Fluorophore-free luminescent organosilica nanoparticles

In this paper, we report the preparation and characterization of fluorophore-free luminescent organosilica nanoparticles (NPs) with sizes varying from 50 to 250 nm. These NPs were synthesized by the St?ber method by incorporating several organosilanes together with the silicate precursor (tetraethyl orthosilicate, TEOS) to the silica matrix. The calcination of these NPs at high temperatures (600 and 700 degrees C) led to fluorescent and phosphorescent properties, which proved to be highly dependent on the initial composition of the silanization mixture and the heating temperature. Further characterization of this material in terms of its structural and optical properties is reported. Although the NPs are not very bright, the lifetime measurements revealed values in the millisecond range, which makes these NPs potentially attractive as luminescent materials and for time-resolved optical spectroscopic studies and bioassays.     

Biomolecular screening with novel organosilica microspheres

Organosilica microspheres synthesised via a novel surfactant-free emulsion-based method show applicability towards optical encoding, solid-phase synthesis and high-throughput screening of bound oligonucleotide and peptide sequences.     

Thermally-regulated molecular selectivity of organosilica sol-gels

The feasibility of using temperature as a control mechanism for altering the selectivity of organosilica sol-gels for a specific molecule is demonstrated in this communication. The porous organosilica sol-gels act as reversible thermoresponsive materials which become hydrophobic at higher temperature and hydrophilic at lower temperature. When exposed to a mixture of molecules, the gels selectively intake the more hydrophobic species at higher temperature. A particularly remarkable feature of these gels is their ability to preferentially sequester the hydrophobic molecule at high temperature and the hydrophilic species at low temperature. Finally, these gels selectively intake hydrophobic molecules at high temperature and then preferentially release them when the temperature is lowered.     

Mesoporous hybrid organosilica containing urethane moieties

Mesoporous hybrid material containing urethane moieties in functionalized long chain organic group have been synthesized by using bis[3-(triethoxysilyl) propyl urethane]ethane (BTESPUE) and tetraethoxysilane as structural ingredients. The incorporation of BTESPUE within the framework of mesoporous material was confirmed by Fourier transform-infrared, X-ray photoelectron spectroscopy, solid-state NMR spectroscopy and thermogravimetric analysis. This material had a thick wall and uniform pore, which may be attributed to the hydrogen bonding inside framework due to urethane moieties.     

Periodic mesoporous organosilica from zwitterionic precursors

Mesoporous hybrid silica bearing zwitterionic species were synthesized via template-directed hydrolysis-polycondensation reactions from zwitterionic ammonium sulfonate precursors. The formation of the nanostructured phases involves specific precursor-template interactions. The obtained materials are efficient heterogeneous catalysts in Biginelli reactions.     

Adsorption characteristics of organosilica based mesoporous materials

Hybrid organosilica mesoporous materials with pores of ordered three-dimensional hexagonal structure were prepared by the hydrolysis and co-condensation of 1,2-bis(triethoxysilyl)ethane with various concentrations of a surfactant as structure directing agents. The materials had high pore volume of 1-1.5 mL/g and high surface area from 1057 to 1445 m(2)/g. Adsorption measurement and adsorption calorimetry revealed that the prepared materials exhibited high hydrophobicity and high affinity toward nonpolar organic vapor such as n-hexane. The dynamic adsorption properties of the materials for n-hexane in the presence of water vapor showed that these hybrid organosilica materials preferentially adsorbed n-hexane vapor and were stable in the presence of water compared to the siliceous MCM48.     

Hydroxyl species in large-pore phenylene-bridged periodic mesoporous organosilica

Silanol species in phenylene-bridged periodic mesoporous organosilica (PMO), templated via tri-block copolymer Pluronic P123 and thus characterized by large pores and amorphous wall structure, have been characterized by means of FT-IR spectroscopy. Investigation has been carried out on both the naked sample outgassed at different temperatures and the sample when interacting with molecular probes able to form H-bonding (ammonia and carbon monoxide). After outgassing at 773 K, the material shows both isolated silanols and silanols engaged in "intraframework" H-bonding with the pi-cloud of structural aromatic rings. Interaction with ammonia showed that a fraction of these species is inaccessible, being probably located inside the pore walls. Thermal treatment above 673 K causes the appearance of SiO3(OH) species formed as a consequence of the cleavage of some Si-C bonds. The presence of hydroxyls slightly more acidic than isolated silanols has been evidenced: these are interpreted as perturbed geminal species.     

