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1.
The thickness of nanolayers formed by adsorption from dilute and semi-dilute solutions on a solid SiO2 surface has been estimated from adsorption isotherms and atomic force microscopy (AFM) measurements for polystyrene, poly(butyl methacrylate), and their mixtures. The thickness of the adsorption layers depends strongly on the adsorption conditions and is controlled by several features of the adsorbing entities. In a low-concentration regime of adsorption, the length of polymer chains and the nature of their interaction with the substrate are the most important factors controlling the adsorption process. Above the critical concentration C*, macromolecular clusters (aggregates of several overlapping chains) are formed in a solution as a result of polymer chains self-assembly. Therefore, the final adsorption layer thickness is determined mainly by the size of the clusters in this concentrated regime of adsorption. We also demonstrate that in the case of polymer mixtures, the adsorption leads to formation of mosaic structures with alternation of the polymeric components in plane of the substrate and a characteristic domain size of approximately 200 nm for each of the components. AFM study reveals that the adsorbed layers are fractal structures whose fractal dimensions depend on the type of the polymer and the adsorption process. We demonstrate therefore that the structure of nanolayers of polymers and their mixtures on the solid surface can be regulated by variation of the adsorption conditions.  相似文献   

2.
The combination of in situ ellipsometry with atomic force microscopy in the liquid for the study of adsorption of creatine phosphokinase (CPK) onto silicon wafers was shown for the first time. The thickness, adsorbed amount, and topographic information of the adsorbed CPK layers were obtained under different pH conditions. The thickness values of adsorbed CPK layer determined by both techniques were in excellent agreement. At pH 4, CPK monomers present in solution adsorb, forming a very thin (approximately 0.8 nm) layer, indicating CPK unfolding. Upon increasing the pH to 6.8, the adsorbed layer is composed of a mixture of CPK dimers (native structure) and intermediates, increasing the film thickness (approximately 2.4 nm). At pH 9, CPK dimers form monolayers with the highest thickness (approximately 4.0 nm). The nature of interactions between CPK and Si wafers associated with the hydration force seems to control the degree of CPK unfolding upon adsorbing. The enzymatic activity of free CPK and of adsorbed CPK at pH 4, pH 6.8, and pH 9 was measured as a function of pH. In comparison to free CPK in solution, adsorbed CPK presented a shift of the optimal pH from 6.8 toward alkaline pH.  相似文献   

3.
To control protein adsorption on surfaces, low-fouling polymer coatings such as poly(ethylene oxide) (PEG or PEO) and polysaccharides are used. Their ability to resist protein adsorption is related to the layer structure, hence the immobilization mode. A polymer array technology was developed to study the structural diversity of carboxymethyl dextran (CMD) layers, whose immobilization conditions were varied. CMD arrays were analyzed by X-ray photoelectron spectroscopy (XPS) and by atomic force microscopy (AFM) colloidal probe force measurements. Serum protein adsorption was studied directly on the CMD arrays using surface plasmon resonance (SPR) microscopy. Physicochemical characterization revealed that pinning density regulates surface coverage and the amount of adsorbed molecules, and that salt concentration influences the surface structure of the charged polymer, forming extended or short layers. Protein adsorption experiments from serum showed that repulsive CMD layers are dense, with extended flexible chains. The present study underlines the usefulness of polymer arrays to study structural diversity of thin graft layers and to relate their physicochemical properties to their resistance to nonspecific protein adsorption.  相似文献   

4.
Thicknesses of nanolayers formed upon the adsorption from dilute and semidilute solutions of polystyrene, poly(butyl methacrylate), and their mixtures on the surface of solid SiO2 are estimated on the basis of adsorption isotherms and atomic force microscopy measurements. It is established that the thickness of an adsorption layer is determined by the sizes of individual macromolecular coils and clusters arising in a solution. In the case of polymer blends, adsorption leads to the formation of mosaic structures with the alternation of polymeric components in the substrate plane; the characteristic size of a domain is ≈200 nm for each component. It is shown that adsorption layers formed on the surface of a silicon single crystal (covered with intact oxide) are fractal objects whose dimension depends on the nature of polymer and conditions of its adsorption.  相似文献   

