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1.
Humic acid fractionation upon sequential adsorption onto goethite   总被引:6,自引:0,他引:6  
Mineral-humic complexes are commonly distributed in natural environments and are important in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study investigated the structural and conformational changes of humic acid (HA) and mineral-HA complexes after sequential HA adsorption by goethite, using UV-visible spectroscopy, high performance size exclusion chromatography (HPSEC), Fourier transform infrared (FT-IR) spectroscopy, and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The HA remaining in the solution after adsorption showed low polarity index values ((N+O)/C), which indicates that polar functional moieties are likely to adsorb on the goethite surface. In addition, we observed decreased E4/E6 and E2/E3 ratios of unbound HA with increasing number of coatings, implying that aliphatic rich HA fractions with polar functional moieties readily adsorb to the goethite surface. According to IR spectra, carbohydrate carbon would be the important fractions associated with goethite. NMR spectra provided evidence for HA fractionation during adsorption onto the mineral surface; that is, aliphatic fractions were preferentially adsorbed by goethite while aromatic fractions were left in solution. Relatively small molecular weight (MW) HA fractions had a greater affinity for the goethite surface based on analyses of the HPSEC chromatograms, which differs from the results reported in the literature. Finally, our results suggest that the polar aliphatic fractions of HA were mainly adsorbed to goethite via electrostatic attraction and/or ligand exchange reactions.  相似文献   

2.
Biofouling of glass and quartz surfaces can be reduced when the surface is coated with photocatalytically active metal oxides, such as TiO2 (anatase form) or SnO2. We measured the attachment of eight strains of bacteria to these two metal oxides (TiO2 and SnO2), and to an uncoated glass (control; designated Si-m) before and after exposure to UV light at wavelengths of 254 nm (UVC) or 340 nm UV (UVA). TiO2-coated surfaces were photocatalytically active at both 254 and 340 nm as evidenced by a decrease in the water contact angle of the surface from 59 degrees +/-2 to <5 degrees. The water contact angle of the SnO2 surface was reduced only at 254 nm, while contact angle of the Si-m glass surface was not altered by light of either wavelength. Bacterial adhesion decreased by 10-50% to photocatalyzed glass surfaces. In all cases, bacteria exposed to the UV light were completely killed due to a combination of exposure to UV light and the photocatalytic activity of the glass surfaces. These results show that UV light irradiation of TiO2-coated surfaces can be an effective method of reducing bacterial adhesion.  相似文献   

3.
The antimicrobial peptide nisin has been observed to preferentially locate at surfaces coated with the poly[ethylene oxide]-poly[propylene oxide]-poly[ethylene oxide] (PEO-PPO-PEO) surfactant Pluronic F108, to an extent similar to its adsorption at uncoated, hydrophobic surfaces. In order to evaluate nisin function following its adsorption to surfaces presenting pendant PEO chains, the antimicrobial activity of nisin-loaded, F108-coated polystyrene microspheres and F108-coated polyurethane catheter segments was evaluated against the Gram-positive indicator strain, Pediococcus pentosaceus. The retained biological activity of these nisin-loaded layers was evaluated after incubation in the presence and absence of blood proteins, for contact periods up to one week. While an increase in serum protein concentration reduced the retained activity on both bare hydrophobic and F108-coated materials, F108-coated surfaces retained more antimicrobial activity than the uncoated surfaces. Circular dichroism spectroscopy experiments conducted with nisin in the presence of F108-coated and uncoated, silanized silica nanoparticles suggested that nisin experienced conformational rearrangement at a greater rate and to a greater extent on bare hydrophobic surfaces relative to F108-coated surfaces. These results support the notion that immobilized, pendant PEO chains confer some degree of conformational stability to nisin while also inhibiting its exchange by blood proteins.  相似文献   

