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1.
A novel method based on electrostatic layer-by-layer self-assembly (LBL) technique for alternate assemblies of polyelectrolyte functionalized multi-walled carbon nanotubes (MWNTs) and platinum nanoparticles (PtNPs) is proposed. The shortened MWNTs can be functionalized with positively charged poly(diallyldimethylammonium chloride) (PDDA) based on electrostatic interaction. Through electrostatic layer-by-layer assembly, the positively charged PDDA functionalized MWNTs (PDWNTs) and negatively charged citrate-stabilized PtNPs were alternately assembled on a 3-mercaptopropanesulfonic sodium (MPS) modified gold electrode and also on other negatively charged surface, e.g. quartz slide and indium–tin-oxide (ITO) plate, directly forming the three-dimensional (3D) nanostructured materials. This is a very general and powerful technique for the assembling three-dimensional nanostructured materials containing carbon nanotubes (CNTs) and nanoparticles. Thus prepared multilayer films were characterized by ultraviolet–visible–near-infrared spectroscopy (UV–vis–NIR), scanning electron microscopy (SEM) and cyclic voltammetry (CV). Regular growth of the mutilayer films is monitored by UV–vis–NIR. SEM provides the morphology of the multilayer films. The PtNPs containing multilayer films exhibit high electrocatalytic activity for the reduction of dioxygen. Furthermore, the electrocatalytic activity of the films could be further tailored by simply choosing different cycles in the LBL process. This assembling method for polyelectrolyte functionalized carbon nanotubes and nanoparticles introduces new opportunities for the incorporation of various functionalities into nanotube devices, which, in turn, opens up the possibility of building more complex multicomponent nanostructures.  相似文献   

2.
Sun Z  Li Y  Zhou T  Liu Y  Shi G  Jin L 《Talanta》2008,74(5):1692-1698
In this paper, layer-by-layer (LBL) {MSU/Hb}(n)/PDDA films assembled by alternate adsorption of positively charged hemoglobin (Hb) and negatively charged mesoporous molecular sieves of Al-MSU-S onto a glassy carbon electrode (GCE) were reported. Al-MSU-S was synthesized by the precursor of zeolite Y and ionic liquids 1-hexadecane-3-methylimidazolium bromide (CMIMB) as a template in basic medium. It exhibited larger pore diameter, pore volume and surface area. Direct electrochemical and electrocatalytic properties of Hb in these layer-by-layer films were investigated. A pair of well-defined nearly reversible cyclic voltammetric peaks was observed and the formal potential of the heme Fe(III)/Fe(II) redox couple was found to be -0.295V (vs. SCE). The influences of layer's number and the pH of the external solution to the electron transfer behavior of Hb in {MSU/Hb}(n)/PDDA films were also estimated by cyclic voltammetry and a set of optimized conditions for film fabrication was inferred. The hemoglobin in{MSU/Hb}(n)/PDDA films displayed a good electrocatalytic activity to the reduction of hydrogen peroxide, which had linear current responses from 1.0 x 10(-6) to 1.86 x 10(-4)mol/L with the detection limit of 5.0 x 10(-7)mol/L (S/N=3). The apparent Michaeli-Menten constant (K(m)(app)) was 0.368 mmol/L. Thus, this methodology shows potential application of the preparation of third-generation biosensors.  相似文献   

3.
Carbon nanotubes have been proposed as support materials for numerous applications, including the development of DNA sensors. One of the challenges is the immobilization of DNA or other biological molecules on the sidewall of carbon nanotubes. This paper introduces a new fabrication of DNA-carbon nanotubes particles using the layer-by-layer (LBL) technique on single-walled carbon nanotubes (SWCNTs). Poly(diallyldimethylammonium) (PDDA), a positively charged polyelectrolyte, and DNA as a negatively charged counterpart macromolecule are alternatively deposited on the water-soluble oxidized SWCNTs. Pure DNA/PDDA/SWCNTs particles can be prepared and separated by simple unltracentrifugation. The characterization of DNA/PDDA/SWCNTs particles was carried out by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy, Raman spectroscopy, and thermogravimetric analysis (TGA). An electrode modified by the DNA/PDDA/SWCNTs particles shows a dramatic change of the electrochemical signal in solutions of tris(2,2'-bipyridyl)ruthenium(II) ((Ru(bpy)(3)2+) as a reporting redox probe. A preliminary application of the DNA-modified carbon nanotubes in the development of DNA sensors used in the investigation of DNA damage by nitric oxide is presented.  相似文献   

