The effect of ozone on plasmon absorption of gold hydrosols. Quasi-metal and metal nanoparticles

The character of the interaction between ultrasmall gold nanoparticles and ozone is shown to be mainly governed by the particle structure. For borohydride sols of gold nanoparticles with sizes of ??3 nm, which are characterized by metallic properties, this interaction is reduced to reversible adsorption of ozone on their surface. At the same time, ozone adsorption on ??nonplasmon?? Au particles that have a diameter of 2 nm and a very defective structure results in their irreversible structural rearrangement and transition to a metallic state, which is accompanied by the appearance of a surface plasmon resonance. The set of the results obtained shows that nanoparticles of borohydride gold sols are more efficient as possible hemosensors of ozone than are larger particles synthesized by the citrate method.     

Electrochemical absorption and oxidation of hydrogen on palladium alloys with platinum, gold and rhodium

Thin layers of Pd and its alloys with Pt, Au and Rh were prepared by electrodeposition on a Au substrate. Hydrogen electrosorption by the obtained electrodes was studied in 0.5 M H(2)SO(4) solution using cyclic voltammetry and chronoamperometry. The influence of the alloying process on selected thermodynamic (the amount of absorbed hydrogen, the stability of the β-phase, the extent of the absorption/desorption hysteresis) and kinetic aspects (the rate of hydrogen absorption and absorbed hydrogen oxidation) of hydrogen absorption and desorption was examined. It was found that the addition of the non-absorbing elements to Pd results in faster kinetics of the hydrogen electrosorption process and a smaller absorption/desorption hysteresis.     

Waveguide surface plasmon resonance studies of surface reactions on gold electrodes

We describe the fabrication and characterisation of gold-coated graded index channel waveguide sensors designed for simultaneous electrochemical and surface plasmon resonance studies. The active sensing electrode area is a thin gold film between 0.5 and 5 mm in length and 200 microm wide deposited on top of a 3 microm wide waveguide which forms one arm of a Y-junction while the other arm of the Y-junction serves as a reference. Using these devices we have measured simultaneously the changes in transmittance through the device whilst carrying out cyclic voltammetry in either sulfuric or perchloric acid solution or during the deposition of an UPD layer of copper at the gold surface. In all cases we obtain stable and reproducible results which demonstrate the very high sensitivity of the devices to sub-monolayer changes occurring at the gold electrode surface. The response of these integrated optoelectrochemical devices is discussed in terms of a numerical model for the propagation of light within the waveguide structure.     

Size effect in plasmon absorption of gold nanoparticles upon adsorption of ozone

A size effect is revealed and analyzed for the shift of the plasmon absorption of gold nanoparticles upon ozone adsorption on their surface. The smaller the nanoparticles, the greater the shift of the band. At the same time, the shift of the Fermi level is a linear function of the inverse radius of nanoparticles. It is shown that the observed variations in the optical characteristics and the Fermi level may be explained within the framework of the model proposed for a decrease in the electron density of nanoparticles due to their partial binding by adsorbed ozone molecules.     

Electrochemical impedance spectroscopy and surface plasmon resonance studies of DNA hybridization on gold/SiOx interfaces

The use of Au/SiO(x) interfaces for the investigation of DNA hybridization using electrochemical impedance spectroscopy (EIS) and surface plasmon resonance (SPR) simultaneously is demonstrated. Standard glass chemistry was used to link single-stranded DNA (ss-DNA) on aldehyde-terminated Au/SiO(x) interfaces. The layer thickness and amount of grafted oligonucleotides (ODNs) were calculated from SPR on the basis of a multilayer system of glass/Ti/Au/SiO(x)/grafted molecule. Capacitance and resistance values of the modified interface before and after hybridization were calculated from EIS data using an equivalent circuit and allowed the affinity rate constant, K(A) = 4.07 x 10(5) M(-1), to be determined. The EIS results were comparable to those obtained by SPR hybridization kinetics recorded in parallel.     