5.
The adsorption of dodecyltrimethylammonium bromide (DTAB) onto natural muscovite mica and a synthetic expandable mica (EM) in aqueous solution has been investigated using both microscopic and macroscopic surface characterization techniques. The electrokinetic properties of the surfaces were monitored as a function of the concentration of DTAB using atomic force microscopy and microelectrophoresis. The adsorption isotherm of DTAB on EM was measured up to a solution concentration just below the critical micelle concentration of the surfactant. The thickness of the adsorbed layer on EM was determined using X-ray diffraction. Results indicate that the adsorbed layer consists of molecules lying quite flat on the mica surface at low concentrations and adsorbed in interleaved aggregate structures at concentrations approaching the critical micelle concentration of the surfactant in solution. Copyright 2001 Academic Press.  相似文献   

6.
Polyethyleneimine (PEI) and Microfibrillated cellulose (MFC) have been used to buildup polyelectrolyte multilayers (PEM) on silicone oxide and silicone oxynitride surfaces at different pH values and with different electrolyte and polyelectrolyte/colloid concentrations of the components. Consecutive adsorption on these surfaces was studied by in situ dual-polarization interferometry (DPI) and quartz crystal microbalance measurements. The adsorption data obtained from both the techniques showed a steady buildup of multilayers. High pH and electrolyte concentration of the PEI solution was found to be beneficial for achieving a high adsorbed amount of PEI, and hence of MFC, during the buildup of the multilayer. On the other hand, an increase in the electrolyte concentration of the MFC dispersion was found to inhibit the adsorption of MFC onto PEI. The adsorbed amount of MFC was independent of the bulk MFC concentration in the investigated concentration range (15-250 mg/L). Atomic force microscopy measurements were used to image a MFC-treated silicone oxynitride chip from DPI measurements. The surface was found to be almost fully covered by randomly oriented microfibrils after the adsorption of only one bilayer of PEI/MFC. The surface roughness expressed as the rms-roughness over 1 microm2 was calculated to be 4.6 nm (1 bilayer). The adsorbed amount of PEI and MFC and the amount of water entrapped by the individual layers in the multilayer structures were estimated by combining results from the two analytical techniques using the de Feijter formula. These results indicate a total water content of ca. 41% in the PEM.  相似文献   

7.
Tapping-mode atomic force microscopy was used to study the time-dependent changes in the structure of fibrinogen under aqueous conditions following adsorption on two model surfaces: hydrophobic graphite and hydrophilic mica. Fibrinogen was observed in the characteristic trinodular form, and the dimensions of the adsorbed molecules were consistent with previously reported values for these surfaces. On the basis of the differences in the relative heights of the D and the E domains, four orientation states were observed for fibrinogen adsorbed on both the surfaces. On graphite, the initial asymmetric orientation states disappeared with spreading over time. Some small lateral movements of the adsorbed proteins were observed on mica during repeated scanning, whereas no such movement was observed on graphite, indicating strong adhesion of fibrinogen to a hydrophobic surface. Spreading kinetics of fibrinogen on the two surfaces was determined by measuring the heights of the D and E domains over a time period of approximately 2 h. On graphite, the heights of both the D and E domains decreased with time to a lower plateau value of 1.0 nm. On mica, the heights of both the D and E domains showed an increase, rising to an upper plateau value of approximately 2.1 nm. The spreading of the D and E domains on graphite was analyzed using an 'exponential-decay-of-height' model. A spreading rate constant of approximately 4.7 x 10(-4) s(-1) was observed for the whole fibrinogen molecule adsorbed on graphite, corresponding to a free energy of unfolding of approximately 37 kT. Extrapolation of the exponential curve in the model to t = 0 yielded values of 2.3 and 2.2 nm for the heights of the D and the E domains at the time of contact with the hydrophobic graphite substrate, significantly less than their free solution diameters. A two-step spreading model is proposed to explain this observation.  相似文献   

