Adsorption and reaction of thiophene and H2S on Mo2C/Al2O3 catalyst studied by in situ FT-IR spectroscopy

The reactions of both thiophene and H2S onMo(2)C/Al2O3 catalyst have been studied by in situ FT-IR spectroscopy. CO adsorption was used to probe the surface sites of Mo2C/Al2O3 catalyst under the interaction and reaction of thiophene and H2S. When the fresh Mo2C/Al2O3 catalyst is treated with a thiophene/H-2 mixture above 473 K, hydrogenated species exhibiting IR bands in the regions 2800-3000 cm(-1) are produced on the surface, indicating that thiophene reacts with the fresh carbide catalyst at relatively low temperatures. IR spectra of adsorbed CO on fresh Mo2C/Al2O3 pretreated by thiophene/H-2 at different temperatures clearly reveal the gradual sulfidation of the carbide catalyst at temperatures higher than 473 K, while H2S/H-2 can sulfide the Mo2C/Al2O3 catalyst surface readily at room temperature (RT). The sulfidation of the carbide surface by the reaction with thiophene or H2S maybe the major cause of the deactivation of carbide catalysts in hydrotreating reactions. The surface of the sulfided carbide catalyst can be only partially regenerated by a recarburization using CH4/H-2 at 1033 K. When the catalyst is first oxidized and then recarburized, the carbide surface can be completely reproduced.

Simultaneous hydrodesulfurization of thiophene and hydrogenation of cyclohexene over dimolybdenum nitride catalysts

A series of unsupported dimolybdenum nitride (gamma-Mo(2)N) catalysts differing in surface area were prepared by temperature programmed reduction of MoO(3) with a mixture of NH(3):N(2) (90:10). Characterization of catalysts by BET, XRD, TPR and XPS techniques was carried out. The samples were used as catalysts in hydrotreating reactions (simultaneous hydrodesulfurization of thiophene and hydrogenation of cyclohexene). Low surface area gamma-Mo(2)N materials show much higher specific conversions than those with higher surface area. These results indicate that HDS and HYD reactions over gamma-Mo(2)N seem to be structure-sensitive. The relative exposure extent of crystalline planes (111) and (200) over the different catalysts can be associated with their hydrogen adsorption capacities and with their catalytic performances. The catalytic activities are significantly affected by the catalyst pretreatment conditions. (C) 1999 Elsevier Science B.V. All rights reserved.

Study of the Adsorption of Fibrinogen on Gold-Coated Silicon Wafer by an Impedance Method

In 0.1 mol/l KH2PO4–Na2HPO4 (pH 7.80) buffer solution, the potential of zero charge (PZC) and the open circuit potential of gold-coated silicon were determined to be about −0.6 and +0.10 V (vs SCE), respectively. The open circuit potential was higher than the PZC, which indicated that the surface of the gold-coated electrode had a positive charge. The ellipsometry experiment showed that the adsorption of fibrinogen onto the gold-coated silicon wafer surface arrived at a saturated state when the adsorption time exceeded 50 min. The percentage of surface without adsorbed protein, θ, was about 63%. This means that the proportion of surface actually occupied by fibrinogen was only about 37% after the adsorption arrived at saturation. The solution/protein capacitance value was determined in an impulse state around −0.59 V (vs SCE) and was stable (4.2×10−5 F) at other potentials.

Influence of Electrostatic Interaction on Fibrinogen Adsorption on Gold Studied by Imaging Ellipsometry Combined with Electrochemical Methods

Imaging ellipsometry was combined with electrochemical methods for studying electrostatic interactions of protein and solid surfaces. The potential of zero charge for gold-coated silicon wafer/solution interfaces wad determined by AC impedance method. The potential of the gold-coated silicon wafer was controlled at the potential of zero charge, and the adsorption of fibrinogen on the potential-controlled and non-controlled surfaces was measured in real time at the same time by imaging ellipsometry The effect of electrostatic interaction was studied by comparing the difference between the potential of controlled adsorption and the Potential of noncontrolled adsorption. It was shown that the rate of fibrinogen adsorption on the potentiostatic surface was faster than that on the nonpotentiostatic surface. The electrostatic influence on fibrinogen adsorption on the gold-coated silicon wafer was weak, so the hydrophobic interaction should be the major affinity.

Competitive protein adsorption studied with atomic force microscopy and imaging ellipsometry

The adsorption and competitive adsorption of collagen and bovine serum albumin (BSA) were directly visualized and quantified using atomic force microscopy (AFM) and imaging ellipsometry. Chemically modified silicon surfaces were used as hydrophilic and hydrophobic substrates. The results showed that collagen and BSA in single component solution adsorbed onto a hydrophobic surface two times more than that onto a hydrophilic surface. The competitive adsorption between collagen and BSA showed that serum albumin preferentially adsorbed onto a hydrophobic surface, while collagen on a hydrophilic surface. In the binary solution of BSA (1 mg/ml BSA) and collagen (0.1 mg/ml), nearly 100% of the protein adsorbed onto the hydrophobic surface was BSA, but on the hydrophilic surface only about 6% was BSA. Surface affinity was the main factor controlling the competitive adsorption.