Electronic excitations induced by hydrogen surface chemical reactions on gold

Associated with chemical reactions at surfaces energy may be dissipated exciting surface electronic degrees of freedom. These excitations are detected using metal-insulator-metal (MIM) heterostructures (Ta-TaOx-Au) and the reactions of H with and on a Au surface are probed. A current corresponding to 5×10(-5) electrons per adsorbing H atom and a marked isotope effect are observed under steady-state conditions. Analysis of the current trace when the H atom flux is intermitted suggests that predominantly the recombination reaction creates electronic excitations. Biasing the front versus the back electrode of the MIM structure provides insights into the spectrum of electronic excitations. The observed spectra differ for the two isotopes H and D and are asymmetric when comparing negative and positive bias voltages. Modeling indicates that the excited electrons and the concurrently created holes differ in their energy distributions.     

Effect of low-temperature treatment on the state of gold hydrosol particles

A shift of the Plasmon absorption spectrum into the long-wave region, which increases with decreasing temperature and increasing duration of low-temperature treatment (LTT), was revealed after LTT at 217–77 K of Au hydrosol with a particle size of 10–11 nm. It was demonstrated that a decrease in the effective concentration of conduction electrons (N _e) after LTT is accompanied by an alteration in the damping coefficient of plasma resonance oscillations (γ) and the volume fraction of Au particles (N _V ). The temperature dependences of γ and N _V , just as for silver sol, are stipulated by the tunnel mechanism of the formation of low-temperature defects in the presence of two-dimensionally mobile positively charged aqua complexes X⁺(H₂O) _n . A feature of Au sol was revealed: the maximum on dependences of γ and N _V on the duration of LTT and the linear γ-N _e correlation.     

Kinetic solvent effects on hydrogen abstraction reactions

Kinetic solvent effects on hydrogen abstractions, namely, acceleration in nonpolar solvents, have been presumed to be restricted to O-H hydrogen donors. We demonstrate that also abstractions from C-H and even Sn-H bonds by cumyloxyl radicals and n,pi*-excited 2,3-diazabicyclo[2.2.2]oct-2-ene are fastest in the gas phase and nonpolar solvents but slowest in acetonitrile. Accordingly, solvent effects on hydrogen abstractions are more general, presumably due to stabilization of the reactive oxygen or nitrogen species in polar solvents.     

Electrochemical enzyme immunoassay using immobilized antibody on gold film with monitoring of surface plasmon resonance signal

Sandwich immunoassay was conducted on a thin gold film set in a surface plasmon resonance (SPR) cell. Monochronal antibody (anti-IgG) was immobilized onto the gold film via 4,4′-dithiodibutyric acid (DDA) and avidin-biotin bonding. Next, IgG sample and alkaline phosphatase-conjugated anti-IgG (ALP anti-IgG) were introduced into the cell successively. Finally, p-aminophenyl phosphate (PAPP) was injected as an enzyme substrate, and the produced p-aminophenol (PAP) was electrochemically measured. Flow did not need to be stopped for incubation for the enzyme reaction, because of the thinness of the cell. In these processes, all the antigen-antibody reactions took place on the gold film. Therefore, the immobilization was performed quickly, and each process could be confirmed by SPR signal. This system had the advantage that the middle of the complicated process could be monitored. For example, the amount of antibody immobilized, which affected on the final electrochemical signal, could be confirmed in the course of immobilization. It was also convenient to investigate process conditions, such as removal of used antigens and labeled antibodies. Good correlation was obtained between the electrochemical current and the SPR signals due to the adsorption of IgG and ALP anti-IgG, and the sensitivity of the electrochemical measurement was much higher than the SPR’s.     