4.
The adsorption and elution of the antimicrobial peptide nisin at hydrophobic, silanized silica surfaces coated with the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) surfactant Pluronic F108 were measured in situ, with ellipsometry. While such layers are known to inhibit protein adsorption, nisin was observed to adsorb in multilayer quantities, to an extent similar to its adsorption at uncoated, hydrophobic surfaces. The rates of nisin adsorption and elution were generally slower at F108-coated surfaces. And, the sequential adsorption of nisin, including two adsorption-elution cycles at each surface, showed greater differences in adsorption rates between the first and second adsorption cycles, when evaluated at identical mass density, for uncoated relative to F108-coated surfaces. These results indicate that nisin adsorption occurs via "entrapment" within the PEO brush layer at F108-coated surfaces, in this way slowing adsorption and spontaneous elution, and inhibiting post-adsorptive molecular rearrangements by reducing the lateral mobility of nisin. While F108-coated layers rejected adsorption of serum albumin, sequential adsorption experiments carried out with nisin and albumin showed a low level of albumin adsorption when nisin was present at the interface.  相似文献   

5.
Two types of experiments were used to study the behavior of both advancing and receding contact angles, namely the dynamic one-cycle contact angle (DOCA) and the dynamic cycling contact angle (DCCA) experiments. For the preliminary study, DOCA measurements of different liquids on different solids were performed using an automated axisymmetric drop shape analysis-profile (ADSA-P). From these experimental results, four patterns of receding contact angle were observed: (1) time-dependent receding contact angle; (2) constant receding contact angle; (3) 'stick/slip'; (4) no receding contact angle. For the purpose of illustration, results from four different solid surfaces are shown. These solids are: FC-732-coated surface; poly(methyl methacrylate/n-butyl methacrylate) [P(MMA/nBMA)]; poly(lactic acid) (DL-PLA); and poly(lactic/glycolic acid) 50/50 (DL-PLGA 50/50). Since most of the surfaces in our studies exhibit time dependence in the receding contact angle, a more extended study was conducted using only FC-732-coated surfaces to better understand the possible causes of decreasing receding contact angle and contact angle hysteresis. Contact angle measurements of 21 liquids from two homologous series (i.e. n-alkanes and 1-alcohols) and octamethylcyclotetrasiloxane (OCMTS) on FC-732-coated surfaces were performed. It is apparent that the contact angle hysteresis decreases with the chain length of the liquid. It was found that the receding contact angle equals the advancing angle when the alkane molecules are infinitely large. These results strongly suggest that the chain length and size of the liquid molecule could contribute to contact angle hysteresis phenomena. Furthermore, DCCA measurements of six liquids from the two homologous series on FC-732-coated surfaces were performed. With these experimental results, one can construe that the time dependence of contact angle hysteresis on relatively smooth and homogeneous surfaces is mainly caused by liquid retention/sorption. The results also suggested that the contact angle hysteresis will eventually approach a steady state, where the rate of liquid retention-evaporation or sorption process would balance out each other. If the existence of contact angle hysteresis can be attributed to liquid sorption/retention, one should only use the advancing contact angles (measured on a dry surface) in conjunction with Young's equation for surface energetic calculations.  相似文献   

6.
Molecular weight (MW) fractionation of Suwannee River fulvic acid (SRFA) and purified Aldrich humic acid (PAHA) by adsorption onto kaolinite and hematite was investigated in equilibrium and rate experiments with a size-exclusion chromatography system using ultraviolet (UV) light detection. The extent of adsorptive fractionation based on UV detection was positively correlated with the percent carbon adsorption for both humic substances (HS), although the specific fractionation pattern observed depended on the particular HS and mineral used. Higher MW fractions of SRFA, an aquatic HS, were preferentially adsorbed to both kaolinite and hematite whereas the fractionation trends for PAHA, a terrestrial peat HS, differed for the two minerals. The contrasting fractionation patterns for SRFA versus PAHA can be explained reasonably well by the different structural trends that occur in their respective MW fractions and the underlying adsorption processes. Rate studies of adsorptive fractionation revealed an initial rapid uptake of smaller HS molecules by the mineral surfaces, followed by their replacement at the surface by a much slower uptake of the larger HS molecules present in aqueous solution.  相似文献   

