How to prevent the loss of surface functionality derived from aminosilanes

Aminosilanes are common coupling agents used to functionalize silica surfaces. A major problem in applications of 3-aminopropylsilane-functionalized silica surfaces in aqueous media was encountered: the loss of covalently attached silane layers upon exposure to water at 40 degrees C. This is attributed to siloxane bond hydrolysis catalyzed by the amine functionality. To address the issue of loss of surface functionality and to find conditions where hydrolytically stable amine-functionalized surfaces can be prepared, silanization with different types of aminosilanes was carried out. Hydrolytic stability of the resulting silane-derived layers was examined as a function of reaction conditions and the structural features of the aminosilanes. Silane layers prepared in anhydrous toluene at elevated temperature are denser and exhibit greater hydrolytic stability than those prepared in the vapor phase at elevated temperature or in toluene at room temperature. Extensive loss of surface functionality was observed in all 3-aminopropylalkoxysilane-derived layers, independent of the number and the nature of the alkoxy groups. The hydrolytic stability of aminosilane monolayers derived from N-(6-aminohexyl)aminomethyltriethoxysilane (AHAMTES) indicates that the amine-catalyzed detachment can be minimized by controlling the length of the alkyl linker in aminosilanes.     

Grafting of montmorillonite with different functional silanes via two different reaction systems

Silane grafted montmorillonites were synthesized by using 3-aminopropyltriethoxysilane and trimethylchlorosilane via two different grafting reaction systems: (a) ethanol-water mixture and (b) vapor of silane. The resulting products were investigated using Fourier transform infrared (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA). XRD patterns demonstrate that silane was intercalated into the montmorillonite gallery, as indicated by the increase of the basal spacing. The product prepared by vapor deposition has a larger basal spacing than that obtained from solution, due to the different extent of silane hydrolysis in various grafting systems. TGA curves indicate that the methyl groups penetrate into the siloxane clay are the primary reason for the decrease of the dehydroxylation temperature of the grafted products. 3-Aminopropyltriethoxysilane in the grafted montmorillonite adopts a bilayer arrangement while trimethylchlorosilane adopts a monolayer arrangement within the clay gallery.     

SYNTHESIS OF CATALYSIS BY THE FUNCTIONALIZATION OF SILICA AND ITS APPLICATIONS

Hybrid organic-inorganic silica materials containing organic functional groups have been preparedby the reaction of activated silica with a silane coupling reagent such as N-(2-aminoethyl)3-aminopropyltrimethoxysilane. The hybrid silica was further modified by organic compounds having abifunctional group. These modified hybrid silicas were used as catalysts for various nucleophilic reactions.And also, these were complexed with metallic ions for use as catalysts for oxygen oxidation of hydrocarbons.     

Selective organic functionalization of polycrystalline silicon-germanium for bioMEMS applications

We selectively immobilized organofunctional silanes on top of polycrystalline silicon-germanium (poly-SiGe) layers, as a first step towards the fabrication of poly-SiGe-based bioMEMS (biomedical MicroElectroMechanicalSystems) by means of standard UV photolithography. 3-aminopropyl-dimethyl-ethoxysilane (APDMES) and 3-aminopropyl-triethoxysilane (APTES) molecules were immobilized onto resist-patterned poly-SiGe surfaces. The protocols for surface hydroxylation and silane immobilization were designed to be CMOS-compatible and to avoid damage to photoresist. Silanized surfaces were investigated both by means of fluorescence microscopy, and by FEG-SEM observation after labeling with 30 nm-diameter gold nanoparticles (NPs). We report the silanization protocols, together with the results indicating successful organic functionalization of the samples.     

Molecular packing density of a self-assembled monolayer formed from N-(2-aminoethyl)-3-aminopropyltriethoxysilane by a vapor phase process

The molecular density of an aminosilane self-assembled monolayer formed from N-(2-aminoethyl)-3-aminopropyltriethoxysilane (AEAPS) by a vapor phase method has been estimated to be about 3 AEAPS molecules per nm(2) based on chemical labeling, optical absorption spectroscopy and X-ray photoelectron spectroscopy.     

Deposition of dense siloxane monolayers from water and trimethoxyorganosilane vapor

A convenient, laboratory-scale method for the vapor deposition of dense siloxane monolayers onto oxide substrates was demonstrated. This method was studied and optimized at 110 °C under reduced pressure with the vapor of tetradecyltris(deuteromethoxy)silane, (CD(3)O)(3)Si(CH(2))(13)CH(3), and water from the dehydration of MgSO(4)·7H(2)O. Ellipsometric thicknesses, water contact angles, Fourier transform infrared (FTIR) spectroscopy, and electrochemical capacitance measurements were used to probe monolayer densification. The CD(3) stretching mode in the FTIR spectrum was monitored as a function of the deposition time and amounts of silane and water reactants. This method probed the unhydrolyzed methoxy groups on adsorbed silanes. Excess silane and water were necessary to achieve dense, completely hydrolyzed monolayers. In the presence of sufficient silane, an excess of water above the calculated stoichiometric amount was necessary to hydrolyze all methoxy groups and achieve dense monolayers. The excess water was partially attributed to the reversibility of the hydrolysis of the methoxy groups.     

