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The persistence length of isotactic poly(hydroxy butyrate) was measured using small-angle neutron scattering. The value obtained from these measurements reflects a high degree of local chain persistence. If this local persistence is accounted for, scattering from these chains can be globally fit with Gaussian scaling. A global scattering function, the unified equation, is used, which decomposes the chain structure into two levels, one corresponding to the Gaussian regime and one to the persistence regime. The persistence length obtained using this global scattering function is compared to that obtained using the graphical approach of Kratky and Porod with good agreement. Additionally, the global fitting approach of Sharp and Bloomfield is also considered. The Kratky and the Sharp and Bloomfield approaches appear to yield different values for the persistence length. Additionally, the Sharp and Bloomfield function does not allow inspection of the component parts of the fit. One advantage of both global functions is that the level of statistical confidence in the persistence length can be determined in a least-squares fit. Another advantage is the removal of ambiguity concerning an apparent regime of non-Gaussian scaling between the persistence scaling regime and the Gaussian regime.

A lattice model of semiflexible linear chains (with equilibrium polydispersity) containing free volume is solved exactly on a Husimi cactus. A metastable liquid (ML) is discovered to exist only at low temperatures and is distinct (and may be disjoint) from the supercooled liquid (SCL) that exists only at high temperatures. The free volume plays a significant role in that the spinodals of the ML and SCL merge and then disappear as the free volume is reduced. The Kauzmann temperature T(K) occurs in the ML without any singularity. At T(MC)>T(K), the ML specific heat has a peak. For infinitely long polymers, the peak height diverges and the free volume vanishes at T(MC), resulting in a continuous liquid-liquid transition. Contrary to the conventional wisdom, both T(K) and T(MC) occur in the ML and not in the SCL.

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The efficiency of synthetic binuclear manganese complexes in reconstituting PS II electron flow and oxygen-evolution capacity was analyzed in PS II enriched preparations deprived of their manganese and of the extrinsic regulatory subunits. Measurements of the variable fluorescence induced by actinic illumination with continuous light led to the following results: (a) the synthetic binuclear complexes are more efficient than MnCl2 in establishing a PS II electron flow; (b) an almost complete restoration is achieved at concentrations of these complexes that correspond with an overall stoichiometry of two manganese per PS II; and (c) the electron flow restored by the binuclear manganese complexes closely resembles that of normal O2-evolving PS II preparations in its resistance to addition of 50 microM EDTA, while that supported by MnCl2 is practically completely suppressed at the same chelator concentration. The rate of O2 evolution was used as a measure of the capability to function as manganese source in reconstitution of the oxygen evolution capacity. It was found that (i) as in the case of PS II electron transport, the synthetic binuclear manganese complexes are significantly more efficient than MnCl2; (ii) with respect to the manganese concentration, the maximum effect is achieved with a mu-oxo bridged binuclear Mn(III) complex (symbolized by M-3) at concentrations corresponding to four manganese per PS II; and (iii) at all concentrations of binuclear manganese complex M-3 a significantly higher restoration of the O2 evolution rate is achieved if the reconstitution assay contains in addition the extrinsic regulatory 33 kDa protein (PS II-O protein).(ABSTRACT TRUNCATED AT 250 WORDS)

We consider a lattice model of a polymer system in which we distinguish between the end (E) and the middle (M) groups. The free volume is represented as a "hole" or "void" (0), which constitutes a separate species in addition to the two "species" M and E. There are three different exchange interaction energies, and correspondingly three Boltzmann weights w(ij), i not equal j=0,E,M between different species. We define the free volume associated with the species j=M or E, as the average number of voids next to j. Using a recently developed equilibrium lattice theory, we calculate the free volume v(E) and v(M) associated with an end group and a middle group, respectively, and investigate the effects of interactions among them. Our calculations show that v(E) and v(M) are intricate functions of w(ij), the pressure and the molecular weight, and that their difference can change sign under certain conditions. These conditions are elucidated. We demonstrate that when the end group is chemically dissimilar from the middle group, the middle group may have more free volume than the end group. We find that the conditions that favor a middle group having more free volume over an end group are w(E0)<1, w(M0)<1, and w(ME)>1. The effect of pressure and molecular weight can be of either type and appears to be dependent on the interactions.

No abstract

Triglycerides and related fatty acid esters constitute a large percentage of the lipid excipients employed in the development of lipid-based drug formulations. Computer simulations can provide useful information on the structural, dynamic, and thermodynamic properties of these systems and may ultimately be valuable in predicting relative drug solubilities in lipid vehicles. This study utilized all-atom molecular dynamics simulations to explore the solvation of several model solutes in lipid vehicles. First, a combined thermodynamic perturbation and integration approach was employed to calculate functional group contributions to the free energy of transfer from n-decane to tricaprylin for a set of polar substituents attached to the 9-position of anthracene. A scaling factor of 0.79 for all atomic charges in the dry lipid (where the unscaled charges were obtained at the level of the HF/6-31G* basis set) was necessary in order to match the calculated group contributions to the free energies of transfer with their experimental values at 37 degrees C. A second set of simulations was performed in water-saturated tricaprylin containing a single molecule of benzamide to explore the state of organization of solvent molecules, the distribution of water molecules, and the local environment surrounding the solute. Radial distribution functions revealed evidence of local structure in the liquid triglyceride. The dissolved water was found to exist approximately 50% as monomers and 50% as self-associated species. Substantial hydrogen-bonding of benzamide with ester carbonyl oxygen atoms was observed.