Inorganic Clusters in Organic Polymers and the Use of Polyfunctional Inorganic Compounds as Polymerization Initiators

Summary.   Silicon oxide or metal oxide clusters or small particles with polymerizable organic groups covalently bonded to their surface can be copolymerized with organic monomers by various polymerization techniques. Whereas the preparation and properties of the polymers reinforced by R ₈Si₈O₁₂ have already been well investigated, analogous materials with incorporated transition metal oxide clusters are only beginning to show their potential as an interesting new class of inorganic-organic hybrid polymers. In the second part of the article, approaches are reviewed in which the inorganic building block serves as an initiator for polymerization reactions. This results in materials in which the organic polymer is grafted from an inorganic core. Most work has been done with surface-modified silica particles. Free radical polymerizations and atom transfer radical polymerizations with macroinitiators are summarized. The latter method results in polymeric particles in which an inorganic core is surrounded by an organic polymer shell. A new approach is the use of polyfunctional inorganic molecules or molecular clusters as initiators. Received July 28, 2000. Accepted August 7, 2000     

稀土配合物杂化发光材料的组装及光物理性质研究进展

稀土配合物兼具无机物稳定性好以及有机物荧光量子效率高的优点,而且具有可设计性,制备简便,容易修饰,荧光性质优异（发射谱带窄、色纯度高、荧光寿命长、量子产率高以及发射光谱范围覆盖可见和近红外光区等）．但配合物的光、热、化学稳定性和机械加工性能相对较差,因而限制了其在很多领域中的实际应用．近年来的研究表明,将稀土配合物引入到各种基质材料中可以改善其稳定性及机械加工性能,并对其光物理性质产生调制作用．根据基质材料的不同,杂化材料可分为无机基质、无机／有机复合基质及有机基质杂化材料．本文综述了这些不同基质稀土配合物杂化发光材料的研究进展,探讨了主客体间相互作用对杂化材料光物理性质及稳定性的影响,为实现稀土配合物杂化发光材料在光学器件领域（LED照明、光纤维、光学放大器及激光等）及生命分析领域的应用提供了重要的理论依据．     

The influence of CO on the surface plasmon absorption band of small silver clusters (D≤20 Å)

The surface plasmon absorption band of small Ag particles (diameter≤100 Å) in the gasphase as well as for clusters embedded in noble gas matrices is known to shift to higher energies and to broaden with decreasing diameter. This size effect depends sensitively on the microscopic surface properties of the clusters, which can be influenced by the interaction with the embedding matrix. Previous experiments with silver clusters in the size range 20 Å≤D≤100 Å proved that for SiO₂ and CO the matrix influence is strong enough to supersede the intrinsic size effect as observed in the noble gas matrices. The investigation of the influence of a CO matrix on smaller clusters with D≤20 Å reveals a novel feature: the position as well as the width of the surface plasmon absorption band become independent of the cluster size.     

Optical Effects Associated with Aggregates of Clusters

The effect of aggregation on the optical properties of nanometer-sized particles is studied. It is shown that for small noble metal clusters as well as for pigments of Fe₂O₃, TiN, or ZrN, the aggregation leads to changes in the color of the colloidal systems which are caused by electromagnetic coupling among the clusters in the aggregates. The model of interacting particles is shown to be helpful also for interpretation of optical properties of organic dyes with incorporated metal clusters and for interpretation of the reflectance of magnetooptical cluster systems. For soot particles it is shown that scattering and absorption are enhanced over the whole visible spectral region compared to isolated carbonaceous clusters. Finally, it is shown that the model of interacting clusters can also be applied for data interpretation in scanning near-field optical microscopy.     

