Organic-inorganic hybrid liquid crystals: hybridization of calamitic liquid-crystalline amines with monodispersed anisotropic TiO2 nanoparticles

A novel organic-inorganic hybrid thermotropic liquid crystal (LC) is developed by the hybridization of an organic amine with a mesogenic core and an acicular anisotropic TiO2 particle through the adsorption of the amino group to the surfaces of the TiO2. The hybrid LC shows nematic phases in wide ranges of temperatures. Variable-temperature small-angle X-ray measurements reveal that the formation of the one-dimensional nematic order of the acicular particles on a submicrometer scale induces thermotropic liquid crystallinity. This technique would lead to induction of dynamic functions in inorganic particles.     

Electric relaxation currents in a cured polyester resin with nitroaniline additives

The influence of a small amount of nitroaniline additive on the thermally stimulated discharge current in a cured polyester resin was investigated. The height of dipole relaxation and space charge relaxation peaks increased and the maxima of the dipole peaks shifted to lower temperatures. The observed effects are explained by the nitroaniline—polyester resin interaction, which causes a structural plasticization of the polymer.     

Thermal degradation of a styrenated unsatured polyester resin

The isothermal and non-isothermal degradation of a typical styrenated phthalic acid-maleic acid-propylene glycol polyester were measured. Non-isothermal and isothermal kinetic analyses were performed on the various degradation steps observed. The values of the non-isothermal and the isothermal kinetic parameters are in good agreement.     

Organic-inorganic hybrid nanomaterial as a new fluorescent chemosensor and adsorbent for copper ion

Functionalized silica nanotube (FSNT) possessing the phenanthroline moiety as a fluorescent receptor was fabricated by solgel reaction, and the binding ability of FSNT with metal ions was evaluated by fluorophotometry.     

Synthesis and characterization of a new magnetic bromochromate hybrid nanomaterial with triethylamine surface modified iron oxide nanoparticles

We describe a novel method for the synthesis a new magnetic bromochromate hybrid nanomaterial, Fe3O4@SiO2@TEA@[CrO3Br], as a catalyst. The physical properties, morphology and magnetic investigations of magnetic bromochromate hybrid nanomaterials are identified by transmission electron microscopy （TEM）, scanning electron microscopy （SEM） and vibrating sample magnetometer （VSM） techniques. Fourier transform infrared （FT-IR）, elemental analysis, X-ray fluorescence （XRF）, X-ray diffraction （XRD） were also used for structural identification. The quantity of chromium is approximately 0.38%, which confirms to the immobilization amount of [CrO3Br]- and is equal to 0.007 mol/100 g.     

Organic-inorganic hybrid compounds of Li with bisimidazole derivatives: Li ion binding study and topochemical properties

The imidazole-based ligands, bis(imidazol-1-yl)methane (Bizm, 1a) and (pyrenyl)bis(imidazol-1-yl) methane (Pbizm,2a) were prepared. With LiClO4, these two compounds formed two novel organic-inorganic hybrid materials: a 3D network polymer Li(Bizm).ClO4 (1b) and a 1D chain polymer Li(Pbizm)2.ClO4 (2b). The intriguing topological and physiochemical characteristics of 1b and 2b are reported on the basis of the X-ray single-crystal structure analysis and Li ion binding studies.     

Biomimetic interactions of proteins with functionalized nanoparticles: a thermodynamic study

Gold nanoparticles (NPs) functionalized with L-amino acid-terminated monolayers provide an effective platform for the recognition of protein surfaces. Isothermal titration calorimetry (ITC) was used to quantify the binding thermodynamics of these functional NPs with alpha-chymotrypsin (ChT), histone, and cytochrome c (CytC). The enthalpy and entropy changes for the complex formation depend upon the nanoparticle structure and the surface characteristics of the proteins, e.g., distributions of charged and hydrophobic residues on the surface. Enthalpy-entropy compensation studies on these NP-protein systems indicate an excellent linear correlation between DeltaH and TDeltaS with a slope (alpha) of 1.07 and an intercept (TDeltaS0) of 35.2 kJ mol(-1). This behavior is closer to those of native protein-protein systems (alpha = 0.92 and TDeltaS0 = 41.1 kJ mol(-1)) than other protein-ligand and synthetic host-guest systems.     

