Imaging of metal ion dissolution and electrodeposition by anodic stripping voltammetry-scanning electrochemical microscopy

We have developed a new imaging method for scanning electrochemical microscopy (SECM) employing fast-scan anodic stripping voltammetry (ASV) to provide sensitive and selective imaging of multiple chemical species at interfaces immersed in solution. A rapid cyclic voltammetry scan (100 V/s) is used along with a short preconcentration time (300-750 ms) to allow images to be acquired in a normal SECM time frame. A Hg-Pt film electrode is developed having an equivalent Hg thickness of 40 nm that has good sensitivity at short preconcentration times and also retains thin-film behavior with high-speed voltammetric stripping. Fast-scan anodic stripping currents are shown to be linear for 1-100 microM of Pb (2+) and Cd (2+) solutions using a preconcentration time of 300 ms. SECM images showing the presence of Pb (2+) and Cd (2+) at concentrations as low as 1 microM are presented. In addition, a single ASV-SECM image is shown to produce unique concentration maps indicating Cd (2+) and Pb (2+), generated in situ from a corroding sample, while simultaneously detecting the depletion of O 2 at this sample. The transient voltammetric response at the film electrode is simulated and shows good agreement with the experimental behavior. We discuss the behavior of images and concentration profiles obtained with different imaging conditions and show that mass-transport limitations in the tip-substrate gap can induce dissolution. ASV-SECM can thus be used to detect and study induced dissolution not only at bulk metal surfaces but also on underpotential deposition layers, in this case Cd and Pb on Pt. In addition, we discuss how surface diffusion phenomena may relate to the observed ASV-SECM behavior.     

Selective deposition of CdSe nanoparticles on reduced graphene oxide to understand photoinduced charge transfer in hybrid nanostructures

A linker-free reduced graphene oxide (R-GO)-CdSe nanoparticle (CdSe NP) hybrid nanostructure was synthesized using a chemical vapor deposition method. CdSe NPs were selectively deposited on the surface of R-GO with controlled NP size and coverage. The distribution and morphology of CdSe NPs on R-GO were characterized by scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The resulting hybrid nanostructure exhibited photoresponse to both laser and simulated sunlight AM 1.5G excitation. The hybrid structure with low CdSe NP coverage showed distinct photoresponse times in air, N(2), NH(3), and NO(2), while high CdSe NP coverage led to nearly constant but three orders of magnitude smaller response time in all gases. Such a difference in photoresponse as a function of NP coverage is attributed to the energy band bending at the interface between the R-GO and the CdSe NP. The selective deposition of CdSe NPs on R-GO and the understanding of the subsequent photoinduced charge transfer can potentially lead to high-performance optoelectronic devices.     

Anodic stripping voltammetry enhancement by redox magnetohydrodynamics

The effect of an external magnetic field on linear scan anodic stripping voltammetry (ASV) in solutions of 10(-6)-10(-7) M concentrations of lead, cadmium, and copper at mercury films on glassy carbon electrodes has been investigated. A high concentration of Hg(2+) was added to the analyte solution to induce a large cathodic current during the deposition step. Therefore, a large Lorentz force from the net flux of charge through the magnetic field resulted in convection due to magnetohydrodynamics. The faster delivery of analytes to the mercury film electrode during deposition caused an increase in the anodic stripping peaks. The effect of varying Hg(2+) concentrations (0-60 mM) and magnetic field strengths (0-1.77 T) on the enhancement of the stripping peaks was investigated. Enhancements as large as 129% for peak currents and 167% for peak areas were observed. An enhancement of approximately 100% was observed when 60 mM Fe(3+) replaced high concentrations of Hg(2+). This method of convection exhibits promise for small-volume ASV analysis with possible improved limits of detection and decreased preconcentration times.     

