Biomedical subjects
Publications and source records attributed to Alexander Y Fadeev.
The covalently attached monolayers of alkylsilanes (R(CH(3))(2)SiX) on Si undergo complete displacement by the solutions of different organosilanes (R'(CH(3))(2)SiX). By varying the reaction time, the degree of displacement can be controlled offering a convenient method for the preparation of surfaces with mixed functionalities (R and R').
We report the use of proteins, lipids, and enzymes for the preparation of surfaces with reversible wettability changes, in particular, surfaces capable of switching from hydrophobic to hydrophilic and back. We demonstrate that these reactions can be used for engineering capillary systems with gating properties.
This work describes a novel class of layered organo-mineral materials manufactured via a single-step solution-phase reaction of n-alkylphosphonic acids (CnH(2n+1)P(O)(OH)2) with calcium hydroxyapatite mineral (CaHAP). TEM, SAXS, WAXS, FTIR, and Vapor Phase Adsorption data suggest that these alkyl-CaHAP materials present a surface-modified CaHAP matrix coated with ordered layers of calcium alkylphosphonates that are strongly adhered to the surface. Interlayer spacing increases from 1.47 (C3-CaHAP) to 4.77 nm (C18-CaHAP). According to FTIR, ordering of alkyl chains improves with the alkyl chain length. The organic loads in these alkyl-CaHAP can be controlled over a wide range (up to approximately 60%) by varying alkyl chain and the concentration of alkylphosphonic acids in the solution.
We report an investigation of the water-hydrophobic interface in well-defined nanochannels (R approximately 2-4 nm). Wetting in these systems cannot be described by classical (macroscopic) capillary theory: (1) water occupies only a fraction ( approximately 60%) of the pore volume, and (2) the capillary pressures are approximately 60-90% greater than predicted by the Laplace equation. The results suggest the presence of approximately 0.6 nm layer of low-density fluid (vapor) separating water from the hydrophobic solid.
The reaction enthalpies for the solution-phase self-assembly of n-alkylphosphonic acids on the surfaces of TiO2 and ZrO2 have been determined using isothermal titration calorimetry at 298 K. The reaction enthalpies were negative (exothermic) for methyl- and n-octylphosphonic acids and positive (endothermic) for n-octadecylphosphonic acid with both metal oxides. The enthalpy/energy analysis showed that the net enthalpy of the formation of self-assembled monolayers (SAMs) at solid-liquid interface can be presented as follows: DeltaHr=-D-(DeltaHsol+DeltaHdil)-(ES-ESAM), where D is the binding energy of the SAM molecules with the solid; DeltaHsol and DeltaHdil are the enthalpies of dissolution and dilution; ES and ESAM are the surface energies of bare solid and SAM, respectively. This equation predicted an increase (and the sign change) of the reaction enthalpy as the alkyl group in n-alkylphosphonic acid increased, which explained the experimental data. Using this equation, the binding energy (D) in the SAMs of n-octyl- and n-octadecylphosphonic acids were estimated: 55+/-5 kJ/mol (for ZrO2) and 58+/-7 kJ/mol (for TiO2).
The thermal degradation of monolayers of alkylsilicon hydrides (RSiH(3)), alkylphosphonic acids (RP(O)(OH)(2)), and alkyldimethylchlorosilanes (R(CH(3))(2)SiCl) supported on silica, alumina, titania, zirconia, and calcium hydroxyapatite particles was investigated using thermal gravimetric analysis (TGA). The common feature in the TGA was a dramatic weight loss between approximately 200 and approximately 600 degrees C (N(2) atmosphere), which was not present for bare minerals, and, thus, was assigned to the degradation of the surface grafted organic species. The onset of weight loss and the temperature of maximal weight loss rate (T(MAX)) showed no dependence on the mineral and were determined by the nature of the chemical group directly attached to the surface. The T(MAX) values were approximately 400-450 degrees C (monolayers of RSiH(3) and RP(O)(OH)(2)) and approximately 250 degrees C (monolayers of RSi(CH(3))(2)Cl). The activation energies (E(A)) of the degradation processes were determined using TGA at multiple heating rates. Surprisingly, the substrate material did not show a significant effect on E(A). For example, all the monolayers of octadecyl groups (R=C(18)H(37)) supported on silica, alumina, titania, and zirconia showed closed E(A) values approximately 265+/-15 kJ/mol. The weight loss, IR, MS, and chemical analysis data suggested that monolayer degradation occurred through pyrolysis of the hydrocarbon moieties (R groups) via cleavage of the CC and SiC (monolayers of silanes) or CC and PC bonds (monolayers of phosphonic acids). The inorganic portion of the molecule remained attached to the surface of the mineral (presumably as silicates or phosphates).
