Ordered structure silica

Ordered mesoporous silica have already been studied as carriers for drug delivery [1,2] recently, their use has also been proposed in bone tissue engineering [3,4], in combination with bioactive glass-ceramic scaffolds [5,6]. The kinetics of ibuprofen release in SBF [7] from MCM-41 silica with similar pore diameter has shown puzzling discontinuities [3,6,8] aim of the present work is to assess whether these anomalies may be related to structural changes in the MCM-41 mesoporous spheres under the adopted conditions. 

The influence of adsorption on the structure of a -chymotrypsin is shown in Fig. 10, where the circular dichroism (CD) spectrum of the protein in solution is compared with that of the protein adsorbed on Teflon and silica. Because of absorbance in the far UV by the aromatic styrene, it is impossible to obtain reliable CD spectra of proteins adsorbed on PS and PS- (EO)8. The CD spectrum of a protein reflects its composition of secondary structural elements (a -helices, / -sheets). The spectrum of dissolved a-chymotrypsin is indicative of a low content of or-helices and a high content of //-sheets. After adsorption at the silica surface, the CD spectrum is shifted, but the shift is much more pronounced when the protein was adsorbed at the Teflon surface. The shifts are in opposite directions for the hydrophobic and hydrophilic surfaces, respectively. The spectrum of the protein on the hydrophilic surface of silica indicates a decrease in ordered secondary structure, i.e., the polypeptide chain in the protein has an increased random structure and, hence, a larger conformational entropy. Adsorption on the hydrophobic Teflon surface induces the formation of ordered structural elements, notably an increase in the content of O -helices (cfi, the discussion in Sect. 3.1.4). 

Figure 1. Scheme for the liquid crystalline templating mechanism proposed by Kresge et al 1 for synthesis of mesoporous silica MCM-41. Formation of a hexagonal array of cylindrical micelles possibly mediated by silicate anions followed by condensation of the silicate anions from the silicate source (tetraethylorthosilicate) leads to templated framework structure. Calcination or extraction of the template produces hexagonally ordered mesoporous silica. 

From above experimental results, Pt nanoparticle arrays were similarly formed in the mesoporous silica film by the photoreduction of H2PtCl6/mesoporous silica film/Si in the presence of vapors of water and methanol. As shown in Figure 15.29, Pt nanoparticles (diameter 3 nm) are packed close to each other in the one-dimensional mesopores, and in some part the arrays of Pt nanoparticles show an ordered structure [27]. 

Self-assembly of highly charged colloidal spheres can, under the correct conditions, lead to 3D crystalline structures. The highly charged spheres used are either polystyrene beads or silica spheres, which are laid down to give the ordered structures by evaporation from a solvent, by sedimentation or by electrostatic repulsion (Figure 5.34). The structures created with these materials do not show full photonic band gap, due to their comparitively low relative permittivity, although the voids can be in-filled with other materials to modify the relative permittivity. 

Similar adsorption isotherms were obtained for samples PS and SPS, and for the lipase immobilized derivatives of silica gels (ADS, CB1, CB2, EN1, and EN2). Typical examples are shown in Fig. 2. We observed hysteresis loops in the adsorption-desorption isotherms, denoting materials with well-defined ordered structures, and the presence of mesopores, with hysteresis loops between isotherms types HI and H2 (8,16). Primarily on the mesopores of silica, a multilayer of adsorbate is formed, increasing the relative pressure, and depending on the mean pore diameter, at P/P0 0.4, capillary condensation takes place on the multilayer, resulting in a further increase in pore volume (1). 

Among the inorganic templates, zeolite produces more regulated pores as compared to the silica template. If nano-channels in zeolite are completely filled with carbonaceous precursor and then the carbon materials are extracted from the zeolite framework, one can obtain the porous carbon of which structure reflects the porosity of the original zeolite template. The ordered mesoporous silica templates, e.g., MCM-4 838,39,47 and SBA-1547 have been employed to prepare the ordered porous carbons by the procedures involving the pore filling of the silica template with carbonaceous precursor followed by carbonization and silica dissolution. The resulting pore sizes of the ordered mesoporous carbons are smaller than about 10 nm. 

The extensive studies on the structure [72, 89] and Raman and Brillouin spectra [68-70, 73], as well as computer simulation results [77-82] have revealed that in the 8-50 GPa pressure range and at room temperatures, the silica glass is subject to a broad transformation accompanied by a change in the short-range order structure and an increase in the coordination number from 4 to 6. It should be noted that during coordination transformation at intermediate pressures, many silicon atoms have a fivefold coordination. The main part of the transformation takes place in a narrower pressure range of 10-40 GPa. 

The copolymer formed in the presence of modified silica had a pseudocrystalline isotactic well-ordered structure,7 and is characterized by absorption bands at 1030 and 1113 cm-1 in the spectrum (Figure la). These bands can be detected only at significant sample dilution with KBr. Though a band at 1700 cm-1 characteristic for aromatic groups is not manifested in the spectrum, there is a band at 1584 cm-1 which may be attributed to a C = C vibration of the benzene rings orientated near the silica surface. 

After adsorption one side of the protein molecule is oriented towards the sorbent surface, turned away from the aqueous solution. As a consequence, hydrophobic parts of the protein that are buried in the interior of the dissolved molecule may become exposed to the sorbent surface where they are still shielded from contact with water. Because hydrophobic interaction between apolar amino acid residues in the protein s interior support the formation of secondary structures as a-helices and P-sheets, a reduction of this interaction destabilizes such structures. Breakdown of the a-helices and/or P-sheets content is, indeed, expected to occur if peptide units released from these ordered structures can form hydrogen bonds with the sorbent surface. This is the case for polar surfaces such as oxides, e.g. silica and metal oxides, and with sorbent retaining residual water at their surfaces. Then the decrease in ordered secondary structures leads to an increased conformational entropy of the protein. This may favour the protein adsorption process considerably.13 It may be understood that proteins having an intrinsically low structural stability are more prone to undergo adsorption-induced structural changes. 

One of the first examples of mesoscopic-macroscopic two-dimensional ordering within a structure involved a bacterial superstructure formed from the co-aligned multicellular filaments of Bacillus subtilis that was used to template macroporous fibers of either amorphous or ordered mesoporous silica [82], The interfilament space was mineralized with mesoporous silica and, following removal of the organic, a macroporous framework with 0.5 pm wide channels remained. Mesoporous silica channel walls in this hierarchical structure were curved and approximately 100 nm in thickness. Dense, amorphous walls were obtained by replacing the surfactant-silicate synthesis mixture with a silica sol solution. The difference in the mode of formation between porous and non-porous wall structures was explained in terms of assembly from close-packed mesoporous silica coated bacterial filaments in the former compared to consolidation of silica nanoparticles within interfilament voids in the latter. 

Several approaches towards the synthesis of hierarchical meso- and macro-porous materials have been described. For instance, a mixture that comprised a block co-polymer and polymer latex spheres was utilized to obtain large pore silicas with a bimodal pore size distribution [84]. Rather than pre-organizing latex spheres into an ordered structure they were instead mixed with block-copolymer precursor sols and the resulting structures were disordered. A similar approach that utilized a latex colloidal crystal template was used to assemble a macroporous crystal with amesoporous silica framework [67]. 

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