Molecular rotors in hierarchically ordered mesoporous organosilica frameworks

Diphenylene moieties, molecularly ordered in the framework of periodic mesoporous organosilicas, behave as molecular rotors and show a mobility with correlation times as short as a few nanoseconds.     

Functionalized organosilica microspheres via a novel emulsion-based route

Thiol-functionalized organosilica microspheres were synthesized via a two-step process: (1) acid-catalyzed hydrolysis and condensation of 3-mercaptopropyltrimethoxysilane (MPTMS), followed by (2) base-catalyzed condensation, which led to the rapid formation of emulsion droplets with a narrow size distribution. These droplets continued to condense to form solid microspheres. Solution (29)Si NMR and optical microscopy were applied to study the mechanism of this novel synthetic route. Solid-state (29)Si NMR, SEM, zeta potential titration, and Coulter counter measurements were used to study the bulk and surface properties and to determine the particle size distributions of the final microspheres. Compared to conventional St?ber silica particles, these microspheres were shown to have a lower degree of cross-linking (average degree of condensation, r = 1.25), a larger average size (up to 6 microm), and a higher isoelectric point (pH = 4.4). Confocal microscopy of dye-labeled microspheres showed an even distribution of dye molecules throughout the interior, characteristic of a readily accessible and permeable organosilica network. These findings have implications for the production of functionalized solid supports for use in catalysis and biological applications, such as optically encoded carriers for combinatorial synthesis.     

Fluorescent organosilica micro- and nanoparticles with controllable size

This paper reports on the synthesis of uniformly dye-doped organosilica particles with narrow size distribution. The particle size can be controlled from tenths of nanometers up to several micrometers, whilst still maintaining monodispersity. Microparticles were observed to swell in various solvents up to approximately 2.5 times their original volume, suggesting the presence of a gel-like internal structure. As shown by confocal microscopy, this morphological control of particle swelling has important implications for the encoding of the nano/micro particles with organic dyes, such as rhodamine B isothiocyanate. Swelling allows the dye to penetrate the organosilica matrix and produce uniformly dye-doped nano- and microparticles. Finally, we suggest a coagulation model for the particle formation which significantly differs from conventional St?ber synthesis.     

Periodic mesoporous organosilica with large heterocyclic bridging groups

Periodic mesoporous organosilica with a heterocyclic bridging group of large molecular weight, tris[3-(trimethoxysilyl)propyl]isocyanurate, is reported. Incorporation of an organic moiety into the silica framework afforded material attractive for adsorption of mercury and related heavy metal ions from aqueous solutions.     

Development of robust organosilica membranes for reverse osmosis

Hybrid organically bridged silica membranes have attracted considerable attention because of their high performances in a variety of applications. Development of robust reverse osmosis (RO) membranes to withstand aggressive operating conditions is still a major challenge. Here, a new type of microporous organosilica membrane has been developed and applied in reverse osmosis. Sol-gel derived organosilica RO membranes reject isopropanol with rejection higher than 95%, demonstrating superior molecular sieving ability for neutral solutes of low molecular weight. Due to the introduction of an inherently stable hybrid network structure, the membrane withstands higher temperatures in comparison with commercial polyamide RO membranes, and is resistant to water to at least 90 °C with no obvious changes in filtration performance. Furthermore, both an accelerated chlorine-resistance test and Fourier transform infrared analysis confirm excellent chlorine stability in this material, which demonstrates promise for a new generation of chlorine-resistant RO membrane materials.     

