Sol-gel matrix

In a similar vein, Gelman et al. [25] demonstrated encapsulation by the use of two SiC>2 sol-gel matrices [26,27] to immobilize two catalysts Wilkinson s catalyst and an amine that acts as a base catalyst. The reaction is illustrated in Scheme 5.10. 

Furthermore, the same sol-gel matrices have been used in a system where acid and base catalysis occur in the same pot without quenching either catalyst [29]. In this case, the acids were either entrapped Nafion (perfluorinated resin sulfonic super acid, a3) or entrapped molybdic acid (M03-Si02, a2), while the bases were two ORMOSILs (organically modified silica sol-gel materials), one with H2N (CH2)2NH(CH2)3 groups (bi) and the other guanidine base residues (b2) (Scheme 5.12). 

Fig. 1.3 Schematic representation of the entrapped enzyme in a silica matrix (left side). Enzymatic activity, under extreme alkaline conditions, of acid phosphatase (A) immobilized in silica sol-gel matrices with or without CTAB, or (B) in solution. Reprinted with permission from [56]. Copyright 2005, American Chemical Society.

Encapsulation of proteins in bulk and thin film sol-gel matrices. Journal of Sol-Gel Science and Technology, 8, 629-634. 

A wide range of additives can also be introduced into the sol-gel matrices in order to modulate the hydrophobicity of the materials and to improve enzyme stability, activity and accessibility, leading to hybrid or even composite sol-gel matrices. Polymers [157,179,180] such as polyethyleneglycol, polyvinylpyrrolidone, polyvinylalcohol, polyglycidol, polyethyleneimine, polyacrylate have been simultaneously entrapped with enzymes in a siloxane matrix, as well as organic additives (sugar, amino add)... 

Inclusion of inorganic compounds such as graphite, quartz fiber felt, days and metal oxides is another way to modify the porosity of the sol-gel matrices... 

With regard to biosensor applications, a wide variety of electrochemically active species (ferrocene, ruthenium complexes, or carbon and metal (Pt, Pd, Au...) [185,186] were also introduced into the sol-gel matrices or adsorbed to improve the electron transfer from the biomolecules to the conductive support [187,188]. For instance, glucose oxidase has been trapped in organically modified sol-gel chitosan composite with adsorbed ferrocene to construct a low-cost biosensor exhibiting high sensitivity and good stability [189]. 

The way of enzyme entrapment has been described79 proposing the application of sol-gel matrices. The optodes of urea sensor were prepared by the sol-gel method and were stored in a refrigerator. As the pH sensitive dye the bromothymol blue was used. Since it is best acting in pH range 6 to 7.6, the pH of sol-gel bulks obtained in the experiment was chosen as pH 6. Before measurements, the optodes were incubated in the temperature 36.6°C. 

Andrzejewski D., Podbielska H., Mutual influences of sol-gel matrices and dopants on the materials optical properties, Opt. Appl. 2001 31 223-229. 

Delmarre D., Meallet-Renault R., Bied-Charreton C., Pasternack R., Incorporation of water-soluble porphyrins in sol-gel matrices and application to pH sensing, Anal. Chim. Acta 1999 401 125-128. 

Several enzymes have been immobilized in sol-gel matrices effectively and employed in diverse applications. Urease, catalase, and adenylic acid deaminase were first encapsulated in sol-gel matrices [72], The encapsulated urease and catalase retained partial activity but adenylic acid deaminase completely lost its activity. After three decades considerable attention has been paid again towards the bioencapsulation using sol-gel glasses. Braun et al. [73] successfully encapsulated alkaline phosphatase in silica gel, which retained its activity up to 2 months (30% of initial) with improved thermal stability. Further Shtelzer et al. [58] sequestered trypsin within a binary sol-gel-derived composite using TEOS and PEG. Ellerby et al. [74] entrapped other proteins such as cytochrome c and Mb in TEOS sol-gel. Later several proteins such as Mb [8], hemoglobin (Hb) [56], cyt c [55, 75], bacteriorhodopsin (bR) [76], lactate oxidase [77], alkaline phosphatase (AP) [78], GOD [51], HRP [79], urease [80], superoxide dismutase [8], tyrosinase [81], acetylcholinesterase [82], etc. have been immobilized into different sol-gel matrices. Hitherto some reports have described the various aspects of sol-gel entrapped biomolecules such as conformation [50, 60], dynamics [12, 83], accessibility [46], reaction kinetics [50, 54], activity [7, 84], and stability [1, 80],... 