Preparation and self-assembly of carboxylic acid-functionalized silica

A simple method for the fabrication of silica nanoparticle film based on the covalent-bonding interaction between carboxylic acid-functionalized silica nanoparticles (SiO(2)-COOH) and amino-terminated silicon wafer was developed. Prior to assembly, silica nanoparticles with an average diameter 80 nm were prepared using the St?ber method, amino-functionalized silica nanoparticles (SiO(2)-NH(2)) were prepared by a silanization with 3-aminopropyltriethoxysilane (APTES), while carboxylic acid-functionalized silica nanoparticles (SiO(2)-COOH) were prepared by a ring opening linker elongation reaction of the amine functions with succinic anhydride, at the same time, amino-terminated silicon wafer (Si-NH(2)) was obtained by self-assembling 3-aminopropyltriethoxysilane, then one layer relative close-packed carboxylic acid-functionalized silica nanoparticles (SiO(2)-COOH) was arranged on silicon wafer through amidation reaction under DCC coupling agent.     

银纳米微球和银纳米棒自组装膜的制备及SERS研究

采用硼氢化钠还原硝酸银,用振荡器在不同转速下振荡得到单分散的银纳米微球和银纳米棒,再将银纳米微球及银纳米棒自组装于被3-氨丙基-三甲氧基硅烷(APTMS)修饰的玻璃基片上,制得了具有表面增强拉曼(SERS)活性的基底,分别以罗丹明6G(R6G)和罗丹明B(RB)为探针分子对这两种基底进行SERS活性检测,结果发现这两种基底均为较理想的SERS衬底。     

Formation, structure, and reactivity of amino-terminated organic films on silicon substrates

Amino-functionalized organic films were prepared by self-assembling 3-aminopropyltriethoxysilane (APTES) on silicon wafers in either anhydrous toluene or phosphate-buffered saline (PBS) for varied deposition times. Fourier transform infrared spectroscopy (FTIR) and ellipsometry have shown that the structure and thickness of APTES films are governed by the deposition time and reaction solution. Deposition from an anhydrous toluene solution produces APTES films ranging from 10 to 144 A in thickness, depending on the reaction time. FTIR spectra indicate that film growth initially proceeds by adsorption of APTES to the silicon surface followed by siloxane condensation, and after an extended period of time APTES molecules accumulate on the underlying APTES film by either covalent or noncovalent interactions. In contrast, spectroscopically indistinguishable APTES films in thickness ranging from 8 to 13 A were formed when deposition was conducted in aqueous solutions. Measured water contact angles indicate that APTES films deposited in aqueous solutions are more hydrophilic compared to those prepared in toluene solutions. Fluorescence measurements revealed that APTES films prepared in toluene solutions contain more reactive surface amino groups by ca. 3 to 10 times than those prepared in aqueous solutions for the identical reaction time.     

Sum frequency generation studies at poly(ethylene terephthalate)/silane interfaces: hydrogen bond formation and molecular conformation determination

To better understand the effects of interfacial molecular orientation on adhesion to plastics, the interfaces between poly(ethylene terephthalate) (PET) and different silane coupling agents were probed using sum frequency generation (SFG) vibrational spectroscopy. The polymer/air interface was dominated by the ester carbonyl, methylene, and phenyl groups. Upon contacting the PET film with the amino-functional silane 3-aminopropyltrimethoxysilane (ATMS), the ester carbonyl stretch shifted to a lower energy indicating the formation of hydrogen bonds between the polymer surface and the silane molecules. This shift was not observed when silanes that contained no hydrogen bond donors, such as (3-glycidoxypropyl)-trimethoxysilane and n-butyltrimethoxysilane, were placed into contact with the PET surface. Further evidence of silane ordering at the interface was observed as vibrational peaks attributed to the C-H stretching of the silane methoxy headgroups dominated the PET/silane spectra. It was determined that the conformation of the ATMS molecules at the interface was such that the amino endgroups were oriented toward the interface while the methoxy headgroups were directed toward the silane bulk.     