Immunosensor Interface Based on Physical and Chemical Immunogylobulin G Adsorption onto Mixed Self-Assembled Monolayers

An immunosensor interface based on mixed hydrophobic self-assembled monolayers (SAMs) of methyl and carboxylic acid terminated thiols with covalently attached human Immunoglobulin G (hIgG), is investigated. The densely packed and organised SAMs were characterised by contact angle measurements and cyclic voltammetry. The effect of the non-ionic surfactant, Tween 20, in preventing nonspecific adsorption is addressed by ellipsometry during physical and covalent hIgG immobilization on pure and mixed SAMs, respectively. It is clearly demonstrated that nonspecific adsorption due to hydrophobic interactions of hIgG on methyl ended groups is totally inhibited, whereas electrostatic/hydrogen bonding interactions with the exposed carboxylic groups prevail in the presence of surfactant. Results of ellipsometry and Atomic Force Microscopy, reveal that the surface concentration of covalently immobilized hIgG is determined by the ratio of COOH/CH3-terminated thiols in SAM forming solution. Moreover, the ellipsometric data demonstrates that the ratio of bound anti-hIgG/hIgG depends on the density of hIgG on the surface and that the highest ratio is close to three. We also report the selectivity and high sensitivity achieved by chronoamperometry in the detection of adsorbed hIgG and the reaction with its antibody.

Surface Stress Induced By Adatoms Adsorption On Solid Surfaces

Based on the statistical thermodynamics theory, a theoretical model of adsorbate induced surface stress of adatoms adsorption on solid surface is presented. For the low coverage, the interaction between the adsorbed molecules is entirely negligible and the adsorption induced surface stress is found to be the function of the coverage and the adsorption energy change with strain. For the high coverage, the adsorbate-adsorbate interaction contributes to the adsorption-induced surface stress effectively. In the case of carbon adsorption on the Ni(100) surface, the value of 0.5 is obtained as a characteristic coverage to decide whether to take the interaction between the adsorabtes into consideration and the results also show that the adsorption induces a compressive surface stress.

Competitive adsorption between bovine serum albumin and collagen observed by atomic force microscope

Atomic force microscopy (AFM) was used to study the competitive adsorption between bovine serum albumin (BSA) and type I collagen on hydrophilic and hydrophobic silicon wafers. BSA showed a grain shape and the type I collagen displayed fibril-like molecules with relatively homogeneous height and width, characterized with clear twisting (helical formation). These AFM images illustrated that quite a lot of type I collagen appeared in the adsorption layer on hydrophilic surface in a competitive adsorption state, but the adsorption of BSA was more preponderant than that of type I collagen on hydrophobic silicon wafer surface. The experiments showed that the influence of BSA on type I collagen adsorption on hydrophilic surface was less than that on hydrophobic surface.

Adsorption of human serum albumin onto gold: a combined electrochemical and ellipsometric study

Human serum albumin adsorption onto gold surfaces was investigated by electrochemical and ellipsometric methods. Albumin adsorption onto gold was confirmed by the change of the open circuit potential of gold and by the ellipsometric parameter variation during albumin immobilization. In both experiments the parameters reached stable values within 10-15 min. The albumin adsorption layer thickness measured with the ellipsometer was about 1.5 nm. The adsorption of albumin Under applied potential was also investigated and it was found that both positive and negative applied potential promote albumin adsorption. Changes in the optical parameters of bare gold and albumin adsorbed onto gold surface under applied potential were investigated with in Situ ellipsometry. The similarity and reversibility of the optical changes showed that adsorbed albumin was stable on the gold surface Under the applied potential range (-200-600 mV). The cyclic voltammograms of K3Fe(CN)(6) on the modified gold surface showed that albumin Could partly block the oxidation and reduction reaction. (C) 2004 Elsevier Inc. All rights reserved.

Competitive adsorption of collagen and bovine serum albumin - effect of the surface wettability

The competitive adsorption of collagen and bovine serum albumin (BSA) on surfaces with varied wettability was investigated with imaging ellipsometry, and ellipsometry. Silane modified silicon surfaces were used as substrates. The results showed that surface wettability had an important effect on protein competitive adsorption. With the decrease of surface wettability, the adsorption of collagen from the mixture solution of collagen and BSA decreased, while the adsorption of BSA increased. (C) 2003 Elsevier B.V. All rights reserved.

Adsorption of His-tagged peptide to Ni, Cu and Au (100) surfaces: Molecular dynamics simulation

Molecular dynamics (MD) simulations are performed to study the interaction of His-tagged peptide with three different metal surfaces in explicit water. The equilibrium properties are analyzed by using pair correlation functions (PCF) to give an insight into the behavior of the peptide adsorption to metal surfaces in water solvent. The intermolecular interactions between peptide residues and the metal surfaces are evaluated. By pulling the peptide away from the peptide in the presence of solvent water, peeling forces are obtained and reveal the binding strength of peptide adsorption on nickel, copper and gold. From the analysis of the dynamics properties of the peptide interaction with the metal surfaces, it is shown that the affinity of peptide to Ni surface is the strongest, while on Cu and An the affinity is a little weaker. In MD simulations including metals, the His-tagged region interacts with the substrate to an extent greater than the other regions. The work presented here reveals various interactions between His-tagged peptide and Ni/Cu/Au surfaces. The interesting affinities and dynamical properties of the peptide are also derived. The results give predictions for the structure of His-tagged peptide adsorbing on three different metal surfaces and show the different affinities between them, which assist the understanding of how peptides behave on metal surfaces and of how designers select amino sequences in molecule devices design. (c) 2007 Elsevier Ltd. All rights reserved.