8.
We have studied the effect of the pH and surface charge of mica on the adsorption of the positively charged weak polyelectrolyte (PE) poly(2-vinylpyridine) (P2VP) using atomic force microscopy (AFM) single-molecule experiments. These AFM experiments were performed in situ directly under aqueous media. If the mica's surface and the PE are oppositely charged (pH > 3), the PE forms a flat adsorbed layer of two-dimensionally (2D) equilibrated self-avoiding random walk coils. The adsorbed layer's structure remains almost unchanged if the pH is decreased to pH 3 (the mica's surface is weakly charged). At pH 2 (the mica surface is decorated by spots of different electrical charges), the polyelectrolyte chains take the form of a 2D compressed coil. In this pH range, at an increased P2VP concentration in solution, the PE segments preferentially adsorb onto the top of previously adsorbed segments, rather than onto an unoccupied surface. We explain this behavior as being caused by the heterogeneous character of the charged surface and the competitive adsorption of hydronium ions. The further increase of polymer concentration results in a complete coverage of the mica substrate and the charge overcompensation by P2VP chains adsorbed on the similarly charged substrate, due to van der Waals forces.  相似文献   

9.
There is a large interest in mixed protein/polysaccharide layers at air-water and oil-water interfaces because of their ability to stabilize foams and emulsions. Mixed protein/polysaccharide adsorbed layers at air-water interfaces can be prepared either by adsorption of soluble protein/polysaccharide complexes or by sequential adsorption of complexes or polysaccharides to a previously formed protein layer. Even though the final protein and polysaccharide bulk concentrations are the same, the behavior of the adsorbed layers can be very different, depending on the method of preparation. The surface shear modulus of a sequentially formed beta-lactoglobulin/pectin layer can be up to a factor of 6 higher than that of a layer made by simultaneous adsorption. Furthermore, the surface dilatational modulus and surface shear modulus strongly (up to factors of 2 and 7, respectively) depend on the bulk -lactoglobulin/pectin mixing ratio. On the basis of the surface rheological behavior, a mechanistic understanding of how the structure of the adsorbed layers depends on the protein/polysaccharide interaction in bulk solution, mixing ratio, ionic strength, and order of adsorption to the interface (simultaneous or sequential) is derived. Insight into the effect of protein/polysaccharide interactions on the properties of adsorbed layers provides a solid basis to modulate surface rheological behavior.  相似文献   

10.
A quartz crystal microbalance with dissipation (QCM-D) has been used to determine the adsorption rate of ampicillin-resistant linear and supercoiled plasmid DNA onto a silica surface coated with natural organic matter (NOM). The structure of the resulting adsorbed DNA layer was determined by analyzing the viscoelastic properties of the adsorbed DNA layers as they formed and were then exposed to solutions of different ionic composition. The QCM-D data were complemented by dynamic light scattering measurements of diffusion coefficients of the DNA molecules as a function of solution ionic composition. The obtained results suggest that electrostatic interactions control the adsorption and structural changes of the adsorbed plasmid DNA on the NOM-coated silica surface. The adsorption of DNA molecules to the NOM layer took place at moderately high monovalent (sodium) electrolyte concentrations. A sharp decrease in solution ionic strength did not result in the release of the adsorbed DNA, indicating that DNA adsorption on the NOM-coated silica surface is irreversible under the studied solution conditions. However, the decrease in electrolyte concentration influenced the structure of the adsorbed layer, causing the adsorbed DNA to adopt a less compact conformation. The linear and supercoiled DNA had similar adsorption rates, but the linear DNA formed a thicker and less compact adsorbed layer than the supercoiled DNA.  相似文献   