4.
Layer‐by‐layer (LBL) assembly is a versatile nanofabrication technique, and investigation of its kinetics is essential for understanding the assembly mechanism and optimizing the assembly procedure. In this work, the LBL assembly of polyelectrolyte and nanoparticles were monitored in situ by capillary electrophoresis (CE) for the first time. The assembly of poly(diallyldimethylammonium chloride) (PDDA), and gold nanoparticles (AuNPs) on capillary walls causes surface‐charge neutralization and resaturation, and thus yields synchronous changes in the electroosmotic flow (EOF). The EOF data show that formation of multilayers follows first‐order adsorption kinetics. On the basis of the fit results, influencing factors, including number of layers, concentration of materials, flow rate, and size of AuNPs, were investigated. The stability and robustness of the assembled coatings were also characterized by CE. It was found that degradation of PDDA layers follows first‐order chemical kinetics, while desorption of AuNPs takes place in a disorderly manner. The substrate strongly affects assembly of the underlying layer, while this effect is rapidly screened with increasing number of layers. Furthermore, we demonstrate that the EOF measuring step does not disturb LBL assembly, and the proposed method is reliable and rugged. This work not only studies in detail the LBL adsorption/desorption process of polyelectrolyte and nanoparticles, but also offers an alternative tool for monitoring multilayer buildup. It may also reveal the potential of CE in fields other than analytical separation.  相似文献   

5.
Layer-by-layer(LBL)self-assembly method was used to fabricate siliceous ultrathin films by using polyhedral oligomeric silsesquioxanes as building blocks.Ammonium salt of kctasilsesquioxane acid (OSi8) and bply(diallyldimethylammonium chloride)(PDDA) were altermately assembled onto CaF2 slide to form nanocomposite multilqyers,Linear build-up of the LBL films was confirmed by UV-Vis spectroscopy.IR spectrum suggests existence of OSi8 and PDDA in the LBL films.Atomic force microscopic surface topography of the LBL films indicates the OSi8 covers the entire surface of the topmost layer and shows a granular morphology.  相似文献   

6.
《先进技术聚合物》2018,29(1):151-159
Super porous gum Arabic (GA) cryogels were synthesized by crosslinking of natural GA with divinyl sulfone at cryogenic conditions, −20°C for potential biomedical applications. Humic acid (HA) nanoparticles were also prepared by using degradable and biocompatible crosslinkers such as trimethylolpropane triglycidyl ether, poly(ethylene glycol) diglycidyl ether, and trisodium trimetaphosphate in a single step and then entrapped within GA cryogel network as GA/HA particle cryogel. Furthermore, GA/HA cryogel was used as a template for Ag, Cu, and Fe nanoparticle preparation, and their antimicrobial properties were tested against Escherichia coli, Staphylococcus aureus, and Bacillus subtilis strains. The minimum inhibition concentration values of Ag and Cu nanoparticle‐loaded GA/HA cryogel composites were determined as 10 mg mL−1. Furthermore, the blood compatibility tests such as hemolysis and blood clotting indexes were determined for GA cryogels and found to be more compatible with 0.08 ± 0.01% hemolysis and 89.4 ± 6.1 blood clotting values, whereas the hemolysis of the Ag, Cu, and Fe nanoparticle‐loaded GA/HA Ag, Cu, and Fe metal nanoparticle cryogel composites decreased in the order of Fe > Cu > Ag nanoparticles.  相似文献   

