Triplet state of 4-methoxybenzyl alcohol chemisorbed on silica nanoparticles.

The knowledge of photochemical kinetics in colloidal systems is important in understanding environmental photochemistry on dispersed solid surfaces. As model materials for the chemically sorbed organic compounds present in natural environments, modified silica nanoparticles (NPs) were obtained here by condensation of the silanol groups of fumed silica nanoparticles with 4-methoxybenzyl alcohol. These particles were characterized by different techniques. To evaluate their toxicity, the inhibition of the natural luminescence emission of the marine bacterium Vibrio fischeri in suspensions of the particles was measured. Laser flash-photolysis experiments (λ(exc) = 266 nm) performed with NP suspensions in acetonitrile-aqueous phosphate buffer mixtures showed the formation of the lowest triplet excited state of the chemisorbed organic groups (λ(max) = 390 nm). DFT calculations of the absorption spectrum of this radical support the assignment. From the calculated triplet energy, a thermodynamically favorable energy transfer from these triplet states to oxygen to yield singlet molecular oxygen is predicted. A value of 0.09 was measured for the quantum yield of singlet molecular oxygen generation by air-saturated suspensions of the nanoparticles in the mixture of solvents acetonitrile-aqueous phosphate buffer. The quantum yield of singlet molecular oxygen generation by the free 4-methoxybenzyl alcohol in the same solvent is 0.31.

The use of molecular probes for the characterization of dispersions of functionalized silica nanoparticles.

Butoxylated silica nanoparticles (BSN) were prepared by esterification of the silanol groups of fumed silica nanoparticles with butanol and characterized by 13C and 29Si NMR and thermogravimetry. The molecular probes benzophenone (BP) and safranine-T were used to investigate the BSN suspensions in water:acetonitrile. Laser flash-photolysis experiments at lambda(exc)=266 nm performed with BSN suspended in acetonitrile:aqueous phosphate buffer supported previous results of our group obtained by time-resolved phosphorescence experiments and showed that only free and adsorbed excited triplet states of BP and diphenylketyl radicals contribute to the signals. The UV-vis spectroscopic and photophysical properties of safranine-T are strongly solvent-dependent. Thus, the analysis of the emission spectra and fluorescence lifetimes yielded information on the localization of this probe molecule in suspensions of BSN and of the bare silica nanoparticles. The values of the equilibrium constant for the adsorption of the ground-state safranine-T on the particles were found to be (9.2+/-0.8)x10(4), (7.2+/-0.8)x10(5), and (3.0+/-0.1)x10(4) for the BSN in 1:1 acetonitrile:water, SiO2 in 1:1 acetonitrile:water, and SiO2 in acetonitrile, respectively.

Mesoporous silica originating from a gaseous ammonia epoxide ring opening and the thermodynamic data on some divalent cation adsorptions.

An organofunctionalized mesoporous HMS-like compound has been synthesized by reacting the silylating agent 3-glycidoxypropyltrimethoxysilane with gaseous ammonia. The reaction path leads to the opening of the three membered epoxide ring to incorporate ammonia to give the modified silylating agent. This new silylating agent was used to synthesize a mesostructure inorganic-organic hybrid through the neutral template directing agent, dodecylamine, using a co-condensation process, and exploring the ability of the silicon source tetraethoxysilane. The final solid named HMS-NH has been characterized through elemental analysis, X-ray powder diffraction, nitrogen gas adsorption, infrared spectroscopy and solid state NMR for the 29Si nucleus. An amount of 1.06+/-0.10 mmol of pendant groups is covalently bonded to the inorganic backbone. The attached basic centers adsorbed divalent cations to give the maxima adsorption capacity of 0.74+/-0.03, 0.55+/-0.06, 0.53+/-0.05 and 0.51+/-0.06 mmolg(-1) for copper, nickel, zinc and cobalt, respectively. From calorimetric determinations the quantitative thermal effects for all these cation/basic center interactions gave exothermic enthalpy, negative Gibbs free energy and positive entropy. These thermodynamic data confirmed the energetically favorable condition of such interactions at the solid/liquid interface for all systems.

Some features associated with organosilane groups grafted by the sol-gel process onto synthetic talc-like phyllosilicate.

Two new lamellar inorganic-organic magnesium silicates have been successfully synthesized by using sol-gel based processes under mild temperature conditions. The talc-organosilicates derived using two silylating agents as the silicon source, (i) 3-chloropropyltrimethoxysilane, and (ii) from the attachment of 5-amino-1,3,4-thiadiazole-2-thiol molecule to this precursor agent, yielded PhMg-Cl and PhMg-Tz phyllosilicates. These organoclays were characterized through elemental analyses, infrared spectroscopy, X-ray diffractometry, surface area, thermogravimetry, and carbon and silicon solid state nuclear magnetic resonance spectroscopy. The results confirmed the presence of organic moieties covalently bonded to the inorganic silicon sheet network of the 2:1 class of phyllosilicates, with a density of organic molecules of 6.6+/-0.1 and 2.7+/-0.2 mmol g(-1) anchored on the inorganic layer and with interlayer distances of 1158 and 1628 pm, respectively. The nuclear magnetic resonances results in the solid state are in agreement with the sequence of carbons distributed in the pendant chains of the original silylating agents and the silicon bonded to oxygen atoms or carbon atoms of the inorganic sheets, as expected for the organically functionalized phyllosilicates. The enhanced potential of the new compound PhMg-Tz as a multi property material was explored in adsorbing cations from aqueous solution. The basic sulfur and nitrogen centers attached to the pendant chains inside the lamellar cavity can coordinate mercury, by presenting an isotherm saturated at 0.19 mmol g(-1) of this heavy metal. The functionality of this organoclay-like material expresses its potential for heavy cation removal from an ecosystem.

Generation of chemisorbed benzyl radicals on silica nanoparticles.

Functionalized silica nanoparticles (NP) were obtained by esterification of the silanol groups of fumed silica nanoparticles with benzyl alcohol. These particles were characterized by Fourier transform infrared spectroscopy, (13)C and (29)Si NMR spectroscopy, thermogravimetry, total organic carbon, Brunauer-Emmett-Teller analysis, UV-visible spectroscopy, and transmission electron microscopy. NP suspensions in water/acetonitrile mixtures were used as quenchers of benzophenone (BP) phosphorescence in time-resolved experiments at the excitation wavelength of 266 nm. The phosphorescence signals obtained in the presence of the nanoparticles were fitted to biexponential decays. Both decays were accelerated in the presence of increasing amounts of NP. A model, including the reversible adsorption of BP on the NP, which was supported by computer simulations accounts for the observed results. Laser flash-photolysis experiments with excitation at 266 nm of NP suspensions in water/acetonitrile in the presence of BP generated benzyl radicals that were attached to the silica surface. These radicals were detected at their absorption maxima (320 nm) by transient optical techniques.