Bound water

Abstract: This paper is the second in a series evaluating the microwave dielectric behavior of soil-water mixtures as a function of water content and soil textural composition. Part II draws upon the data presented in Part 1 [13] to develop appropriate empirical and theoretical dielectric mixing models for the 1.4-to 18-GHz region. A semiempirical mixing model based upon the index of refraction is presented, requiring only easily ascertained soil physical parameters such as volumetric moisture and soil textural composition as inputs. In addition, a theoretical model accounting explicitly for the presence of a hydration layer of bound water adjacent to hydrophilic soil particle surfaces is presented. A four-component dielectric mixing model treats the soil-water system as a host medium of dry soil solids containing randomly distributed and randomly oriented disc-shaped inclusions of bound water, bulk water, and air. The bulk water component is considered to be dependent upon frequency, temperature, and salinity. The soil solution is differentiated by means of a soil physical model into 1) a bound component and 2) a bulk soil solution. The performance of each model is evaluated as a function of soil moisture, soil texture, and frequency, using the dielectric measurements of five soils ranging from sandy loam to silty clay (as presented in Part I [13]) at frequencies between 1.4 and 18 GHz. The semiempirical mixing model yields an excellent fit to the measured data at frequencies above 4 GHz. At 1.

Abstract: Th?e atomic structure of the light-driven ion pump bacteriorhodopsin and the surrounding lipid matrix was determined by X-ray diffraction of crystals grown in cubic lipid phase. In the extracellular region, an extensive three-dimensional hydrogen-bonded network of protein residues and seven water molecules leads from the buried retinal Schiff base and the proton acceptor Asp85 to the membrane surface. Near Lys216 where the retinal binds, transmembrane helix G contains a pi-bulge that causes a non-proline? kink. The bulge is stabilized by hydrogen-bonding of the main-chain carbonyl groups of Ala215 and Lys216 with two buried water molecules located between the Schiff base and the proton donor Asp96 in the cytoplasmic region. The results indicate extensive involvement of bound water molecules in both the structure and the function of this seven-helical membrane protein. A bilayer of 18 tightly bound lipid chains forms an annulus around the protein in the crystal. Contacts between the trimers in the membrane plane are mediated almost exclusively by lipids.

Abstract: This is the first paper in a two-part sequence that evaluates the microwave dielectric behavior of soil-water mixtures as a function of water content, temperature, and soil textural composition. Part I presents the results of dielectric constant measurements conducted for five different soil types at frequencies between 1.4 and 18 GHz. Soil texture is shown to have an effect on dielectric behavior over the entire frequency range and is most pronounced at frequencies below 5 GHz. In addition, the dielectric properties of frozen soils suggest that a fraction of the soil water component remains liquid even at temperatures of -24° C. The dielectric data as measured at room temperature are summarized at each frequency by polynomial expressions dependent upon both the volumetric moisture content m and the percentage of sand and clay contained in the soil; separate polynomial expressions are given for the real and imaginary parts of the dielectric constant. In Part II, two dielectric mixing models will be presented to account for the observed behavior: 1) a semiempirical refractive mixing model that accurately describes the data and requires only volumetric moisture and soil texture as inputs, and 2) a theoretical four-component mixing model that explicitly accounts for the presence of bound water.

Abstract: Three model, unrelated enzymes (yeast alcohol oxidase, mushroom polyphenol oxidase, and horse liver alcohol dehydrogenase) were found to be catalytically active in a variety of organic solvents. For all enzymes and solvents tested, the enzymatic activity greatly increased upon an increase in the water content in the solvents (which always remained below the solubility limit). Much less water was required to reach the maximal activity in hydrophobic solvents than in their hydrophilic counterparts. However, when the catalytic activity was plotted versus the amount of water bound to the enzymes, a common pattern emerged for different solvents. These data suggest that the effect of organic solvents on an enzyme is primarily due to interactions with the enzyme-bound, essential layer of water rather than with the enzyme itself. At optimal water contents, enzymatic activities in organic solvents were in the range from 20 to 40% of those in aqueous solutions. From experiments on (i) replacement of water with other hydrogen bond-forming additives and (ii) titration of enzyme amino groups in an organic medium, as well as the literature data on dehydrated enzymes, it is concluded that the water required by enzymes in nonaqueous solvents provides them with sufficient conformational flexibility needed for catalysis.

Abstract: Aquaporins are transmembrane channels found in cell membranes of all life forms. We examine their apparently paradoxical property, facilitation of efficient permeation of water while excluding protons, which is of critical importance to preserving the electrochemical potential across the cell membrane. We have determined the structure of the Escherichia coliaquaglyceroporin GlpF with bound water, in native (2.7 angstroms) and in W48F/F200T mutant (2.1 angstroms) forms, and carried out 12-nanosecond molecular dynamics simulations that define the spatial and temporal probability distribution and orientation of a single file of seven to nine water molecules inside the channel. Two conserved asparagines force a central water molecule to serve strictly as a hydrogen bond donor to its neighboring water molecules. Assisted by the electrostatic potential generated by two half-membrane spanning loops, this dictates opposite orientations of water molecules in the two halves of the channel, and thus prevents the formation of a “proton wire,” while permitting rapid water diffusion. Both simulations and observations revealed a more regular distribution of channel water and an increased water permeability for the W48F/F200T mutant.