Organically Modified Silicate Research Articles

Preferential formation of electroactive crystalline phases in poly(vinylidene fluoride)/organically modified silicate nanocomposites

AbstractThe role of organically modified silicate (OMS), Lucentite STN on the formation of β‐crystalline phase of poly(vinylidene fluoride) (PVDF) is investigated in the present study. The OMS was solution blended with PVDF and cast on glass slide to form PVDF‐OMS nanocomposites. Solution cast samples were subjected to various thermal treatments including annealing (AC‐AN), melt‐quenching followed by annealing (MQ‐AN), and melt‐slow cooling (MSC). Fourier‐transform infrared spectroscopy (FT‐IR), wide angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC) were used to investigate the crystalline structure of thermally treated samples. As a special effort, the combination of in situ thermal FT‐IR, WAXD, and DSC studies was utilized to clearly assess the thermal properties. FT‐IR and WAXD results of MQ‐AN samples revealed the presence of β‐phase of PVDF. Ion‐dipole interaction between the exfoliated clay nanolayers and PVDF was considered as a main factor for the formation of β‐phase. Melt‐crystallization temperature and subsequent melting point were enhanced by the addition of OMS. Solid β‐ to γ‐crystal phase transition was observed from in situ FT‐IR and WAXD curves when the representative MQ‐AN sample was subjected to thermal scanning. Upon heating, β‐phase was found to disappear through transformation to the thermodynamically stable γ‐phase rather than melting directly. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2173–2187, 2008

Controlling cell-material interactions with polymer nanocomposites by use of surface modifying additives

Polymer nanocomposites (NC) are fabricated by incorporating well dispersed nanoscale particles within a polymer matrix. This study focuses on elastomeric polyurethane (PU) based nanocomposites, containing organically modified silicates (OMS), as bioactive materials. Nanocomposites incorporating chlorhexidine diacetate as an organic modifier (OM) were demonstrated to be antibacterial with a dose dependence related to both the silicate loading and the loading of OM. When the non-antibacterial OM dodecylamine was used, both cell and platelet adhesion were decreased on the nanocomposite surface. These results suggest that OM is released from the polymer and can impact on cell behaviour at the interface. Nanocomposites have potential use as bioactive materials in a range of biomedical applications.

Functionalized Europium Nanorods for In Vitro Imaging

Emissive europium hydroxide nanorods (ENR) (20 nm x 500 nm) functionalized by a surface coating of chromophore-containing organically modified silicate (ORMOSIL) layer, have been synthesized and characterized by high-resolution transmission electron microscopy (TEM). Low-temperature photophysical characterization of the functionalized nanorods (FENR) demonstrated a strong red 5D0 luminescence both in solid and in suspended solutions. Potentials of this nanorod material for live cell imaging have also been explored. Both the bare and functionalized nanorods are able to enter living human cells with no discernible cytotoxicity. Chromophore-to-Eu3+ energy-transfer in the functionalized nanorods enables staining of the cytoplasm of living human cells. This is confirmed by costaining with fluorescent dextran. The red chromophore-sensitized luminescence from the internalized nanorods in live human lung carcinoma cells (A549) can be observed by confocal microscopy 2 h after loading and reaches maximal emission after 24 h.

Optical waveguide fabrication using a fast sol–gel method

In this work we present a method for fabrication of embedded waveguides using a class of organically modified silicates (ORMOSILs) with low organic content and glass like properties. The manufacturing of the ORMOSILs was done by a fast sol–gel method. This method allows for preparation of materials with finely controlled optical and mechanical properties. Optical waveguides with width and thickness ranges from a few micrometers up to hundreds of micrometers were fabricated. They were prepared using clad and core layers with tailored refractive indices over a wide range. The optical and mechanical performances of such waveguides are currently under investigation.

SANS study of hybrid silica aerogels under “in situ” uniaxial compression

We have modified the inorganic silica network of aerogels with polydimethylsiloxane (PDMS), a hydroxyl-terminated polymer, to obtain an organic modified silicate (ORMOSIL). Reactions were assisted by high-power ultrasounds. The resulting gels were dried under supercritical conditions of the solvent to obtain a monolithic sono-aerogel. The mechanical behaviour of these aerogels can be tuned from brittle to rubbery as a function of the organic polymer content. In order to determine the links between the mechanical behaviour and modifications made to the microstructure, SANS (small-angle neutron scattering) experiments were carried out. To measure the intensities under “in situ” uniaxial compression of the aerogel, a specific sample-holder was built. Under uniaxial compression the 2D-diagrams were significantly anisotropic (butterfly pattern), indicating the rearrangement of the polymer. The form factor of these aerogels is described well by two correlation lengths, small microporous silica clusters surrounded by entangled polymer chains of 6 nm average size (blobs), which form a larger secondary level of agglomerates governed by the “frozen-in” elastic constraints.