The sol-gel-entrapped microbial cells have shown excellent tolerance to different alcohols [99], The immobilized E. coli cells followed the Michaelis-Menten equation when quantified with the (3-glucosidase activity via the hydrolysis of 4-nitrophenyl-(3-D-galactopyranosdie [142], The sol-gel matrices doped with gelatin prevented the cell lysis, which usually occurs during the initial gelation process [143], Microorganisms are now widely used in the biosorption of different pollutants and toxicants. Bacillus sphaericus JG-A12 isolated from uranium mining water has been entrapped in aqueous silica nanosol for the accumulation of copper and uranium [144], Premkumar et al. [145] immobilized recombinant luminous bacteria into TEOS sol-gel to study the effect of sol-gel conditions on the cell response (luminescence). The entrapped and free cells showed almost the same intensity of luminescence (little lower), but the entrapped cells were more stable than the free cells (4 weeks at 4°C). This kind of stable cell could be employed in biosensors in the near future. 

Relatively less work has been done on immobilization of plant and animal cells and spores of microbes in silica matrixes. The main drawback is less viability of the cells in sol-gel matrices. Thus more refined methods are required to utilize harness of the whole cells entrapped in sol-gel matrices and biosensing applications. At the same time studies such as interactions between sol-gel matrices and whole cells and metabolic changes during immobilization have to be closely monitored for the exploration of new matrices and methods. 

First demonstrated by David Avnir in 1984, the principle is as simple as it is potent. Due to the low temperature needed for the preparation of sol-gel matrices, almost all of the 18 million existing organic and bio organic molecules that could not be doped in glass, because glass is prepared at elevated temperatures (about 1000 °C), can now be entrapped in sol-gel glasses. 

Figure 1.12 Photochemical titration curves of crystal violet co-entrapped in silica sol-gel matrices with different surfactants, no surfactant ( ) and in solution (x) show the impressive variations in the sensing properties for the same entrapped dye. (Reproduced from ref. 26, with permission.)... 

Initially, the sol gel compositions were optimized using Congo red dye as the dopant because of its optical properties. This facilitates monitoring of the release process by optical spectroscopy. Next, the gels were evaluated for their stabilization and release of subtilisin. These sol gel matrices bring about controlled release of the encapsulated enzyme molecules as a response to a change in the water content of the medium (Figure 2.20).15... 

Leach-proof sol-gel entrapment can be exploited to carry out one-pot reactions with mutually destructive reactants while still allowing these reagents to activate or participate in desired reactions. For instance, three different one-pot redox reactions can be carried out in sequence in one pot over two separate sol-gel matrices doped with an oxidant (pyridinium dichromate) and with a reducing species (RhCl[P(C6H5)3]3) without their mutual destruction and with no need for separation steps (Figure 5.12).24... 

Biological species such as enzymes, whole cells, antibodies and even bacteria can all be successfully entrapped in silica sol-gel matrices, often with enhancement of activity with respect to the free biologicals. In these cases, the process is adapted to eliminate toxic alcohols which are typically released in conventional sol-gel processes based on the hydrolysis of silicon alkoxides. Two such methods are the use of silicon alkoxide... 

The chemical inertness and optical transparency of Si02 sol-gel matrices make the doping methodology ideal for sensor developments, even if leaching is an issue that must be often addressed. Another attractive, unique feature is that non-toxic sol-gel silicas can be made in... 

When a system contains a fluorophore in different environments (e.g. a fluo-rophore embedded in microheterogeneous materials such as sol-gel matrices, polymers, etc.) or more than one fluorophore (e.g. different tryptophanyl residues of a protein), the preceding relations must be modified. If dynamic quenching is predominant, the Stem-Volmer relation should be rewritten as... 

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