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Mesoporous silicas with vesicular and onion-like morphologies were assembled through hydrogen-bonding pathway from sodium silicate as silica source and electrically neutral α,ω-diamine, Jeffamine D2000 surfactant (H2NCH(CH3)CH2[OCH2CH(CH3)]33NH2) as template in aqueous media at different synthesis temperatures (25, 60 and 100 °C). Assembling the material at 100 °C afforded onion-like core shell mesoporous silica, while at relatively lower temperature, e.g. 25 and 60 °C, multilamellar vesicles were obtained. Mesoporous silica with onion-like morphology was also obtained by a two-step synthesis involving an aging period of 20 h at room temperature followed by a hydrothermal stage (1–12 h) at 100 °C. The heavily cross-linked (Q4/Q3 ratio of 4.43) onion-like mesophase silica exhibited high hydrothermal stability. The BET surface area, pore volume and KJS (Kruk-Jaroniec-Sayari) pore diameter of the onion-like mesoporous silica were found to be 464 m2 g−1, 1.16 m3 g−1 and 7.2 nm, respectively.

Mesoporous silica with regular geometries have been recently paid much attention owing to their scientific importance and great potentials in practical applications such as catalysis, adsorption, separation, sensing, medical usage, ecology, and nanotechnology. Especially, applications often require immobilization of the related functional groups in the mesopores. In order to achieve desire applications, modification of these mesoporous silica are indispensable. In this review, recent progresses of functionalization of mesoporous silica are comprehensively summarized. In the first parts, advances in three major methods, grafting (post-synthetic modification), co-condensation (direct synthesis), and techniques related with periodic mesoporous organosilicates, are explained. In the latter parts, new concepts for functionalization of mesoporous silica including functional template method and lizard template method are introduced. Most of the examples described here have been published in a new millennium.

The preparation of a series of organically functionalized wormhole-motif microspherical MSU-X silicas mesostructures was achieved by a direct synthesis process involving the addition of tetraethoxysilane (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) to mildly acidified solutions of a structure-directing nonionic surfactant (Igepal CA-720), followed by fluoride-mediated hydrolysis/cross-linking and surfactant extraction. The influence of organosilane content (MPTMS/TEOS ratio) and synthesis temperature on the framework order, pore structure, and particle size of the resulting mesostructures was investigated. The lattice spacings, pore volumes, and pore diameters were found to systematically increase as a function of increasing synthesis temperature. Although very poorly ordered and microporous when prepared at lower synthesis temperatures, the framework ordering and pore channel diameters of the microspheres dramatically improved when these were synthesized at temperatures above 40−45 °C. Moreover, i...

A procedure for isolation of cyclic AMP (cAMP) by thin-layer chromatography on silica gel is described. One-dimensional ascending chromatograms were developed using [H(2)O/C(2)H(5)OH/NH(4)HCO(3) (30%:70%:0.2M)] as the mobile phase. This procedure separated [32P]cAMP from other radioactive metabolites of [32P]ATP in up to 19 samples on one sheet (20 x 10 cm) over 40-60 min at room temperature (21 degrees C). This simple and rapid isolation method provides a novel and convenient technique for the assay of adenylyl cyclase.

A new method for the quantitative extraction and separation of trace amounts of rhodium from nitric acid and sodium trichloroacetate media has been established based on the formation of an ion-association complex of hexahydrated rhodium cation Rh(H2O)6 3+ and the trichloroacetate (TCA) anion in tri-n-butyl phosphate (TBP). The effect of various factors (solvent, pH, sodium trichloroacetate, shaking time, phase volume ratio, composition of the extracted species, foreign ions, transformation of rhodium chlorocomplexes into hexahydrated cation, etc.) on the extraction and back-extraction of rhodium has been investigated. The method can be combined with subsequent FAAS determination of rhodium. The procedure was applied to determine rhodium traces in chloroplatinic acid and palladium chloride.

A new method for the separation of trace amounts of palladium from hydrochloric acid and potassium thiocyanate media has been established based on the formation of an ion-pair complex of palladium thiocyanate anion Pd(SCN)4(2-) and the cationic potassium complex of dicyclohexyl- 18-crown-6 (DC18C6) in chloroform. The effect of various factors (solvent, crown ether, potassium thiocyanate, hydrochloric acid, reagent concentration, shaking time, phase volume ratio, composition of the extracted species, foreign ions, etc.) on the extraction and back-extraction of palladium has been investigated. The method can be combined with subsequent FAAS determination of palladium. The procedure was applied to determine palladium traces in chloroplatinic acid and rhodium chloride.

