Protein adsorption and surface patterning

Surface patterning has become an important discipline of biologically oriented surface science over the past decades. Many methods have been developed that allow the formation of patterns on the micro- and nanoscale. This Opinion discusses the role of protein adsorption in patterning technologies, highlighting how it can be used as an integrated part of the patterning process, how it can be controlled by patterns with appropriate properties, and how it may lead to disruption of formed patterns if not properly accounted for. Recent examples from literature are used to emphasize some of the most interesting developments in the field, such as novel surface chemistries only allowing specific protein adsorption, directed self-sorting adsorption of proteins on patterned surfaces, and control of protein adsorption through nanopatterning.     

Protein concentration and adsorption time effects on fibrinogen adsorption at heparinized silica interfaces

Heparin was modified with adipic dihydrazide and covalently linked to surface-activated silica wafers. X-ray photoelectron spectroscopy was used at each stage of derivatization and showed that successful immobilization had taken place. Surfaces were imaged with atomic force microscopy to determine the uniformity of the heparin layer as well as its thickness. In situ ellipsometry was used to estimate layer thickness as well, and to study protein concentration and adsorption time effects on the adsorption and elution kinetics exhibited by human plasma fibrinogen. The adsorbed amount of fibrinogen increased with time and concentration on each type of surface. Under all experimental conditions, fibrinogen adsorbed at a lower rate and to a lower extent on heparinized as compared to unheparinized silica. In addition, buffer elution experiments showed that fibrinogen was less tightly bound to heparinized silica. In order to examine behavior relative to fibrinogen mobility at these interfaces, the sequential adsorption of fibrinogen was recorded. The difference in adsorption rates between the first and second adsorption cycles, evaluated at identical mass density, indicated that post-adsorptive molecular rearrangements had taken place. In general, higher solution concentration and longer adsorption time in the first adsorption step led to more rearrangement, and these history dependent effects were more pronounced on the heparinized silica. These rearrangements are suggested to involve clustering of adsorbed fibrinogen, in this way increasing the amount of unoccupied area at the interface. These rearrangements were presumably facilitated on the heparinized silica by enhanced lateral mobility of fibrinogen at this negatively charged, highly hydrophilic interface.     

Protein adsorption on a nanoparticle with a nanostructured surface

In the present study, the adsorption of a protein on a nanoparticle with a nanostructured surface, which is created using successively patterned Gaussian pillars (GPs), is simulated by considering the charge regulation within the electrical double layer of a silica nanoparticle (NP). Namely, the mathematical models for the adsorption mechanism, such as classical Langmuir model, extended Langmuir model, and two-state model, are coupled with charge regulation model. By this means, size and pH variables are able to included to the calculations. Moreover, free space, surface curvature, and conformational changes are also taken into account. For systematic investigation, the solution's pH, surface charge density, initial protein concentration, electrostatic charge of the protein, and the diameter of the spherical NP are varied. As a result, the vital properties of a nanoparticle, such as protonation/deprotonation, polarization, topography, and morphology, are considered in the current simulations. The surface charge density and surface chemistry change with NP and GP sizes. The present results reveal that the protein adsorption on an NP with a smooth surface reaches a faster complete surface coverage than an NP with a nanostructured surface. Both states of conformational changes are also affected by the presence of the GP.     

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.     

硅胶的表面硅烷化处理及其吸附性能研究

为研究改性硅胶对挥发性有机废气的吸附性能,分别采用十六烷基三甲氧基硅烷、辛基三乙氧基硅烷、苯基三甲氧基硅烷、一甲基三乙氧基硅烷对硅胶进行气相改性处理,试验研究了不同改性剂、改性时间对硅胶饱和吸附率的影响,考察了改性硅胶对甲苯、水二组分体系的吸附选择性.结果表明,硅胶对甲苯的吸附主要为物理吸附,长链的硅烷改性剂在60℃、...     

Protein adsorption on to low-temperature isotropic carbon 4. Competitive adsorption on carbon and silica studied by two-dimensional electrophoresis

Two-dimensional polyacrylamide gel electrophoresis (2D PAGE) was applied to the study of competitive protein adsorption from diluted human plasma. We obtained the depletion (adsorption) of some 25 plasma proteins in the presence of low-temperature isotropic carbon (LTIC) or silica powders. The depletion data are used as a measure of protein adsorptivity. Generally, proteins of lowest abundance have the highest tendency to associate with the two solid surfaces studied. The adsorptivity of a protein is largely determined by its solubility. Most proteins detected exhibit similar depletion behavior on both adsorbents, suggesting a multilayer adsorption process. Three proteins, hemopexin, apolipoprotein A I, and apolipoprotein A II, are depleted differently in the presence of LTIC and silica powders.     

