Quasielastic light scattering investigation of the isothermal ?helix to extended-coil? transition of poly-L-lysine HBr (original) (raw)

A detailed light scattering study of the polystyrene (PSI in carbon tetrachloride (CC14) solution at various scattering angles and PS concentrations has been carried out. Both static and dynamic light scattering measurements have been made on the solution covering dilute, semidilute, and concentrated concentration regimes. The dynamic light scattering measurement spans a time scale of 10-6-102 s. The static light scattering measurement provides osmotic modulus and static correlation length data at various PS concentrations. The homodyne intensity-intensity time correlation function is single exponential in the dilute concentration regime, but it deviates from single exponential in the semidilute and concentrated concentration regimes. The deviation is interpreted as due to the coupling of the concentration fluctuation to longitudinal stress relaxation modes. With the help of a theory, recently developed in this laboratory, information concerning the cooperative diffusion coefficient, longitudinal stress modulus, the distribution of stress relaxation times, dynamic correlation length, and friction coefficient associated with the concentration fluctuation is obtained as a function of PS concentration. Much of the experimental data for the PS/CC14 system is new.

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Dynamic light scattering studies of poly(methyl methacrylate)–polystyrene copolymers in their theta solvents

Polymer, 2001

The coil-globule transitions of random (statistical) and alternating copolymers of styrene and methyl methacrylate in their theta solvents, cyclohexanol and 2-ethoxy ethanol were studied by using dynamic light scattering technique. The dimensions of the copolymeric chains show smooth and continous contractions below u temperatures. The hydrodynamic size, R h , of a random copolymer P(St-co-MMA) M w 4:59 £ 10 6 g=mol in cyclohexanol u 68:68C decreases to 48% of that in the unperturbed state at 56.58C. This copolymer shows a similar contraction behavior in a second theta solvent 2-ethoxy ethanol u 58:48C: The R h of this copolymer decreases again to 48% of that in the unperturbed state at 45.38C. An alternating copolymer of the same monomers P(St-alt-MMA) M w 2:62 £ 10 6 g=mol displayed a comparable chain contraction. The hydrodynamic size of this sample in cyclohexanol was reduced to 59% of that in the unperturbed state by decreasing temperature from 60.8 to 53.38C. For the random and alternating copolymers studied in this work, the temperature interval from the u-state to the collapsed state is narrower compared to that of the PMMA homopolymer. q

Dynamics of Semirigid Rod Polymers from Experimental Studies

2006

Experimental measurements of static and dynamic properties of non-ionic polymer solutions provide good testing grounds for existing and new models of polymer solution dynamics. We extensively studied aqueous solutions of the high molecular weight, rodlike, semiflexible polymer hydroxypropylcellulose (HPC). Here we present our systematic analysis of measurements of: a) low-shear viscosity η, b) quasi-elastic light scattering spectra of HPC solutions, including mode structure analysis at a range of temperatures and concentrations, c) quasi-elastic light scattering spectra of optical probe particles diffusing through HPC solutions, including careful characterization of modes of diffusive relaxation for tracer particles of different sizes, and d) static light scattering. We found a variety of novel phenomena. (i) The functional dependence of η on concentration has a transition at c + , with disparate small-and large-concentration dependences being seen. For c < c + , η depends on c via a stretched exponential exp(−ac ν) in c ("solution-like" behavior). For c > c + , η depends on c via a power law η ∼ c x with x ≈ 4 ("meltlike" behavior). The viscometric crossover at c + is echoed by the probe diffusion data, confirming the physical reality of the solutionto-meltlike transition. (ii) Optical probe spectra and polymer spectra are both strongly non-exponential and can be decomposed into two or (at larger polymer concentrations) three spectral modes. Mode structure analysis reveals that probe relaxations and polymer relaxations in the same solution sample different aspects of polymer dynamics. (iii) Except for the largest (0.76µm) probes, diffusion coefficients of tracer particles in polymer solutions are not determined by the solution macroscopic viscosity. (iv) At concentrations above c + , light scattering spectra of HPC in solution have an ultraslow relaxational mode. This mode exhibits properties expected for long-lived dynamic structures but not the properties expected for local equilibrium regions of elevated polymer concentration. Properties of the slow mode are consistent with predictions from some models of glass formation. Finally, (v) polymer solutions have a 292 Phillies and Streletzky characteristic dynamic length, which is approximately the hydrodynamic radius of the polymer.