11.
The interaction of lysozyme protein (M.W. 14.7 kD) with two sizes of silica nanoparticles (16 and 25 nm) has been examined in aqueous solution using UV-vis spectroscopy and small-angle neutron scattering (SANS). The measurements were performed on fixed concentration (1 wt %) of nanoparticles and varying concentration of protein in the range 0 to 2 wt %. The adsorption isotherm as obtained using UV-vis spectroscopy suggests strong interaction of the two components and shows an exponential behavior. The saturation values of adsorption are found to be around 90 and 270 protein molecules per particle for 16 and 25 nm sized nanoparticles, respectively. The adsorption of protein on nanoparticles leads to the aggregation of particles and these structures have been studied by SANS. The aggregates are characterized by fractal structure coexisting with unaggregated particles at low protein concentrations and free proteins at higher protein concentrations. Further, contrast variation SANS measurements have been carried out to differentiate the adsorbed and free protein in these systems.  相似文献   

12.
Tablets of microcrystalline cellulose were formed at different compaction pressures and physical properties, such as pore size distribution, surface area, and pore surface fractality, were extracted from N2 adsorption isotherms. These properties were compared to previously published data on the water-induced ionic conductivity of the tablets. The conduction process was shown to follow a percolation model with a percolation exponent of 2 and a porosity percolation threshold of approximately 0.1. The critical pore diameter for facilitated charge transport was shown to be in the 5-20 nm range. When the network of pores with a diameter in this interval is reduced to the point where it no longer forms a continuous passageway throughout the compact, the conduction process is dominated by charge transport on the surfaces of individual microfibrils mainly situated in the bulk of fibril aggregates. A fractal analysis of nitrogen adsorption isotherms showed that the dominant interface forces during adsorption is attributed to surface tensions between the gas and the adsorbed liquid phase. The extracted fractal dimension of the analyzed pore surfaces remained unaffected by the densification process at low compaction pressures (< approximately 200 MPa). At increased densification, however, pore-surface structures smaller than approximately 100 nm become smoother as the fractal dimension decreases from approximately 2.5 at high porosities to approximately 2.3 for the densest tablets under study.  相似文献   

13.
 The adsorption of the diblock polyampholyte poly (methacrylic acid)-block-poly((dimethylamino)ethyl methacrylate) from aqueous solution on silicon substrates was investigated as a function of polymer concentration and pH. Dynamic light scattering and electrokinetic measurements were used to characterize the polyampholyte in solution. The amount of polymer adsorbed was determined by ellipsometry and lateral structures of the polymer layer were investigated by scanning force microscopy. The amount of polymer adsorbed was found to be strongly influenced by the pH of the polymer solution, while the size of the polyampholyte micelles adsorbed on the surface was hardly affected by pH during adsorption. From investigations by scanning force microscopy well-seperated micelles were seen in the dried monolayers adsorbed directly from solution. The structures at the surface are correlated to structures in solution, and the adsorbed amount depends on the relative charge of the micelles and the surface. Received: 13 September 1999 Accepted in revised form: 8 December 1999  相似文献   

14.
The adsorption of a 14-amino acid amphiphilic peptide, LK14, which is composed of leucine (L, nonpolar) and lysine (K, charged), on hydrophobic polystyrene (PS) and hydrophilic silica (SiO2) was investigated in situ by quartz crystal microbalance (QCM), atomic force microscopy (AFM), and sum frequency generation (SFG) vibrational spectroscopy. The LK14 peptide, adsorbed from a pH 7.4 phosphate-buffered saline (PBS) solution, displayed very different coverage, surface roughness and friction, topography, and surface-induced orientation when adsorbed onto PS versus SiO2 surfaces. Real-time QCM adsorption data revealed that the peptide adsorbed onto hydrophobic PS through a fast (t < 2 min) process, while a much slower (t > 30 min) multistep adsorption and rearrangement occurred on the hydrophilic SiO2. AFM measurements showed different surface morphologies and friction coefficients for LK14 adsorbed on the two surfaces. Surface-specific SFG spectra indicate very different ordering of the adsorbed peptide on hydrophobic PS as compared to hydrophilic SiO2. At the LK14 solution/PS interface, CH resonances corresponding to the hydrophobic leucine side chains are evident. Conversely, only NH modes are observed at the peptide solution/SiO2 interface, indicating a different average molecular orientation on this hydrophilic surface. The surface-dependent difference in the molecular-scale peptide interaction at the solution/hydrophobic solid versus solution/hydrophilic solid interfaces (measured by SFG) is manifested as significantly different macromolecular-level adsorption properties on the two surfaces (determined via AFM and QCM experiments).  相似文献   

