Interaction of supramolecular centers of silica surface with aromatic amino acids

Surface grafting of β-cyclodextrin onto aminopropylsilica has been carried out under mild conditions using 1,1'-carbonyldiimidazole as an activator. The obtained β-cyclodextrin-silica has been characterized by means of chemical and IR spectral analysis. Adsorption of para-aminobenzoic and para-aminosalicylic acids onto the surface of hydroxylated silica, aminopropylsilica, and silica with chemically attached β-cyclodextrin moieties has been studied in relation to duration of contact, equilibrium concentration, and solution pH. Chemical immobilization of β-cyclodextrin onto silica surface improves adsorption parameters for aromatic amino acids. The well-known mathematical models for the kinetic and equilibrium adsorption processes have been used, and the main adsorption parameters have been calculated. Kinetic curves of aromatic amino acids adsorption correspond to the model of pseudo-second order reaction. The major contribution to the equilibrium adsorption of para-aminobenzoic and para-aminosalicylic acids onto β-cyclodextrin-containing silica is due to the formation of surface inclusion complexes between grafted oligosaccharide molecules and aromatic amino acids.     

The adsorption of amino acids on the surface of highly dispersed silica

The adsorption of arginine, histidine, lysine, and ornithine on the surface of highly dispersed silica from aqueous solutions was studied as a function of pH. The equilibrium constants of the formation of surface complexes were calculated using the Stern model for the electrical double layer. It was shown that the possibility of adsorption of amino acids on the silica surface is determined by the presence of additional basic groups in their molecules.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 733–738.Original Russian Text Copyright © 2004 by Vlasova, Golovkova.     

Role of the surface of silica gel in the radiation chemical conversions of adsorbed hydrocarbons

The action of gamma radiation on the systems benzene-silica gel and hexane-silica gel has been studied by EPR for different ratios of the components. It is shown that H-atoms detached from the surface OH groups during irradiation react with the adsorbed hydrocarbons to give C₆H ₇ ^. (C₆H₆D in the case of deuterated silica gel) and C₆H ₁₃ ^. radicals. It is ascertained that the SiO^. radicals also formed with the H-atoms during irradiation react with the adsorbate. Confirmation that H-atoms and SiO^. radicals participate in the radiation chemical conversions of adsorbed hydrocarbons is obtained by experiments with silica gels previously dehydrated at various temperatures. A possible mechanism of energy migration within the silica beads is discussed.     

Extrathermodynamic study of surface diffusion in reversed-phase liquid chromatography with silica gels bonded with alkyl ligands of different chain lengths

Surface diffusion on adsorbents made of silica gels bonded to C1, C4, C8, and C18 alkyl ligands was studied in reversed-phase liquid chromatography (RPLC) from the viewpoints of two extrathermodynamic relationships: enthalpy-entropy compensation (EEC) and linear free-energy relationship (LFER). First, the values of the surface diffusion coefficient (D(s)), normalized by the density of the alkyl ligands, were analyzed with the modified Arrhenius equation, following the four approaches proposed in earlier research. This showed that an actual EEC resulting from substantial physicochemical effects occurs for surface diffusion and suggested a mechanistic similarity of molecular migration by surface diffusion, irrespective of the alkyl chain length. Second, a new model based on EEC was derived to explain the LFER between the logarithms of D(s) measured under different RPLC conditions. This showed that the changes of free energy, enthalpy, and entropy of surface diffusion are linearly correlated with the carbon number in the alkyl ligands of the bonded phases and that the contribution of the C18 ligand to the changes of the thermodynamic parameters corresponds to that of the C10 ligand. The new LFER model correlates the slope and intercept of the LFER to the compensation temperatures derived from the EEC analyses and to several parameters characterizing the molecular contributions to the changes in enthalpy and entropy. Finally, the new model was used to estimate D(s) under various RPLC conditions. The values of D(s) that were estimated from only two original experimental D(s) data were in agreement with corresponding experimental D(s) values, with relative errors of approximately 20%, irrespective of some RPLC conditions.     

Adsorption of amino acids on a cerium dioxide surface

Adsorption of glutamic, aspartic, and pteroylglutamic (folic) acids from aqueous solutions on the surface of nanocrystalline cerium dioxide has been studied as depending on the pH and ionic strength of the solutions. Stability constants have been calculated for surface complexes that result from the interaction of anionic forms of the amino acids with protonated surface groups of cerium dioxide. The structure of the surface complexes has been confirmed by IR spectroscopy.     

Adsorption of quaternary ammonium chlorides with various hydrocarbon chain lengths to glass

Contact angles, measured with various liquids, have been employed to calculate the surface free energies of glass after adsorption of quaternary ammonium chlorides with a variable hydrocarbon chain length 8n16. The thickness of the adsorbed layers has been determined ellipsometrically. A clear relation is observed between the measured parameters and the hydrocarbon chain lengthn, if only the extremesn=8 andn=16 are considered. Surface free energies decrease from 138 erg.cm^–2 for clean glass to 101 and 64 erg.cm^–2 forn=8 andn=16, respectively, at the highest concentration tested (7.5 mM). The adsorbed layer thickness of C₈ amounts to approximately 50 % of the thickness observed for C₁₆. No clear relation between the measured parameters is observed for the intermediate hydrocarbon chain lengths, which presumably reflects the many configurations possible in these adsorbed layers. It is envisaged that adsorption of C₈ as well as C₁₆ is restricted to a monolayer, which is completed at approximately 2 mM. In the case of C₈ electrostatic repulsion between the polar headgroups will inhibit further adsorption, whereas in the case of C₁₆ the van der Waals attraction from the adsorbed layer and the glass will probably not be sufficient to stimulate further adsorption.     