Bioanalysis by Immobilization of Antibodies on Hafnium(IV) Oxide with 3-Aminopropyltriethoxysilane

Self-assembled monolayers of 3-aminopropyltriethoxysilane (APTES) are commonly used to promote adhesion between substrates and organic or metallic materials with applications ranging from advanced composites to biomolecular lab-on-a-chip devices. In this work, the silanization on hafnium oxide (HfO₂) films is reported. The layers of HfO₂ were deposited on Si (001) substrates by atomic layer deposition. The grown HfO₂ films were modified in accordance with three main steps: oxidation, silanization, and cross-linking of the APTES monolayer using glutaraldehyde as cross-linking agent. Microscopic features were characterized by atomic force microscopy. Further, both bovine serum albumin and antibovine serum albumin agents were deposited on the samples to test their potential use as the immunosensor.     

Hydrolytically stable chemically bonded silica supports with metal complexating ligands: Synthesis,characterization and use in high-performance ligand-exchange chromatography (HPLEC)

Summary A silica of 14 nm pore size was reacted according to two procedures with the following silanes: -aminopropyltriethoxysilane (1), N-aminoethyl-N-aminopropyltrimethoxysilane (2), N-aminoethyl-N-aminoethyl-N-aminopropyltrimethoxysilane (3), N-(3-triethoxysilanepropyl)-N, N-diacetic dimethylester (4), N-(3-trisodiumsilanolatepropyl)-N, N-diacetic acid disodium salt (5) and N-(3-trisodiumsilanolatepropyl)-ethylenediamine-N, N, N-triacetic acid trisodium salt (6). The reaction of silanes 1–4 with the silica was carried out under anhydrous conditions (procedure A). Silanes 1–6 were subjected to surface modification under essentially hydrous conditions applying a two-step procedure (procedure B). Procedure B is much simpler to perform and allows binding of high and definite amounts of silane onto the surface. Complexation of all bonded phases with Cu²⁺ was examined by measuring the sorption isotherms at constant pH. The pH-dependence of Cu²⁺ uptake at constant Cu²⁺ concentration was evaluated. Tests on the chemical and chromatographic stability of the packings showed that only the silicas with bonded iminodiacetate and ethylenediaminetriacetate groups remain hydrolytically stable. Retention of aliphatic and -amino acids on these two packings was found to be mainly controlled by the pH and the ionic strength of the eluent.Presented at the 14th International Symposium on Chromatography London, September, 1982     

CO2 as a supramolecular assembly agent: a route for lamellar materials with a high content of amine groups

The uptake of carbon dioxide on N-(2-aminoethyl)-3-aminopropyltrimethoxysilane 1 and N-(6-aminohexyl)-3-aminopropyltrimethoxysilane 2 afforded a supramolecular network of bis-silylated ammonium carbamate salts, the hydrolytic polycondensation of which gave rise to structured hybrid materials. Subsequent loss of CO2 was readily achieved upon heating, thus generating materials in which the structure was maintained (well-defined lamellar structure from 2) and contains free amino groups. The accessibility of amine-functionalized groups was shown by their ability to complex transition metal or lanthanide salts.     

Synthesis and characterization of amino-functionalized silica nanoparticles

Monodispersed raw silica nanoparticles (RSNPs) with the particle size of 40 nm were successfully fabricated by condensation reaction of tetraethylorthosilicate in methanol with high concentration ammonia (1.2 M). The RSNPs were treated with the coupling agent 3-aminopropyltrimethoxysilane (APTMS) for grafting amine groups on the surface to obtain the amino-functionalized silica nanoparticles (ASNPs). The chemical structure and surface morphology of RSNPs and ASNPs were characterized by Fourier-transform infrared spectra, solid-state NMR spectra and scanning electron microscopy. In addition, a method to quantify the grafted amine groups on the surface of ASNPs was developed by using the ninhydrin assay. The ninhydrin analysis showed that 60 mol % of the APTMS molecules were immobilized on the surface, that is, 4.4 amine groups per nm2 of surface area were bonded on nonporous ASNPs. The weight loss of particles obtained from thermogravimetry analysis indicated the amount of grafted amine groups and was used as a reference to compare with the value determined from ninhydrin method.     

Photopatterned surfaces for site-specific and functional immobilization of proteins

Photosensitive silanes containing nitroveratryl (Nvoc)-caged amine groups and protein repellent tetraethylene glycol units were synthesized and used for modification of silica surfaces. Functional surface layers containing different densities of caged amine groups were prepared and activated by UV-irradiation of the surface. The performance of these layers for functional and site-selective immobilization of proteins was tested. For this purpose, biotin and tris-nitrilotriacetic acid (tris-NTA) were fist coupled to the activated surface, and the interaction of streptavidin and His-tagged proteins with the functionalized surfaces was monitored by real-time label-free detection. After optimizing the coupling protocols, highly selective functionalization of the deprotected amine groups was possible. Furthermore, the degree of functionalization (and therefore the amount of immobilized protein) was controlled by diluting the surface concentration of the amine-functionalized silane with a nonreactive (OMe-terminated) tetraethylene glycol silane. Immobilized proteins were highly functional on these surfaces, as demonstrated by protein-protein interaction assays with the type I interferon receptor. Protein micropatterns were successfully generated after masked irradiation and functionalization of the caged surface following the optimized coupling protocols.     