Ultrasensitive detection of ovarian cancer marker using immunoliposomes and gold nanoelectrodes

Mucin-16 (MUC16) is the established ovarian cancer marker used to follow the disease during or after treatment for epithelial ovarian cancer. The emerging science of cancer markers also demands for the new sensitive detection methods. In this work, we have developed an electrochemical immunosensor for antigen MUC16 using gold nanoelectrode ensemble (GNEE) and ferrocene carboxylic acid encapsulated liposomes tethered with monoclonal anti-Mucin-16 antibodies (αMUC16). GNEEs were fabricated by electroless deposition of the gold within the pores of polycarbonate track-etched membranes. Afterwards, αMUC16 were immobilized on preformed self-assembled monolayer of cysteamine on the GNEE via cross-linking with EDC-Sulfo-NHS. A sandwich immunoassay was performed on αMUC16 functionalized GNEE with MUC16 and immunoliposomes. The differential pulse voltammetry was employed to quantify the faradic redox response of ferrocene carboxylic acid released from immunoliposomes. The dose–response curve for MUC16 concentration was found between the range of 0.001–300 U mL⁻¹. The lowest detection limit was found to be 5 × 10⁻⁴ U mL⁻¹ (S/N = 3). We evaluated the performance of this developed immunosensor with commercial ELISA assay by comparing results obtained from spiked serum samples and real blood serum samples from volunteers.     

Dielectric medium effects on collective surface plasmon coupling interactions in oligothiophene-linked gold nanoparticles

The near-field coupling interactions between surface plasmon modes of neighboring metal nanoparticles (NPs) are investigated in thin films of oligothiophene-linked Au NPs. The oligothiophene linker facilitates near-field coupling between adjacent NPs, and disruption of the conjugation in the oligothiophene by chemical oxidation leads to a decrease in surface plasmon resonance (SPR) coupling between neighboring particles. The SPR coupling between NPs was found to be highly dependent on the dielectric constant of the medium that the films are exposed to, where a higher dielectric medium leads to weaker coupling. The dependence of the SPR coupling on the dielectric constant of the medium is explained using electrodynamic theory.     

Electrochemical assembly and potential-dependent plasmon absorption of au nanoclusters covered with a 4-aminothiophenol self-assembled monolayer

Gold nanoclusters covered with 4-aminothiophenol (4-ATP) self-assembled monolayers (SAMs) were electrochemically assembled on an Au or ITO electrode. The assembly mechanism is discussed on the basis of results of electrochemical, FT-IR, and XPS measurements. The intensity of plasmon absorption of the gold nanocluster assembly was shown to be dependent on applied potential as a result of electrochemical doping/undoping of a counteranion in the polyaniline film.     

A study of the reactions of molecular hydrogen with small gold clusters

This work presents a study of reactions between neutral and negatively charged Au(n) clusters (n=2,3) and molecular hydrogen. The binding energies of the first and second hydrogen molecule to the gold clusters were determined using density functional theory (DFT), second order perturbation theory (MP2) and coupled cluster (CCSD(T)) methods. It is found that molecular hydrogen easily binds to neutral Au(2) and Au(3) clusters with binding energies of 0.55 eV and 0.71 eV, respectively. The barriers to H(2) dissociation on these clusters with respect to Au(n)H(2) complexes are 1.10 eV and 0.59 eV for n=2 and 3. Although negatively charged Au(n) (-) clusters do not bind molecular hydrogen, H(2) dissociation can occur with energy barriers of 0.93 eV for Au(2) (-) and 1.39 eV for Au(3) (-). The energies of the Au(2)H(2) (-) and Au(3)H(2) (-) complexes with dissociated hydrogen molecules are lower than the energies of Au(2) (-)+H(2) and Au(3) (-)+H(2) by 0.49 eV and 0.96 eV, respectively. There is satisfactory agreement between the DFT and CCSD(T) results for binding energies, but the agreement is not as good for barrier heights.     

Ensembles of nanoelectrodes modified with gold nanoparticles: characterization and application to DNA-hybridization detection