7.
Bimetallic nanoparticles (NPs) are known to exhibit enhanced optical and catalytic properties that can be optimized by tailoring NP composition, size, and morphology. Galvanic deposition of a second metal onto a primary metal NP template is a versatile method for fabricating bimetallic NPs using a scalable, solution-based synthesis. We demonstrate that the galvanic displacement reaction pathway can be controlled through appropriate surface modification of the NP template. To synthesize bimetallic Au-Ag NPs, we used colloidal Ag NPs modified by layer-by-layer (LBL) assembled polyelectrolyte layers to template the reduction of HAuCl(4). NPs terminated with positively and negatively charged polyelectrolytes yield highly contrasting morphologies and Au surface concentrations. We propose that these charged surface layers control galvanic charge transfer by controlling nucleation and diffusion at the deposition front. This surface-directed synthetic strategy can be advantageously used to tailor both overall NP morphology and Au surface concentrations.  相似文献   

8.
Marquis BJ  Liu Z  Braun KL  Haynes CL 《The Analyst》2011,136(17):3478-3486
Since noble metal nanoparticles are increasingly found in consumer goods, there is a need for information about potential impacts of these nanoparticles on cellular function to avoid environmental and health risks associated with exposure. In this study, spherical Au and Ag nanoparticles of similar size were synthesized and modified to assess the effects of ζ-potential on immune cell function. Nanoparticle ζ-potential was controlled by employing surfactant exchange to generate nanoparticles with positive or negative surface charge. Mouse peritoneal mast cells (MPMCs) were then exposed to 5-15 μg ml(-1) of these nanomaterials, and uptake was assessed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Uptake for positively charged nanoparticles was more efficient than for negatively charged nanomaterials, and all nanoparticles were taken up in a concentration-dependent manner. Following uptake, MPMC degranulation function was assessed using carbon-fiber microelectrode amperometry (CFMA), showing decreased quantal secretion of serotonin by MPMCs exposed to the positively charged Au nanoparticles and negatively charged Ag nanoparticles. The overall efficiency of the degranulation process (indicated by amperometric spike frequency) decreased for all Au-exposed MPMCs. However, only the negatively charged version of the Ag nanomaterial resulted in decreased MPMC degranulation efficiency. Further studies revealed that ionic Ag was partially responsible for the observed effects. Overall, these studies reveal the complex nature of interactions between noble metal nanomaterials and cells that result in perturbed cellular function and illustrate the necessity of thorough nanoparticle characterization for interpretation of cellular function assays.  相似文献   

9.
Yang T  Zhang W  Du M  Jiao K 《Talanta》2008,75(4):987-994
2,6-Pyridinedicarboxylic acid (PDC) was electropolymerized on the glassy carbon electrode (GCE) surface combined with carboxylic group-functionalized single-walled carbon nanotubes (SWNTs) by cyclic voltammetry (CV) to form PDC-SWNTs composite film, which was rich in negatively charged carboxylic group. Then, poly(diallyldimethyl ammonium chloride) (PDDA), a linear cationic polyelectrolyte, was electrostatically adsorbed on the PDC-SWNTs/GCE surface. DNA probes with negatively charged phosphate group at the 5' end were immobilized on the PDDA/PDC-SWNTs/GCE due to the strong electrostatic attraction between PDDA and phosphate group of DNA. It has been found that modification of the electrode with PDC-SWNTs film has enhanced the effective electrode surface area and electron-transfer ability, in addition to providing negatively charged groups for the electrostatic assembly of cationic polyelectrolyte. PDDA plays a key role in the attachment of DNA probes to the PDC-SWNTs composite film and acts as a bridge to connect DNA with PDC-SWNTs film. The cathodic peak current of methylene blue (MB), an electroactive label, decreased obviously after the hybridization of DNA probe (ssDNA) with the complementary DNA (cDNA). This peak current change was used to monitor the recognition of the specific sequences related to PAT gene in the transgenic corn and the polymerase chain reaction (PCR) amplification of NOS gene from the sample of transgenic soybean with satisfactory results. Under optimal conditions, the dynamic detection range of the sensor to PAT gene target sequence was from 1.0x10(-11) to 1.0x10(-6) mol/L with the detection limit of 2.6x10(-12) mol/L.  相似文献   