Reference materials for small-sample analysis

Many modern analytical techniques use small solid samples and lack proper reference materials for their calibration and quality assurance. A remedy to this deficiency may be in the development of a new genre of highly homogeneous natural matrix materials, their properties being studied with analytical techniques such as PIXE and μ-PIXE, solid sampling AAS, scanning electron microscopy in combination with electron probe X-ray microanalysis, and INAA. Suitable natural materials may be obtained in form of single cell biological materials, finely dispersed suspensions and precipitates such as air particulate matter or sediments, and by appropriate particle size reduction of complex matrices. Initial studies have been carried out on single cell green algae biomass and air particulate matter, as well as several processed materials. Narrow particle size distributions with particles preferably below 10 μm diameter may assure the desired analytical homogeneity. The determination of sampling parameters for individual measurands will ascertain the utility of a material for small-sample analysis. Received: 16 June 1997 / Revised: 24 September 1997 / Accepted: 27 September 1997     

Preparation, characterization, and catalysis of mecro-catalysts

Because catalysis by metals is a surface phenomenon, many technological catalysts contain small (typically nanometre-sired) supported metal particles with a large fraction of the atoms exposed. Many reactions, such as hydrocarbon hydrogenations, are structure-insensitive, proceeding at approximately the same rates on metal particles of various sizes provided that they are larger than 1 nm and show bulk-like metallic behavior. But the catalytic properties are not known when metal particles become so small that their sizes are indium clusters consisting of several indium atoms. Here the catalytic behavior of precisely defined clusters of just four and six indium atoms on solid supports is shown. It is found that the Ir4 and Ir6 clusters differ in catalytic activity both from each other and from metallic Ir particles.     

Organic nanocrystals grown in sol-gel matrices: new hybrid organic-inorganic materials for optics

We have developed a simple and generic preparation of stable organic nanocry stals grown in gel-glass matrices. The synthesis of these hybrid organic-inorganic materials is based on the confined nucleation and growth of organic phases in the pores of dense gels. For bulk nanocomposite samples, narrow size distributions of particles (10–20 nm in diameter) are obtained. We have extended this method to the preparation of organic nanocrystals embedded in sol-gel thin films prepared by spin-coating. For all these nanocomposite materials, we have significantly increased the dye stability and obtained promising optical properties: luminescence, non-linear optical properties or photochromism. Moreover, we have also demonstrated basic working principles of a new type of fluorescent nanosensor through the preparation of organic luminescent nanocrystals grown in silicate films.     

Organofunctional Metal Oxide Clusters as Building Blocks for Inorganic-Organic Hybrid Materials

The controlled hydrolysis of metal alkoxides in the presence of methacrylic acid results in metal oxide clusters capped by polymerizable methacrylate ligands. Radical polymerization of small portions of such clusters with organic co-monomers allows the preparation of an interesting new type of inorganic-organic hybrid polymers in which the metal oxo clusters efficiently crosslink the organic polymers chains. SAXS investigations revealed that the clusters may aggregate to form clusters of clusters. The properties of the hybrid materials, such as thermal stability, swelling, dielectric and mechanical properties, depend not only on the portion of incorporated cluster, i.e. the crosslinking density, but also on the kind of employed cluster.     

New Inorganic Components for Dental Filling Composites

Dental composite filling materials are improved by incorporating nanofillers. They impart increased hardness and wear resistance to composites. In addition, they produce better polishing results than macrofillers. If the particles are sufficiently small, transparent composite pastes are obtainable, independent of the refractive index of the polymerisable monomers. In this context, organosols, non-agglomerated nanoparticles in organic liquid media, are especially interesting. Some of our own results on organosols are presented in this paper. Their relatively low viscosity enables the preparation of composites with a high filler load, thus reducing the shrinkage of the dental composite during polymerisation and improving the mechanical properties. Inorganic–organic hybrids are an attractive class of materials for dental fillings. The synthesis of different polymerisable ormocers for dental composites is reviewed in the second part. Ormocers can be applied as a polymerisable matrix, improving biocompatibility and wear resistance. Their use as inorganic fillers improves the thermodynamic compatibility of the filler with the matrix and enhances the polishability. Functionalised inorganic clusters used as new additives combine the properties of very small nanoparticulate fillers and well-designed highly functional monomers with high crosslinking capabilities. Xerogel colour pigments are advantageous alternative additives to conventional pigments. 3-D structural colour pigments, which are obtained by the self-assembly of monodisperse spherical particles, produce an opalescent effect resembling that of the natural enamel in highly aesthetic composites.     