7.
To accurately model metal mobility and bioavailability in soils and sediments, systematic adsorption studies are needed in considering heterogeneous, well characterized minerals. Two important surfaces are iron oxide and silica, which are ubiquitous and associated with one another in the environment playing important roles in metal distribution. This study focuses on the synthesis and characterization of such a system, iron oxide-coated silica. A three-level fractional factorial study was used to determine the optimum conditions for producing goethite-coated silica. The amount of coating achieved was between 0.59 and 21.36 mg Fe g(-1) solid. The most significant factor in coating using either adsorption or precipitation was the particle size of silica, where Fe increased from an average of 0.85 to 9.6 mg Fe g(-1) solid as silica size decreased from 1.5 to 0.2 mm. Other factors investigated, including coating temperature, initial iron concentration, and contact time, were of less importance. The iron oxide coatings were observed to be non-uniform, concentrated in rough concave areas. FTIR revealed a band shift as well as a new band indicating changes in the chemical environment of FeO and SiO bonds; these results along with abrasion studies suggest that the interaction between the oxide coating and silica surface potentially involves chemical forces. Because the nano-sized iron oxide coatings increased surface area, introduced small pores, and changed the surface charge distribution of silica, the coated system demonstrates a greater affinity for Ni compared to that of uncoated silica.  相似文献   

8.
The contribution of various bacterial surface functional groups to adhesion at hematite and ZnSe surfaces was examined using attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy. When live Shewanella oneidensis, Pseudomonas aeruginosa, and Bacillus subtilis cells were introduced to a horizontal hematite (alpha-Fe(2)O(3))-coated internal reflection element (IRE), FTIR peaks emerged corresponding to bacterial phosphate group binding. These IR peaks were not observed when bacteria were introduced to the uncoated ZnSe IRE. When cells were added to colloidal suspensions of alpha-Fe(2)O(3) at pH 7, spectra included peaks corresponding to P-OFe and nu(COOH), the latter being attributed to bridging of carboxylate at mineral surface OH groups. Selected model organic compounds with P-containing functionalities (phenylphosphonic acid [PPA], adenosine 5'-monophosphate [AMP], 2'-deoxyadenyl(3'-->5')-2'-deoxyadenosine [DADA], and deoxyribonucleic acid [DNA]) produce spectra with similar peaks corresponding to P-OFe when adsorbed to alpha-Fe(2)O(3). The data indicate that both terminal phosphate/phosphonate and phosphodiester groups, either exuded from the cell or present as surface biomolecules, are involved in bacterial adhesion to Fe-oxides through formation of innersphere Fe-phosphate/phosphonate complexes.  相似文献   

9.
Silica-coated, Au/Ag striped nanowires for bioanalysis   总被引:1,自引:0,他引:1  
Striped metallic nanowires (NW) have been coated with a silica shell of controllable thickness (6-150 nm), and the assay performance of coated vs uncoated NW has been compared. The silica coating does not interfere with identification of the metal striping pattern and protects Ag segments from oxidation, extending the range of assay conditions under which barcoded NW can be used. Much higher and more uniform fluorescence intensities were observed for dye-labeled ssDNA bound to SiO2-coated as compared to intensities for uncoated NW. Simultaneous, multiplexed DNA hybridization assays for three pathogen-specific target sequences on SiO2-coated NW showed good discrimination of complementary from noncomplementary targets. Application of SiO2-coated NW in discrimination of single base mismatches corresponding to a mutation of the p53 gene was also demonstrated. Finally, we have shown that thiolated probe DNA resists desorption under thermocycling conditions if attached via siloxane chemistry to SiO2-coated NW, but not if it is attached via direct adsorption to bare Au/Ag NW.  相似文献   

10.
The interaction of organic molecules with mineral surfaces is a subject of interest in a variety of disciplines. Enzymes are able to be sorbed and immobilized by clay minerals and humic colloids in soil environment. The present study was done to elucidate some aspects of sorption and immobilization of cellulase on soil components by analysis of the sorption, and immobilization of cellulase on Avicel, a soil sample, illite, kaolinite, montmorillonite, and palygorskite. Palygorskite displayed the highest sorption capacity. Sorbents coated with hydroxyaluminum displayed significantly higher capacity than uncoated sorbents. The positive effects of Al(OH)(x) coating on sorption capacities of the different sorbents were not equal. The effect decreased in the order soil > palygorskite > kaolinite > Avicel > montmorillonite > illite. The amount of sorbed cellulase desorbed from external surfaces of soil was quite low (about 16%), especially in coated samples (about 6%). X-ray diffraction analysis of K-montmorillonite and Ca-montmorillonite showed that Al(OH)(x) was intercalated between the montmorillonite layers. Immobilization of cellulase on the sorbents did not result in expansion of their crystal structures. Therefore, it may be concluded that the amount of cellulase immobilized on internal surfaces of the sorbents was negligible.  相似文献   

