CHLOROPHYLLS IN POLYMERS. I. STATE OF CHLOROPHYLL a IN UNSTRETCHED POLYMER SYSTEMS

Abstract— Model systems for the study of energy transfer processes are useful for the elucidation of the various factors governing the mechanism of energy transfer in photosynthetic systems. Here we describe the characterization of two systems, consisting of chlorophyll a incorporated in anhydrous nitrocellulose and polyvinylalcohol films. First, optical spectroscopy and time-resolved fluorescence techniques are used to characterize the state of the chlorophyll molecules in the films. We find that in nitrocellulose films the state of chlorophyll a depends strongly on the ratio of nitrocellulose to dimeth-ylsulfoxide in the solutions from which the films are cast. The state of chlorophyll a in polyvinylalcohol films does not depend on the amount of polymer originally dissolved in dimethylsulfoxide. In these films the pigment is monomeric at low concentrations of chlorophyll a, but aggregates are formed at much lower concentrations than in nitrocellulose. The latter fact is explained by the existence of pockets in polyvinylalcohol, leading to high local concentrations.
To further test the suitability of the nitrocellulose polymer films as model systems for energy transfer processes, time-resolved fluorescence anisotropy profiles are measured in dependence of the concentration of pigments in the matrix. Fits of the observed decay profiles to the predicted decay show good correspondence, as long as no traps are present. Furthermore, the fitted decay times yield the correct value of the Forster radius R₀ as compared to the value obtained spectroscopically. We thus conclude that the chlorophyll a-nitrocellulose system can be very appropriate for the study of energy transfer processes between photosynthetic pigment, since the pigments are uniformally distributed in the matrix.     

Diffusion of spheres in crowded suspensions of rods

Translational tracer diffusion of spherical macromolecules in crowded suspensions of rodlike colloids is investigated. Experiments are done using several kinds of spherical tracers in fd-virus suspensions. A wide range of size ratios L/2a of the length L of the rods and the diameter 2a of the tracer sphere is covered by combining several experimental methods: fluorescence correlation spectroscopy for small tracer spheres, dynamic light scattering for intermediate sized spheres, and video microscopy for large spheres. Fluorescence correlation spectroscopy is shown to measure long-time diffusion only for relatively small tracer spheres. Scaling of diffusion coefficients with a/xi, predicted for static networks, is not found for our dynamical network of rods (with xi the mesh size of the network). Self-diffusion of tracer spheres in the dynamical network of freely suspended rods is thus fundamentally different as compared to cross-linked networks. A theory is developed for the rod-concentration dependence of the translational diffusion coefficient at low rod concentrations for freely suspended rods. The proposed theory is based on a variational solution of the appropriate Smoluchowski equation without hydrodynamic interactions. The theory can, in principle, be further developed to describe diffusion through dynamical networks at higher rod concentrations with the inclusion of hydrodynamic interactions. Quantitative agreement with the experiments is found for large tracer spheres, and qualitative agreement for smaller spheres. This is probably due to the increasing importance of hydrodynamic interactions as compared to direct interactions as the size of the tracer sphere decreases.     

Two-step upflow anaerobic sludge bed system for sewage treatment under subtropical conditions with posttreatment in waste stabilization ponds

A pilot-scale sewage treatment system consisting of two upflow anaerobic sludge bed (UASB) reactors followed by five waste stabilization ponds (WSPs) in series was studied under subtropical conditions. The first UASB reactor started up in only 1 mo (stable operation, high chemical oxygen demand [COD] removal efficiency, low volatile fatty acids concentration in the effluent, alkalinity ratio above 0.7, biogas production above 0.1 Nm3/kg of CODremoved). Removal efficiencies up to 90% were obtained in the anaerobic steps at a hydraulic retention time of 6 + 4 h (80% removal in the first step). Fecal coliform removal in the whole system was 99.9999% (99.94% in anaerobic steps and 99.98% in WSPs). COD balances over UASB reactors are provided. A minimum set of data necessary to build COD balances is proposed. Intermittent sludge washout was detected in the reactors with the COD balances. Sludge washout from single-step UASB reactors should be monitored and minimized in order to ensure constant compliance with discharge standards, especially when no posttreatment is provided. The system combined high COD and fecal coliform removal efficiency with an extremely low effluent concentration, complying with discharge standards, and making it an attractive option for sewage treatment in subtropical regions.     