10.
Surface modification of poly(ethylene terephthalate) (PET) film was performed by surface hydrolysis and layer-by-layer (LBL) assembly followed a mechanism of electrostatic adsorption of oppositely charged polymers, exemplified with chitosan and chondroitin sulfate (CS). Hydrolysis of PET in concentrated alkaline solution produced a carboxyl-enriched surface. The changes of weight loss and surface chemistry, morphology and wettability were monitored and verified by UV-vis spectroscopy, atomic force microscopy (AFM) and water contact angle. Assembly of positively charged chitosan and negatively charged CS was then conducted in a LBL manner to create multilayers on the hydrolyzed PET film. The process of layer growth and oscillation of surface wettability were monitored by UV-vis spectroscopy and water contact angle measurement, respectively. In vitro cell culture revealed that the adherence of endothelial cells was significantly enhanced on the biomacromolecules-modified PET film with preserved endothelial cell function, in particular on those assembled with larger number of chitosan/CS layers. However, with regard to cell proliferation and viability properties after cultured for 4 days, minor difference was determined between the modified and the unmodified PET films.  相似文献   

11.
The principle of alternate adsorption can be used to design and control specific molecular architectures1. Protein-polyion layer-by-layer assembly opens a possibility of organizing proteins with specific molecular architectural plan1 and studying redox proteins with electrochemical methods2. Recently, we reported electrochemistry of layer-by-layer {PSS/Mb}n films grown on PG electrodes1. In this work, layer-by-layer {PDDA/Hb}n films were fabricated on PG electrodes. Electrochemistry and …  相似文献   

12.
羟基磷灰石与牛血清白蛋白相互作用的原位红外光谱研究   总被引:2,自引:0,他引:2  
应用原位(in situ)全反射红外光谱研究牛血清白蛋白在电化学法制备的羟基磷灰石表面的吸附和成键行为, 探索电化学法制备的HA生物材料/生物环境界面过程和生物相容性的微观本质.  相似文献   

13.
In this paper, we propose two new approaches for preparing active substrates for surface-enhanced Raman scattering (SERS). In the first approach (method 1), one transfers AgI nanoparticles capped by negatively charged mercaptoacetic acid from a AgI colloid solution onto a quartz slide and then deoxidizes AgI to Ag nanoparticles on the substrate. The second approach (method 2) deoxidizes AgI to Ag nanoparticles in a colloid solution and then transfers the Ag nanoparticles capped by negatively charged mercaptoacetic acid onto a quartz slide. By transfer of the AgI/Ag nanoparticles from the colloid solutions to the solid substrates, the problem of instability of the colloid solutions can largely be overcome. The films thus prepared by both approaches retain the merits of metal colloid solutions while they discharge their shortcomings. Accordingly, the obtained Ag particle films are very suitable as SERS active substrates. SERS active substrates with different coverages can be formed in a layer-by-layer electrostatic assembly by exposing positively charged surfaces to the colloid solutions containing oppositely charged AgI/Ag nanoparticles. The SERS active substrates fabricated by the two novel methods have been characterized by means of atomic force microscopy (AFM) and ultraviolet-visible (UV-vis) spectroscopy. The results of AFM and UV-vis spectroscopy show that the Ag nanoparticles grow with the increase in the number of coverage and that most of them remain isolated even at high coverages. Consequently, the surface optical properties are dominated by the absorption due to the isolated Ag nanoparticles. The relationship between SERS intensity and surface morphology of the new active substrates has been investigated for Rhodamine 6G (R6G) adsorbed on them. It has been found that the SERS enhancement depends on the size and aggregation of the Ag particles on the substrates. Especially, we can obtain a stronger SERS signal from the substrate prepared by method 1, implying that for the metal nanoparticles capped with stabilizer molecules such as mercaptoacetic acid, the in situ deoxidization in the film is of great use in preparing SERS active substrates. Furthermore, we have found that the addition of Cl- into the AgI colloid solution changes the surface morphology of the SERS active substrates and favors stronger SERS enhancement.  相似文献   

14.
Adsorption of nanoparticles at the solid-liquid interface   总被引:1,自引:0,他引:1  
The adsorption of differently charged nanoparticles at liquid-solid interfaces was investigated by in situ X-ray reflectivity measurements. The layer formation of positively charged maghemite (γ-Fe(2)O(3)) nanoparticles at the aqueous solution-SiO(2) interface was observed while negatively charged gold nanoparticles show no adsorption at this interface. Thus, the electrostatic interaction between the particles and the charged surface was determined as the driving force for the adsorption process. The data analysis shows that a logarithmic particle size distribution describes the density profile of the thin adsorbed maghemite layer. The size distribution in the nanoparticle solution determined by small angle X-ray scattering shows an average particle size which is similar to that found for the adsorbed film. The formed magehemite film exhibits a rather high stability.  相似文献   

