In situ synthesis of monodisperse luminescent terbium complex-silica nanocomposites

A facile strategy for the in situ synthesis of terbium complex-silica nanocomposites is described. The resultant spherical nanocomposites possess good monodispersity and exhibit luminescent properties of terbium complex.

Electrogenerated chemiluminescence sensing platform using Ru(bpy)(3)(2+) doped silica nanoparticles and carbon nanotubes

An effective electrogenerated chemiluminescence (ECL) sensor was developed by coimmobilization of the Ru(bpy)(2)(3+)-doped silica (RuDS) nanoparticles and carbon nanotubes (CNTs) on glassy carbon electrode through hydrophobic interaction. The uniform RuDS nanoparticles were prepared by a water-in-oil (W/O) microemulsion method and Ru(bpy)(3)(2+) doped inside could still maintain its high ECL efficiency. With such unique immobilization method, a great deal of Ru(bpy)(3)(2+) was immobilized three-dimensionally on the electrode , which could greatly enhance the ECL response and result in the increased sensitivity. On the other hand, CNTs played dual roles as matrix to immobilize RuDS nanoparticles and promoter to accelerate the electron transfer between Ru(bpy)(3)(2+) and the electrode. The as-prepared ECL sensor displayed good sensitivity and stability.

Macroporous fluoropolymeric films templated by silica colloidal assembly: A possible route to super-hydrophobic surfaces

A super-hydrophobic surface was obtained on a three-dimensional (313) polyvinylidene fluoride (PVDF) macroporous film. The porous films were fabricated through self-assembled silica colloidal templates. The apparent water contact angle of the surface can be tuned from 106 degrees to 153 degrees through altering the sintering temperature and the diameter of the colloidal templates. A composite structure of micro-cavities and nanoholes on the PVDF surface was responsible for the super-hydrophobicity. The wettability of the porous surfaces was described by the use of the Cassie-Baxter model and Wenzel's equation.

Luminescent hybrid films obtained by covalent grafting of terbium complex to silica network

Luminescent hybrid thin films consisting of terbium complex covalently bonded to a silica-based network have been obtained in situ via a sol-gel approach. A new monomer, N-(4-benzoic acid-yl), N'-(propylthiethoxysilyl)urea (PABI), has been synthesized by grafting isocyanatopropyltriethoxysilane (ICPTES) to p-aminobenzoic acid and characterized by H-1 NMR IR and MS, The monomer acts as a ligand for Tb3+ ion and as a sol-gel precursor. Band emission front Tb3+ ion due to an efficient ligand-to-metal energy transfer was observed by UV excitation. The decay curves of Tb3+ in the hybrid films were measured. The energy difference between the triplet state energy of PABI and the D-5(4) level of Tb3+ ion falls in the exciting range to sensitize Tb3+ ion fluorescence.

Preparation of polymer/silica nanoscale hybrids through sol-gel method involving emulsion polymers. II. Poly(ethyl acrylate)/SiO2

Poly(ethyl acrylate) (PEA)/SiO2 hybrids with different compositions were prepared under different casting temperatures and pH values. Their morphology as investigated by transmission electron microscopy (TEM) shows that samples with different compositions have different morphologies. When the SiO2 content is lower, PEA is the continuous phase and SiO2 is the dispersed phase. At higher SiO2 content, the change in phase morphology takes place, nd PEA gradually dispersing in the form of latex particles in SiO2 matrix. Change in phase morphology depends mainly on the time the sol-gel transition occurs. At suitable casting temperature and pH value, PEA/SiO2 in 95/5 and 50/50 hybrids with even dispersion was obtained.

Preparation of stable mesoporous silica FSM-16 from water glass in the presence of cetylpyridium bromide

The synthesis and characterization of the mesoporous materials FSM-16 (folded sheets mesoporous materials) with highly ordered structure in open-vessel by using cetylpyridium bromide (CPBr) and the single-layered polysilica Kanemite as new template and silicon source, respectively, has been investigated systematically. The hexagonal arrangements of uniformly size pores were characterized by FTIR. XRD. nitrogen adsorption. TG-DTA. SEM and TEM. Especially, the porous products with higher surface areas show remarkable thermal stability up to 1000 C. The potential application as carrier of catalysts or host-guest materials is anticipated. (C) 2001 Elsevier Science B.V. All rights reserved.

Deposition of silver nanoparticles in geochemically heterogeneous porous media: predicting affinity from surface composition analysis.