Ultrasensitive flow injection chemiluminescence detection of DNA hybridization using signal DNA probe modified with Au and CuS nanoparticles

A novel and sensitive flow injection chemiluminescence assay for sequence-specific DNA detection based on signal amplification with nanoparticles (NPs) is reported in the present work. The "sandwich-type" DNA biosensor was fabricated with the thiol-functionalized capture DNA first immobilized on an Au electrode and hybridized with one end of target DNA, the other end of which was recognized with a signal DNA probe labeled with CuS NPs and Au NPs on the 3'- and 5'-terminus, respectively. The hybridization events were monitored by the CL intensity of luminol-H2O2-Cu(2+) after the cupric ions were dissolved from the hybrids. We demonstrated that the incorporation of Au NPs in this sensor design significantly enhanced the sensitivity and the selectivity because a single Au NP can be loaded with hundreds of signal DNA probe strands, which were modified with CuS NPs. The ratios of Au NPs, signal DNA probes, and CuS NPs modified on the gold electrode were approximately 1/101/103. A preconcentration process of cupric ions performed by anodic stripping voltammetry technology further increased the sensor performance. As a result of these two combined effects, this DNA sensor could detect as low as femtomolar target DNA and exhibited excellent selectivity against two-base mismatched DNA. Under the optimum conditions, the CL intensity was increased with the increase of the concentration of target DNA in the range of 2.0 x 10(-14)-2.0 x 10(-12) M. A detection limit of 4.8 x 10(-15) M target DNA was achieved.     

Directed self-assembly of nanogold using a chemically modified nanopatterned surface

Electron-beam lithography (EBL) was used to define an aminosilane nanopatterned surface in order to electrostatically self-assemble gold nanoparticles (Au NPs). The chemically modified nanopatterned surfaces were immersed into a Au NP solution to allow the Au NPs to self-assemble. Equilibrium self-assembly was achieved in only 20 min. The number of Au NPs that self-assembled on an aminosilane dot was controlled by manipulating the diameters of both the Au NPs and the dots. Adding salt to the Au NP solution enabled the Au NPs to self-assemble in greater numbers on the same sized dot. However, the preparation of the Au NP solution containing salt was sensitive to spikes in the salt concentration. These spikes led to aggregation of the Au NPs and non-specific deposition of Au NPs on the substrate. The Au NP patterned surfaces were immersed in a sodium hydroxide solution in order to lift-off the patterned Au NPs, but no lift-off was observed without adequate physical agitation. The van der Waals forces are too strong to allow for lift-off despite the absence of electrostatic forces.     

Sensitive immunoassay of a biomarker tumor necrosis factor-alpha based on poly(guanine)-functionalized silica nanoparticle label

A novel electrochemical immunosensor for the detection of tumor necrosis factor-alpha (TNF-alpha) based on poly(guanine)-functionalized silica nanoparticles (NPs) label is presented. The detection of mouse TNF-alpha via immunological reaction is based on a dual signal amplification: (1) a large amount of guanine residues introduced on the electrode surface through sandwich immunoreaction and poly(guanine)-functionalized silica NP label; (2) Ru(bpy)3(2+)-induced catalytic oxidation of guanine, which results in great enhancement of anodic current. The synthesized silica NP conjugates were characterized with atomic force microscopy, X-ray photoelectron spectroscopy, and electrochemistry. These experiments confirmed that poly(guanine) and avidin were immobilized on the surface of silica NPs. The performance of the electrochemical immunosensor was evaluated and some experiment parameters (e.g., concentration of Ru(bpy)3(2+), incubation time of TNF-alpha, etc.) were optimized. The detection limit for TNF-alpha is found to be 5.0 x 10(-11) g mL(-1) (2.0 pM), which corresponds to 60 amol of TNF-alpha in 30 microL of sample. This immunosensor based on the poly(guanine)-functionalized silica NP label offers great promise for rapid, simple, cost-effective analysis of biological samples.     

