Project description:An inorganic sol-gel polymerization process was used as a cross-linking reaction during three-dimensional (3D) bioprinting of cell-containing hydrogel scaffolds. Hybrid hydroxypropyl methyl cellulose (HPMC), with a controlled ratio of silylation, was prepared and isolated as a 3D-network precursor. When dissolved in a biological buffer containing human mesenchymal stem cells, it yields a bioink that can be printed during polymerization by extrusion. It is worth noting that the sol-gel process proceeded at pH 7.4 using biocompatible mode of catalysis (NaF and glycine). The printing window was determined by rheology and viscosity measurements. The physicochemical properties of hydrogels were studied. Covalent functionalization of the network can be easily performed by adding a triethoxysilyl-containing molecule; a fluorescent hybrid molecule was used as a proof of concept.
Project description:Condensation reactions of chlorosilanes (SiCl4 and CH3SiCl3) and bis(trimethylsilyl)ethers of rigid, quasi-linear diols (CH3)3SiO-AR-OSi(CH3)3 (AR = 4,4'-biphenylene (1) and 2,6-naphthylene (2)), with release of (CH3)3SiCl as a volatile byproduct, afforded novel hybrid materials that feature Si-O-C bridges. The precursors 1 and 2 were characterized using FTIR and multinuclear (1H, 13C, 29Si) NMR spectroscopy as well as single-crystal X-ray diffraction analysis in case of 2. Pyridine-catalyzed and non-catalyzed transformations were performed in THF at room temperature and at 60 °C. In most cases, soluble oligomers were obtained. The progress of these transsilylations was monitored in solution with 29Si NMR spectroscopy. Pyridine-catalyzed reactions with CH3SiCl3 proceeded until complete substitution of all chlorine atoms; however, no gelation or precipitation was found. In case of pyridine-catalyzed reactions of 1 and 2 with SiCl4, a Sol-Gel transition was observed. Ageing and syneresis yielded xerogels 1A and 2A, which exhibited large linear shrinkage of 57-59% and consequently low BET surface area of 10 m2⋅g-1. The xerogels were analyzed using powder-XRD, solid state 29Si NMR and FTIR spectroscopy, SEM/EDX, elemental analysis, and thermal gravimetric analysis. The SiCl4-derived amorphous xerogels consist of hydrolytically sensitive three-dimensional networks of SiO4-units linked by the arylene groups. The non-hydrolytic approach to hybrid materials may be applied to other silylated precursors, if the reactivity of the corresponding chlorine compound is sufficient.
Project description:Highly fluorescent blue and green-emitting carbon dots have been designed to be integrated into sol-gel processing of hybrid organic-inorganic materials through surface modification with an organosilane, 3-(aminopropyl)triethoxysilane (APTES). The carbon dots have been synthesised using citric acid and urea as precursors; the intense fluorescence exhibited by the nanoparticles, among the highest reported in the scientific literature, has been stabilised against quenching by APTES. When the modification is carried out in an aqueous solution, it leads to the formation of silica around the C-dots and an increase of luminescence, but also to the formation of large clusters which do not allow the deposition of optically transparent films. On the contrary, when the C-dots are modified in ethanol, the APTES improves the stability in the precursor sol even if any passivating thin silica shell does not form. Hybrid films containing APTES-functionalized C-dots are transparent with no traces of C-dots aggregation and show an intense luminescence in the blue and green range.
Project description:In this article experimental data are presented for inorganic gel based smart window fabricated using silica sol-gel process. Parallel beam transmittances were measured as functions of voltages for samples fabricated with different concentrations of nitric acid. Spectroscopic transmittance data at different driving voltages for samples fabricated with different LC concentrations are shown. Transmittance spectra of the Si-Ti based gel-based-liquid-crystal (GDLC) device measured as different driving voltages were compared with those of PDLC. GDLC showed much lower operating voltages, 10-15 V, for on-state. Formation of the LC droplet in gelation process is illustrated. The methyl organic group surrounds LC droplets. Demonstration of GDLC based smart window showed the successful operation with low driving voltages. GDLC window shows clear color, even at off-state, compared with PDLC.
Project description:Tm3+ has obvious emission characteristics in the near-infrared band. Thulium ions combined with different organic ligands lead to different fluorescent properties. In the near-infrared region, Tm3+ is a down-conversion fluorescent material that is unstable under high temperature and acidic conditions. Moreover, in those complex environments, the fluorescence from Tm3+ complex is usually degraded. In this work, two kinds of near-infrared fluorescent complexes, Tm(TTA)3phen and Tm(DBM)3phen, were prepared, and the intensity of their fluorescence is compared. The fluorescence intensity at 802 nm is greatly improved compared with Tm(TTA)3phen, and the intensity of the emission at 1235 nm and 1400-1500 nm is also enhanced. Moreover, the emission lifetime of SiO2-Tm(TTA)3phen is 50.38 μs. Tm(TTA)3phen complex and SiO2-Tm(TTA)3phen hybrid materials have better fluorescence than Tm(DBM)3phen and SiO2-Tm(DBM)3phen. Therefore, HTTA is a better choice of organic ligands for Tm3+. The NIR-fluorescent hybrid materials prepared have stronger fluorescence after combining with nano-SiO2compared with pure Tm3+ complexes, and have stronger structural stability compared with pure nano-SiO2.