11.
The anti-bacterial adhesion properties of TiO2-coated polymethyl methacrylate (PMMA) surfaces are investigated systematically. In detail, the adhesion of S. aureus (gram positive) and E. coli (gram negative) to TiO2-coated and uncoated PMMA surfaces are performed by the plate counting method. Afterwards, the adhesion free energy of bacteria on both supporting materials is quantified using the thermodynamic approach of Lifshitz van der Waals and acid/base interactions. The superior anti-adhesion capability of TiO2-coated PMMA is demonstrated when compared to native PMMA, both experimentally and theoretically.  相似文献   

12.
In order to identify the cellular mechanisms leading to the biocompatibility of hydroxyapatite implants, we studied the interaction of human bone marrow derived stromal (mesenchymal) stem cells (hMSCs) with fibronectin-coated gold (Au) and hydroxyapatite (HA) surfaces. The adsorption of fibronectin was monitored by Quartz Crystal Microbalance with Dissipation (QCM-D) at two different concentrations, 20 μg/ml and 200 μg/ml, and the fibronectin adsorption experiments were complemented with antibody measurements. The QCM-D results show that the surface mass uptake is largest on the Au surfaces, while the number of polyclonal and monoclonal antibodies directed against the cell-binding domain (CB-domain) on the fibronectin (Fn) is significantly larger on the (HA) surfaces. Moreover, a higher number of antibodies bound to the fibronectin coatings formed from the highest bulk fibronection concentration. In subsequent cell studies with hMSC's we studied the cell spreading, cytoskeletal organization and cell morphology on the respective surfaces. When the cells were adsorbed on the uncoated substrates, a diffuse cell actin cytoskeleton was revealed, and the cells had a highly elongated shape. On the fibronectin coated surfaces the cells adapted to a more polygonal shape with a well-defined actin cytoskeleton, while a larger cell area and roundness values were observed for cells cultured on the coated surfaces. Among the coated surfaces a slightly larger cell area and roundness values was observed on HA as compared to Au. Moreover, the results revealed that the morphology of cells cultured on fibronectin coated HA surfaces were less irregular. In summary we find that fibronectin adsorbs in a more activated state on the HA surfaces, resulting in a slightly different cellular response as compared to the fibronectin coated Au surfaces.  相似文献   

13.
The adsorption of natural organic matter (NOM) on mineral (hydr)oxide plays an important role in the evaluation of the speciation of toxic metal ions in the environment. Because both NOM and mineral oxide have variable charges that adjust upon adsorption, a good understanding of proton binding is required before the binding of metal ions can be understood. In this study, the adsorption of purified Aldrich humic acid (PAHA) on goethite was examined as a function of the environmental conditions (pH, salt concentration, and free concentration of PAHA) together with the proton adsorption to PAHA, goethite, and their mixtures. The induced charges on both components were separated on the basis of the difference between the charge/pH curves of the mixture and those of the single components. The electrostatic potential profile across the adsorbed layer was obtained as a numerical solution of the Poisson-Boltzmann equation using the charge density of the adsorbed PAHA and the goethite surface. From the quantitative evaluation of the induced charge on both components, it is revealed that the degree of the charge adjustment is related to the electrostatic affinity between the PAHA segments and the goethite surface, the electrostatic repulsion between the PAHA segments, and the electrostatic shielding by salt ions. Considering the charge distribution of the adsorbed PAHA at the goethite surface, it is concluded that the change of the charge adjustment is sensitive to that of the conformation of the adsorbed PAHA. From the detailed inspection of the assumptions made and the comparison with the reported theoretical calculations, the obtained potential profiles are considered to broadly reflect the true potential profiles. Because a charge adjustment is not frequently considered in detail in relation to the NOM adsorption on metal (hydr)oxides, the obtained results can form the basis for the further development of modeling of the adsorption of NOM on (hydr)oxide surfaces.  相似文献   