Light Scattering Studies of Polymer Solutions and Melts

Polymer Journal, 1985

Static and dynamic properties of polymer solutions and melts can be investigated by means of modern scattering techniques. While small angle X-ray scattering (SAXS) and smallangle neutron scattering (SANS) have made advances particularly in studies related to the static structure factor S(K), laser light scattering including the use of Fabry-Perot interferometry and photon correlation spectroscopy has become a standard tool in studying polymer molecular motions. In polymer solutions, the main technique is to use measurements of angular distribution of integrated scattered intensity by means of visible light, SAXS or SANS for S(K) and measurements of angular distribution of the spectrum of scattered light by means of photon correlation spectroscopy for the dynamic structure factor, S(K, w). Recent advances have been made in the method of data analysis related to the ill-posed Laplace inversion problem. The new approaches include the singular value decomposition technique and methods of regularization with different criteria for the smoothing operator. By combining static and dynamic light scattering measurements with appropriate algorithms for the Laplace inversion of the time correlation function, a new analytical technique has been developed for polymer molecular weight characterizations. The nonintrusive method has been applied to determine the molecular weight distributions of linear and branched polyethylene in 1,2,4-trichlorobenzene at 135°C and of poly(l,4-phenyleneterephthalamide) in concentrated sulfuric acid. In addition, a new prism light scattering cell is being developed to integrate the above capabilities with chromatographic and other separation techniques. Aside from translational motions of the center of mass of polymers in dilute solution, photon correlation spectroscopy also permits us to investigate rotational, flexual and internal segmental motions. Polymer molecules entangle in semidilute solution. Light-scattering spectroscopy measures a cooperative diffusion coefficient and a slow mode which has been shown to be different in magnitude from the self-diffusion coefficient. The entanglement behavior varies from coils to rod-like polymers. Static and dynamic properties of polymer solutions in semidilute and semiconcentrated regimes can be related to those of bulk polymer melts where measurements of polarized Rayleigh-Brillouin spectra and depolarized Rayleigh spectra yield information on localized structural relaxation and collective segmentallmolecular orientational motions. Relaxation times covering a very broad frequency range will be discussed.

Dynamics of Flexible Coils in an Isorefractive Rod/Coil Composite Liquid. 1. Binary Polystyrene/Solvent Solutions

Macromolecules, 1994

Dynamic light scattering (DLS) and static light scattering (SLS) were used to characterize the structure and dynamics of solutions of polystyrene of molecular weight 390 OOO in 1,1,2,2-tetrachloroethane. Mutual diffusion coefficients were determined as functions of concentration and temperature. The diffusion virial coefficients were determined and compared to several theoretical predictions. The DLS intensity autocorrelation function was also carefully examined for the possible presence of fast modes in order to provide a comparison to polystyrene studied in ternary solutions including a rodlike polymer (paper 2). 11. Experimental Section Sample Preparation. The polystyrene was purchased from Pressure Chemical Corp. with stated molecular weight 390 000,

Effect of the monomer structure on the dynamics of semidilute polyalkylmethacrylate solutions: A quasielastic light and neutron scattering investigation

The Journal of Chemical Physics, 2002

The study of the microscopic origin of the slow relaxation modes in the autocorrelation functions of some entangled polymer solutions has recently given rise to much experimental and theoretical work. The aim is to highlight the role of concentration, molecular weight, and temperature on the slow modes and to what extent the entanglement phenomena are responsible for their appearance. The present work reports on the comparison between the dynamics of homologous polymers with different side unit lengths, by use of quasi-elastic light and neutron scattering. The investigation, carried out on both mesoscopic and microscopic scales, with different concentrations and chain lengths, evidenced different dynamical properties in the three polymer solutions. In particular, longer side chains give rise to a bigger volume excluded to the other segments, obstructing the entanglements responsible for the slow relaxation modes and favoring the mobility of segments.

Dynamic light scattering study of a 1,4-isoprene-b-styrene copolymer

2000

Local optical anisotropy fluctuations within polystyrene (PS)-rich region in a disordered 1,4-isoprene-b-styrene (PI-b-PS) copolymer with XN≈5.3 (N=44) and glass transition temperature T g=13°C were analyzed by photon correlation spectroscopy (PCS) over a broad time range (10−7−103 s). There is strong experimental evidence that composition fluctuations in the present system can affect the segmental orientational fluctuations of the two foreign blocks.

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