Mesoporous silicates

The other type of porous glass that has cylindrical pores is mesoporous silicate (MPS) (14,15). The advantage of MPS is in its feasibility to make a small pore diameter, typically below 10 nm. A columnar-phase liquid crystal, formed from surfactant molecules with a long alkyl chain tail and silicate molecules, is calcined to remove hydrocarbons. At the end, a hexagonal array of straight and uniform cylindrical holes is created in a crystalline order. MPS is not available commercially either. 

Metalloporphyrinosilicas as a new class of hybrid organic-inorganic materials were prepared by polymerization of 3- er -butyl-5-vinylsalicylaldehyde with styrene and divinylbenzene and used as selective biomimetic oxidation catalyst.27 Synthesis and structural characterization of rare-earth bisfdimethyl-silyl)amides and their surface organometallic chemistry on mesoporous silicate MCM-41 have been reported.28... 

McEleney, K., Allen, D.P., Holliday, A.E. and Crudden, C.M. (2006) Functionalized mesoporous silicates for the removal of ruthenium from reaction mixtures. Organic Letters, 8 (13), 2663-2666. 

Fig. 4.5 Monolayer adsorption capacities of lysozyme onto (A) MCM-41-type mesoporous silicates ((a) MCM-41 and (b) AIMCM-41) and (B) SBA-15-type mesoporous silicates ((a) SBA-15 and (b) AISBA-15). Reprinted with permission from [119],...

Nucleic acids, DNA and RNA, are attractive biopolymers that can be used for biomedical applications [175,176], nanostructure fabrication [177,178], computing [179,180], and materials for electron-conduction [181,182]. Immobilization of DNA and RNA in well-defined nanostructures would be one of the most unique subjects in current nanotechnology. Unfortunately, a silica surface cannot usually adsorb duplex DNA in aqueous solution due to the electrostatic repulsion between the silica surface and polyanionic DNA. However, Fujiwara et al. recently found that duplex DNA in protonated phosphoric acid form can adsorb on mesoporous silicates, even in low-salt aqueous solution [183]. The DNA adsorption behavior depended much on the pore size of the mesoporous silica. Plausible models of DNA accommodation in mesopore silica channels are depicted in Figure 4.20. Inclusion of duplex DNA in mesoporous silicates with larger pores, around 3.8 nm diameter, would be accompanied by the formation of four water monolayers on the silica surface of the mesoporous inner channel (Figure 4.20A), where sufficient quantities of Si—OH groups remained after solvent extraction of the template (not by calcination). 

One of the most promising applications of enzyme-immobilized mesoporous materials is as microscopic reactors. Galameau et al. investigated the effect of mesoporous silica structures and their surface natures on the activity of immobilized lipases [199]. Too hydrophilic (pure silica) or too hydrophobic (butyl-grafted silica) supports are not appropriate for the development of high activity for lipases. An adequate hydrophobic/hydrophilic balance of the support, such as a supported-micelle, provides the best route to enhance lipase activity. They also encapsulated the lipases in sponge mesoporous silicates, a new procedure based on the addition of a mixture of lecithin and amines to a sol-gel synthesis to provide pore-size control. 

Fig. 4.28 Cate-controlled molecular recognition and fluorescence detection by selective functionalization of external and internal surfaces of mesoporous silicates. Reprinted with permission from [225], R. D. Radu et al.,J. Am. Chem. Soc. 2004, 126, 1640. 2004, American Chemical Society.

A. Bleloch, B. F. G. Johnsons, S. V. Ley, A. J. Price, D. S. Shepard and A. W. Thomas, Modified Mesoporous Silicate MCM-41 Immobilized Perruthenate - A New Highly Active Heterogeneos Oxidation Catalyst for Clean Organie Synthesis using Molecular Oxygen, Chem. Commun. 18 (1999) 1907-1908. 

The influence of the nature of the aluminum source on the acidic properties of mesostructured materials (MCM41) has also been studied in the literature [244]. Microcalorimetry experiments using ammonia as a probe molecule have shown that Al insertion into the mesoporous silicate framework affected acid site strength and distribution in a manner controlled by the synthesis conditions (materials prepared... 

Most of the one-pot syntheses of organically functionalized mesoporous silicates have been done under basic conditions. Only hexagonal phases (2d, p6m) were reported so far, except one very recent example of a phenyl-functionalized cubic phase [17], analogous to the bicontinuous MCM-48 phase (la3d) [8]. The cubic phase prepared under acidic conditions from PTES and TEOS is indeed related to a different type of cubic mesophases, micellar mesophases, reported in the literature for various surfactant/solvent systems [23] as well as for lipid-containing systems [24]. 

---