The effect of salt stoichiometry on protein-salt interactions determined by ternary diffusion in aqueous solutions

We report the four diffusion coefficients for the lysozyme-MgCl2-water ternary system at 25 degrees C and pH 4.5. The comparison with previous results for the lysozyme-NaCl-water ternary system is used to examine the effect of salt stoichiometry on the transport properties of lysozyme-salt aqueous mixtures. We find that the two cross-diffusion coefficients are very sensitive to salt stoichiometry. One of the cross-diffusion coefficients is examined in terms of common-ion, excluded-volume, and protein-preferential hydration effects. We use the four ternary diffusion coefficients to extract chemical-potential cross-derivatives and protein-preferential interaction coefficients. These thermodynamic data characterize the protein-salt thermodynamic interactions. We demonstrate the presence of the common-ion effect (Donnan effect) by analyzing the dependence of the preferential-interaction coefficient not only with respect to salt concentration but also with respect to salt stoichiometry. We conclude that the common-ion effect and the protein-preferential hydration are both important for describing the lysozyme-MgCl2 thermodynamic interaction.     

On the *-Polynomial Identities of a Class of *-Minimal Algebras

Let F be an infinite field. We consider certain block-triangular algebras with involution U _n , with n ∈ ?, having minimal *-exponent. We describe their *-polynomial identities, and in case char.F = 0, their structure as a T _*-ideal under the action of general linear groups. These goals are achieved by means of Y-proper polynomials. We also compute explicitly the irreducible modules occurring in the decomposition of B _Y (U ₃) and their multiplicities.     

Effect of macromolecular polydispersity on diffusion coefficients measured by Rayleigh interferometry

Rayleigh interferometry has been extensively used for the precise determination of diffusion coefficients for binary and ternary liquid mixtures. For ternary mixtures, the 2x2 matrix of multicomponent diffusion coefficients is obtained. Polydispersity adds complexity to the meaning of these measured diffusion coefficients. Here we discuss three important issues of polydispersity regarding the diffusion measurements extracted from this interferometric technique. First, we report novel equations for the extraction of diffusion moments from the Rayleigh interferometric pattern. These moments are used to define polydispersity parameters for macromolecular systems. We have experimentally determined mean diffusion coefficients and polydispersity parameters for aqueous solutions of poly(ethylene glycol) and poly(vinyl alcohol) at 25 degrees C. Aqueous solutions of poly(ethylene glycol) mixtures were used to examine the accuracy of the polydispersity parameters. Second, we compare Rayleigh interferometry to dynamic light scattering. Specifically, we have performed diffusion measurements on the same system using both techniques. To our knowledge, no direct experimental comparison between dynamic light scattering and classical methods for the measurements of diffusion coefficients has been previously reported in relation to polydispersity. We find that substantial discrepancies (i.e., 1 order of magnitude) between the mean diffusion coefficients obtained from these two different techniques can be observed when polydispersity is large. Third, for two-solute mixtures with one polydisperse solute, we report a novel corrective procedure for extracting accurate ternary diffusion coefficients from Rayleigh interferometry. Computer simulations were used to examine the accuracy of the extracted ternary diffusion coefficients.     

Liquid-liquid phase transition of protein aqueous solutions isothermally induced by protein cross-linking

We experimentally demonstrated that liquid-liquid phase separation (LLPS) of protein aqueous solutions can be induced by isothermal protein oligomerization. This phenomenon is analogous to LLPS induced by the polymerization of small organic molecules in solution. Specifically, using glutaraldehyde for protein cross-linking, we observed the formation of protein-rich liquid droplets for bovine serum albumin and chicken egg lysozyme at 25 degrees C. These droplets evolved into cross-linked protein microspheres. If the aqueous solutions of the protein monomer do not show LLPS at temperatures lower than the oligomerization temperature, protein-rich droplets are not observed. We experimentally linked the formation of these droplets to the increase of LLPS temperature during protein oligomerization. When macroscopic aggregation competes with LLPS, a rationale choice of pH, polyethylene glycol, and salt concentrations can be used to favor LLPS relative to aggregation. Although glutaraldehyde has been extensively used to cross-link protein molecules, to our knowledge, its use in homogeneous aqueous solutions to induce LLPS has not been previously described. This work contributes to the fundamental understanding of both phase transitions of protein solutions and the morphology of protein condensed phases. It also provides guidance for the development of new methods based on mild experimental conditions for the preparation of protein-based materials.     