Magnetic nanoparticles with hybrid shape

Co₅₀Ni₅₀ particles with very unusual shapes, resembling dumbbells or diabolos, are obtained by reducing mixtures of cobalt and nickel acetates in sodium hydroxide solution in 1,2-propane diol. These particles consist of a central column richer in cobalt than the overall composition, capped with two terminal platelets that are richer in nickel. These hybrid shapes are the result of a two-step growth mechanism due to a difference in reactivity of the two metal ions. The sodium hydroxide concentration controls the length and diameter of the column, in the ranges 50–250 nm and 5–15 nm, respectively, and the diameter of the platelets in the range 25–50 nm. The X-ray diffraction patterns show a mixture of hcp and fcc phases in various proportions depending on the particle shape. High-resolution electron microscopy shows that the hcp phase is located mainly in the central column and the fcc phase mainly in the terminal platelets. The particles are ferromagnetic at room temperature. When the volume fraction of the central column is high enough and the hcp phase is predominant and not much faulted, high coercivity (up to 1900 Oe) is observed.     

Organic-inorganic hybrid mesoporous silicas: functionalization, pore size, and morphology control

Topological design of mesoporous silica materials, pore architecture, pore size, and morphology are currently major issues in areas such as catalytic conversion of bulky molecules, adsorption, host-guest chemistry, etc. In this sense, we discuss the pore size-controlled mesostructure, framework functionalization, and morphology control of organic-inorganic hybrid mesoporous silicas by which we can improve the applicability of mesoporous materials. First, we explain that the sizes of hexagonal- and cubic-type pores in organic-inorganic hybrid mesoporous silicas are well controlled from 24.3 to 98.0 A by the direct micelle-control method using an organosilica precursor and surfactants with different alkyl chain lengths or triblock copolymers as templates and swelling agents incorporated in the formed micelles. Second, we describe that organic-inorganic hybrid mesoporous materials with various functional groups form various external morphologies such as rod, cauliflower, film, rope, spheroid, monolith, and fiber shapes. Third, we discuss that transition metals (Ti and Ru) and rare-earth ions (Eu(3+) and Tb(3+)) are used to modify organic-inorganic hybrid mesoporous silica materials. Such hybrid mesoporous silica materials are expected to be applied as excellent catalysts for organic reactions, photocatalysis, optical devices, etc.     

Amphiphilic polysaccharides: useful tools for the preparation of nanoparticles with controlled surface characteristics

Polymeric surfactants obtained by hydrophobic modification of dextran are used as stabilizers for oil-in-water emulsions. The kinetics of interfacial tension decrease is studied as a function of polymer structural characteristics (degree of hydrophobic substitution) and at various polymer concentrations. Several hydrocarbon oils, either aliphatic (octane, decane, dodecane, and hexadecane) or aromatic (styrene), are tested. Kinetics exhibits the same general trends no matter which oil or polymer is considered. The emulsifying properties of the polymeric surfactants are illustrated by the preparation of oil-in-water emulsions. The droplet size at the preparation is correlated to the amount of oil and to the polymer concentration in the aqueous phase. For low polymer/oil ratios, it is shown that the droplet size is limited by the initial amount of polymer. On the contrary, for high polymer/oil ratios, the droplet size seems to level down, indicating that other parameters become predominant. Emulsion aging occurs by Ostwald ripening, and it is demonstrated that the theoretical equation of Lifshitz, Slyozov, and Wagner (LSW) correctly describes the experimental results. The nature of the oil has important effects on emulsion aging, as described by the LSW equation. The aging of emulsions containing oil mixtures is quantitatively described on the basis of the results with pure oils. The influence of polymer chemical structure can be conveniently correlated to interfacial tension results through the LSW equation. On the contrary, the influence of oil volume fraction seems to be overestimated by the usual correction factor, k(phi). The effect of temperature on emulsion aging is finally examined. Miniemulsions stabilized with dextran derivatives are used for the radical polymerization of styrene. Following this procedure, polysaccharide-covered polystyrene nanoparticles are prepared and characterized (size and surface coverage). The size of the particles is directly correlated to that of the initial droplets for styrene volume fractions around 10%. On the contrary, for initial styrene volume fractions around 20%, particles exhibit a larger size than the initial droplets, indicating that coalescence processes take place during polymerization. The amount of dextran at the surface of the particles is determined and compared to the adsorbed amounts resulting from emulsion preparation.     

Tensile properties of ligno-cellulosic fabrics coated with styrenated polyester resin

Ligno-cellulosic fabrics from the tree Hildegardia populifolia were coated with styrenated polyester resin, and their tensile strength, elastic modulus, and the percent elongation at break were determined. The effects of sodium hydroxide and a silane-coupling agent on the tensile properties of the fabric were also studied. It was observed that the tensile strength and the modulus decreased whereas the percent elongation at break increased with coating. The coupling agent improved the properties of the untreated and polyester-coated fabric, but a reverse trend was observed when the fabric was treated with sodium hydroxide. The possible reasons for this behavior are discussed.     