Localized surface plasmon resonance of single silver nanoparticles studied by dark-field optical microscopy and spectroscopy

Localized surface plasmon resonance (LSPR) of Ag nanoparticles (NPs) with different shapes and disk-shaped Ag NP pairs with varying interparticle distance is studied using dark-field optical microscopy and spectroscopy (DFOMS). Disk-, square-, and triangular-shaped Ag NPs were fabricated on indium tin oxide-coated glass substrates by electron beam lithography. The LSPR spectra collected from single Ag NPs within 5×5 arrays using DFOMS exhibited pronounced redshifts as the NP shape changed from disk to square and to triangular. The shape-dependent experimental LSPR spectra are in good agreement with simulations using the discrete dipole approximation model, although there are small deviations in the peak wavelengths for square- and triangular-shaped NPs. The LSPR spectra of disk-shaped Ag NP pairs with varying interparticle distances were acquired from five different locations across the pair axis. It was clearly observed that the LSPR wavelength redshifts as the interparticle distance decreases, indicating a strong interaction when two Ag NPs are close to each other.     

ZnO nanorods arrays with Ag nanoparticles on the (002) plane derived by liquid epitaxy growth and electrodeposition process

Well-aligned ZnO nanorods (NRs) arrays with Ag nanoparticles (NPs) on the (002) plane are obtained by combining a liquid epitaxy technique with an electrodeposition process. Cyclic voltammetry study is employed to understand the electrochemical behaviors of the electrodeposition system, and potentiostatic method is employed to deposit silver NPs on the ZnO NRs in the electrolyte with an Ag⁺ concentration of 1 mM. X-ray diffraction analysis is used to study the crystalline properties of the as-prepared samples, and energy dispersive X-ray is adopted to confirm the composition at the surface of the deposited samples. Results indicate only a small quantity of silver can be deposited on the surface of the samples. Effect of the deposition potential and time on the morphological properties of the resultant Ag NPs/ZnO NRs are investigated in detail. Scanning electron microscopy images and transmission electron microscopy images indicate that the Ag NPs deposited on the (002) plane of the ZnO NRs with a large dispersion in diameter can be obtained by a single potentiostatic deposition process, while dense Ag NPs with a much smaller diameter dispersion on the top of the ZnO NRs, most of which locate on the conical tip of the ZnO NRs, can be obtained by a two-potentiostatic deposition process, The mechanism of this deposition process is also suggested.     

Antimony film electrode for electrochemical stripping analysis

In this work, an antimony film electrode (SbFE) is reported for the first time as a possible alternative for electrochemical stripping analysis of trace heavy metals. The SbFE was prepared in situ on a glassy carbon substrate electrode and employed in combination with either anodic stripping voltammetry or stripping chronopotentiometry in nondeaerated solutions of 0.01 M hydrochloric acid (pH 2). Several key operational parameters influencing the electroanalytical response of SbFE were examined and optimized, such as deposition potential, deposition time, and composition of the measurement solution. The SbFE exhibited well-defined and separated stripping signals for both model metal ions, Cd(II) and Pb(II), surrounded with low background contribution and a relatively large negative potential range. The electrode revealed good linear behavior in the examined concentration range from 20 to 140 microg L-1 for both test metal ions, with a limit of detection (3sigma) of 0.7 microg L-1 for Cd(II) and 0.9 microg L-1 for Pb(II) obtained after a 120 s deposition step, and good reproducibility, with a relative standard deviation (RSD) of +/-3.6% for Cd(II) and +/-6.2% for Pb(II) (60 microg L-1, n = 12). When comparing the SbFE with the commonly used mercury film electrode and recently introduced bismuth film electrode, the newly proposed electrode offers a remarkable performance in more acidic solutions (pH < or = 2), which can be advantageous in electrochemical analysis of trace heavy metals, hence contributing to the wider applicability of electrochemical stripping techniques in connection with "mercury-free" electrodes.     

