Silica surface acidity

Protein-Pak packings are designed for the size exclusion chromatography of proteins and related compounds. They are based on silica, which is deactivated with glycidylpropylsilane. The diol function prevents the interaction of the target analytes with the silica surface. However, because coverage of the silica surface is always incomplete, residual acidic silanols can interact with the analytes. For this reason, most applications are carried out with a salt concentration above 0.2 mol/liter, which eliminates the interaction of analytes with surface silanols. Protein-Pak packings are stable from pH 2 to pH 8. 

Theoretically, a fully hydroxylated silica surface should have a pK, 7.1 t 0.5 [28]. In practice, commercially available silica gels have an apparent pH which is very different from that predicted from theory. Table 4.3 [26,28,29,43,44], The range of apparent pH values, determined from the pH of a suspension of silica in neutral, salt free water, range from 3.8 to 9.5. Tha most acidic and the most basic pH values are found for spherical... 

Before reaction, the silica is treated with acid (eg refluxed for a few hours with 0.1 mol dm-3 HC1). This treatment produces a high concentration of reactive silanol groups at the silica surface, and also removes metal contamination and fines from the pores of the material. After drying, the silica is then refluxed with the dimethylchlorosi-lane in a suitable solvent, washed free of unreacted silane and dried. This reaction produces what is called a monomeric bonded phase, as each molecule of the silylating agent can react with only one silanol group. 

Metal alkyl reagents react with the acidic OH groups of silica, probably by the electrophilic cleavage of the metal-carbon bond. For example, the electrophilic cleavage of the metal-carbon bond occurs when organometallic reagents react with the electrophilic OH groups of the silica surface (Scheme... 

Nucleic acids, DNA and RNA, are attractive biopolymers that can be used for biomedical applications [175,176], nanostructure fabrication [177,178], computing [179,180], and materials for electron-conduction [181,182]. Immobilization of DNA and RNA in well-defined nanostructures would be one of the most unique subjects in current nanotechnology. Unfortunately, a silica surface cannot usually adsorb duplex DNA in aqueous solution due to the electrostatic repulsion between the silica surface and polyanionic DNA. However, Fujiwara et al. recently found that duplex DNA in protonated phosphoric acid form can adsorb on mesoporous silicates, even in low-salt aqueous solution [183]. The DNA adsorption behavior depended much on the pore size of the mesoporous silica. Plausible models of DNA accommodation in mesopore silica channels are depicted in Figure 4.20. Inclusion of duplex DNA in mesoporous silicates with larger pores, around 3.8 nm diameter, would be accompanied by the formation of four water monolayers on the silica surface of the mesoporous inner channel (Figure 4.20A), where sufficient quantities of Si—OH groups remained after solvent extraction of the template (not by calcination). 

The pH optical fiber sensor without any pH-sensitive dye was also described70. Porous silica layer made by the sol-gel method was cladded onto optical fibre core and was exploited as the optical transducer. Acid-base properties of silica surface caused that the surface charge of silica changed with pH of the solution. For example saturation of the sol-gel layer with cations leads to an increase of the electron density of the film, hence, the refractive index of the film. Since the surface charge of silica depends on pH, the refractive index of silica film varies also with pH. Thus, changes of... 

The method of catalyst immobilisation appeared to affect its performance in catalysis. Catalyst obtained by method II showed a low selectivity in the hydroformylation of 1-octene (l b aldehyde ratio was even lower than 2) at a very high rate and high yields of isomerised alkenes (Table 3.2, entry 2), whereas procedure IV resulted in a catalyst that was highly selective for the linear aldehyde (with a l b ratio of 37) (entry 5). In accordance with examples from literature it is likely that procedure II gave rise to the ionic bonding of ligand-free rhodium cations on the slightly acidic silica surface [29],... 

Gulina, L. B. Tolstoi, V. P. 2004. Synthesis on silica surface by the ionic deposition technique of nanolayers of heteropolycompounds on the basis of phospho-molybdic acid. Russ. J. Gen. Chem. 74 327-330. 

Triflic acid has also been supported on a porous silica carrier (220). The authors emphasized the importance of a strong interaction between the acid and the support to prevent leaching of the acid. In pulsed liquid-phase isobutane/ 1-butene alkylation experiments at 298 K, the catalysts produced a very high-quality alkylate, made up almost exclusively of isooctanes. With silanol groups on the silica surface or with added water, triflic acid was found to form a monohydrate that was firmly grafted to the silica surface. 

Various novel imprinting techniques have also been presented recently. For instance, latex particles surfaces were imprinted with a cholesterol derivative in a core-shell emulsion polymerization. This was performed in a two-step procedure starting with polymerizing DVB over a polystyrene core followed by a second polymerization with a vinyl surfactant and a surfactant/cholesterol-hybrid molecule as monomer and template, respectively. The submicrometer particles did bind cholesterol in a mixture of 2-propanol (60%) and water [134]. Also new is a technique for the orientated immobilization of templates on silica surfaces [ 135]. Molecular imprinting was performed in this case by generating a polymer covering the silica as well as templates. This step was followed by the dissolution of the silica support with hydrofluoric acid. Theophylline selective MIP were obtained. 

The silanol groups on the silica surface also show acidic character, the pKa value being 6.8 ... 

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