Morphology and water barrier properties of organosilane films: the effect of curing temperature

The morphology of silane films and the response of these films to water vapor are studied by neutron reflectivity, X-ray reflectivity, ellipsometry, and contact angle. The systems studied include bis-[3-(triethoxysilyl)propyl]tetrasulfide (bis-sulfur) and bis-[trimethoxysilylpropyl]amine (bis-amino), as well as mixtures of these two silanes. The effect of curing temperature on water-barrier properties is determined by comparing data for films cured at 180 degrees C with existing data for films cured at 80 degrees C. Higher curing temperature leads to an increase of the crosslink density as well as chemical modification for the sulfur-containing films. For bis-amino silane films, on the other hand, the effect on the water-barrier ability is negligible. Bis-amino silane is fully hydrolyzed and condensed at the curing temperature of 80 degrees C, so further increasing cure temperature does not affect the bulk structure of the film. For bis-sulfur and mixed films, however, higher curing temperature accelerates the hydrolysis and condensation, leading to denser films with better water-barrier performance.     

The effect of methylene chain length on the chromatographic behaviour of aminobonded silicas in high-performance thin layer chromatography

Summary High-performance thin layer chromatography has been carried out on 3-aminopropyltriethoxysilane, N-(2-aminoethyl)--aminopropyltrimethoxysilane or trimethoxysilylpropyldiethylenetriamine-treated thin layer plates, the chromatographic properties of the amino-modified plates depends largely on the amino-methylene (alkylamino) chain length bonded to the surface of the silica gel.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Vibrational spectra of a ferrocenyl phosphine derivative chemisorbed on 3-aminopropylsilyl modified silica gel

Samples of silica gel dried at different temperatures, silica gel modified with 3-aminopropylsilyl (APS) and silica gel modified with APS and further with a ferrocenyl phosphine derivative were investigated by DRIFT, transmission FTIR and MicroRaman spectroscopy. The reaction between 3-aminopropyltrimethoxysilane (APTMS) and silica gel was mainly identified by the diminishing or vanishing intensity of the stretching band of the free OH groups in the silica gel. Further chemical reaction of the APS groups with a ferrocenyl phosphine derivative (suitable as ligand in homogeneous catalysis) was identified in the IR spectra by the appearance of the CN stretching band of the formed Schiff base, and diminishing intensity of the δ(NH₂) modes. According to the IR spectra the reaction of the ferrocenyl phosphine derivative with the APS-modified silica gel is almost quantitative. From the recorded IR and Raman spectra, conclusions concerning the substitution of APTMS methoxy groups during the chemisorption on silica gel were derived. Through deconvolution of the complex Raman band in the siloxy stretching region of the APS-modified silica gel, the newly formed siloxy bond was identified.     

Dispersion and functionalization of nonaqueous synthesized zirconia nanocrystals via attachment of silane coupling agents

Zirconia (ZrO 2) nanocrystals, synthesized from zirconium(IV) isopropoxide isopropanol complex and benzyl alcohol, were dispersed and functionalized in organic solvents using three kinds of bifunctional silane coupling agents (SCAs), 3-glycidoxypropyltrimethoxysilane (GPTMS), 3-aminopropyltriethoxysilane (APTES), and 3-isocyanatopropyltriethoxysilane (IPTES). Completely transparent ZrO 2 dispersions were achieved in tetrahydrofuran (THF) with all three SCAs, in pyridine and toluene with APTES and IPTES, and in N, N-dimethylformamide with IPTES. Dynamic laser scattering (DLS) measurements and high-resolution transmission electron microscopical (HRTEM) observation indicated that the ZrO 2 nanocrystals are dispersed on a primary particle size level. Fourier transform infrared spectroscopy, solid-state (13)C- and (29)Si NMR spectroscopy, and thermogravimetric analysis demonstrated that all three SCAs are chemically attached to the surface of the ZrO 2 nanoparticles, however, in different bonding modes. Except for GPTMS/ZrO 2/THF dispersion and IPTES/ZrO 2/pyridine dispersion, all other transparent dispersions have poor long-term stability. The increasing polarity, due to high amount of APTES attached and high hydrolysis and condensation degree of the bonded APTES, and the aggregation, due to interparticle coupling via the bonded triethoxysilyl group, are the causes of the poor long-term stability for the ZrO 2 dispersions with APTES and IPTES, respectively. Nevertheless, the APTES-functionalized ZrO 2 precipitates can be deagglomerated in water to get a stable and transparent aqueous ZrO 2 dispersion via addition of a little hydrochloric acid.