High resolution 29Si NMR has been used to study the extent of cross condensation taking place in a hybrid organic/inorganic sol-gel system. Tetraethoxysilane (TEOS) and methyltriethoxysilane (MTEOS) sol-gels were chosen for this purpose. The sols were prepared by acid catalyzed hydrolysis of TEOS and MTEOS with a H2O/Si ratio of 0.3. 29Si NMR shows signals due to both self-condensation and cross-condensation between TEOS and MTEOS. Resonance assignments were made by comparing the positions and intensities of peaks in the spectra of single and multicomponent systems. It was found that, within experimental error, the self- and cross-condensation rates are equal and that extensive molecular level mixing takes place during the early stages of the reaction.

Silica aerogels have numerous properties which suggest applications such as ultra high efficiency thermal insulation. These properties relate directly to the aerogel's pore size distribution. The micro and meso pore size ranges can be investigated by normal small angle x-ray scattering and possibly, nitrogen adsorption. However, the measurement of larger pores (> 250 Å) is more difficult. Due to their limited mechanical strength, mercury porosimetry and nitrogen condensation can disrupt the gel structure and electron microscopy provides only limited large scale structure information. The use of small angle light scattering techniques seems to have promise, the only hurdle is that aerogels exhibit significant multiple scattering. This can be avoided if one observes the gels in the wet stage since the structure of the aerogel should be very similar to the wet gel (as the result of supercritical drying). Thus, if one can match the refractive index, the morphology can be probed. The combination of certain alcoholic solvents fit this index matching criteria. Preliminary results for the gel network (micron range) and primary particle structure (nanometer) are reported by using small angle light scattering and ultra-small angle x-ray scattering. The effects on structure over the length scale range of <1 nm to >5 μπι under different conditions (precursors, pH, etc.) are presented. The change in structure of an aerogel during isostatic compaction to 228 MPa (to simulate drying from wetting solvents) are also discussed.

Many biological systems have evolved means of controlling the architecture of inorganic-organic composites at a nanometer scale. The principles of biochemistry and materials science underlying the potential use of biochemical processing to develop new molecularly tailored materials are discussed, with emphasis on:

1. methods of stereochemical control of the organic-inorganic interface,

2. genetic and enzymic control of biosynthesis and biomineralization,

3. molecular orbital modelling of bio organic-inorganic interfaces,

4. barriers and limitations of biomimetic and hierarchical processing,

5. examples of unique materials made with biochemical processing.

6. needs and potential applications in human prostheses.

A new sol-gel procedure using micellar solutions has been developed to immobilize local anesthetic drugs in optically transparent glass. Dibucaine was selected as a direct emission probe at 77 K for determining the forms of the anesthetic drug (free base, monoprotonated, and/or diprotonated) and its location (hydrophobic core, interfacial layer or hydrophilic region) in micelles. The photophysical properties of local anesthetics obtained in gels are compared to those in solutions. During the gelation stage, the predominant drug species was identified as free base dibucaine embedded in the hydrophobic core of neutral as well as charged micelles. This observation suggests that the micellar interface was modified by the large hydrophilic gel surface during the gelation stage. The modified micellar interface allows an increase in the partition of free base dibucaine into the hydrophobic region. At the xerogel stage, however, the collapse of micellar structure provides a direct interaction of dibucaine with the acidic gel surface, leading to a formation of diprotonated dibucaine. The results are discussed in terms of molecular basis of pharmacological implications such as drug delivery, release, and transport under microencapsulation conditions.

Sol-gel derived composite silica-carbon electrodes exhibit favorable electrochemical characteristics. The electrodes benefit from the conductivity and electrochemical advantages of the carbon powder, from the favorable properties of the ceramic network and from the versatility of the sol-gel process. Hydrophobie composite electrodes reject water, only their outermost surface is wetted and they exhibit good signal to background currents. A comparison of several types of carbon powders reveals that higher carbon loading and larger surface area electrodes can be attained by incorporation of dense graphite powder. When high surface area, small size carbon-black powder is used, a homogeneous distribution of microelectrodes, separated by insulating modified silica is formed. This ensemble of microelectrodes increases the sensitivity of the CCEs by more than two orders of magnitude as compared to glassy carbon electrode and graphite CCEs.

The proteins copper-zinc Superoxide dismutase (CuZnSOD), cytochrome c, myoglobin, hemoglobin, and bacterio-rhodopsin are encapsulated in stable, optically transparent, porous, silica glass matrices prepared by the sol-gel method such that the biomolecules retain their characteristic reactivities and spectroscopic properties. The resulting glasses allow transport of small molecules into and out of the glasses at reasonable rates but retain the protein molecules within their pores. The transparency of the glasses enables the chemical reactions of the immobilized proteins to be monitored by means of changes in their visible absorption spectra. Silica glasses containing the immobilized proteins have similar reactivities and spectroscopic properties to those found for the proteins in solution. The enzymes glucose oxidase and peroxidase were also encapsulated in transparent silica glass matrices. Upon exposure to glucose solutions, a colored glass is formed that can be used as the active element in a solid state optically based glucose sensor. Likewise, gels containing oxalate oxidase and peroxidase exhibit spectroscopic changes upon exposure to aqueous solutions containing oxalic acid.

A system is described for forming three-dimensional parts from a polymerizable slurry. This liquid is delivered from a fine nozzle to build up the component as a series of layers described from a CAD drawing of the part. This is one of a family of solid freebody forming methods. The layerwise process lends itself particularly to chemically syntheized materials where shrinkage and mass transport are major problems. The technique also has considerable potential for combining various materials into a single component.

In order to develop an optical immunosensor based on Surface Plasmon Resonance (SPR) and guided waves propagation, the sol-gel process has been used to prepare thin films of amorphous silica, deposited by spin coating on a gold-coated glass slide, and possessing chemically active functional groups (SH, NH2...). After activation of the sol-gel film in aqueous buffers by a bifunctional coupling agent, biological molecules such as antibodies could be covalently bonded on or inside the sol-gel film. Therefore, the behaviour of the functionalized silica thin films in aqueous solutions has been analyzed by SPR and guided waves propagation. The matrix hydrophilicity has been studied with different mixtures of functionalized silicon precursors forming organic-inorganic hybrid films. Immunoassays outline the possibility of obtaining covalent binding of antibodies to the sol-gel matrix with optimal stability and biological activity.