First Eu3+@Organo-Si(HIPE) Hybrid Macro-Mesocellular Foams Generation and Associated Luminescent Properties

AbstractUsing both β-diketone and malonamide organosilane derivatives and silica Si-HIPE macro-mesocellular foams (acronym refers to the High Internal Phase Emulsion process), organically modified silicates (ORMOSILs) with chelating functionality have been synthesized. The organic functionalities have been anchored to the silica porous networks by both a two-steps grafting method, relating to grafted gOrgano-Si(HIPE), and a one-step co-condensation process, relating to Organo-Si(HIPE). The loading of monoliths by lanthanides was performed by impregnation of an europium (III) salt in solution, leading to a new Eu3+@(g)Organo-Si(HIPE) hybrid foams series. The resulting materials have been thoroughly characterized via a large set of techniques such as SEM, TEM, SAXS, mercury intrusion porosimetry, nitrogen adsorption, FTIR and 29Si CP MAS NMR. Luminescence behavior of this Eu3+@Organo-Si(HIPE) series was also studied and the effects of environment and europium concentration will be discussed.

Novel hybrid optical sensor materials for in-breath O2analysis

This study focuses on the optimisation and characterisation of novel, ORganically MOdified SILicate (ORMOSIL)-based, hybrid sensor films for use in the detection of O(2) on a breath-by-breath basis in human health monitoring applications. The sensing principle is based on the luminescence quenching of the O(2)-sensitive ruthenium complex [Ru(ii)-tris(4,7-diphenyl-1,10-phenanthroline)], which has been entrapped in a porous sol-gel film. The detection method employed is that of phase fluorometry using blue LED excitation and photodiode detection. Candidate sensor films include those based on the organosilicon precursors, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane and phenyltriethoxysilane. While it has been established previously by the authors that these films exhibit a stable, highly sensitive response to O(2), this study focuses on selecting the material most suited for use in a breath monitor, based on the sensitivity, response time and humidity sensitivity of these films. Key parameters to be optimised include the O(2) sensitivity of the film and the film polarity, i.e. the degree of hydrophobicity. These parameters are directly linked to the precursors used. In this study a n-propyltriethoxysilane-derived O(2) sensor platform was selected as the optimum material for in-breath O(2) analysis due to its short response time, negligible humidity interference and suitable O(2) sensitivity in the relevant range in addition to its compatibility with a single-point calibration strategy.

Photoluminiscence response of Ru(II) complex immobilized in SiO 2-based matrix to dissolved oxygen in beer

The possibility to use the photoluminescence of Ru(II) tris(4,7-diphenyl-1,10-phenathroline) dichloride, immobilized in sol–gel produced SiO 2-based matrix for the determination of dissolved oxygen concentration in beer is studied. Organically-modified silane (octyltriethoxysilane) and mixtures from tetraethoxysilane and octyltriethoxysilane are used as precursors for matrix production. Spin- and dip-coating techniques are applied for films deposition. The predeposition ultrasound treatment of the sol ensures a good sensitivity and a linear sensor quenching response to oxygen in 1 ÷ 6 ppm O 2-concentration interval. The CO 2 present practically has no effect on the films performance. Their photoluminescence show rather good stability on prolonged storage in beer.