Non-chemical approach toward 2D self-assemblies of Ag nanoparticles via cold plasma treatment of substrates

The nano-modification of selected substrates by means of atmospheric cold plasma treatment was exploited for the two-dimensional (2D) self-assembling of silver nanoparticles (Ag NPs). Such a useful combination of the cold plasma treatment of substrate surface and an immediate easy deposition of Ag NPs creating the 2D self-assemblies on the substrates is published for the first time, to the best of our knowledge. Except for the cold plasma treatment, mainly the following parameters influenced the resulting NP assemblies: the choice of solvent mixture, concentration of Ag NP dispersions, and the deposition technique. The 2D self-assemblies of Ag NPs, providing the same work function as a Ag electrode, were formed on the cold plasma-treated substrates when a drop-casting technique was employed. The possibility of an easy preparation of the Ag NP 2D self-assemblies on substrates without using any chemical agents and/or evaporating chamber could be exploited, e.g.?in photovoltaic and light-emitting diode devices.     

Metal nanoparticle plasmon-enhanced light-harvesting in a photosystem I thin film

Silver metal nanoparticle (NP) enhanced fluorescence is investigated in thin films of cyanobacterial Photosystem I trimer complexes (PSI) by correlating confocal laser scanning microscopy, dark-field imaging, and fluorescence lifetime measurements. PSI represents an interesting light-harvesting complex with a 20 nm diameter that is not uniformly contained within the surface-localized plasmon field of the NPs. With weak far-field illumination, 5- to 20-fold fluorescence enhancement is observed for PSI complexes adjacent to NPs, arising from efficient nanoparticle light collection and subsequent localized, surface plasmon excitation of PSI. Enhanced PSI fluorescence is detected most prominently near "rafts" of aggregated NPs that more completely fill the confocal field of view. These results demonstrate opportunities to probe energy transfer within photosynthetic complexes using plasmonic excitation and to design nanostructures for optimizing artificial light-harvesting systems.     

Quinolino-triazole linked gold nanoparticles as sensitive 'turn-on' fluorescent Cd(2+) probes

Quinoline derivatives were brought into the surface of gold nanoparticles (Au NPs) through click chemistry. The fluorescence was quenched by Au NPs because of electron transfer between Au NPs and quinoline. However, upon addition of Cd(2+) to the quinoline-triazole Au NP solution, it exhibited an effective switch-on fluorescence response, owing to the coordination between quinoline and Cd(2+) which can efficiently block the electron transfer. What's more, the fluorescent sensor can effectively detect Cd(2+) in aqueous solution with a detection limit of 1.0 × 10(-5) M.     

Development of a method for total inorganic arsenic analysis using anodic stripping voltammetry and a Au-coated, diamond thin-film electrode

We demonstrate that a Au-coated, boron-doped, diamond thin-film electrode provides a sensitive, reproducible, and stable response for total inorganic arsenic (As(III) and As(V)) using differential pulse anodic stripping voltammetry (DPASV). As is preconcentrated with Au on the diamond surface during the deposition step and detected oxidatively during the stripping step. Au deposition was uniform over the electrode surface with a nominal particle size of 23 +/- 5 nm and a particle density of 109 cm-2. The electrode and method were used to measure the As(III) concentration in standard and river water samples. The detection figures of merit were compared with those obtained using conventional Au-coated glassy carbon and Au foil electrodes. The method was also used to determine the As(V) concentration in standard solutions after first being chemically reduced to As(III) with Na2SO3, followed by the normal DPASV determination of As(III). Sharp and symmetric stripping peaks were generally observed for the Au-coated diamond electrode. LODs were 0.005 ppb (S/N = 3) for As(III) and 0.08 ppb (S/N = 3) for As(V) in standard solutions. An As(III) concentration of 0.6 ppb was found in local river water. The relative standard deviation of the As stripping peak current for river water was 1.5% for 10 consecutive measurements and was less than 9.1% over a 10-h period. Excellent electrode response stability was observed even in the presence of up to 5 ppm of added humic acid. In summary, the Au-coated diamond electrode exhibited better performance for total inorganic As analysis than did Au-coated glassy carbon or Au foil electrodes. Clearly, the substrate on which the Au is supported influences the detection figures of merit.     