A new method for the preconcentration and determination of trace amounts of lead at the μg/L level in natural waters has been established based on the formation of the thenoyltrifluoroacetone (TTA) complex with dibenzo-18-crown-6 (DB18C6) by means of synergistic extraction and back-extraction combined with atomic absorption spectrometry (AAS). The effect of various factors (synergism with TTA and DB18C6, shaking time, preconcentration factor, composition of the extracted species, and foreign ions etc.) on the extraction and back-extraction of lead has been investigated in detail. The lead-TTA chelate in o-dichlorobenzene forms a stable adduct with DB18C6 as Pb(TTA)2 DB18C6. The stability constant (β) of the adduct determined by curve fitting method was log β = 4.2. The amount of lead in natural waters such as tap water (Kanazawa University) and Kakehashi river (Komatsu City) determined by the present method was found to be 0.64 ± 0.02 μg/L and 5.10 ± 0.03 μg/L, respectively.

Pore-expanded MCM-41 (PE-MCM-41) silica exhibits a unique combination of high specific surface area (ca.1000 m2/g), pore size (up to 25 nm) and pore volume (up to 3.5 cm3/g). The current study focused primarily on the application of PE-MCM-41 material as suitable host for urease in controlled hydrolysis of urea. Urease adsorbed on PEMCM-41, regular MCM-41 and silica gel adsorbent (SGA) were used as catalysts for urea hydrolysis reaction. Adsorption studies of urease on these materials from aqueous solution at pH 7.2 revealed that the adsorption capacity of PE-MCM-41 (102 mglg) is significantly higher than that of MCM-41 (56 mglg) and SGA (21 mglg). The equilibrium adsorption data were well fitted using the Langmuir-Freundlich model. Furthermore, the kinetic study revealed that the uptake of urease follows the pseudo-first order kinetics. The in-vitro urea hydrolysis reaction on pristine urease and different urease-loaded catalysts showed that the rate of hydrolysis reaction is significantly slower on UPE-MCM-41 compared to that of bulk urease and urease on MCM-41 and SGA.

Hydrothermally stable mesoporous silicas with onion-like morphology was assembled at 100°C through hydrogen-bonding pathway from sodium silicate as silica source and electrically neutral α,ω-diamine surfactant as template. Mesoporous silica with onion-like morphology was also obtained by a two-step synthesis involving an aging period of 20 h at room temperature followed by a post-synthesis hydrothermal stage (1–12 h) at 100°C.

Pore-expanded MCM-41 (PE-MCM-41) silica exhibits a unique combination of high specific surface area (ca. 1000 m2/g), pore size (up to 25 nm) and pore volume (up to 3.5 cm3/g). As such, this material is highly suitable for the adsorption of large biomolecules. The current study focused primarily on the application of PE-MCM-41 material as suitable host for urease (nickel-based large metalloenzyme) in controlled hydrolysis of urea. Urease adsorbed on PE-MCM-41, regular MCM-41 and silica gel (SGA) were used as catalysts for urea hydrolysis reaction. Adsorption studies of urease on these materials from aqueous solution at pH 7.2 revealed that the adsorption capacity of PE-MCM-41 (102 mg/g) is significantly higher than that of MCM-41 (56 mg/g) and SGA (21 mg/g). The equilibrium adsorption data were well fitted using the Langmuir–Freundlich model. Furthermore, the kinetic study revealed that the uptake of urease follow the pseudo-first order kinetics. The in vitro urea hydrolysis reaction on pristine urease and different urease-loaded catalysts showed that the rate of hydrolysis reaction is significantly slower on U/PE-MCM-41 compared to that of bulk urease and urease on MCM-41 and SGA. This technique could be an alternative means to the use of urease inhibitors to control the ammonia release from urea fertilizer.

A new method for the quantitative extraction and determination of trace amounts of iridium from hydrochloric acid media has been established based on the formation of an ion-association complex of iridium hexachloro anion IrCl6 2– with dicyclohexyl-18-crown-6 (DC18C6) oxonium cation in chloroform, then determination by inductively coupled plasma atomic emission spectrometry (ICP–AES). The effect of various factors (solvent, acid concentration, crown ether, reagent concentration, shaking time, composition of the extracted species, foreign ions, etc.) on the extraction and back-extraction of iridium has been investigated. The procedure was used to determine traces of iridium in palladium chloride and rhodium chloride.