 1H NMR spectroscopy. After the temperature jump, we record the time dependences of (i) the mobile fraction of the polymer chain as revealed by the intensity of the liquid-like NMR signal, (ii) the local mobility of those chains as revealed by the transverse relaxation time T2, and (iii) their self-diffusion coefficient D. The same data are also reported at their temperature-dependent long-time limits. The results suggest a sudden, faster than one second, collapse and intermolecular aggregation into globules and a slower reorganization/redistribution of the individual chains among and within the globular and mobile states. We found that all molecular changes are reversible if the temperature remains less than ca. 6,8 K above the LCST for less than a few minutes; under those conditions, experiments upon sudden temperature quench below the LCST show that the aggregates disintegrate and swell into coils in less than a few seconds. 1H NMR signal intensity of the methyl groups of 1 wt.-% PNIPAM dissolved in 0.1 M NaCl solution in D2O in a temperature-jump experiment from 300 to 312 K. The data were recorded by the 90°,,,(180°,2, -)n -detection of the CPMG pulse sequence. [source] Advancing the Solid State Properties of Metallo-Supramolecular Materials: Poly(, -caprolactone) Modified , -Conjugated Bis(terpyridine)s and their Zn(II) Based Metallo-PolymersMACROMOLECULAR RAPID COMMUNICATIONS, Issue 20 2008Andreas Winter Abstract A set of rigid , -conjugated bis(terpyridine) macroligands with poly(, -caprolactone) (pCL) on their side chains was synthesized and investigated. The introduced pCL chains gave rise to enhanced processability and film-forming properties of the materials. Blue photoluminescence with high quantum yields was observed in dilute solution and in the solid state, indicating that intermolecular aggregation of the , -conjugated systems was effectively suppressed. The macroligands were further used for coordination with zinc(II) ions leading to new metallo-polymers with high solubility, improved film-forming behavior and promising photophysical properties with respect to potential OLED applications. [source] Thermal denaturation pathway of starch phosphorylase from Corynebacterium callunae: Oxyanion binding provides the glue that efficiently stabilizes the dimer structure of the proteinPROTEIN SCIENCE, Issue 6 2000Richard GrießLer Abstract Starch phosphorylase from Corynebacterium callunae is a dimeric protein in which each mol of 90 kDa subunit contains 1 mol pyridoxal 5,-phosphate as an active-site cofactor. To determine the mechanism by which phosphate or sulfate ions bring about a greater than 500-fold stabilization against irreversible inactivation at elevated temperatures (,50°C), enzyme/oxyanion interactions and their role during thermal denaturation of phosphorylase have been studied. By binding to a protein site distinguishable from the catalytic site with dissociation constants of Ksulfate = 4.5 mM and Kphosphate,16 mM, dianionic oxyanions induce formation of a more compact structure of phosphorylase, manifested by (a) an increase by about 5% in the relative composition of the ,-helical secondary structure, (b) reduced 1H/2H exchange, and (c) protection of a cofactor fluorescence against quenching by iodide. Irreversible loss of enzyme activity is triggered by the release into solution of pyridoxal 5,-phosphate, and results from subsequent intermolecular aggregation driven by hydrophobic interactions between phosphorylase subunits that display a temperature-dependent degree of melting of secondary structure. By specifically increasing the stability of the dimer structure of phosphorylase (probably due to tightened intersubunit contacts), phosphate, and sulfate, this indirectly (1) preserves a functional active site up to, 50°C, and (2) stabilizes the covalent protein cofactor linkage up to , 70°C. The effect on thermostability shows a sigmoidal and saturatable dependence on the concentration of phosphate, with an apparent binding constant at 50°C of , 25 mM. The extra stability conferred by oxyanion-ligand binding to starch phosphorylase is expressed as a dramatic shift of the entire denaturation pathway to a , 20°C higher value on the temperature scale. [source] A Mechanically Interlocked [3]Rotaxane as a Light-Harvesting Antenna: Synthesis, Characterization, and Intramolecular Energy TransferCHEMISTRY - A EUROPEAN JOURNAL, Issue 14 2009Jie-Yu Wang Abstract Mimicking photosynthesis: The concept of light-harvesting by using a mechanically interlocked [3]rotaxane is developed through synthesis and characterization. Our results provide a new candidate for light-harvesting systems and also open up the possibility of creating intelligent or controllable energy-collecting machines (see figure). A mechanically interlocked light-harvesting system [3]rotaxane A has been synthesized in high yield through Cu(I)-catalyzed azide,alkyne cycloaddition; the hexyl-substituted truxene units are introduced into the wheels as donors and an oligo(para -phenylenevinylene) (OPV) unit into the axis as the acceptor. The structure and the purity of [3]rotaxane A were confirmed by 1H and 13C,NMR spectroscopy and ESI HRMS. The azide,alkyne cycloaddition is demonstrated to be an efficient stoppering method in the synthesis of the rotaxane containing dibenzo[24]crown-8 and dibenzyl ammonium units. Detailed steady-state UV/Vis absorption, photoluminescent, and time-resolved fluorescence spectroscopy were performed to investigate the photophysical properties of [3]rotaxane A and its reference compounds in solution and as thin films. Even in dilute solution, efficient energy transfer from the truxene-functionalized wheels to the OPV-based axis, through the dibenzo[24]crown-8 and dibenzyl ammonium interaction, is observed in [3]rotaxane A. The unique topology of [3]rotaxane A not only efficiently promotes the intramolecular energy-transfer process, but also prevents intermolecular aggregation in the solid state. The new antenna system opens up the possibility of controllable light-harvesting molecular machines or other optoelectronic devices on the nanometer scale. [source] | |||||||||||||