The transport of uncoated silver nanoparticles (AgNPs) in a porous medium composed of silica glass beads modified with a partial coverage of iron oxide (hematite) was studied and compared to that in a porous medium composed of unmodified glass beads (GB). At a pH lower than the point of zero charge (PZC) of hematite, the affinity of AgNPs for a hematite-coated glass bead (FeO-GB) surface was significantly higher than that for an uncoated surface. There was a linear correlation between the average nanoparticle affinity for media composed of mixtures of FeO-GB and GB collectors and the relative composition of those media as quantified by the attachment efficiency over a range of mixing mass ratios of the two types of collectors, so that the average AgNPs affinity for these media is readily predicted from the mass (or surface) weighted average of affinities for each of the surface types. X-ray photoelectron spectroscopy (XPS) was used to quantify the composition of the collector surface as a basis for predicting the affinity between the nanoparticles for a heterogeneous collector surface. A correlation was also observed between the local abundances of AgNPs and FeO on the collector surface.

Monitoring microbial sulfate reduction in porous media using multi-purpose electrodes

There is growing interest in the application of electrode-based measurements for monitoring microbial processes in the Earth using biogeophysical methods. In this study, reactive electrode measurements were combined to electrical geophysical measurements during microbial sulfate reduction occurring in a column of silica beads saturated with natural river water. Electrodic potential (EP), self potential (SP) and complex conductivity signals were recorded using a dual electrode design (Ag/AgCl metal as sensing/EP electrode, Ag/AgCl metal in KCl gel as reference/SP electrode). Open-circuit potentials, representing the tendency for electrochemical reactions to occur on the electrode surfaces, were recorded between sensing/EP electrode and reference/SP electrode and showed significant spatiotemporal variability associated with microbial activity. The dual electrode design isolates the microbial driven sulfide reactions to the sensing electrode and permits removal of any SP signal from the EP measurement. Based on the known sensitivity of a Ag electrode to dissolved sulfide, we interpret EP signals exceeding 550 mV recorded in this experiment in terms of bisulfide (HS-) concentration near multiple sensing electrodes. Complex conductivity measurements capture an imaginary conductivity (s?) signal interpreted as the response of microbial growth and biomass formation in the column. Our results suggest that the implementation of multipurpose electrodes, combining reactive measurements with electrical geophysical measurements, could improve efforts to monitor microbial processes in the Earth using electrodes.

Quantifying mircoorganism/organic matter interactions in saturated porous media.

Proteins and humic acids are common constituents of waste water. Latex colloids (colloids) acted as surrogates for microorganisms in multiple pulse dynamic column experiments (MPEs) that permitted colloid mobility to be quantified before and after the injection of either BSA (a protein), or Suwannee River humic acid (SRHA).
At low OM coverage colloid breakthrough curves demonstrated both BSA and SRHA reduced colloid deposition rates, but did not affect colloid irreversible deposition mechanisms. By contrast, high levels of SRHA surface coverage not only further reduced the matrix’s ability to attenuate colloids, but also resulted in reversible adsorption of a significant fraction of colloids deposited. Modelling of colloid responses using random sequential adsorption modelling suggested that 1 microgram of SRHA had the same effect as the deposition of 5.90±0.14 x109 colloids; the model suggested that adsorption of the same mass of BSA was equivalent to the deposition of between 7.1x108 and 2.3x109 colloids.
Colloid responses in MPEs where BSA coverage of colloid deposition sites approached saturation demonstrated the sand matrix remained capable of adsorbing colloids. However, in contrast to responses observed in MPEs at low surface coverage, continued colloid injection showed that the sand’s attenuation capacity increased with time, i.e. colloid concentrations declined as more were deposited (filter ripening).
Importance: Study results highlight the contrasting responses that may arise due to the interactions between colloids and OM in porous media. Results not only underscore that colloids can interact differently with various forms of deposited OM, but also that a single type of OM may generate dramatically different responses depending on the degree of surface coverage. The MPE method provides a means of quantifying the influence of OM on microorganism mobility in porous media such as filter beds, which may be used for either drinking water treatment or waste water treatment. In the wider environment study findings have potential to allow more confident predictions of the mobility of sewage derived pathogens discharging to groundwater.

Application of AAO Matrix in Aligned Gold Nanorod Array Substrates for Surface-Enhanced Fluorescence and Raman Scattering

In this paper, we probed surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) from probe molecule Rhodamine 6G (R6G) on self-standing Au nanorod array substrates made using a combination of anodization and potentiostatic electrodeposition. The initial substrates were embedded within a porous alumina template (AAO). By controlling the thickness of the AAO matrix, SEF and SERS were observed exhibiting an inverse relationship. SERS and SEF showed a non-linear response to the removal of AAO matrix due to an inhomogeneous plasmon activity across the nanorod which was supported by FDTD calculations. We showed that by optimizing the level of AAO thickness, we could obtain either maximized SERS, SEF or simultaneously observe both SERS and SEF together.