The solution-phase reactions of octadecylsilane (C(18)H(37)SiH(3)) with 10 high surface area metal oxides (groups II-VIII) were investigated. C(18)H(37)SiH(3) reacted with most metal oxides at room temperature and produced supported monolayers (self-assembled monolayers, SAMs) with a high grafting density of C(18), approximately 4.5-5 groups/nm(2). According to the FTIR and (29)Si NMR spectra, molecules in the SAMs demonstrated "horizontal" cross-linking (Si-O-Si and Si-OH.HO-Si bonds) and little or no "vertical" bonds with the metal oxide forming an amorphous, yet ordered film. Also, approximately 3 mol of H(2) was formed per each mole of grafted C(18), indicating complete hydrolysis of C(18)H(37)SiH(3) during the reaction. On the basis of the activity of different metal oxides, we concluded that the hydrolysis of C(18)H(37)SiH(3), the key step in the reaction mechanism, is catalyzed by water adsorbed on acidic and basic centers (Lewis and Brönsted) of the surface of metal oxide. Metal oxides and solids with weak acidic and basic properties, like silica, carbon, and organic polymers, do not react with C(18)H(37)SiH(3). Increasing the temperature of the reaction or doping neutral surfaces with acids or bases greatly increases their activity in the reaction with RSiH(3).
The hydrolytic stability of C18 monolayers supported on TiO2 and ZrO2 was studied. Three types of monolayers were prepared from the following octadecyl modifiers: (1) octadecyldimethylchlorosilane (C18H37Si(CH3)2Cl); (2) octadecylsilane (C18H37SiH3); and (3) octadecylphosphonic acid (C18H37P(O)(OH)2). The hydrolysis of the surfaces prepared was studied under static conditions at 25 and 65 degrees C at pH 1-10. On the basis of the loss of grafted material, the stability of the monolayers fall in the following range: C18H37P(O)(OH)2 > or = C18H37SiH3 >> C18H37Si(CH3)2Cl. At 25 degrees C, monolayers from C18H37P(O)(OH)2 showed only approximately 2-5% loss in grafting density after one week at pH 1-10. The high stability of these monolayers was explained because of the strong interactions of the phosphonic acids with the substrates. Monolayers from C18H37Si(CH3)2Cl showed poor hydrolytic stability at any pH, which was explained because of the low stability of Ti-O-Si and Zr-O-Si bonds. Unlike monofunctional silanes, trifunctional silane (C18H37SiH3) yielded surfaces that showed good hydrolytic stability. This suggests that the stability of the monolayers from trifunctional silanes is primarily due to "horizontal" bonding (Si-O-Si or Si-OH...HO-Si) rather than due to bondingwith the matrix (M-O-Si). At 65 degrees C, all C18 surfaces become more susceptible to hydrolysis; however, the trend observed for 25 degrees C remained unchanged. Low-temperature nitrogen adsorption was used to study the adsorption properties of the monolayers as a function of their grafting density. The energy of adsorption interactions showed a significant increase as the grafting density of the monolayers decreased. The order of the alkyl groups in the monolayers, as assessed from CH2 stretching, decreased as the grafting density of the monolayers decreased.