Mesoscale Clusters in the Crystallisation of Organic Molecules

The early stages of the molecular self-assembly pathway leading to crystal nucleation have a significant influence on the properties and purity of organic materials. This mini review collates the work on organic mesoscale clusters and discusses their importance in nucleation processes, with a particular focus on their critical properties and susceptibility to sample treatment parameters. This is accomplished by a review of detection methods, including dynamic light scattering, nanoparticle tracking analysis, small angle X-ray scattering, and transmission electron microscopy. Considering the challenges associated with crystallisation of flexible and large-molecule active pharmaceutical ingredients, the dynamic nature of mesoscale clusters has the potential to expand the discovery of novel crystal forms. By collating literature on mesoscale clusters for organic molecules, a more comprehensive understanding of their role in nucleation will evolve and can guide further research efforts.     

SPE and purification of DNA using magnetic particles

Superparamagnetic particles have been attractive for molecular diagnostics and analytical chemistry applications due to their unique magnetic properties and their ability to interact with various biomolecules of interest. This paper presents a critical overview of magnetic nano ‐ and microparticles used as a solid phase for extraction and purification of DNAs. The mechanisms of DNA binding to the surface of functionalised magnetic particles are described. The most widely used materials including silica supports, organic polymers and other materials, mostly containing magnetite or paramagnetic metallic elements are reviewed. The main application areas of magnetic particles for DNA separation are briefly described.     

Functionalized porous silica microspheres as scavengers in parallel synthesis

The use of solid scavengers in parallel solution-phase organic synthesis is an effective method for work-up and purification. Functionalized macroreticular or gel-form polystyrene particles are generally used for scavenging applications, how ever these materials have some limitations. We have developed new scavenging reagents based on ultrapure silica microspheres displaying a variety of functional groups useful for sequestering impurities from reaction products. These materials are easy to handle, have excellent mass-transfer properties, and are efficient scavengers in both polar and nonpolar organic solvents. The properties of these materials were tailored specifically to fit the needs of a medicinal chemist employing parallel synthesis techniques in current commercial equipment. Results are presented from head-to-head comparisons with conventional scavengers in tests designed to demonstrate the versatility of these new materials.     

Infrared spectra of water clusters in krypton and xenon matrices

The infrared absorption spectra of the water molecules and small water clusters, (H(2)O)(n) with n = 2-6, trapped in solid argon, krypton, and xenon matrices have been investigated. The infrared bands of the water clusters with n = 5 and 6 in krypton and n = 3, 4, 5, and 6 in xenon matrices have been identified for the first time in the bonded OH stretching region. The frequency shifts in the bonded OH stretching band of the water dimer and trimer in xenon matrices show fairly large deviations to the red from the empirical correlation between the matrix shifts and the square root of the critical temperatures of the matrix material. The observed anomalous shifts suggest that the water dimer and trimer in solid xenon are trapped in multiple sites, and that the structures of the preferential trapping sites are different from those in argon and krypton matrices.     

New Inorganic Components for Dental Filling Composites

Summary. Dental composite filling materials are improved by incorporating nanofillers. They impart increased hardness and wear resistance to composites. In addition, they produce better polishing results than macrofillers. If the particles are sufficiently small, transparent composite pastes are obtainable, independent of the refractive index of the polymerisable monomers. In this context, organosols, non-agglomerated nanoparticles in organic liquid media, are especially interesting. Some of our own results on organosols are presented in this paper. Their relatively low viscosity enables the preparation of composites with a high filler load, thus reducing the shrinkage of the dental composite during polymerisation and improving the mechanical properties. Inorganic–organic hybrids are an attractive class of materials for dental fillings. The synthesis of different polymerisable ormocers for dental composites is reviewed in the second part. Ormocers can be applied as a polymerisable matrix, improving biocompatibility and wear resistance. Their use as inorganic fillers improves the thermodynamic compatibility of the filler with the matrix and enhances the polishability. Functionalised inorganic clusters used as new additives combine the properties of very small nanoparticulate fillers and well-designed highly functional monomers with high crosslinking capabilities. Xerogel colour pigments are advantageous alternative additives to conventional pigments. 3-D structural colour pigments, which are obtained by the self-assembly of monodisperse spherical particles, produce an opalescent effect resembling that of the natural enamel in highly aesthetic composites.This revised version was published online in February 2005. In the previous version the issue was not marked as a special issue, and the issue title and the editor was missing     