15.
Collagen (type I from calf skin) adsorption on polystyrene (PS) and plasma-oxidized polystyrene (PSox) was studied, using a quartz crystal microbalance with energy dissipation measurements (QCM-D) and atomic force microscopy (AFM) in tapping mode. Radio-labeled collagen was used to measure the adsorbed amount and the ability of adsorbed collagen to exchange with molecules in the solution. The results show that the collagen adlayer consists of two parts: a dense and thin sheet in which fibrils are formed (directly observed by AFM) and an overlying thick layer (up to 200 nm) containing protruding molecules or bundles which are in very low concentration but modify noticeably the local viscosity. The thickness and viscosity of the semi-liquid adlayer both increase with adsorption time and collagen concentration. Fibril formation near the surface also increases with time and collagen concentration and occurs more readily on PS compared to PSox. Radiochemical measurements show that this may be related to the larger mobility of molecules adsorbed on PS, presumably owing to a smaller number of binding points.  相似文献   

16.
We report about the surface modification of polystyrene (PSt) with photoreactive alpha-4-azidobenzoyl-omega-methoxy poly(ethylene glycol)s (ABMPEG) of three different molecular weights (MWs of approximately 2, approximately 5, and approximately 10 kg/mol) and with two poly(ethylene glycol)/poly(propylene glycol) triblock copolymers (PEG-PPG-PEG) of about identical PEG/PPG ratio (80/20, w/w) and MW(PEG) of approximately 3 and approximately 6 kg/mol, all via adsorption from aqueous solutions. For ABMPEGs, an additional UV irradiation was used for photografting to the PSt. Contact angle (CA) and atomic force microscopy data revealed pronounced differences of the hydrophilicity/hydrophobicity and topography of the surfaces as a function of PEG type and concentration used for the modification. In all cases, an incomplete coverage of the PSt was observed even after modification at the highest solution concentrations (10 g/L). However, clear differences were seen between PEG-PPG-PEGs and ABMPEGs; only for the latter was a nanoscale-ordered interphase structure with an influence of MW(PEG) on the PEG density observed; after modification at the same solution concentrations, the density was significantly higher for lower MW(PEG). The adsorption of three proteins, myoglobin (Mgb), bovine serum albumin (BSA), and fibrinogen to the various surfaces was analyzed by surface plasmon resonance. Pronounced differences between the two PEG types with respect to the reduction of protein adsorption were found. At high, but still incomplete, surface coverage and similar CA, the shielding of ABMPEG layers toward the adsorption of Mgb and BSA was much more efficient; e.g., the adsorbed Mgb mass relative to that of unmodified PSt was reduced to 10% for ABMPEG 2 kg/mol while for both PEG-PPG-PEGs the Mgb mass was still around 100%. In addition, for the ABMPEG layers an effect of MW(PEG) on adsorbed protein mass-decrease with decreasing MW-could be confirmed; and the highest Mgb/BSA selectivities were also observed. A "two-dimensional molecular sieving", based on PEG molecules having a nanoscale order at the hydrophobic substrate polymer surface has been proposed, and the main prerequisites were the use of PEG conjugates which are suitable for an "end-on" grafting (e.g., ABMPEGs), the use of suitable (not too high) concentrations for the surface modification via adsorption/self-assembly, optionally the photografting on the substrate (possible only for ABMPEG), and presumably, a washing step to remove the excess of unbound PEGs. The results of this study also strongly support the hypothesis that the biocompatibility of hydrophobic materials can be very much improved by PEG modifications at surface coverages that are incomplete but have an ordered layer structure controlled by the size and steric interactions of surface-bound PEGs.  相似文献   