Project description:This paper presents a comparison of the simultaneous preparation of di-O-alkylated and ether-ester derivatives of fluorescein using different methods (conventional or microwave heating). Shortening of the reaction time and increased efficiency were observed when using a microwave reactor. Moreover, described here for the first time is the application of a fast, simple, and eco-friendly ball-assisted method to exclusively obtain ether-ester derivatives. We also demonstrate that fluorescein can be effectively functionalized by O-alkylation carried out under microwave or ball-milling conditions, saving time and energy and affording the desired products with good yields and minimal byproduct formation. All the synthesized products as well as pH-dependent (prototropic) forms trapped in the SiO2 matrix were examined using UV-Vis and fluorescence spectroscopy.
Project description:Novel organic-inorganic hybrid coating materials were developed using amino silanes and acetoacetylated soybean oil. The acetoacetylated soybean oil was prepared from soybean oil (a renewable resource) using a solvent-free method involving a thiol-ene and transesterification reactions, and the chemical structure was characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), Fourier-transform infrared (FTIR) spectroscopy, and viscosity analyses. On the basis of the acetoacetylated soybean oil, several organic-inorganic hybrid coating materials were prepared using different amino silanes by a catalyst-free method involving one-step comprising two reactions (an amine-acetoacetate reaction and an in situ sol-gel technique), and their crosslinked structures were determined from their FT-IR and solid-state 29Si NMR spectra. The resulting coating materials have good mechanical/chemical performance. This method for preparing renewable organic-inorganic hybrid coating materials may have wide uses because plant oils contain many unsaturated C[double bond, length as m-dash]C bonds and easy access to acetoacetate functional groups.
Project description:Organosilanes (e.g., R'-SiOR3) provide hydrophobic functionality in thin-film coatings, porous gels, and particles. Compared with tetraalkoxysilanes (SiOR4), organosilanes exhibit distinct reaction kinetics and assembly mechanisms arising from steric and electronic properties of the R' group on the silicon atom. Here, the hydrolysis and condensation pathways of n-propyltrimethoxy silane (nPM) and a tri-fluorinated analog of nPM, 3,3,3-trifluoropropyl trimethoxy silane (3F), were investigated under aqueous conditions at pH 1.7, 2.0, 3.0, and 4.0. Prior to hydrolysis, 3F and nPM are insoluble in water and form a lens at the bottom (3F) or top (nPM) of the solutions. This phase separation was employed to follow reaction kinetics using a Turbiscan instrument to monitor hydrolysis through solubilization of the neat silane lens while simultaneously tracking condensation-induced turbidity throughout the bulk solution. Dynamic light scattering confirmed the silane condensation and particle aggregation processes reported by the turbidity scanning. Employing macroscopic phase separation of the starting reactants from the solvent further allows for control over the reaction kinetics, as the interfacial area can be readily controlled by reaction vessel geometry, namely by controlling the surface area to volume. In-situ turbidity scanning and dynamic light scattering revealed distinct reaction kinetics for nPM and 3F, attributable to the electron withdrawing and donating nature of the fluoro- and organo-side chains of 3F and nPM, respectively.
Project description:Chlorogenic acid (CGA) is a very common dietary polyphenolic compound. CGA is becoming very attractive due to its potential use as preventive and therapeutic agent in many diseases, including cancer. Inorganic/organic hybrid materials are gaining considerable attention in the biomedical field. The sol-gel process provides a useful way to obtain functional organic/inorganic hybrids. The aim of this study was to synthesize silica/polyethylene glycol (PEG) hybrids with different percentages of CGA by sol-gel technique and to investigate their impact on the cancer cell proliferation. Synthesized materials have been chemically characterized through the FTIR spectroscopy and their bioactivity evaluated looking by SEM at their ability to produce a hydroxyapatite layer on their surface upon incubation with simulated body fluid (SBF). Finally, their effects on cell proliferation were studied in cell lines by direct cell number counting, MTT, flow cytometry-based cell-cycle and cell death assays, and immunoblotting experiments. Notably, we found that SiO?/PEG/CGA hybrids exhibit clear antiproliferative effects in different tumor, including breast cancer and osteosarcoma, cell lines in a CGA dependent manner, but not in normal cells. Overall, our results increase the evidence of CGA as a possible anticancer agent and illustrate the potential for clinical applications of sol-gel synthesized SiO?/PEG/CGA materials.
Project description:This work describes the preparation of an analytical microextraction sorbent using a simple and versatile sol-gel hybrid composite, i.e., aramid oligomers wrapping multi-walled carbon nanotubes (CNTs) covalently bonded to a porous silica network. To overcome the inherent shortcomings of the CNTs' solubility and dispersion in both organic phases and in the sol-gel solution, the outer surface of the CNTs was initially functionalized with carboxylic acid groups and then reacted with both aramid oligomers and 3-aminopropyl triethoxysilane (APTES). The obtained sorbent was characterized by FT-IR, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). Using sol-gel chemistry, the functionalized CNTs were coated onto SPME fibers and used in conjunction with GC-MS for the analysis of polycyclic aromatic hydrocarbons (PAHs) in water and soil samples. Excellent repeatability (run-to-run RSD% ∼ 8) and reproducibility (fiber-to-fiber RSD% ∼ 6) were achieved in addition to low LODs (0.10-0.30 ng mL-1) and noticeable recovery%. The present method of sorbent preparation led to enhanced thermal and chemical stabilities, a long sorbent lifetime and good affinity towards PAHs. Moreover, the present sorbent enhanced the extraction capability by more than 30% compared to that of commercially available PDMS counterparts.