14.
The vibrational characteristics of outer-sphere complexes of sulfate at several mineral oxide-water interfaces were investigated by in situ attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy. In the IR spectra obtained from surface outer-sphere complexes, only one peak of the asymmetric stretching vibrational mode υ(3) similar to that of free sulfate ion SO(4)(2-) in aqueous solution is observed. However, on the investigated (hydr)oxide surfaces of Al(3+), Ti(4+), Fe(2+/3+), Cr(3+), Ce(4+), Cu(2+), Y(3+), Zn(2+), and Nd(3+), a shift of up to 14 cm(-1) was found, which was correlated to the polarizing power of the metal cations. A high polarizing power was found to result in a stronger shift of υ(3) compared to that of the aqueous SO(4)(2-) ion. Furthermore, the impact of the metal oxide structure on the characteristics of the formed outer-sphere complex was negligible because different Al and Fe (hydr)oxides did not show any changes in the respective IR spectra. Finally, the ionic strength (1-10(-4) M) and pH (6.8-3.1) have been modified to change the surface potential, showing no direct influence on the spectra (i.e., on the geometry of the outer-sphere complex).  相似文献   

15.
Molecular imprinting of surfaces of mesoporous sorbents is a novel method for introducing template-selective recognition sites. This method makes use of the unique surface environment of hexagonally packed mesopore surfaces of selected pore sizes (see the schematic representation) and coats such surfaces with functional ligands by binding to a metal ion template.  相似文献   

16.
In this paper, the icephobic properties of superhydrophobic surfaces are investigated under dynamic flow conditions using a closed-loop low-temperature wind tunnel. Superhydrophobic surfaces were prepared by coating aluminum and steel substrate plates with nano-structured hydrophobic particles. The superhydrophobic plates, along with uncoated controls, were exposed to a wind tunnel air flow of 12 m/s and ?7 °C with deviations of ±1 m/s and ±2.5 °C, respectively, containing micrometer-sized (~50 μm in diameter) water droplets. The ice formation and accretion were observed by CCD cameras. Results show that the superhydrophobic coatings significantly delay ice formation and accretion even under the dynamic flow condition of highly energetic impingement of accelerated supercooled water droplets. It is found that there is a time scale for this phenomenon (delay in ice formation) which has a clear correlation with contact angle hysteresis and the length scale of the surface roughness of the superhydrophobic surface samples, being the highest for the plate with the lowest contact angle hysteresis and finest surface roughness. The results suggest that the key for designing icephobic surfaces under the hydrodynamic pressure of impinging droplets is to retain a non-wetting superhydrophobic state with low contact angle hysteresis, rather than to only have a high apparent contact angle (conventionally referred to as a “static” contact angle).  相似文献   

17.
A series of chromatographic sorbents, which differ by way of applying modifying chelates of acetylacetone was obtained. The acid-base and chromatographic properties of sorbents with thermally and chemically grafted layers of metal acetylacetonates were investigated. It was shown that the modifi cation of the mineral sorbents with metal acetylacetonates leads to a change in the surface acidity, as well as to an increase in the polarity and selectivity with respect to different classes of compounds.  相似文献   

