Molecular imprinting science and technology: a survey of the literature for the years up to and including 2003

The class of hybrid organic−inorganic materials called bridged polysilsesquioxanes are used for everything from surface modifiers and coatings to catalysts and membrane materials. This paper examines how bridged polysilsesquioxanes are prepared, processed, characterized, and used. In particular, it describes how attaching several “inorganic” cross-linking trialkoxysilanes on organic bridging groups permits facile formation of network polymers and gels with high levels of chemical functionality. There are a number of synthetic entries into bridged polysilsesquioxane monomers that have allowed a multitude of different bridging groups to be integrated into xerogels (dry gels) or aerogels (supercritically dried “air gels”). Much of the research to date has been successfully focused on engineering of the size of pores through the choice of the bridging groups. For example, materials with some of the highest known surface areas in porous materials have been prepared, and parameters allowing control of the pore ...

Bridged polysilsesquioxanes. molecular-engineered hybrid organic-inorganic materials

Selective recognition of metal ions is a real challenge for a large range of applications in the analytical field (from extraction to detection and quantification). For that purpose, ion-imprinted polymers (IIPs) have been increasingly developed during the last 15 years on the principle of molecularly imprinted polymers (MIPs). Those imprinted materials are designed to mimic the binding sites of biological entities and assure an improved recognition of the template species. The aim of this review is to give the current state of the art in the conception of IIPs from the components to the polymerization process. Some applications of those materials will be also discussed.

Recent advances on ion-imprinted polymers

Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometalate anions, and radionuclides. Details addressing the design, synthesis, and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental cleanup necessary after 40 years of weapons-grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented.

Actinide sequestration using self-assembled monolayers on mesoporous supports.

Preparation and evaluation of a molecularly imprinted sol-gel material for on-line solid-phase extraction coupled with high performance liquid chromatography for the determination of trace pentachlorophenol in water samples.

Molecular imprinting involves arranging monomers of polymerization synthesis around a template molecule so that complexes between the monomer and template molecules are formed. Subsequent polymerization of the monomer molecules results in trapping template molecules in a highly cross-linked amorphous polymer matrix. Extraction of the imprint molecules leaves a predetermined arrangement of ligands and a tailored binding pocket. Such imprinted polymers have been used to mimic antibody functions to resolve racemates, and to separate mixtures of metal cations. Thus far, the organization of precursor monomers has been achieved mainly in inhomogeneous organic polymer matrices, with little control over structural parameters, such as pore sizes and surface areas. The authors report the first synthesis of imprinted hybrid sorbent materials with precise control of not only adsorption sites but also pore structures. The concepts behind multilevel imprinting are as follows. Surfactant micelles and metal ions both act as templates in these hierarchically imprinted sorbents. The metal ion and the surfactant are removed from the silica matrix via acid leaching and ethanol extraction, respectively. This results in the formation of different-sized imprints within the silica matrix, each with a specific function.

Hierarchically Imprinted Sorbents for the Separation of Metal Ions

Mesoporous titanosilicate sol-gel materials with different Silicon to titanium ratios were prepared by hydrothermal synthesis through the micellar template approach. The prepared samples have been characterized via infrared spectroscopy, nitrogen Sorption, powder X-ray diffraction, and acid-base titration. The uptake of uranyl ion (UOi\"^) by the samples was determined at pH = 5.10. The uranyl loading capacity of the pure mesoporous titania was determined to be the largest. This capacity is much higher than that of the corresponding microporous material. The increase of capacity is correlated to the large surface area induced by the Surfactant template synthetic method for mesoporous materials, increased concentrations of TiO\" surface functional ligands, and large pore openings of the mesoporous materials allowing for access to the inner pore surfaces. The adsorption kinetics of our mesoporous sorbents are much faster than those of the corresponding microporous materials. The adsorption equilibria can be reached in less than 15 min.

Investigation of Uranyl Adsorption on Mesoporous Titanium-based Sorbents

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Hierarchically Imprinted Sorbents for the Separation of Metal Ions

Investigation of Uranyl Adsorption on Mesoporous Titanium-based Sorbents