Fiber-optic carbon dioxide sensor based on fluorinated xerogels doped with HPTS

Abstract This paper presents a high-performance fiber-optic carbon dioxide (CO 2 ) sensor based on hybrid xerogels composed of alkyl and perfluoroalkyl ORMOSILs (organically modified silicates) doped with pH-sensitive fluorescent dye. The sensor film consists of 1-hydroxy-3,6,8-pyrenetrisulfonic acid trisodium salt (HPTS, PTS − ), tetraoctylammonium cation (TOA + ), and a tetraoctylammonium hydroxide (TOAOH) phase transfer agent (i.e. the base) immobilized within the hybrid xerogels. The experimental results indicate that the fluorescence intensity of the HPTS dye decreases as the CO 2 gas phase concentration increases. The sensor has a response level of ( I 0 − I )/ I ≈ 18, where I 0 and I are the fluorescence intensities in 100% N 2 and in 100% CO 2 , respectively, and exhibits a linear response to CO 2 concentrations in the range 0–30%. The resolution is ±2.5% in this level and the limit of detection (LOD) is 0.03% CO 2 , calculated as three times the standard deviation (3 σ ). The response time of the sensor is 1.7 s when switching from a pure nitrogen atmosphere to a pure CO 2 atmosphere and 38.5 s when switching from CO 2 to nitrogen. The signal changes are fully reversible as the atmosphere is switched repeatedly between nitrogen and CO 2 . Overall, the experimental results demonstrate that the use of hybrid xerogels doped with HPTS enhances both the response level and the response speed of the proposed optic-fiber CO 2 sensor.

An optical biosensing film for biochemical oxygen demand determination in seawater with an automatic flow sampling system

An on-line roboticized apparatus, including an optical biosensing film with an automatic flow sampling system, has been developed for biochemical oxygen demand (BOD) determination of seawater. The sensing film employed in the apparatus consisted of an organically modified silicate (ORMOSIL) film embedded with tri(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) perchlorate. Three species of microorganism cultivated from seawater were immobilized in an ORMOSIL-polyvinyl alcohol matrix. Possible factors affecting BOD determination were studied, including sampling frequency, temperature, pH and sodium chloride concentration. Based on measurements of the linear fluctuant coefficients and the reproducibility of its response to seawater, the BOD apparatus showed the advantages of high veracity and short response time. Generally, the linear fluctuant coefficient (R2) in the BOD range 0.2–40 mg l−1 was 0.9945 when using a glucose/glutamate (GGA) BOD standard solution. A reproducible response for the BOD sensing film of within ±2.8% could be obtained in the 2 mg l−1 GGA solution. The BOD apparatus was applied to the BOD determination of seawater, and the values estimated by this biosensing apparatus correlated well with those determined by the conventional 5 day BOD (BOD5) test.

Tris(2,2′-bipyridyl)ruthenium(II) electrochemiluminescence sensor based on carbon nanotube/organically modified silicate films

In this paper, a novel electrochemiluminescence (ECL) sensor was constructed to determine herring sperm (HS) double-stranded (ds) DNA. Tetramethoxysilane and dimethyldimethoxysilane were selected as co-precursors to form an organically modified silicate (ORMOSIL) film for the immobilization of multiwall carbon nanotubes (MWNTs) wrapped by poly( p-styrenesulfonate) (PSS), and then Tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy) 3 2+) was successfully immobilized on a glassy carbon electrode via ion-association. PSS was employed to increase the conductivity of the ORMOSIL film and disperse the cut MWNTs, which were cut and shortened in a mixture of concentrated sulfuric and nitric acids, in the film. It was found that MWNTs could adsorb Ru(bpy) 3 2+ and acted as conducting pathways to connect Ru(bpy) 3 2+ sites to the electrode. MWNTs also played a key role as materials for the mechanical and thermal properties. The ECL performance of this modified electrode was evaluated in a flow injection analysis (FIA) system, and the detection limit ( S/ N = 3) for HS ds-DNA was 2.0 × 10 −7 g mL −1 with a linear range from 1.34 × 10 −6 to 6.67 × 10 −4 g mL −1 ( R 2 = 0.9876). In addition, the ECL sensor presented excellent characteristics in terms of stability, reproducibility and application life.

Influence of Coumarin Dyes on the Laser Performance of Pyrromethene and Perylene Dyes Co-Doped into ORMOSILs

Laser dyes perylene red (p-red) or pyrromethene 567 (p567) were co-doped with coumarin 440 (C440) or coumarin 500 (C500) into MTES- and VTES-derived organically modified silicates (ORMOSILs) by sol-gel process. The effects of coumarin dye concentration on the laser performances of p-red and p567 were investigated. The results from laser efficiency measurements illustrated that at optimized coumarin concentration, the slope efficiency of co-doped p-red increased by a factor of 2 while that of co-doped p567 increased marginally. It was also found that by co-doping coumarin, the laser wavelength of p-red blue shifted and the laser thresholds for p567 and p-red could be reduced. The energy transfer mechanisms involved were also discussed.