Silver cluster-biomolecule hybrids: from basics towards sensors

We focus on the functional role of small silver clusters in model hybrid systems involving peptides in the context of a new generation of nanostructured materials for biosensing. The optical properties of hybrids in the gas phase and at support will be addressed with the aim to bridge fundamental and application aspects. We show that extension and enhancement of absorption of peptides can be achieved by small silver clusters due to the interaction of intense intracluster excitations with the π-π* excitations of chromophoric aminoacids. Moreover, we demonstrate that the binding of a peptide to a supported silver cluster can be detected by the optical fingerprint. This illustrates that supported silver clusters can serve as building blocks for biosensing materials. Moreover, the clusters can be used simultaneously to immobilize biomolecules and to increase the sensitivity of detection, thus replacing the standard use of organic dyes and providing label-free detection. Complementary to that, we show that protected silver clusters containing a cluster core and a shell liganded by thiolates exhibit absorption properties with intense transitions in the visible regime which are also suitable for biosensing applications.     

The Role of Interface on the Properties of Cluster Assemblies

Atomic clusters characterized by finite size, low dimensionality, and reduced coordination number exhibit many novel properties that are very different from their bulk. As these clusters are assembled, their properties can be significantly altered due to the interaction of these clusters with each other as well as with their support. This paper provides a brief review of the cluster properties that are affected when clusters are deposited on metallic or organic substrates, isolated in matrices or in zeolite cages, coated with acetate ligands, or simply allowed to self-assemble without the presence of any reactive species. It is shown that the interface between the clusters and their support can play an important role on the properties of clusters as their unique characteristics do.     

Controlling adsorption and release of drug and small molecules by organic functionalization of mesoporous materials

A series of mesoporous nanosphere materials that are functionalized with various terminal and bridging organic groups were synthesized. They have improved adsorption capacity and different release properties for drug and small molecules. The materials contained terminal vinyl, 3-mercaptopropyl, 3-aminopropyl, and secondary amine functional groups and bridging ethane, ethene, and benzene groups within their mesopore channel walls. The samples containing mercaptopropyl and vinyl groups showed greater adsorption capacity and better controlled release behavior for rhodamine 6G molecules. On the other hand, mesoporous matrices containing amine functional groups showed higher adsorption capacity and better release properties for ibuprofen molecules. Further studies revealed that the bridging organic groups in the mesopore channel walls also improved the adsorption capacity and release properties of the materials compared to the corresponding samples containing no bridging organic groups. Such improved adsorption and controlled release properties of molecules by simple changes of functional groups on mesoporous materials are important for the development of nanomaterial drug delivery vehicles and for controlled release of drugs over long time periods at specific targeted sites in the body. By judicious choice of organic groups and by systematic design and synthetic approaches, nanoporous materials having different adsorption capacity and release properties for many other drug molecules can also be achieved.     

离子液体固定化材料在固相萃取中的应用研究进展

离子液体是由阴、阳离子组成的低温熔融盐,几乎没有蒸汽压,具有稳定性好、溶解能力强、结构可设计、导电性好等优良性能.离子液体作为一种广受关注的新型“绿色溶剂”,具有代替传统有机溶剂的潜力,其制备方法和应用范围研究日趋完善和多样,已广泛应用于催化化学、光电化学、材料化学和分析化学等领域.离子液体通过功能化导向设计后,可以将...     

Synthesis and luminescence properties of Ag2S and PbS clusters in zeolite A

Zeolite A provides a suitable environment to host Ag2S and PbS clusters, so that spectroscopic investigations on very small particles are possible. The Ag2S monomer is colorless and shows photoluminescence at 490 nm with a lifetime of 300 micros, while the absorption and luminescence of Ag4S2 and larger clusters are red-shifted. The properties of these Ag2S/zeolite A materials depend on the co-cations. Results for Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, and Sr2+ are reported. Excitation energy transfer between Ag2S and Ag4S2 has been studied in materials containing Ca2+ co-cations. PbS particles can be prepared by the same method as Ag2S in the cavities of zeolite A. The PbS monomers obtained are yellow and show photoluminescence at 570 nm, with a lifetime of 700 ns.