18.
Glycoproteins, such as lubricin, and hyaluronic acid (HA) play a prominent role in the boundary lubrication mechanism in diarthrodial joints. Although many studies have tried to elucidate the lubrication mechanisms of articular cartilage, the molecular details of how lubricin and HA interact with cartilage surfaces and mediate their interaction still remain poorly understood. Here we used model substrates, functionalized with self-assembled monolayers terminating in hydroxyl or methyl groups, (1) to determine the effect of surface chemistry on lubricin and HA adsorption using surface plasmon resonance (SPR) and (2) to study normal force interactions between these surfaces as a function of lubricin and HA concentration using colloidal probe microscopy. We found that lubricin is amphiphilic and adsorbed strongly onto both methyl- and hydroxyl-terminated surfaces. On hydrophobic surfaces, lubricin likely adopts a compact, looplike conformation in which its hydrophobic domains at the N and C termini serve as surface anchors. On hydrophilic surfaces, lubricin likely adsorbs anywhere along its hydrophilic central domain and adopts, with increasing solution concentration, an extended tail-like conformation. Overall, lubricin develops strong repulsive interactions when compressing two surfaces into contact. Furthermore, upon surface separation, adhesion occurs between the surfaces as a result of molecular bridging and chain disentanglement. This behavior is in contrast to that of HA, which does not adsorb appreciably on either of the model surfaces and does not develop significant repulsive interactions. Adhesive forces, particularly between the hydrophobic surfaces, are large and not appreciably affected by HA. For a mixture of lubricin and HA, we observed slightly larger adsorptions and repulsions than those found for lubricin alone. Our experiments suggest that this interaction depends on unspecific physical rather than chemical interactions between lubricin and HA. We speculate that in mediating interactions at the cartilage surface, an important role of lubricin, possibly in conjunction with HA, is one of providing a protective coating on cartilage surfaces that maintains the contacting surfaces in a sterically repulsive state.  相似文献   

19.
Zirconium, titanium, and hafnium oxide-coated stainless steel surfaces are fabricated by reactive landing of gas-phase ions produced by electrospray ionization of group IVB metal alkoxides. The surfaces are used for in situ enrichment of phosphopeptides before analysis by matrix-assisted laser desorption ionization (MALDI) mass spectrometry. To evaluate this method we characterized ZrO2 (zirconia) surfaces by (1) comparison with the other group IVB metal oxides of TiO2 (titania) and HfO2 (hafnia), (2) morphological characterization by SEM image analysis, and (3) dependence of phosphopeptide enrichment on the metal oxide layer thickness. Furthermore, we evaluated the necessity of the reactive landing process for the construction of useful metal oxide surfaces by preparing surfaces by electrospray deposition of Zr, Ti, and Hf alkoxides directly onto polished metal surfaces at atmospheric pressure. Although all three metal oxide surfaces evaluated were capable of phosphopeptide enrichment from complex peptide mixtures, zirconia performed better than hafnia or titania as a result of morphological characteristics illustrated by the SEM analysis. Metal oxide coatings that were fabricated by atmospheric pressure deposition were still capable of in situ phosphopeptide enrichment, although with inferior efficiency and surface durability. We show that zirconia surfaces prepared by reactive landing of gas-phase ions can be a useful tool for high throughput screening of novel phosphorylation sites and quantitation of phosphorylation kinetics.  相似文献   

20.
Adsorption of As(III) from aqueous solutions by iron oxide-coated sand   总被引:1,自引:0,他引:1  
Arsenic is a toxic element and may be found in natural waters as well as in industrial waters. Leaching of arsenic from industrial wastewater into groundwater may cause significant contamination, which requires proper treatment before its use as drinking water. The present study describes removal of arsenic(III) on iron oxide-coated sand in batch studies conducted as a function of pH, time, initial arsenic concentration, and adsorbent dosage. The results were compared with those for uncoated sand. The adsorption data fitted well in the Langmuir model at different initial concentration of As(III) at 20 g/l fixed adsorbent dose. Maximum adsorption of As(III) for coated sand is found to be much higher (28.57 microg/g) than that for uncoated sand (5.63 microg/g) at pH 7.5 in 2 h. The maximum As(III) removal efficiency achieved is 99% for coated sand at an adsorbent dose of 20 g/l with initial As(III) concentration of 100 microg/l in batch studies. Column studies have also been carried out with 400 microg/l arsenic (pH 7.5) by varying the contact time, filtration rate, and bed depth. Results of column studies demonstrated that at a filtration rate of 4 ml/min the maximum removal of As(III) observed was 94% for coated sand in a contact time of 2 h. The results observed in batch and column studies indicate that iron oxide-coated sand is a suitable adsorbent for reducing As(III) concentration to the limit (50 microg/l) recommended by Indian Standards for Drinking Water.  相似文献   

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