Capabilities of polymer-modified monodisperse colloidal silica particles as biomaterial carrier

 Polymer modification of monodispersed colloidal silica (0.5 μm) with poly(maleic anhydride-co-styrene) (P(MA-ST)) and poly (maleic anhydride-co-methyl methacrylate) (P(MA-MMA)) and application of the composite particles to biomaterial carriers were investigated. The reaction of bovine serum albumin(BSA)-immobilized P(MA-MMA)/SiO₂ with the anti-BSA antibody showed higher sensitivity in immunological agglutination test than BSA–P(MA-ST)/SiO₂, though immobilization efficiency of BSA on P(MA-MMA)/SiO₂ was lower than that on P(MA-ST)/SiO₂. Alkaline phosphatase and glucose oxidase immobilized on the composite particles exhibited extremely low activities, but α-chymotrypsin immobilized on P(MA-MMA)/SiO₂ and its derivative particles showed the relative activity of 12.5% and 16.1% to the native enzyme, respectively. Grafting of a hydrophilic polymer of poly(acrylic acid) to P(MA-ST)/SiO₂ let to an increase of the immobilized α-chymotrypsin activity to give the maximum relative activity of 55.5%. Received: 23 August 1996 Accepted: 16 October 1996     

硅胶表面苯并噻吩分子印迹聚合物的分子识别与吸附性能

选用γ-氨丙基三乙氧基硅烷和α-甲基丙烯酸修饰的硅胶作为载体,以甲基丙烯酸为功能单体,二甲基丙烯酸乙二醇酯为交联剂,苯并噻吩为模板分子,合成一种具有选择性识别苯并噻吩分子的印迹聚合物。采用红外光谱、元素分析及N2吸附对其结构进行了表征,以模拟汽油通过静态吸附对其吸附性能进行了研究。结果表明,在硅胶载体表面成功地嫁接了多孔的分子印迹聚合物薄层。印迹聚合物对苯并噻吩具有良好的识别性能,对苯并噻吩的吸附动力学满足Langergren准一级反应动力学方程,吸附过程属于单分子层吸附。符合Langmuir吸附模型印迹聚合物对苯并噻吩的平衡吸附容量达57.4×10-3,而非印迹聚合物的吸附容量为33.1×10-3。印迹聚合物在经过多次再生后其吸附容量基本不变,从而为在汽油深度脱硫中有效脱除噻吩类硫化物提供了一种新技术途径。     

Effect of chemical nature of nanosized silica surface on the adsorption of D-glucose

The powders of unmodified silica, as well as silicas modified with poly(ethyleneimine) and 3-aminopropyltriethoxysilane are synthesized by the sol-gel method. The obtained powders and their suspensions in water are characterized by IR spectroscopy, atomic force microscopy, and spectroturbidimetry. The adsorption ability of D-glucose on the surface of the aforementioned powders is studied. It is shown that this monosaccharide is not adsorbed on the surface of unmodified silica, but is adsorbed on the surface of aminated silicas. The differences in the interaction of D-glucose with the studied particles are discussed from the viewpoint of the nature of surface chemical groups.     

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.     

DFT study of the adsorption of microsolvated glycine on a hydrophilic amorphous silica surface

Density functional theory (DFT) periodic ab initio molecular dynamics calculations are used to study the adsorption of gaseous and microsolvated glycine on a hydroxylated, hydrophilic silica surface. The silica model is presented and the interaction of water with surface silanols is studied. The heat of interaction of water is higher with the associated silanols (be they terminal or geminal ones) studied here than with isolated silanols presented in past works. Glycine is stabilized in a parallel mode on the hydroxylated surface. Terminal silanols do not allow the stabilization of the zwitterionic form, whereas geminal silanols do. Molecular dynamics (MD) first-principle calculations show that microsolvated zwitterion glycine directly binds through the carboxylate function to a surface silanol rather than through water molecules. The adsorption mode, whether with or without additional water molecules, is parallel to the surface. The ammonium function does not interact directly with the silanol groups but rather through water molecules. Thus, the carboxylate and ammonium functions exhibit two different reactivities towards silanols. The calculated free energies, taking into account the chemical potentials of water and glycine in the gas phase, suggest the existence of a thermodynamic domain in which the glycine is present in the gas phase as well as strongly adsorbed on specific sites of the surface.     

