Surface microenvironment

Utilizing time resolved internal reflection spectroscopic technique (Fig. 6), we were able to isolate the tryptophan intrinsic fluorescence and observe its = 20 ns fluorescence lifetime for albumin in bulk and in the surface microenvironment of a hydrophilic quartz material. The pH dependence of bulk albumin fluorescence lifetime served to "calibrate albumin in terms of native ( 7 ns time constant) protein at pH 7.2 and unfolded (c 4 ns) protein at the isoelectric pH 3.8. The fluorescence lifetime data (Tables I/II) supported the hypothesis that the adsorbed albumin exists in two forms on a hydrophilic quartz surface, each with a possibly different structure (] ). A loosely held "layer," consisting of microaggregates, native and partially unfolded albumin molecules with... 

Byrom D (1991) Miscellaneous biomaterials. In Byrom D (ed) Biomaterials novel materials from biological sources. Macmillan, New York, pp 335-359 Cacciari I, Quatrini P, Zirletta G, Mincione E, Vinciguerra V, Lupattelli P, Sermanni GG (1993) Isotactic polypropylene biodegradation by a microbial community physicochemical characterization of metabolites produced. Appl Environ Microbiol 59 3695-3700 Caldwell DE, Lawrence JR (1986) Growth kinetics of Pseudomonas fluorescens microcolonies within the hydrodynamic boundary layers of surface microenvironments. Microb Ecol 12 299-312... 

Lawrence JR, Delaquis PJ, Korber DR, Caldwell DE (1987) Behavior of Pseudo-moms fluorescens within the hydrodynamic boundary layers of surface microenvironments. Arch Ecol 14 1-14... 

Mass-action model of surfactant micelle formation was used for development of the conceptual retention model in micellar liquid chromatography. The retention model is based upon the analysis of changing of the sorbat microenvironment in going from mobile phase (micellar surfactant solution, containing organic solvent-modifier) to stationary phase (the surfactant covered surface of the alkyl bonded silica gel) according to equation ... 

Morishima et al. [30, 50-54, 73-76] have made extensive investigations on photoinduced ET, using polycyclic aromatic chromophores covalently attached to polyelectrolytes. They were the first to show that the polyeletrolyte molecular surface provides an unusual microenvironment which greatly changes the rate of photoinduced ET and the fate of the charged photoproducts. 

The immobilization procedure may alter the behavior of the enzyme (compared to its behavior in homogeneous solution). For example, the apparent parameters of an enzyme-catalyzed reaction (optimum temperature or pH, maximum velocity, etc.) may all be changed when an enzyme is immobilized. Improved stability may also accrue from the minimization of enzyme unfolding associated with the immobilization step. Overall, careful engineering of the enzyme microenvironment (on the surface) can be used to greatly enhance the sensor performance. More information on enzyme immobilization schemes can be found in several reviews (7,8). 

In polar solvents, the structure of the acridine 13 involves some zwitterionic character 13 a [Eq. (7)] and the interior of the cleft becomes an intensely polar microenvironment. On the periphery of the molecule a heavy lipophilic coating is provided by the hydrocarbon skeleton and methyl groups. A third domain, the large, flat aromatic surface is exposed by the acridine spacer unit. This unusual combination of ionic, hydrophobic and stacking opportunities endows these molecules with the ability to interact with the zwitterionic forms of amino acids which exist at neutral pH 24). For example, the acridine diacids can extract zwitterionic phenylalanine from water into chloroform, andNMR evidence indicates the formation of 2 1 complexes 39 such as were previously described for other P-phenyl-ethylammonium salts. Similar behavior is seen with tryptophan 40 and tyrosine methyl ether 41. The structures lacking well-placed aromatics such as leucine or methionine are not extracted to measureable degrees under these conditions. 

We have now adjusted our molecular systems to provide a model in which both forces can operate simultaneously. The U-shaped relationship that exists between the imide function and amides of aryl amines creates a hydrogen bonding edge and a planar stacking surface that converge from perpendicular directions as in 44 to provide a microenvironment complementary to nucleic acid components. A large number of aromatic rings can be functionalized with this simple scaffold, and spacers (R) can also be incorporated. The imide function is a mimic of the thymine residues. 

Screening the molecular heterogeneity of receptor expression in endothelial cell surfaces is required for the development of vascular-targeted therapies. First, as opposed to targeting purified proteins as discussed above, membrane-bound receptors are more likely to preserve their functional conformation, which can be lost upon purification and immobilization outside the context of intact cells. Moreover, many cell surface receptors require the cell membrane microenvironment to function so that protein-protein interaction may occur. Finally, combinatorial approaches may allow the selection of cell membrane ligands in a functional assay and without any bias about the cellular surface receptor. Therefore, even as yet unidentified receptors may be targeted. 

Several metallophthalocyanines have been reported to be active toward the electroreduction of C02 in aqueous electrolyte especially when immobilized on an electrode surface.125-127 CoPc and, to a lesser extent, NiPc appear to be the most active phthalocyanine complexes in this respect. Several techniques have been used for their immobilization.128,129 In a typical experiment, controlled potential electrolysis conducted with such modified electrodes at —1.0 vs. SCE (pH 5) leads to CO as the major reduction product (rj = 60%) besides H2, although another study indicates that HCOO is mainly obtained.129 It has been more recently shown that the reduction selectivity is improved when the CoPc is incorporated in a polyvinyl pyridine membrane (ratio of CO to H2 around 6 at pH 5). This was ascribed to the nature of the membrane which is coordinative and weakly basic. The microenvironment around CoPc provided by partially protonated pyridine species was suggested to be important.130,131 The mechanism of C02 reduction on CoPc is thought to involve the initial formation of a hydride derivative followed by its reduction associated with the insertion of C02.128... 

Even where it is not occluded, the mineral surface may not be reactive. In the va-dose zone, the surface may not be fully in contact with water or may contact water only intermittently. In the saturated zone, a mineral may touch virtually immobile water within isolated portions of the sediment s pore structure. Fluid chemistry in such microenvironments may bear little relationship to the bulk chemistry of the pore water. Since groundwater flow tends to be channeled through the most permeable portions of the subsurface, furthermore, fluids may bypass many or most of the mineral grains in a sediment or rock. The latter phenomenon is especially pronounced in fractured rocks, where only the mineral surfaces lining the fracture may be reactive. 

In many biological systems the biological membrane is a type of surface on which hydrophilic molecules can be attached. Then a microenvironment is created in which the ionic composition can be tuned in a controlled way. Such a fluffy polymer layer is sometimes called a slimy layer. Here we report on the first attempt to generate a realistic slimy layer around the bilayer. This is done by grafting a polyelectrolyte chain on the end of a PC lipid molecule. When doing so, it was found that the density in which one can pack such a polyelectrolyte layer depends on the size of the hydrophobic anchor. For this reason, we used stearoyl Ci8 tails. The results of such a calculation are given in Figure 26. 

Gill microenvironment the surface layers of water/mucus adjacent to the gills, inside the opercular cavity of fishes. 

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