17.
Wet silica gels with approximately 1.4 x 10(-3) mol SiO2/cm3 and approximately 92 vol % liquid phase were obtained from sonohydrolysis of tetraethoxysilane (TEOS) with different additions of isopropyl alcohol (IPA). The IPA/TEOS molar ratio R was changed from 0 to 4. Aerogels were obtained by supercritical CO2 extraction. The samples were analyzed by small-angle X-ray scattering (SAXS) and nitrogen adsorption. The wet gels exhibit mass fractal structure with fractal dimension increasing from D approximately 2.10 to D approximately 2.22, characteristic length xi decreasing from approximately 9.5 to approximately 6.9 nm, as R increases from 0 to 4, and an estimated characteristic length for the primary silica particles lower than approximately 0.3 nm. The supercritical process apparently eliminates a fraction of the porosity, increasing the mass fractal dimension and shortening the fractality domain in the mesopore region. The fundamental role of isopropyl alcohol on the structure of the resulting aerogels is to decrease the porosity and the pore mean size as R changes from pure TEOS to R = 4. A secondary structure appearing in the micropore region of the aerogels can be described as a mass/surface fractal structure, with correlated mass fractal dimension Dm approximately 2.7 and surface fractal dimension Ds approximately 2.3, as inferred from SAXS and nitrogen adsorption data.  相似文献   

18.
Adsorption of beta-2-microglobulin from aqueous solution onto unmodified and methylated silicon wafers and subsequent displacement of the small globular protein by fibrinogen were studied by spectroscopic ellipsometry, immunosorbent assays and atomic force microscopy. The results provide evidence that hydrophobicity of the substrate increases the maximum adsorbed amount of beta-2-microglobulin and the resistance of the adsorbed protein to displacement from the interface by competing species, respectively. Further, the dynamics of beta-2-microglobulin adsorption was found to induce significant differences in the degree of displacement achieved at given conditions. The observed variations in displacement behavior of adsorbed beta-2-microglobulin were interpreted based on information on the layer structure gained by atomic force microscopy. More compact and relatively smooth protein layers were formed on the hydrophobic surface corresponding to lower displacement by fibrinogen.  相似文献   

19.
Nanocrystalline ZSM-5 with a Si/Al ratio of 20 was synthesized using clear solutions and a hydrothermal synthesis procedure. The resulting ZSM-5 materials were characterized by powder X-ray diffraction, scanning electron microscopy (SEM), nitrogen adsorption isotherms, solid-state nuclear magnetic resonance, and toluene adsorption. A commercial ZSM-5 sample was similarly characterized for comparison with the synthesized materials. The particle sizes of the synthesized ZSM-5 samples were calculated using the measured external surface areas and were determined to be 15 and 60 nm. SEM images indicated that the ZSM-5 samples consist of agglomerated and possibly intergrown particles. Toluene adsorption measurements showed that the ZSM-5 sample with a particle size of 15 nm adsorbed approximately 50% more toluene than the other ZSM-5 samples, most likely due to the adsorption of toluene on the external surface. For the toluene adsorbed on the internal zeolite surface, approximately one toluene molecule was adsorbed per channel intersection for each of the ZSM-5 samples.  相似文献   

20.
The adsorption and viscoelastic properties of cationic xylan layers adsorbed from an aqueous electrolyte solution (NaCl 0, 1, 10, 100 mM) on a cellulose model surface were studied using quartz crystal microbalance with dissipation (QCM-D). Three cationic xylans with different charge densities were used (molecular weight, 9,600 g/mol with degrees of substitution, DS = 0.150, 0.191, and 0.259). The influences of the electrolyte concentration and charge density of cationic xylan on its adsorption onto a cellulose surface were investigated. Low charged cationic xylan was substantially more efficient in surface adsorption on cellulose compared to high charged cationic xylan at a low concentration of electrolytes. Adsorption of low charged cationic xylan decreased with increases in electrolyte concentration. However, adsorption of high cationic xylan increased with electrolyte concentration. The conformation and viscoelastic properties of the layers were interpreted by modeling the data under the assumption that the layers can be explained by the a Voigt model. Low charged cationic xylan adsorbed relatively weakly onto the cellulose surface, and formed a thicker, softer layer than high charged cationic xylan. On the other hand, high charged cationic xylan formed a thinner adsorption layer onto the cellulose surface.  相似文献   

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