The Control of Shrinkage of Silica Aerogel at Ambient Pressure

The drying process at ambient pressure of silica aerogel is an important improvement of the process of aerogels. But, the irreversible shrinkage during the drying of wet alcohol gel usually results in the destroy of aerogel networks. In this paper, two ways are used to control the drying shrinkage, including organically modified silicates (ORMOSIL) and Si0 2 power doped silicates. ORMOSIL have been prepared by incorporating polymethyl methacrylate (PMMA) into silica xerogels, with tetraethoxysilane (TEOS) as the precursor, vinyltriethoxysilane as silane coupling agent. Power Si0 2 is doped to strengthen silica xerogel with weight ratio to TEOS from 0% to 30%. The silica xerogels are characterized by scanning electron microscopy, nitrogen adsorption techniques, Fourier transform infrared rays analysis and so on. The results show that large changes are found in pore structure, volume shrinkage ratio and modulus.

Organic–inorganic materials for fabrication of integrated optical circuits

In the last few years, ORganically MOdified SIlicates (ORMOSILS) [R x Si(OR) 4− x ] prepared by sol–gel process were particularly attractive for integrated optics fabrication. A composition based on 3-(trimethoxysilyl)propylmethacrylate (MAPTMS) has already allowed the industrial fabrication of optical integrated devices. For this kind of materials, the polymerization of the organic network is typical of free radical curing. In this work, we try to obtain waveguides with another hybrid precursor [2-(3,4-epoxycyclohexylethyltrimethoxysilane)] using cationic polymerization. The main advantage of cationic polymerization is its ability to allow spontaneous cure reaction in presence of oxygen, in contrast with radical polymerization. We choose cycloaliphatic compounds because of their well-known high polymerization rates. The polymerization of the organic network of this hybrid material requires a cationic photoinitiator. The purpose of this paper is dedicated to the inorganic part of the material. Hydrolysis and polycondensation are followed by 29Si NMR. The main objective is to obtain the highest reactive multifunctional oligomer with the lowest OH groups content. Based on our results, we obtained 3D waveguides with a cross-section of 5 μm × 5 μm.

Preparation of Porous Organically-Modified Silicate Hybrids for Cell Culture Matrix

Porous & rubbery organic-inorganic hybrids were synthesized from tetraethoxysilane (TEOS) and polydimethylsiloxane (PDMS) through a sol-gel route using sieved sucrose granules as a porogen. The porous hybrids with a high content of PDMS behaved like polymer sponge. The porosity was over 90% irrespective of the hybrid composition and the pore diameter ranged from 100 to 500 μm. In the three-dimensional cell culture, mammalian cells were well cultured in the porous hybrids. The present results indicate that the hybrids may be a promising scaffold for developing such functional culture methods.

Electrochemiluminescence determination of codeine or morphine with an organically modified silicate film immobilizing Ru(bpy)32+

An ECL approach was developed for the determination of codeine or morphine based on tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3)(2+)) immobilized in organically modified silicates (ORMOSILs). Tetramethoxysilane (TMOS) and dimethyldimethoxysilane (DiMe-DiMOS) were selected as co-precursors for ORMOSILs, which were then immobilized on a surface of glassy carbon electrode (GCE) by a dip-coating process. Ru(bpy)(3)(2+) was immobilized in the ORMOSIL film via ion-association with poly(p-styrenesulphonate). The ORMOSIL-modified GCE presented good electrochemical and photochemical activities. In a flow system, the eluted codeine or morphine was oxidized on the modified GCE and reacted with immobilized Ru(bpy)(3)(2+) at a potential of +1.20 V (vs. Ag/AgCl). The modified electrode was used for the ECL determination of codeine or morphine and showed high sensitivity. The calibration curves were linear in the range 2 x 10(-8)-5 x 10(-5) mol/L for codeine and 1 x 10(-7)-3 x 10(-4) mol/L for morphine. The detection limit was 5 x 10(-9) mol/L for codeine and 3 x 10(-8) mol/L for morphine, at signal:noise ratio (S:N)=3. Both codeine and morphine showed reproducibility with RSD values <2.5% at 1.0 x 10(-6) mol/L. Furthermore, the modified electrode immobilized Ru(bpy)(3)(2+) was applied to the ECL determination of codeine or morphine in incitant samples.

