Theory of the nucleation of protein macromolecular ions

Protein molecules are amphoteric and exist in aqueous solution as macromolecular ions that carry a charge which depends upon temperature and pH. Despite the repulsive Coulomb forces acting between them, protein macromolecular ions can form crystals in pH buffered solutions of strong electrolytes. It is proposed that the first step in the mechanism of crystallization is the formation of crystal nuclei made from partially discharged macromolecular ions that have exchanged H⁺ with the buffer. We suggest that the strength of the bare Coulomb repulsive force is weakened by the Debye-Hückel plasma screening provided by the inert electrolyte. This screening causes the rate of nucleus formation to increase with increasing ionic strength. Extending classic nucleation theory to account for these various charge effects, the results are applied to the case of lysozyme and a calculation is made of the dependence of the steady state nucleation rate upon temperature, pH, ionic strength, and protein supersaturation. It is found that the nucleation rate increases with increasing temperature and increasing ionic strength. Under condition of fixed temperature, supersaturation, and inionic strength, the nucleation rate has local maxima at low pH, where individual lysozyme macro ions are highly charged, and at pH ? 11, where they have zero average net charge. At both pH values, the nucleus that determines the rate has minimum size. In contrast to standard nucleation theory, which ignores charge, it is found that the size of the nucleus that controls the rate is different from the size of the nucleus that has the lowest concentration. All other conditions being the same, it is predicted that lysozyme crystals should nucleate most rapidly near pH = 2 and near pH = 11.     

Exploring complex CIDEP of p-benzosemiquinones with time resolved CW-EPR

The time and magnetic field dependent magnetization of polarized signals in the presence of chemically induced magnetization transfer is described by means of a kinetic matrix incorporated into the Bloch equations. The approach is transformed into a computer algorithm accounting for all hyperfine lines present in the system. Solutions are readily obtained by numerical methods. Calculations are applied to the time resolved EPR (TR-EPR) spectroscopic signals of p-benzoquinone after laser flash photolysis. In an aqueous alcoholic solution at pH 2.0, chemical exchange via intermolecular proton transfer is found present between neutral semiquinones. At pH 8.3, the TR-EPR spectrum shows only a uniform signal of the semiquinone. At pH 5.4, a superposition of neutral and anionic radicals is observed together with a protonation-deprotonation equilibrium. A two-step hydrogen atom transfer, consisting of electron transfer followed by protonation, is proposed to account for the formation of both neutral and anionic semiquinone species prior to observation. Experiments in partly deuterated solvent mixtures indicate the existence of three semiquinone forms: BQH^?, BQ^?-, and BQD^? prior to observation. The origin of the proton/deuteron transferred to the anion radical in the precursor state is discussed.     

Extracting science from surveys of our Galaxy

Our knowledge of the Galaxy is being revolutionized by a series of photometric, spectroscopic and astrometric surveys. Already an enormous body of data is available from completed surveys, and data of ever-increasing quality and richness will accrue at least until the end of this decade. To extract science from these surveys, we need a class of models that can give probability density functions in the space of the observables of a survey – we should not attempt to ‘invert’ the data from the space of observables into the physical space of the Galaxy. Currently just one class of model has the required capability, the so-called ‘torus models’. A pilot application of torus models to understand the structure of the Galaxy’s thin and thick discs has already produced two significant results: a major revision of our best estimate of the Sun’s velocity with respect to the local standard of rest, and a successful prediction of the way in which the vertical velocity dispersion in the disc varies with distance from the Galactic plane.     

HABITAT PATCH OCCUPANCY DYNAMICS OF GLAUCOUS‐WINGED GULLS (LARUS GLAUCESCENS) II: A CONTINUOUS‐TIME MODEL

ABSTRACT. The diurnal distribution and abundance dynamics of loafing Glaucous‐winged Gulls (Larus glaucescens) were examined at Protection Island National Wildlife Refuge, Strait of Juan de Fuca, Washington. Asynchronous movement of gulls among three habitat patches dedicated to loafing was modeled as a function of environmental variables using differential equations. Multiple time scale analysis led to the derivation of algebraic models for habitat patch occupancy dynamics. The models were parameterized with hourly census data collected from each habitat patch, and the resulting model predictions were compared with observed census data. A four‐compartment model explained 41% of the variability in the data. Models that predict the dynamics of organism distribution and abundance enhance understanding of the temporal and spatial organization of ecological systems, as well as the decision‐making process in natural resource management.     

Linear-Feedback Recruitment polices for Constant-Size Manpower Systems

Feedback control principles are used to develop recruitmentpolicies for manpower systems, with and without vacancies beingconsidered. The problem of reaching a desired steady-state distributionis also formulated and discussed as a linear programming problem.