Multiple shear-banding transitions in a supramolecular polymer solution

We report on the nonlinear rheology of a reversible supramolecular polymer based on hydrogen bonding. The coupling between the flow-induced chain alignment and breakage and recombination of bonds between monomers leads to a very unusual flow behavior. Measured velocity profiles indicate three different shear-banding regimes upon increasing shear rate, each with different characteristics. While the first of these regimes has features of a mechanical instability, the second shear-banding regime is related to a shear-induced phase separation and the appearance of birefringent textures. The shear-induced phase itself becomes unstable at very high shear rates, giving rise to a third banding regime.     

Many-body hydrodynamic interactions in charge-stabilized suspensions

In this joint experimental-theoretical work we study hydrodynamic interaction effects in dense suspensions of charged colloidal spheres. Using x-ray photon correlation spectroscopy we have determined the hydrodynamic function H(q), for a varying range of electrosteric repulsion. We show that H(q) can be quantitatively described by means of a novel Stokesian dynamics simulation method for charged Brownian spheres, and by a modification of a many-body theory developed originally by Beenakker and Mazur. Very importantly, we can explain the behavior of H(q) for strongly correlated particles without resorting to the controversial concept of hydrodynamic screening, as was attempted in earlier work by Riese [Phys. Rev. Lett. 85, 5460 (2000)].     

Determination of the directions of the transition dipoles in tetrabutylperylene in stretched polymers

The directions of the transition dipole moments of 2,5,8,11,-tetra-butylperylene were determined from angle-resolved fluorescence depolarization experiments on molecules embedded in a stretched anhydrous nitrocellulose matrix. The absorption transition moments lies almost parallel to the elongated axis of the molecule, but the emission transition moment makes an angle of 20° with the axis. The orientational distribution of the molecules in the polymer indicates significant deviations from a circular form.     

Dispersions and mixtures of particles with complex architectures in shear flow

We review the effect of shear flow on the phase behavior and structure of colloidal dispersions with increasing degree of complexity. We discuss dispersions of colloidal rods, stiff living polymers like wormlike micelles, and colloidal platelets. In addition, a review is presented on sheared binary dispersions. For all cases we discuss the interplay between thermodynamic instabilities and hydrodynamic instabilities.     

Capillary nematisation of colloidal rods in confinement

ABSTRACT

We confine a colloidal liquid crystal between parallel plates separated down to several times the rod length. By connecting the system to a reservoir we effectively create a grand canonical system, in which the liquid crystal displays an isotropic phase in the reservoir, but upon strong confinement becomes nematic between the parallel plates. This capillary nematisation transition can be followed down to the single particle level by means of laser scanning confocal microscopy. We compare the experimental findings to density functional theories (DFTs), within the Zwanzig model as well as a more advanced DFT, in which the effect of rod flexibility is taken into account.     

Colloidal dispersions of octadecyl grafted silica spheres in toluene: a global analysis of small angle neutron scattering contrast variation and concentration dependence measurements

In this paper we report measurements of the form factor and the structure factor of a sterically stabilized colloidal dispersion consisting of silica spheres coated with octadecane in toluene by small angle neutron scattering (SANS). The phase diagram of this system shows the liquid-liquid coexistence line and also a jamming transition at higher concentrations, where the jamming line intersects the coexistence line roughly at the critical point. We have performed SANS experiments at a temperature well above the transition temperature and at various volume fractions phi, spanning from the very dilute regime (phi=0.2%) to the critical concentration (phi=16%) and the highly viscous regime (phi=39.2%). Except for the very dilute regime, we observe a structure factor S(q) in all other cases. We fitted our data over the whole concentration regime using a global fitting routine with a core-shell model for the form factor P(q), taking into account the structure factor, which we describe with the Robertus model for an adhesive polydisperse core-shell particle. At a volume fraction of phi=5% a SANS contrast variation experiment has been performed. From that the product of the volume of the shell and the amount of solvent within the corona of our core-shell particle could be determined. At the most probable shell thickness of 2.3 nm a solvent content of about 50% within the corona was found. Moreover we could conclude that the core is not interpenetrated by solvent molecules. From the contrast variation experiment followed that the structure factor at zero average contrast exhibits a strong q dependence, which is an effect of an inhomogeneous particle in combination with a size distribution.