Site selectivity in the reactions of the hexanuclear platinum cluster [Pt6(mu-PtBu2)4(CO)6][CF3SO3]2

The previously reported hexanuclear cluster [Pt(6)(mu-PtBu(2))(4)(CO)(6)](2+)[Y](2) (1-Y(2): Y=CF(3)SO(3) (-)) contains a central Pt(4) tetrahedron bridged at each of the opposite edges by another platinum atom; in turn, four phosphido ligands bridge the four Pt-Pt bonds not involved in the tetrahedron, and, finally, one carbonyl ligand is terminally bonded to each metal centre. Interestingly, the two outer carbonyls are more easily substituted or attacked by nucleophiles than the inner four, which are bonded to the tetrahedron vertices. In fact, the reaction of 1-Y(2) with 1 equiv of [nBu(4)N]Cl or with an excess of halide salts gives the monochloride [Pt(6)(mu-PtBu(2))(4)(CO)(5)Cl](+)[Y], 2-Y, or the neutral dihalide derivatives [Pt(6)(mu-PtBu(2))(4)(CO)(4)X(2)] (3: X=Cl; 4: X=Br; 5: X=I). Moreover, the useful unsymmetrically substituted [Pt(6)(mu-PtBu(2))(4)(CO)(4)ICl] (6) was obtained by reacting equimolar amounts of 2 and [nBu(4)N]I, and the dicationic derivatives [Pt(6)(mu-PtBu(2))(4)(CO)(4)L(2)](2+)[Y](2) (7-Y(2): L=(13)CO; 8-Y(2): L=CNtBu; 9-Y(2): L=PMe(3)) were obtained by reaction of an excess of the ligand L with 1-Y(2). Weaker nitrogen ligands were introduced by dissolving the dichloride 3 in acetonitrile or pyridyne in the presence of TlPF(6) to afford [Pt(6)(mu-PtBu(2))(4) (CO)(4)L(2)](2+)[Z](2) (Z=PF(6) (-), 10-Z(2): L=MeCN; 11-Z(2): L=Py). The "apical" carbonyls in 1-Y(2) are also prone to nucleophilic addition (Nu(-): H(-), MeO(-)) affording the acyl derivatives [Pt(6)(mu-PtBu(2))(4)(CO)(4)(CONu)(2)] (12: Nu=H; 13: Nu=OMe). Complex 12 is slowly converted into the dihydride [Pt(6)(mu-PtBu(2))(4)(CO)(4)H(2)] (14), which was more cleanly prepared by reacting 3 with NaBH(4). In a unique case we observed a reaction involving also the inner carbonyls of complex 1, that is, in the reaction with a large excess of the isocyanides R-NC, which form the corresponding persubstituted derivatives [Pt(6)(mu-tPBu(2))(4)(CN-R)(6)](2+)[Y](2), (15-Y(2): R=tBu; 16-Y(2) (2-): R=-C(6)H(4)-4-C triple bond CH). All complexes were characterized by microanalysis, IR and multinuclear NMR spectroscopy. The crystal and molecular structures of complexes 3, 5, 6 and 9-Y(2) are also reported. From the redox viewpoint, all complexes display two reversible one-electron reduction steps, the location of which depends both upon the electronic effects of the substituents, and the overall charge of the original complex.     

Solid-solid phase transitions: interface controlled reactivity and formation of intermediate structures

Finding new pathways to novel materials is an open challenge in modern solid-state chemistry. Among the reasons that still prevent a rational planning of synthetic routes is the lack of an atomistic understanding at the moment of phase formation. Metastable phases are, in this respect, powerful points of access to new materials. For the synthetic efforts to fully take advantage of such peculiar intermediates, a precise atomistic understanding of critical processes in the solid state in its many facets, that is, nucleation patterns, formation and propagation of interfaces, intermediate structures, and phase growth, is mandatory. Recently we have started a systematic theoretical study of phase transitions, especially of processes with first-order thermodynamics, to reach a firm understanding of the atomistic mechanisms governing polymorphism in the solid state. A clear picture is emerging of the interplay between nucleation patterns, the evolution of domain interfaces and final material morphology. Therein intermediate metastable structural motifs with distinct atomic patterns are identified, which become exciting targets for chemical synthesis. Accordingly, a new way of implementing simulation strategies as a powerful support to the chemical intuition is emerging. Simulations of real materials under conditions corresponding to the experiments are shedding light onto yet elusive aspects of solid-solid transformations. Particularly, sharp insights into local nucleation and growth events allow the formulation of new concepts for rationalizing interfaces formed during phase nucleation and growth. Structurally different and confined in space, metastable interfaces occurring during polymorph transformations bring about distinct diffusion behavior of the chemical species involved. More generally, stable structures emerge as a result of the concurrence of the transformation mechanism and of chemical reactions within the phase-growth fronts.