Externally tunable dynamic confinement effect in organosilica sol-gels

The feasibility of using the pores of organosilica sol-gels for dynamic confinement of a luminescent molecule is demonstrated in this paper. The porous organosilica sol-gels act as reversible thermoresponsive materials which exhibit reduced pore volume at higher temperature and enlarged pores at lower temperature, which causes dynamic alterations in the nanoenvironment of encapsulated entities. A particularly remarkable feature of this system is that the temperature-dependent confinement effect provided by the gels is reversible and can be efficiently modulated by simply changing the temperature.     

Flexible and iridescent chiral nematic mesoporous organosilica films

Nanocrystalline cellulose (NCC) has been used to template ethylene-bridged mesoporous organosilica films with long-range chirality and photonic properties. The structural color of the organosilica films results from their chiral nematic ordering, can be varied across the entire visible spectrum, and responds to the presence of chemicals within the mesopores. To synthesize these materials, acid hydrolysis was used to remove the NCC template without disrupting the organosilica framework. The resulting mesoporous organosilica films are much more flexible than brittle mesoporous silica films templated by NCC. These materials are the first of a novel family of chiral mesoporous organosilicas with photonic properties.     

Periodic mesoporous organosilica from micellar oligomer template solution

Periodic mesoporous organosilica (PMO) with two-dimensional hexagonal symmetry was synthesised using a bridged silsesquioxane (CH3O)3Si-CH2-CH2-Si(CH3O)3 as precursor and polyoxyethylene non-ionic surfactant (Brij-56) as template. The hybrid material was characterised by X-ray diffraction, N2 adsorption, TEM, and solid-state 29Si MAS NMR spectroscopy.     

In situ synthesis and photoresponsive rupture of organosilica nanocapsules

This communication describes in situ synthesis of thiocyanato-functionalized organosilica nanocapsules by a sol-gel reaction using 3-thiocyanatopropyltriethoxysilane as a precursor. Moreover, the nanocapsules are photoresponsive and burst under light irradiation, resulting in release of the encapsulated drug or dye.     

Low-k periodic mesoporous organosilica with air walls: POSS-PMO

Periodic mesoporous organosilica (PMO) with polyhedral oligomeric silsesquioxane (POSS) air pockets integrated into the pore walls has been prepared by a template-directed, evaporation-induced self-assembly spin-coating procedure to create a hybrid POSS-PMO thin film. A 10-fold increase in the porosity of the POSS-PMO film compared to a reference POSS film is achieved by incorporating ～1.5 nm pores. The increased porosity results in a decrease in the dielectric constant, k, which goes from 2.03 in a reference POSS film to 1.73 in the POSS-PMO film.     

Periodic mesoporous organosilica hollow spheres with tunable wall thickness

Periodic mesoporous organosilica (PMO) hollow spheres with tunable wall thickness have been successfully synthesized by a new vesicle and a liquid crystal "dual templating" mechanism, which may be applicable for drug and DNA delivery systems, biomolecular encapsulation, as well as nanoreactors for conducting biological reactions at the molecular levels.     

Synthesis of bifunctionalized mesoporous organosilica spheres for high-performance liquid chromatography

Phenyl-functionalized mesoporous ethane-silicas with spherical morphology were synthesized by one-step co-condensation of phenyltrimethoxysilane (PTMS) and 1,2-bis(trimethoxysily)ethane (BTME) using a triblock copolymer EO(20)PO(70)EO(20) (P123) as template with the aid of a co-surfactant (cetyltrimethylammonium bromide, CTAB) and a co-solvent (ethanol) in acidic medium. Powder X-ray diffraction (XRD), nitrogen sorption measurement and scanning electron microscopy (SEM) show that phenyl-functionalized ethane-silica has wormhole-like mesostructure and perfect spherical morphology. The chemical stability of phenyl-functionalized mesoporous ethane-silica in basic medium is greatly improved owing to the ethane groups bridged in the mesoporous framework. This work also demonstrates that the phenyl-functionalized mesoporous ethane-silica spheres are excellent packing materials for potential application in the reversed-phase high-performance liquid chromatography (HPLC).