Fabrication of organically modified oxygen sensing film based on fluorescent quenching

An organically modified silicate (ORMOSIL) as a matrix for oxygen-sensitive sensor, in which dimethyldimethoxysilane was selected as an organic modifier in the precursor, is described. The sensing film with tris-(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) as an indicator developed in this paper was characterized by efficient quenching by oxygen. Blue light-emitting diodes (λmax = 475 nm) were employed as light excitation source. The linear range of the dissolved oxygen was from 0.5 to 16 μg/mL. The measured RSD was 2%, the response time (t95) was 60 s, and the determination limit was 0.2 μg/mL. A portable and inexpensive luminescence-based sensor was established and applied to the determination of dissolved oxygen in the surface water.

Influence of various coumarin dyes on the laser performance of laser dyes co-doped into ORMOSILs

Several kinds of coumarin dyes (C440, C460, C500, C503 and C540A) were co-doped with perylene red (p-red) or pyrromethene 567 (p567) into VTES- and MTES-derived organically modified silicates (ORMOSILs) respectively, by the sol-gel process. The effects of coumarin dyes and their concentration on the laser properties and photostabilities of p-redand p567 were studied and the mechanisms involved were discussed. At optimized coumarin dye concentration, the slope efficiency of co-doped p-redincreased by a factor of 2 while only minor increases in the laser efficiency of p567 were observed. A broader tunable range with increased conversion efficiency and at least a 3-fold improvement in the photostabilities of p-redand p567 in the presence of coumarin family dyes have also been achieved. The mechanism responsible for the improvement in the laser performances and photostabilities of p-redand p567 resulted from the energy transfer between p-red/567 and coumarin dyes.

Hard UV-curable organo-mineral coatings for optical applications

Organically-modified silicate incorporating various amounts of zirconium precursor was synthesized via a sol–gel route. The material was deposited as thin films on PMMA substrates and densified by UV-curing. Mechanical properties were measured by nanoindentation and data were recorded continuously as a function of the penetration depth during the loading–unloading cycles. Values of hardness and Young modulus were found in the range 340–440 MPa and 4–6 GPa, respectively. It was shown that these values could be tailored by varying the relative amount of zirconium in the layer. The material exhibited a very elastic behaviour that was related to its high degree of cross-linking assessed by infrared spectroscopy. Results were compared with measurements published by various groups on related materials. The mechanical and optical properties of the samples made this class of materials promising as hard coatings for optical applications.

Nanocomposites of poly(vinylidene fluoride) with organically modified silicate

We report a study of the impact of cold crystallization on the structure of nanocomposites comprising poly(vinylidene fluoride) (PVDF) and Lucentite STN™ organically modified silicate (OMS). Nanocomposites were prepared from solution over a very wide composition range, from 0.01 to 20% OMS by weight. Thermal preparation involved cold crystallization at 145°C of quenched, compression-molded plaques. Static and real-time wide and small angle X-ray scattering (WAXS, SAXS), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC) were used to investigate the crystalline phase of PVDF. For OMS content greater than 0.50wt%, WAXS studies show that that the silicate gallery spacing increases modestly in the nanocomposites compared to neat OMS film, indicating a level of polymer intercalation.Using Gaussian peak fitting of WAXS profiles, we determine that the composition range can be divided into three parts. First, for OMS greater than 0.5wt%, alpha phase fraction, ϕalpha, is insignificant (ϕalpha∼0–0.01). Second, at the intermediate range, for OMS between 0.5wt% down to 0.025wt%, beta phase dominates and the beta fraction, ϕbeta, is related to alpha by ϕbeta>ϕalpha. Third, below 0.025wt% OMS, alpha dominates and ϕalpha>ϕbeta. The ability of small amounts of OMS (≥0.025wt%) to cause beta crystal domination is remarkable. Overall, crystallinity index (from the ratio of WAXS crystal peak area to total area) ranges from about 0.36 to 0.51 after cold crystallization. Real-time WAXS studies during heating of initially cold crystallized nanocomposites show that there is no inter-conversion between the alpha and beta phase PVDF crystals, where these crystals coexist at room temperature. While all samples showed a strong SAXS Bragg peak, indicating existence of two-phase lamellar stacks, the sample containing predominantly beta phase had poorly correlated lamellar stacks, compared to samples containing predominantly alpha phase.