Optical and structural characterization of silver islands films on glass substrates

Metal island films (MIFs) of Ag on glass substrates were fabricated by the e-beam evaporation technique. The dependence of the surface plasmon (SP) absorption properties on the deposition mass thickness and substrate temperature was quantified. The structural and optical characterization of the MIFs, obtained using spectrometry, grazing-incidence small-angle X-ray scattering (GISAXS) and atomic force microscopy (AFM) evidences the evolution of SP characteristics depending on the fabrication parameters: the red shift of the absorption peaks with the increase of deposition thickness accompanied by peak widening and the blue-shift of peaks with the increase of deposition temperature followed by the peak narrowing. These findings were explained by the differences in the concentration, shape and size of the obtained silver islands.     

Ta/BDD薄膜材料电极在检测苯胺中的应用

制作钽衬底掺硼金刚石薄膜材料电极(Ta/BDD),并利用此薄膜材料电极为工作电极通过阴极溶出伏安法检测水中的苯胺.用热丝化学气相沉积(HFCVD)方法沉积Ta/BDD薄膜电极,扫描电镜和拉曼光谱表明电极具有良好的物理性质,循环扫描测试表明电极具有宽的电势窗口4.1V(-1.8～+2.3V vs SCE)和低背景电流,此特性对于电化学检测有着明显的优势.发现苯胺在氧化处理的Ta/BDD电极上有可逆的氧化还原峰,检测过程中未发生电极钝化现象.Ta/BDD电极在酸性介质中苯胺检测效果较明显,苯胺在1～40靘ol/L范围内浓度与溶出峰电流值有较好的线性关系.     

Amplified surface plasmon resonance and electrochemical detection of Pb2+ ions using the Pb2+-dependent DNAzyme and hemin/G-quadruplex as a label

The hemin/G-quadruplex nanostructure and the Pb(2+)-dependent DNAzyme are implemented to develop sensitive surface plasmon resonance (SPR) and electrochemical sensing platforms for Pb(2+) ions. A complex consisting of the Pb(2+)-dependent DNAzyme sequence and a ribonuclease-containing nucleic acid sequence (corresponding to the substrate of the DNAzyme) linked to a G-rich domain, which is "caged" in the complex structure, is assembled on Au-coated glass surfaces or Au electrodes. In the presence of Pb(2+) ions, the Pb(2+)-dependent DNAzyme cleaves the substrate, leading to the separation of the complex and to the self-assembly of the hemin/G-quadruplex on the Au support. In one sensing platform, the Pb(2+) ions are analyzed by following the dielectric changes at the surface as a result of the formation of the hemin/G-quadruplex label using SPR. This sensing platform is further amplified by the immobilization of the sensing complex on Au NPs (13 nm) and using the electronic coupling between the NPs and the surface plasmon wave as an amplification mechanism. This method enables the sensing of Pb(2+) ions with a detection limit that corresponds to 5 fM. The second sensing platform implements the resulting hemin/G-quadruplex as an electrocatalytic label that catalyzes the electrochemical reduction of H(2)O(2). This method enables the detection of Pb(2+) with a detection limit of 1 pM. Both sensing platforms reveal selectivity toward the detection of Pb(2+) ions.     

Factors influencing redox magnetohydrodynamic-induced convection for enhancement of stripping analysis

Factors affecting the use of redox magnetohydrodynamics (MHD) to enhance the stripping analysis response to heavy metals have been investigated. The analytes were Pb2+, Cd2+, Cu2+, and Tl+ at concentrations ranging from 5 nM to 2 microM. Co-deposition of analytes with Hg2+ (to form a thin Hg film electrode) occurs along with reduction of a high concentration of Fe3+. The Fe3+ provides the high cathodic current necessary to produce a significant Lorentz force, and therefore enhanced convection and larger stripping signals and sensitivities, when the analysis is performed in the presence of an external magnetic field. The effects of varying Fe3+ concentration (1-100 mM), working electrode size (10 microm-3 mm), and magnetic field strengths (0-1.77 T) generated with electromagnets and NdFeB permanent magnets were investigated. Using 100 mM Fe3+ as the MHD-generating redox species at a 3-mm working electrode and in a magnetic field of 1.77 T, peak areas from linear sweep voltammetry were increased by as much as 159 +/- 5%, compared to the signal obtained in the absence of a magnetic field. Experimental detection limits as low as 5 nM were achieved with only a 1-min preconcentration time. A field strength as low as 0.12 T offers some signal enhancement with 100 mM Fe3+. While linear scan anodic stripping voltammetry was used primarily to obtain the signals after the deposition step, potentiometric stripping analysis was also investigated. Redox MHD is an attractive alternative convection method for applications involving sample volumes too small for mechanical stirring or for in-field applications using portable devices that cannot be complicated by the instrumentation required for mechanical stirring.     