How silanization of silica particles affects the adsorption of PDMS chains on its surface

A series of six fumed silica types, with different surface areas in the 50–400 m²/g range, were modified by grafting with trimethylchlorosilane. The grafting reaction was controlled by elemental analyses, surface hydroxyl titration, and combustion techniques. The silica surface energy was determined as a function of silanization degree by inverse gas chromatography (IGC). Adsorption of a series of poly(dimethylsiloxane) elastomers with molecular weights ranging between 4 and 420 kg/mol on silica was followed using flow microcalorimeter (FMC). IGC results show that free adsorption energies of two series of alkanes and siloxanes as well as the dispersive component of the surface energy were found to decrease monotonously with surface silanization and so does the polymer molar heat of adsorption. FMC results indicate, however, that the conformation of the macromolecules on silica depends on the silica surface area but remains unaffected by the surface treatments. A given polymer chain was found to remain adsorbed on the surface preserving its same conformation until its molar heat of adsorption falls bellow a critical value. These findings offer a better monitoring of surface–polymer interactions as it defined a comprehensive relationship between the degree of modifications of the filler surface and polymer adsorption conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Calorimetric studies of cationic surfactant adsorption at low surface coverages on different silica samples

Calorimetric measurements of adsorption for the surfactant (benzyldimethyldodecylammonium bromide) and its polar head-group (benzyltrimethylammonium bromide) from aqueous solutions on two different silica surfaces (hydrophilic and hydrophobic one) allow a more detailed picture of the subsequent stages of the adsorption process to be drawn. It is possible to determine more precisely a boundary between the adsorption of individual molecules and the formation of surface aggregates. The local disruption of the structure of the interfacial water molecules by surfactant cations gives an endothermic contribution to the total enthalpy of displacement. This contribution depends on the length of alkyl chain as well as on the type and the origin of solid surface.     

Heat of adsorption of cysteine enzymes on mesoporous silica with high specific surface area

The adsorption of a cysteine enzyme, on mesoporous silica with high specific surface area synthesized by the sol-gel method, was studied in a heat flow calorimeter, to determine the energy involved in the adsorption process of the protein. The adsorption was carried out at a constant temperature of 30°C to avoid the denaturation of the enzyme. The observed results indicate that the obtained biomaterials (silica-enzyme) have possibilities for their application in several biotechnology processes. The heat of papain adsorption and the solid-enzyme (SiO₂-Papain) interactions at different pH are presented.     

Polyethylene glycol adsorption on silica: from bulk phase behavior to surface phase diagram

A characterization of the bulk-phase diagram from literature data and new NMR and DSC measurements provided us with valuable elements that are helpful for gaining, from aqueous solution, better insight into the surface behavior of polyethylene glycol on Aerosil 200. Adsorption isotherms built further to measurements by a depletion method showed a strong and temperature-dependent variation of the isotherm shape in agreement with the variations of interactions already evidenced in the bulk. In temperature-concentration areas, where water is behaving as a helix-promoting solvent, the finding of positive PEG adsorptions and stairlike isotherms agrees with observations reported in the literature. We identified some of the vertical parts as corresponding to the formation of monolayers of helix-shaped PEG molecules. In poor-solvent zones, adsorptions were null or negative, and the isotherms exhibited oscillations suggesting very different surface behavior. Our data analysis evidenced the presence of a much greater amount of water than in the previous surface states; however, the similar analysis of PEG behavior remains relevant. Indeed, the occurrence of first-order transitions in the surface layer implies some water reorganization, permitting the PEG molecules to move closer to the surface and become helix-shaped to rearrange in a monolayer. The surface phase diagram confirmed this analysis in a very satisfying way.     

Tuning particle morphology of mesoporous silica nanoparticles for adsorption of dyes from aqueous solution

Spherical and rod mesoporous silica nanoparticles with hexagonal mesostructure were prepared using the modified Stöber method. The morphology, size and internal pore structure can be controlled by simple changing of surfactant concentration and water:ethanol molar ratio. Monodispersed spheroid MCM-41 was obtained at 40 °C under basic conditions using cetyltrimethylammonium bromide (C₁₆TAB) as template. Obtained materials were characterized by X-ray diffraction (XRD), nitrogen physisorption (BET), transmission electron microscopy (TEM) and scanning electronic microscopy (SEM). The results reveal that the pore volume and surface area increase when the amount of C₁₆TAB increases whereas the pore diameter and particle size decrease. However, the use of ethanol as cosolvent led to an increase in the particles’ size. Moreover, the addition of a 3-aminopropyltriethoxysilane greatly influenced the final particle shape. The material was effectively used for the removal of two fluorescent dyes (Hoechst 33342 and rhodamine 6g) from aqueous solution. Adsorption isotherm models, Langmuir, Freundlich and Temkin were used to simulate the equilibrium data. The Langmuir model was found to fit the experimental data better than others models.     

A novel surface designed technique to disperse silica nano particle into polymer

In order to synthesize highly functionalized organic/inorganic nanocomposites, it is important to improve particles dispersability by surface modification. In this study, a novel technique to design surface of particles on a molecular level was proposed. This new technique has the potential of decreasing an apparent van der Waals interaction between particles and reducing difference of surface interfacial energy between particles and matrix. The results of FT-IR indicated the successful modification of particle surface by designed reaction. TEM results verified the improvement of particle dispersability in the matrix.