15.
We have fabricated gold nanoparticle (AuNP) arrays on indium-tin oxide (ITO) substrates in a nearly one-dimensional fashion. AuNPs were site-selectively immobilized on ITO of which the surface had been patterned by a nanolithography process based on scanning probe microscopy. The fabricated nanoscale lines covered with aminosilane self-assembled monolayer served as chemisorption sites for citrate-stabilized AuNPs of 20 nm in diameter, accordingly, AuNP nanolines with a thickness of single nanoparticle diameter were spontaneously assembled on the lines. In this 1D array, the AuNPs were almost separated from each other due to the electrostatic repulsion between their negatively charged surface layers. Furthermore, a reorganization process of the immobilized AuNP arrays has been successfully demonstrated by replacing each AuNP's surface layer from citric acid to dodecanethiol. By this process, the AuNPs lost their electrostatic repulsion and became hydrophobic so as to be attracted to each other through hydrophobic interaction, resulting in reorganization of the AuNP array. By repeating the deposition and reorganization cycle, AuNPs were more densely packed. The optical absorption peak of the arrays due to their plasmonic resonance was found to shift from 526 to 590 nm in wavelength with repeating cycles, indicating that the resonance manner was changed from the single nanoparticle mode to the multiple particle mode with interparticle coupling.  相似文献   

16.
Multilayered manganese oxide nanocomposites intercalated with strong (poly(diallyldimethylammonium) chloride, PDDA) and weak (poly(allylamine hydrochloride), PAH) polyelectrolytes can be produced on polycrystalline platinum electrode in a thin film form by a simple, one-step electrochemical route. The process involves a potentiostatic oxidation of aqueous Mn2+ ions at around +1.0 V (vs Ag/AgCl) in the presence of polyelectrolytes. Fully charged PDDA polycations are accommodated tightly in the interlayer space by electrostatic interaction with negative charges on the manganese oxide layers, leading to an interlayer distance of 0.97 nm. The layered film prepared with PAH has a larger polymer content (PAH/Mn molar ratio of 0.98) than that (PDDA/Mn molar ratio of 0.43) made with PDDA because of the smaller charging degree of PAH, exhibiting a larger interlayer distance (1.19 nm). The interlayer PAH contains neutral (-NH2) and positively charged (-NH3(+)) amine groups, and the -NH3(+) groups are associated with Cl- (to generate -NH3(+) Cl- ion pairs) as well as the negatively charged manganese oxide layers. Both polyelectrolytes once incorporated were not ion exchanged with small cations in solution. The layered structure of PDDA/MnO(x) was collapsed during the reduction process in a KCl electrolyte solution, accompanying an expansion of the interlayer as a result of incorporation of K+ ions for charge neutrality. On the contrary, the layered PAH/MnO(x) film showed a good electrochemical response due to the redox reaction of Mn3+/Mn4+ couple with no change in the structure. X-ray photoelectron spectroscopy revealed that, in this case, excess negative charges generated on the manganese oxide layers upon reduction can be balanced by the protons being released from the -NH3(+) Cl- sites in the interlayer PAH; the Cl- anions becoming unnecessary are inevitably excluded from the interlayer, and vice versa upon oxidation.  相似文献   

17.
We describe a general one-step facile method for depositing gold nanoparticle (GNP) thin films onto any type of substrates by the in situ reduction of AuCl(3) using a newly designed redox-active ionic liquid (IL), tetrabutylphosphonium citrate ([TBP][Ci]). Various substrates such as positively charged glass, negatively charged glass/quartz, neutral hydrophobic glass, polypropylene, polystyrene, plain paper, and cellophane paper are successfully coated with a thin film of GNPs. This IL ([TBP][Ci]) is prepared by the simple neutralization of tetrabutylphosphonium hydroxide with citric acid. We also demonstrate that the [TBP][Ci] ionic liquid can be successfully used to generate GNPs in an aqueous colloidal suspension in situ. The deposited GNP thin films on various surfaces are made up of mostly discrete spherical GNPs that are well distributed throughout the film, as confirmed by field-emission scanning electron microscopy. However, it seems that some GNPs are arranged to form arrays depending on the nature of surface. We also characterize these GNP thin films via UV-vis spectroscopy and X-ray diffractometry. The as-formed GNP thin films show excellent stability toward solvent washing. We demonstrate that the thin film of GNPs on a glass/quartz surface can be successfully used as a refractive index (RI) sensor for different polar and nonpolar organic solvents. The as-formed GNP thin films on different surfaces show excellent catalytic activity in the borohydride reduction of p-nitrophenol.  相似文献   

