Ormosil matrices

Figure 1.20 Encapsulation of microdroplets of liquid crystals in ORMOSIL matrices results in materials with better transparency and thermal stability than polymer-dispersed liquid crystals. Gel-glass dispersed liquid crystal device switched between the OFF and ON state (thickness 10 pm, 4 x 2 cm, Fp p = 90V). (Reproduced from ref. 45, with permission.)...

Zayat, M., Pardo, R., and Levy, D. (2003) The role of organic groups in ormosil matrices in the photochromism of naphthopyrans in sol-gel thin films. 

LC) NC-4 (cH2) CH3 FIGURE 20.6 Schematic representation of a pore strncture in silica and ormosil matrices. 

An optical sensor for the measurement of carbon dioxide in modified atmosphere packaging (MAP) applications was developed89. It was based on the fluorescent pH indicator l-hydroxypyrene-3,6,8-trisulfonate (HPTS) immobilized in a hydrophobic organically modified (ormosil) matrix. The CO2 sensor was stable over a period of at least 7 months and its output was in excellent agreement with a standard reference method for carbon dioxide analysis. 

In other cases, organic modification of the sol gel cages markedly protects the entrapped molecular dopant from degradation by external reactants, as shown for instance by the entrapment of the radical 2,2,6,6-tetramethylpiperidine-l-oxyl (TEMPO). This is a highly active catalyst which in the NaOCl oxidation of alcohols to carbonyls in a CH2CI2-H20 biphasic system becomes highly stabilized upon sol gel entrapment in an ORMOSIL matrix it progressively loses it activity when entrapped at the external surface of commercial silica.25... 

An example of the appropriate application of organically-modified silica precursors is alkoxides with an alkyl group. When methyltrimethoxy- or methyl-triethoxysilane (Figure 3.2) was added in formulations to increase the hydro-phobicity of ORMOSILs, it resulted in a better enzymatic activity of lipases immobilized in the alkyl-modified silica than in a hydrophilic matrix fabricated by means ofTEOS alone [51,80,129-133]. Similarly, an increased stability of lipase from Candida antarctica B was observed after its immobilization in a silica matrix... 

Fig. 12.8 Electron microscopy study of a PDMS-Si02-CaO ormosil (A) Original HRTEM image of the amorphous matrix, (B) filtered HRTEM image and (C) Fourier transform pattern. Distances up to 0.53 nmfor (Si04)4-can be observed in the filtered image, indicating the presence of Ca2+ between the tetrahedra.

For example, the mechanical properties—hardness and elastic modulus—of ORMOSIL can be tuned by varying the degree of alkylation and thus the fraction of six- and four-member siloxane rings in the organosilica matrix. This enables fine tuneability of parameters of crucial practical importance (Figure 4.2).2... 

Figure 4.2 Loading curves for ORMOSIL thin films with varying degrees of alkylation of the silica matrix. (Reproduced from ref. 2, with permission.)...

The trend was studied and verified, for instance, for reactions catalysed by transition metal, organo- and enzyme catalysts entrapped in ORMOSIL prepared by copolymerization of tetramethoxysilane (TMOS) and the modifying co-precursor methyltrimethoxysilane (MTMS). It has been correlated with the encapsulation itself but also with the structure of the sol-gel matrix, namely the hydrophobicity-lipophilicity balance (HLB) and the textural properties of the materials.9... 

Ormosil-TEMPO is a sol-gel hydrophobized nanostructured silica matrix... 

PEBBLEs are water-soluble nanoparticles based on biologically inert matrices of cross-linked polymers, typically poly(acrylamide), poly(decylmethacrylate), silica, or organically modified silicates (ORMOSILs), which encapsulate a fluorescent chemo-sensor and, often, a reference dye. These matrices have been used to make sensors for pH, metal ions, as well as for some nonionic species. The small size of the PEBBLE sensors (from 20 to 600 nm) enables their noninvasive insertion into a living cell, minimizing physical interference. The semipermeable and transparent nature of the matrix allows the analyte to interact with the indicator dye that reports the interaction via a change in the emitted fluorescence. Moreover, when compared to naked chemosensors, nanoparticles can protect the indicator from chemical interferences and minimize its toxicity. Another important feature of PEBBLEs, particularly valuable in intracellular sensing applications, is that the polymer matrix creates a separate... 

The confinement of a relatively large number of dye molecules in the small volume of a nanoparticle may trigger collective phenomena otherwise not observable in bulk solution. This has been demonstrated by Prasad and coworkers in the case of an ORMOSIL pH sensor.69 The PEBBLEs contain a naphthalenylvinylpyridine derivative (NVP) as pH-sensitive fluorescent dye which has been functionalized with a triethoxysilane anchor by reaction with an excess of (3-isocyanatopropyl)triethoxysi-lane (ICTES). The sol-gel polymerization in aqueous micellar solution of the NVP-ICTES derivative with VTES gives spherically shaped 33 nm silica nanoparticles in which the dye is covalently linked to the silica matrix and uniformly distributed in the nanoparticle volume. The NVP dye responds ratiometrically to protons, with a... 

In form of thin films Ormosils are superior to pure oxides in their lower tendency to fracture because of the presence of organic groups in their structure. The films are flexible although the Si02 content may be about 70 wt%. They have already been successfully used as matrix in solid-state dye lasers [484]. 

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