A new method to increase the active area (A _act) of nanoelectrode ensembles (NEEs) is described. To this aim, gold nanoparticles (AuNPs) are immobilized onto the surface of NEEs using cysteamine as a cross-linker able to bind the AuNPs to the heads of the nanoelectrodes to obtain the so-called AuNPs-NEEs. The analysis of the cyclic voltammograms recorded in pure supporting electrolyte showed that the presence of the nanoparticles reflects in an, approximately, ten-times increase in the electrochemically active area of the ensemble. The measurement of the amount of electroactive polyoxometalates, which can be adsorbed on the gold surface of NEEs vs. AuNPs-NEEs, confirmed a significant increase of active area for the latter. These evidences indicate that there is a good electronic connection between the AuNPs and the underlying nanoelectrodes. The possibility to exploit AuNPs-NEEs for biosensing application was tested for the case of DNA-hybridization detection. After immobilization on the gold surface of AuNPs-NEEs of a thiolated single-stranded DNA, the hybridization with complementary sequences labeled with glucose oxidase (GOx) was performed. The detection of the hybridization was achieved by adding to the electrolyte solution the GOx substrate (i.e., glucose) and a suitable redox mediator, namely the (ferrocenylmethyl) trimethylammonium (FA⁺) cation; when the hybridization occurs, an electrocatalytic increase of the oxidation current of FA⁺ is recorded. Comparison of electrocatalytic current recorded at DNA modified NEEs and AuNPs-NEEs indicate, for the latter, a significant increase in sensitivity in the detection of the DNA-hybridization event.     

Influence of ph on the reduction of thick anodic oxide films on gold

The reduction of thick oxide films, produced anodically on gold under constant potential conditions in the oxygen gas evolution region, was examined as a function of sweep-rate in both acid and base. Although peak maxima potential values for the reduction reactions were not totally independent of sweep-rate, even at very low values of the latter, the earlier assumption that the film is composed of at least two (and in some cases, according to the present results, as many as five) different oxygold species was shown to be a reasonable one. The other assumption, namely that the hydrous film in the case of gold is anionic (due to excess hydroxide-ion incorporation) was also shown to be a reasonable one by comparison with recent work with hydrous nickel oxide films for which structural data is available. In these systems counterbalancing cations (H⁺, Na⁺, etc.) are assumed to be present in water contained in pores or layers in the structure. Furthermore, the unusual potential-pH dependence of the hydrous film reduction process can easily be explained in terms of the excess hydroxide incorporation model.     

Surface plasmon enhancement of two- and three-photon absorption of Hoechst 33 258 dye in activated gold colloid solution

Herein we present experimental evidence of the strong surface plasmon enhancement of two- and three-photon absorption of Hoechst 33 258 (2'-(4-hydrophenyl)-5-(4-methyl-1-piperazinyl)-2,5'-bis(1H-benzimidazole)) pentahydrate in an aqueous solution containing activated gold colloid. The 480-fold enhancement in two-photon absorption and 30-fold in three-photon absorption are predominantly attributed to the electric-field enhancement via surface plasmon resonance. The greater enhancement observed in two-photon absorption is due to the characteristic two- and three-photon absorption cross-sections of the dye.     

Synthesis of gold nanoparticles by laser ablation in toluene: quenching and recovery of the surface plasmon absorption

Gold nanoparticles are synthesized by laser ablation of a gold plate in toluene. The nanoparticles do not show their characteristic surface plasmon absorption (SPA) and are found to be included in a graphitic matrix. The absence of this absorption is found to derive from the presence of the matrix which prevents the growth of large nanoparticles and covers them, suppressing the SPA according to the Mie model for core@shell particles. It is possible to recover the nanoparticle SPA by oxidizing the carbon matrix, obtaining, therefore, some control on the activity of this absorption.     

The study of the possibility of gold hydrosol stabilization with nonthiolated homooligonucleotides with different lengths and sequences

The stabilization of citrate gold hydrosols with nonthiolated oligonucleotides having different lengths and sequences has been studied, with the oligonucleotides being added both at the stage of hydrosol synthesis (at 37 and 60°C) and after it. The oligonucleotides have been found to exhibit a pronounced stabilizing effect irrespective of the moment of their addition to the hydrosols. The only exception is the situation, in which adenine-based oligonucleotides are heated to 60°C in the course of the synthesis, when they, on the contrary, destabilize the hydrosols. Short-chain oligonucleotides (hexamers) exhibit a stronger stabilization effect than dodecamers do. Moreover, it has been shown that adenine-based and cytosine-based oligonucleotides show the strongest stabilizing effect.