Sites specific surface

Huang Y, Leobandung W, Poss A, Peppas NA. Molecular aspects of muco- and bioadhesion tethered structures and site-specific surfaces. J Control Release 2000,... 

The application of the (bio)availability concepts for the aquatic compartment consists of the translation of the conventional estimated effect thresholds (e.g. NOEC/ ECio values) towards conditions prevailing in a certain region or for a certain site-specific surface water, using either transformation to soluble fractions, speciation or bioavailability algorithms (e.g. the free metal ion, BLM). At TC NES III (September 2006) it was agreed that the level of refinement that can be obtained depends on the availability and applicability of the concepts and tools for the specific metal/metal compound under consideration, as outlined in Eigure 7.3.2. 

Huang, Y., Leobandung, W., Foss, A., Peppas, N.A. Molecular aspects of muco and bioadhesion Tethered structures and site-specific surfaces. J. Contr. Release, 65, 63, 2000. 

Photoreactive chromophores incorporated into polymer films can be used for inducing site-specific surface reactions and generation of chemical patterns. The chromophore 2-naphthoquinone-3-methide generates highly reactive radicals upon exposure, which can selectively react with vinyl... 

There are complexities. The wetting of carbon blacks is very dependent on the degree of surface oxidation Healey et al. [19] found that q mm in water varied with the fraction of hydrophilic sites as determined by water adsorption isotherms. In the case of oxides such as Ti02 and Si02, can vary considerably with pretreatment and with the specific surface area [17, 20, 21]. Morimoto and co-workers report a considerable variation in q mm of ZnO with the degree of heat treatment (see Ref. 22). 

A variety of experimental data has been found to fit the Langmuir equation reasonably well. Data are generally plotted according to the linear form, Eq. XVn-9, to obtain the constants b and n from the best fitting straight line. The specific surface area, E, can then be obtained from Eq. XVII-10. A widely used practice is to take to be the molecular area of the adsorbate, estimated from liquid or solid adsorbate densities. On the other hand, the Langmuir model is cast around the concept of adsorption sites, whose spacing one would suppose to be characteristic of the adsorbent. See Section XVII-5B for an additional discussion of the problem. 

The site specificity of reaction can also be a state-dependent site specificity, that is, molecules incident in different quantum states react more readily at different sites. This has recently been demonstrated by Kroes and co-workers for the Fl2/Cu(100) system [66]. Additionally, we can find reactivity dominated by certain sites, while inelastic collisions leading to changes in the rotational or vibrational states of the scattering molecules occur primarily at other sites. This spatial separation of the active site according to the change of state occurring (dissociation, vibrational excitation etc) is a very surface specific phenomenon. 

Figure Bl.22.1. Reflection-absorption IR spectra (RAIRS) from palladium flat surfaces in the presence of a 1 X 10 Torr 1 1 NO CO mixture at 200 K. Data are shown here for tluee different surfaces, namely, for Pd (100) (bottom) and Pd(l 11) (middle) single crystals and for palladium particles (about 500 A m diameter) deposited on a 100 A diick Si02 film grown on top of a Mo(l 10) single crystal. These experiments illustrate how RAIRS titration experiments can be used for the identification of specific surface sites in supported catalysts. On Pd(lOO) CO and NO each adsorbs on twofold sites, as indicated by their stretching bands at about 1970 and 1670 cm, respectively. On Pd(l 11), on the other hand, the main IR peaks are seen around 1745 for NO (on-top adsorption) and about 1915 for CO (tlueefold coordination). Using those two spectra as references, the data from the supported Pd system can be analysed to obtain estimates of the relative fractions of (100) and (111) planes exposed in the metal particles [26].

Examination of these and other results indicates that the value of a for a given adsorptive which needs to be used in order to arrive at a value of specific surface consistent with that from nitrogen adsorption, varies according to the nature of the adsorbent. The existence of these variations shows that the conventional picture, in which the value of a corresponds to a monolayer which is completely filled with adsorbate molecules in a liquidlike packing, is over-simplified. Two factors can upset the simple picture (a) there may be a tendency for adsorbed molecules to become localized on lattice sites, or on more active parts of the solid surface and (b) the process... 

Of these, the most extensive use is to identify adsorbed molecules and molecular intermediates on metal single-crystal surfaces. On these well-defined surfaces, a wealth of information can be gained about adlayers, including the nature of the surface chemical bond, molecular structural determination and geometrical orientation, evidence for surface-site specificity, and lateral (adsorbate-adsorbate) interactions. Adsorption and reaction processes in model studies relevant to heterogeneous catalysis, materials science, electrochemistry, and microelectronics device failure and fabrication have been studied by this technique. 

Raman spectroscopy has provided information on catalytically active transition metal oxide species (e. g. V, Nb, Cr, Mo, W, and Re) present on the surface of different oxide supports (e.g. alumina, titania, zirconia, niobia, and silica). The structures of the surface metal oxide species were reflected in the terminal M=0 and bridging M-O-M vibrations. The location of the surface metal oxide species on the oxide supports was determined by monitoring the specific surface hydroxyls of the support that were being titrated. The surface coverage of the metal oxide species on the oxide supports could be quantitatively obtained, because at monolayer coverage all the reactive surface hydroxyls were titrated and additional metal oxide resulted in the formation of crystalline metal oxide particles. The nature of surface Lewis and Bronsted acid sites in supported metal oxide catalysts has been determined by adsorbing probe mole-... 

Many of the factors that influence the c.xtcnt of contamination are site specific, cither climatic or hydrogeological. Other factors that influence the extent of contamintition relate to land surface features such as topography or dcNclopmcnt, which determine exposure routes. Additional important... 

Dehydration reactions are typically both endothermic and reversible. Reported kinetic characteristics for water release show various a—time relationships and rate control has been ascribed to either interface reactions or to diffusion processes. Where water elimination occurs at an interface, this may be characterized by (i) rapid, and perhaps complete, initial nucleation on some or all surfaces [212,213], followed by advance of the coherent interface thus generated, (ii) nucleation at specific surface sites [208], perhaps maintained during reaction [426], followed by growth or (iii) (exceptionally) water elimination at existing crystal surfaces without growth [62]. 

Subtilisin, 170 active site of, 171,173 autocorrelation function of, 216, 216 potential surfaces for, 218 site-specific mutations, 184, 185, 187-188 Sugars, see Oligosaccharides Surface-constrained solvent model, 125... 

Calculate the specific surface site concentration (moles of surface sites per gram) for quartz (Si02) particles 1 jum in diameter. Assume a site density, ris, of 5 sites/nm (1 nm = 10 m). What will be the concentration of silica surface sites if the suspended quartz is present at 2 ppm (mg/L) ... 

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