Forming dense arrays of gold nanoparticles in thin films of yttria stabilized zirconia by magnetron sputtering

Layers of Au nanoparticles (NPs) were formed in films of yttria stabilized zirconia (YSZ) on fusedquartz substrates by layer-by-layer magnetron deposition with subsequent annealing. The obtained structures were studied by applying high-resolution transmission electron microscopy (TEM) to transverse sections and using optical absorption spectroscopy. TEM studies revealed the formation of Au NPs with a diameter of 2?3 nm concentrated in a thin layer within the YSZ film. The optical absorption spectra of the studied samples exhibited peaks of resonance plasmon absorption in Au NPs with a maximum wavelength of ~650 nm. The dependences of geometric and structural parameters of Au NP arrays (size, density, thickness of the Au NP layer, etc.) on the formation conditions were determined, and the regimes of fabrication of dense Au NP arrays that allow for collective plasmon excitations were identified.     

Electrochemical behavior of gold nanoparticles modified nitrogen incorporated tetrahedral amorphous carbon and its application in glucose sensing

Gold nanoparticles (NPs) with 10-50 nm in diameter were synthesized on nitrogen incorporated tetrahedral amorphous carbon (ta-C:N) thin film electrode by electrodeposition. The deposition and nucleation processes of Au on ta-C:N surface were investigated by cyclic voltammetry and chronoamperometry. The morphology of Au NPs was characterized by scanned electron microscopy. The electrochemical properties of Au NPs modified ta-C:N (ta-C:N/Au) electrode and its ability to sense glucose were investigated by voltammetric and amperometric measurements. The potentiostatic current-time transients showed a progressive nucleation process and diffusion growth of Au on the surface of ta-C:N film according to the Scharifker-Hills model. The Au NPs acted as microelectrodes improved the electron transfer and electrocatalytic oxidation of glucose on ta-C:N electrode. The ta-C:N/Au electrode exhibited fast current response, a linear detection range of glucose from 0.5 to 25 mM and a detection limit of 120 microM, which hinted its potential application as a glucose biosensor.     

H-bonding driven assembly of colloidal Au nanoparticles on nanostructured poly(styrene-b-ethylene oxide) block copolymer templates

A facile, cost-effective, and general solution-based “bottom-up” method for nanopatterning dense arrays of colloidal Au nanoparticles (NPs) has been developed. The organization of the NPs has been successfully achieved onto a microphase-separated poly(styrene-block-ethylene oxide) (PS-b-PEO) block copolymer (BCP) thin film which acts as structural template. The NP assembly process occurs by incubating the BCP films in dispersions of the ex situ synthesized Au NPs, not requiring any chemical pre-treatment or activation step of the copolymer surface, and has demonstrated to be distinctively controlled by multiple, cooperative, and selective hydrogen bonding interactions between hydroxyl functionalities of the capping molecules coating the Au NP surface and the hydrophilic PEO block. The effect of incubation time and concentration of NPs on the selectivity of the assembly has been investigated by atomic force and scanning electron microscopy. The results show that the BCP pattern is preserved after decoration with the Au NPs. The fabricated nanopatterns are good candidates for nanostructure integration in sensing and optoelectronic applications, as well as in memory devices and photonic systems. Moreover, the proposed immobilization protocol represents a model system that can be extended to other NPs having different compositions and surface chemistries.