18.
王悦辉  周济  王婷 《无机化学学报》2007,23(8):1485-1490
Stable aqueous dispersive colloidal Ag nanoparticles were prepared by reducing silver nitrate with sodium borohydride in the presence of 3-mercaptopropionic acid. The formation process of the Ag nanoparticles was investigated by UV-Visible spectroscopy and transmission electron microscopy. The results show that the spherical and rodlike particles and aggregates are formed in the initial stage of the reaction, then the rodlike particles and aggregates are gradually decomposed into small spherical particles, and the final obtained Ag nanoparticles with an average size of 8 nm are in uniform shapes and narrow size distribution, and the colloid remains stable for more than one month, which makes it convenient for use in practice. The presence of capping agent plays an extra role over nanoparticles stabilization and morphology. The presence of capping agent on the surface of Ag nanoparticle is confirmed by the X-ray photoelectron spectroscopy. It is found that Ag nanoparticles are negatively charged in alkaline condition, whereas they are positively charged in acid condition. Electrosteric effect is responsible for their long-term stability.  相似文献   

19.
Wang J  Liu G  Lin Y 《The Analyst》2006,131(4):477-483
We report a flow injection amperometric choline biosensor based on the electrostatic assembly of the choline oxidase (ChO) enzyme and a bienzyme of ChO and horseradish peroxidase (HRP) onto multi-wall carbon nanotubes (MWCNT) modified glassy carbon (GC) electrodes. These choline biosensors were fabricated by immobilization of enzymes on the negatively charged MWCNT surface through alternately assembling a cationic poly(diallydimethylammonium chloride) (PDDA) layer and an enzyme layer. Using this layer-by-layer assembling approach, a bioactive nanocomposite film of PDDA/ChO/PDDA/HRP/PDDA/CNT (ChO/HRP/CNT) and PDDA/ChO/PDDA/CNT (ChO/CNT) was fabricated on the GC surface. Owing to the electrocatalytic effect of carbon nanotubes, the measurement of faradic responses resulting from enzymatic reactions has been realized at low potential with acceptable sensitivity. The ChO/HRP/CNT biosensor is more sensitive than the ChO/CNT one. Experimental parameters affecting the sensitivity of biosensors, e.g., applied potential, flow rate, etc., were optimized and potential interference was examined. The response time for this choline biosensor is fast (few seconds). The linear range of detection for the choline biosensor is from 5.0 x 10(-5) to 5.0 x 10(-3) M and the detection limit is about 1.0 x 10(-5) M.  相似文献   

20.
Qingfen Luan  Jun Li  Xin Yao 《Electroanalysis》2009,21(16):1799-1804
(PDDA/CdTe)n layer‐by‐layer (LBL) film immobilized with Fe(CN)63? was fabricated on the gold electrode. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to investigate the electrochemical properties of this film. The peak current of the immobilized Fe(CN)63? increased as the number of the bilayers increased and was proportional to the scan rate. Compared with pure (PDDA/CdTe)n and (PDDA/PSS)n LBL film, Fe(CN)63? immobilized (PDDA/CdTe)n LBL film had good electron transfer ability. The immobility of Fe(CN)63? into the film was attributed to its interaction with Cd2+ on the surface of CdTe QDs. Fe(CN)63? also can interact with other metal ions, which would make Fe(CN)63? release from the film. The concentrations of metal ions will affect the CV response of Fe(CN)63? immobilized LBL film. It has provided a novel prototype of device or sensor for quantitative detection of metal ions.  相似文献   

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