Surface reactivity enhancement of silica-based glass-ceramic scaffolds

A paradigm shift is taking place from using transplanting tissue and synthetic implants to a tissue engineering approach that aims to regenerate damaged tissues by combining cells from the body with highly porous scaffold biomaterials, which act as templates, guiding the growth of new tissue. The central focus of this thesis was to produce porous glass and glass-ceramic scaffolds that exhibits a bioactive and biocompatible behaviour with specific surface reactivity in synthetic physiological fluids and cell-scaffold interactions, enhanced by composition and thermal treatments applied. Understanding the sintering behaviour and the interaction between the densification and crystallization processes of glass powders was essential for assessing the ideal sintering conditions for obtaining a glass scaffolds for tissue engineering applications. Our main goal was to carry out a comprehensive study of the bioactive glass sintering, identifying the powder size and sintering variables effect, for future design of sintered glass scaffolds with competent microstructures. The developed scaffolds prepared by the salt sintering method using a 3CaO.P2O5 - SiO2 - MgO glass system, with additions of Na2O with a salt, NaCl, exhibit high porosity, interconnectivity, pore size distribution and mechanical strength suitable for bone repair applications. The replacement of 6 % MgO by Na2O in the glass network allowed to tailor the dissolution rate and bioactivity of the glass scaffolds. Regarding the biological assessment, the incorporation of sodium to the composition resulted in an inibition cell response for small periods. Nevertheless it was demonstrated that for 21 days the cells response recovered and are similar for both glass compositions. The in vitro behaviour of the glass scaffolds was tested by introducing scaffolds to simulated body fluid for 21 days. Energy-dispersive Xray spectroscopy and SEM analyses proved the existence of CaP crystals for both compositions. Crystallization forming whitlockite was observed to affect the dissolution behaviour in simulated body fluid. By performing different heat treatments, it was possible to control the bioactivity and biocompatability of the glass scaffolds by means of a controlled crystallization. To recover and tune the bioactivity of the glass-ceramic with 82 % crystalline phase, different methods have been applied including functionalization using 3- aminopropyl-triethoxysilane (APTES). The glass ceramic modified surface exhibited an accelerated crystalline hydroxyapatite layer formation upon immersion in SBF after 21 days while the as prepared glass-ceramic had no detected formation of calcium phosphate up to 5 months. A sufficient mechanical support for bone tissue regeneration that biodegrade later at a tailorable rate was achievable with the glass–ceramic scaffold. Considering the biological assessment, scaffolds demonstrated an inductive effect on the proliferation of cells. The cells showed a normal morphology and high growth rate when compared to standard culture plates. This study opens up new possibilities for using 3CaO.P2O5–SiO2–MgO glass to manufacture various structures, while tailoring their bioactivity by controlling the content of the crystalline phase. Additionally, the in vitro behaviour of these structures suggests the high potential of these materials to be used in the field of tissue regeneration.

Sol-Gel Mesoporous Silica Aerogels and Bio Hybrids for Functional Applications

The thesis covers a systematic investigation on the synthesis of silica aerogels and microspheres with tailored porosity, at ambient conditions by varying the experimental parameters as well as using organic templates. Organically modified silica-gelatin and silica-chitosan hybrids were developed for the first time using alkylalkoxysilanes such as MTMS and VTMS. Application of novel silica-biopolymer antiwetting coatings on different substrates such as glass, leather and textile is also demonstrated in the thesis.

Thermal characterization of nanocrystalline porous CePO4 ceramics

A laser-induced photoacoustic technique was employed to investigate thermal transport through nanocrystalline CePO4 samples prepared via the sol–gel route. Evaluation of thermal diffusivity was carried out using the one-dimensional model of Rosencwaig and Gersho for the reflection configuration of the photoacoustic method. Structural analyses of samples revealed that they are nanoporous in nature, possessing micron-sized grains. Analysis of results shows that thermal diffusivity value varies with sintering temperature. Results are explained in terms of the variation in porosity with sintering temperature and the effects of various scattering mechanisms on the propagation of phonons through the nanoporous ceramic matrix. Further analyses confirm that apart from porosity, grain boundary resistance and interface thermal resistance influence the effective value of thermal diffusivity of the samples under investigation.

Optically transparent magnetic nanocomposites based on encapsulated Fe3O4 nanoparticles in a sol–gel silica network

Composite Fe3O4–SiO2 materials were prepared by the sol–gel method with tetraethoxysilane and aqueous-based Fe3O4 ferrofluids as precursors. The monoliths obtained were crack free and showed both optical and magnetic properties. The structural properties were determined by infrared spectroscopy, x-ray diffractometry and transmission electron microscopy. Fe3O4 particles of 20 nm size lie within the pores of the matrix without any strong Si–O–Fe bonding. The well established silica network provides effective confinement to these nanoparticles. The composites were transparent in the 600–800 nm regime and the field dependent magnetization curves suggest that the composite exhibits superparamagnetic characteristics