Poly(ethylene oxide) blends with crosslinking polyester resin

The miscibility of polyethylene oxide (PEO) with oligoester and polyester resin, the morphology of the blends and the kinetics of PEO crystallization in the blends were studied by optical microscopy and differential scanning calorimetry. The blends were found to be miscible with uncured resin at 60°C. After isothermal crystallization of PEO from liquid oligoester or UV cured polyester about 20% of the PEO material is still dissolved in the resin and it is incorporated between lamellae or in the interspherulitic regions. It was observed that the growth rate of PEO spherulites and the degree of crystallinity of PEO in the blends decreases very fast together with a decrease of the PEO content and the progress of the resin crosslinking.     

Organic-inorganic hybrid photonic hydrogels as a colorful platform for visual detection of SCN-

This communication demonstrates a facile method to detect SCN(-) by the naked eye through color change based on responsive organic-inorganic hybrid photonic hydrogels.     

Structure control in PMMA/silica hybrid nanoparticles by surface functionalization

Hydrophilic silica particles need to be hydrophobized to be encapsulated in a polymeric environment, which can be achieved by different methods. We report on the relationship between different hydrophobization techniques of silica and the final structure of poly(methyl methacrylate)/silica hybrid nanoparticles obtained by miniemulsion polymerization. Hydrophobization by cetyltrimethylammonium chloride (CTMA-Cl) uses the ionic interaction between the positively charged ammonium salt and the negatively charged silica surface, as shown by isothermal titration calorimetry. In this case, the interaction between polymer and silica surface needs to be enhanced, so 4-vinylpyridine (4-VP) was used as a co-monomer. Alternatively, the condensation reactions of 3-methacryloxypropyltrimethoxysilane (MPS) and octadecyltrimethoxysilane (ODTMS) were used to provide a covalent bond to the silica surface. The condensation reaction of the trimethoxysilane groups onto the silica surface was proven by Fourier transform infrared spectroscopy and thermogravimetric analysis. Hybrid nanoparticles were successfully formed with silica particles functionalized with the different functionalization agents. However, the structure of the resulting hybrid particles (i.e., the distribution of the silica particles within the polymer matrix) depends on the agent. The MPS-functionalized silica particles copolymerize with poly(methyl methacrylate), leading to a fixation of the silica particles inside the polymer and to a homogeneous distribution. The CTMA-Cl- and ODTMS-functionalized silica particles cannot copolymerize, but aggregate at the interface, leading to a Janus-like structure.     

Surface-grafted hybrid material consisting of gold nanoparticles and dextran exhibits mobility and reversible aggregation on a surface

Gold nanoparticles linked to linear carboxylated dextran chains were attached to 3-aminopropyltriethoxysilane-functionalized glass surfaces. This method provides novel hybrid nanostructures on a surface with the unique optical properties of gold nanoparticles. The particles attached to the surface retain the capability to aggregate and disaggregate in response to their environment. This procedure presents an alternative method to the immobilization of gold nanoparticles onto planar substrates. Compared to gold nanoparticle monolayers, larger particle surface densities were obtained. Exposure to hydrophobic environments changes the conformation of the hydrophilic dextran chains, causing the gold nanoparticles to aggregate and inducing changes in the absorption spectrum such as red-shifting and broadening of the plasmon absorption peaks. These changes, characteristic of particle aggregation, are reversible. When the substrates are dried and then immersed in an aqueous environment, these changes can be visually observed in a reversible fashion and the sample changes color from the red color of colloidal gold to a bluish-purple color of aggregated nanoparticles. Surface-bound nanoparticles that retain their mobility when attached to a surface by means of a flexible polymer chain could expand the use of aggregation-based assays to solid substrates.     

Synthesis of dissymmetrical nanoparticles with a new hybrid silica template

An easy, novel route to prepare Janus nanoparticles and nano-bowls with tunable shapes has been developed. This approach uses a new kind of monodisperse vinyl-silica nanoparticles as templates to obtain large amounts of uniform Janus particles and nano-bowls (several grams). The efficient method adopts water-based hydrolysis-condensation and seed-emulsion polymerization. The uniform Janus nanoparticles and nano-bowls will display wide potential applications in many fields, such as: chemical sensors, construction of complex superstructures and nano-bioreactors.     

Kinetics of thermal oxidative degradation of a polyester resin and of its formulation with diethyldibenzylammonium bromide

The kinetics of thermal oxidative degradation of a polyester resin and of its formulation with diethyldibenzylammonium bromide was studied. The rate constants of the thermal decomposition were determined.