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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 4321-4325 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The inclusion behavior between molecular nanotubes and linear polymer chains in aqueous solutions is experimentally investigated by measuring the optical absorption spectra of the solutions with iodine as a probe. It is found that the amount of polymer chains included into nanotubes increases with polymer length, which indicates a molecular recognition of the nanotube for the polymer length in the complex formation. Furthermore, the experimental results are compared with a theory based on the Flory–Huggins lattice model. They are in good agreement with each other and the inclusion energy between the molecular nanotube and the linear polymer chain is evaluated. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new measurement method for second-order nonlinear after-effect function has been developed. Theoretical calculation starting from a general time-evolution equation connects nonlinear responses in time domain and frequency domain and thus gives the nonlinear response to applied external field of arbitrary form. In addition, it turns out in the frequency domain that the dc component of a second-order nonlinear response function corresponds to a linear response function. For example, the dc component of the electric birefringence relaxation is equivalent to the dielectric relaxation. This simple relation indicates an advantage of a frequency-domain measurement for nonlinear responses. As an example, the electric birefringence relaxation is measured in two-dimensional frequency domain for aqueous solution of sodium poly(styrenesulfonate) to confirm the validity of the theoretical results. © 1999 American Institute of Physics.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 10330-10337 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Using dynamic light scattering, we investigated supersaturated aqueous solutions of hen egg white lysozyme. We could observe the formation of aggregates only in solutions, from which crystals grew within a few days. The aggregates were grouped into smaller "units" and larger "clusters." The units consisted of a few molecules, whereas the clusters grew from about 100 nm to 1 μm. At the beginning of aggregation, the number density of the units decreased, while that of the clusters increased. At this stage, unit-cluster aggregation proceeded. At the next stage, the number density of the units became constant, while that of the clusters began to decrease, which means that the units stopped aggregating and cluster-cluster aggregation started. The aggregation mechanism for the clusters fit well with the diffusion limited cluster aggregation model, but this model alone could not explain that the aggregates separated into two groups, corresponding to units and clusters, and that the units stopped aggregating during the aggregation process. We find that the observed aggregation process has several similarities to the liquid-liquid phase separation process, which occurs metastably in protein solution. Furthermore, using both models for diffusion limited aggregation and the liquid-liquid phase separation together, we could naturally explain the process of the cluster formation. © 1999 American Institute of Physics.
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  • 4
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new formula for the data analysis in the quasielastic light scattering with the sinusoidal electric field (QELS-SEF) was derived from the time-averaged autocorrelation function. This time-average process exactly corresponds to the actual experimental procedure which is performed with a correlator used in the QELS-SEF measurement. The new formula was applied to the power spectrum of the polystyrene latex solution in the heterodyne mode of QELS-SEF, and then was found to fit quite well to the experimental data. By this fitting procedure, we revealed the dependences of the electrophoretic mobility μ and the apparent diffusion constant Dapp of the polystyrene latex on the frequency and amplitude of the applied ac electric field. Thus, the frequency dispersion or relaxation of Dapp was observed in the same frequency region as the dielectric relaxation.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 9137-9141 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The influence of sodium salicylate (NaSal) concentration on the linear micelle formation in an aqueous solution of cetyltrimethylammonium bromide (CTAB) is investigated by the frequency-domain electric birefringence relaxation spectroscopy (FEB method). The contour length L of linear micelles is found to increase with increasing NaSal concentration Cs but for further increase of Cs in excess of the CTAB concentration, L decreases, i.e., linear micelles break into shorter pieces. The FEB result indicates also that the diffusion constant of salicylate ions bound to a linear micelle is nearly independent of Cs with an average value smaller than that of free salicylate ions. © 1996 American Institute of Physics.
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  • 6
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 23 (1990), S. 857-862 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 7653-7660 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new formulation of the transient electric birefringence (TEB) response is presented. By using the method of operator expansion for the nonlinear response function, the TEB rise and decay response functions are generally derived for solutions containing two types of polymer molecules: The first is of the polymer molecules with an induced dipole moment (anisotropy in electric polarizability) alone; and the second is of polymer molecules with a permanent dipole moment alone. For the first type of polymer of any main-chain conformation, the TEB rise and decay responses are related with each other by a simple equation, which is the same as in the linear response. In the second type, a simple relation between the two TEB responses is found to hold for particular cases. We find the examples in rod-like and flexible conformations of polymer molecules. TEB responses of rod-like molecules under various confinement conditions are also discussed.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4920-4925 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new scheme of experimental criterion is proposed for estimating the carrier mobility and main-chain conformation of an electroactive polymer chain by the technique of transient electric birefringence (TEB). The rise response Δnr (t) and the decay response Δnd (t) in the TEB satisfy in the Kerr regime (i) Δnr (t)=Δnst -Δnd (t) for a polymer molecule of arbitrary conformation with an induced dipole moment alone arising from carriers highly mobile along the main chain, (ii) Δnr (t)=Δnst -(3/2)Δnd (t/3)+(1/2)Δnd (t) for a rodlike polymer molecule with a permanent dipole moment alone originating from carriers with low mobility, and (iii) Δnr(t)=Δnst-2Δnd (t/2)+Δnd (t) for a random-coiled polymer with a permanent dipole moment alone due to low-mobility carriers, where Δnst =limt→∞ Δnr(t) . Then, comparison of the TEB rise and decay responses gives us information on the carrier mobility and main-chain conformation. This criterion is valid also for polydispersed polymer samples. By applying the criterion to the exemplifying data of the TEB responses for soluble urethane-substituted polydiacetylenes, it is found that the polydiacetylene molecules take a random-coil conformation with a permanent dipole moment in a good solvent, while in a poor solvent the carrier mobility depends crucially on the solvent condition.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2643-2648 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rotational motion of entangled rod-like polymers in solutions is theoretically treated by using a mean-field Green function formulation for the rotational diffusion in an effective perturbation potential representing the hindrance effect by neighboring rods. A similar procedure to Part I of this series yields an explicit expression of the effective diffusion constant Dr as a function of the rod length and the polymer concentration for solutions in a wide range of concentrations from dilute to semidilute. In the high concentration limit, the present result is consistent with that obtained from the tube model of Doi–Edwards.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 7951-7956 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Quantitative treatment of rotational diffusion of entangled rodlike polymer molecules in semidilute solution is extended to include anisotropy in the orientational distribution of rods. Noting that anisotropy has a similar effect to changing the polymer concentration of the size and form of a tube confining a rodlike molecule, we apply the mean-field argument to the hindered diffusion of entangled rods. The rotational diffusion constant, which depends not only on the orientation but also on the diffusion direction, is derived as a functional of the orientational distribution function. As an example of external force which causes anisotropy, we study stationary elongational flow and obtain the rotational diffusion constant self-consistently as a function of the strain rate. It is found the tube is not a round but an oblate cylinder.
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