Estimate of the activation barriers of chemical reactions on a silica surface

Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 6, pp. 756–757, November–December, 1989.     

Prolinoamino acids as a tool to stabilize β-turns with the side chain of natural amino acids

Molecular mechanics calculations, X-ray, FT-IR, and NMR analysis performed on Piv-d-Pro^c_l-l-Pro-NHMe (d-Pro^c_l=a proline/leucine chimera) show that it possesses a water stable type II^′ β-turn structure. The isopropyl side chain of d-Pro^c_l compares with the leucine side chain of a typical type I β-turn found in a protein (taken from the PDB). Thus cis-3-substituted prolines with the appropriate side chain can be used to mimic type I, II or II^′ β-turns and incorporate the side chain functionalities on both the i+1 and i+2 positions of β-turns.     

Designing of the centers for adsorption of bile acids on a silica surface

Silicas chemically modified with attached aminopropyl, imidazolyl, and trimethylsilyl groups, with adsorptive and coordinative grafted hemin were synthesized. Adsorption of some bile acids on the surface of hydroxylated silica, synthesized siliceous adsorbents and cholestyramine has been studied. It was found that the main contribution to the total adsorption is caused by electrostatic attraction between anions of bile acids and positively charged sites of the surface of modified silica and also by dispersion interactions between steroid skeleton of bile acids and functional groups of modified silicon dioxides. It was established that the kinetic parameters of adsorption and adsorptive capacity for all investigated siliceous adsorbents exceed similar characteristics for cholestyramine. The best of synthesized adsorbents is hemin-containing adsorbent IX, and the sequence of increase in its adsorptive capacity in relation to bile acids corresponds to the following series: I < III < II, IV < VI < V < VIII < VII < IX.     

High-performance liquid chromatographic stationary phases based on polysiloxanes with different chain lengths thermally immobilized on silica supports

Reversed phases for high-performance liquid chromatography (RP-HPLC) were obtained by thermal immobilization of polysiloxanes having different length chains (C1, C8 and C14) onto HPLC silica particles. The importance both of percent loading of the stationary phase promoted by each immobilization procedure and of the length of the lateral chain of the polymer on the chromatographic performances of the phases obtained is compared and discussed.     

Thermal conversions of polymers with macroheterocycles in the chain

Thermal conversion of polyhexazocyclanes and compound modeling the fragments of polymers were explored within 300–600°C under vacuum (10^?5 torr) and in water vapor. At temperatures below 450°C, the hydrolytic degradation plays a key role in the thermal degradation of polyhexazocyclanes. At a higher temperature, the homolytic processes prevail, water, strongly retained by the macroheterocycle, is most important in the hydrolysis process. It was shown that the increase in the thermohydrolytic stability of polymers with the system of condensed cycles in the macroheterocycles and that of polyhexazocyclanes modified by polymer analogous conversion at the secondary amino groups of the isoindole cycle was caused by the absence of bound water.     

Using amino acids for the chromatofocusing of metal ions on silica with bonded tetraethylenepentamine groups

Amino acid-based eluents are used for the chromatofocusing of metal ions on Tetren-SiO₂ chelating sorbent (silica with bonded tetraethylenepentamine groups) for the first time. The smoothest quasilinear pH gradients form for eluents based on glutamic and aspartic acids. The separation of Mn²⁺, Cr³⁺, Co²⁺, Ni²⁺, and Cu²⁺ is achieved.     

Grafting of chains organo-silane on silica surface: a quantum chemical investigation

Theoretical calculations have been carried out on the grafting of two chains organo-silane compounds on SiO₂ hydroxylated solid surfaces. Considering two different silylated coupling agents, two grafting stable complexes are obtained. These complexes are stabilized by two interactions: (i) the chain is grafted to the cluster with a covalent bond SiOSi; (ii) the chain interacts with the cluster via an hydrogen bond HOO in the other side of the chain. The electronic, geometrical and vibrational properties of these systems are analysed. These results give new insight about the grafting of long chains organo-silane on silica surfaces.     

Periodic arrangement of silica nanospheres assisted by amino acids

Uniform-sized silica nanospheres with a well-ordered arrangement were successfully synthesized by a novel and simple method; hydrolysis and condensation reactions of tetraethyl orthosilicate were conducted in the presence of basic amino acids.     

Pretilt angle for BTDA,PMDA and CPDA series polyimides with various side chain lengths

Polyamic acid precursors were prepared by mixing dianhydride of 3,3',4,4'-benzophenone-tetracarboxylic dianhydride (BTDA), 1,2,3,4-benzene-tetracarboxylic dianhydride (pyrromellitic dianhydride PMDA), cis-1,2,3,4-cyclopentane-tetracarboxylic dianhydride (CPDA), the diamine (alkyl 3,5-diaminobenzoate) with side chain, and 4,4'-oxydianiline (ODA) without side chain. Copolyimide films with various side chain lengths were prepared by thermal imidization of polyamic acid precursors. The roughness of rubbed polyimide surface increased with increase in the side chain length. The pretilt angle for the BTDA and PMDA series polyimide (PI) increased exponentially with increase in side chain length. Various pretilt angles were obtained on the synthesized polyimides. In the case of CPDA series PI, the pretilt angle was nearly constant at 0 until the alkyl side chain length reached 12 (C12) and then increased markedly at C18. Models of pretilt angle generation were tested.