Electrochemical detection of scDNA cleavage in the presence of macrocyclic hexaaza-copper(II) complex

The hexaaza macrocyclic copper(II) complex Cu(II)L(L=1,8-Dihydroxyethyl-1,3,6,8,10,13-hexaazacyclotetradecane), which has octahedral structure similar to some natural complexes, is synthesized and purified. In this study, oxidative breakage DNA by the reaction of Cu(II)L with H2O2 and ascorbate has been investigated by gel electrophoresis experiments. In electrochemical experiments, the on scDNA-modified glassy carbon electrode(GCE) is cleaved by the Cu(II)L and redox changing of the metal catalyst without adding any other reagents. Above all, the need for concentration of scDNA is much lower than that of gel electrophoresis experiments and the process of the performance is easy. Furthermore, Cyclic Voltammetry (CV) and A.C. Impedance, which are performed to monitor scDNA cleavage at the scDNA-modified glassy carbon electrode (GCE), are fast, simple and highly efficient. The mechanism of the damage can be suggested: Fenton.     

Detecting DNA Damage with a Silver Solid Amalgam Electrode

Mercury electrodes modified with supercoiled (sc) DNA have been used as highly sensitive tools for the detection of DNA strand breaks or as sensors for DNA cleaving substances. In this paper we show that silver solid amalgam electrode (AgSAE), in connection with alternating current voltammetry, provides similar information about DNA damage as the hanging mercury drop electrode. The AgSAE can be used for the detection of enzymatic or chemical DNA cleavage in solution or at the electrode surface. AgSAE modified with scDNA can be utilized as a sensor for DNA nicking substances.     

Oxidation of Sanguinarine and Its Dihydro‐Derivative at a Pyrolytic Graphite Electrode Using Ex Situ Voltammetry. Study of the Interactions of the Alkaloids with DNA

This study describes the oxidation of sanguinarine (SG) and its metabolite dihydrosanguinarine (DHSG) on the surface of a basal‐plane pyrolytic graphite electrode (PGE). Since both alkaloids strongly adsorb onto the surface of pyrolytic graphite, measurements were performed using ex situ voltammetric methods, adsorptive transfer (AdT) cyclic voltammetry (CV) and square‐wave voltammetry (SWV). Oxidation peaks of SG (peak A) and DHSG (peak A*) were observed around the potential of +0.7 V (vs. Ag/AgCl/3 M KCl), depending on the experimental conditions. The voltammetric peaks A and A* are probably related to the oxidation of N‐methylphenanthridine nitrogenous heterocycle of SG and oxidation of DHSG back to SG, respectively. The electrochemical results and optimized AdT SWV were subsequently applied to the study of the interactions of SG and DHSG with DNA in vitro. Analysis of the alkaloid/DNA interactions was based on observing heights of oxidation peaks A and A* after incubation of SG and/or DHSG with supercoiled (sc) DNA [pBSK_(?)]. Electrochemical study of the interactions was supported and complemented with measurements using gel electrophoresis (Topoisomerase I scDNA relaxation assay) and steady‐state and time‐resolved fluorescence spectroscopy. The results suggest that SG intercalates into the double‐stranded structure of scDNA (the SG/base pair ratio is max. 1/4) while increased binding affinity was observed for quaternary cation (SG⁺). DHSG which, unlike SG⁺, does not possess a strictly planar molecular structure, did not show intercalative DNA binding in any of the three methods applied.     

Study of interactions between DNA-ethidium bromide (EB) and DNA-acridine orange (AO), in solution, using hanging mercury drop electrode (HMDE)

The interaction of ethidium bromide (EB) and acridine orange (AO) with double stranded (ds), thermally denatured (ss) and supercoiled (sc) DNA, in solution, was studied by alternating current voltammetry (AC voltammetry) at the hanging mercury drop electrode (HMDE) in 0.3 M NaCl+50 mM sodium phosphate buffer (pH 8.5). Their interaction with DNA is shown to be time dependent and completely different. The changes at peak 2 (peak at −1.20 V) of dsDNA form and the appearance of peak 3 (peak at −1.42 V) in scDNA form are presented as criteria declaring the different mechanism of interaction of EB and AO with DNA. Additionally, the appearance of a new peak at around −0.44 V as a result of DNA and AO interaction, differentiates the studied behaviors. The comparison of the electrochemical behaviors of these compounds highlights the differences in the mechanism of interaction.     

Au/Al2O3催化剂的制备及其在CH4/CO2重整反应中的催化活性

采用浸渍法和沉积－沉淀法制备了四种不同的Au/Al2O3催化剂，测定了它们在氢气还原前后及催化反应后的金含量及比表面积，结果表明，制备方法明显影响催化剂的金含量，应用X－光粉末衍射技术研究了这些催化剂经还原处理及反应后的物相变化，金以Au^0物相存在，没有发现氧化态的金物相，考察了该催化剂在CH4／CO2重整反应中的催化活性，发现金催化剂的活性取决于金粒子的大小，浸渍法制备的金催化剂具有较大的金晶粒尺寸，催化活性低，沉积－沉淀法制备的金催化剂金晶粒尺寸较小，催化活性较高，以尿素为沉淀剂制备的催化剂给出1073K时的CH4和CO2转化率分别为8．1％和17．6％，高温反应不仅导致金晶粒的聚集，而且存在明显的金流失现象。     

Detection of DNA immobilized on bare gold electrodes and gold nanoparticle-modified electrodes via electrogenerated chemiluminescence using a ruthenium complex as a tag

Electrogenerated chemiluminescence (ECL) for DNA hybridization detection is demonstrated based on DNA that was self-assembled onto a bare gold electrode and onto a gold nanoparticles modified gold electrode. A ruthenium complex served as an ECL tag. Gold nanoparticles were self-assembled on a gold electrode associated with a 1,6-hexanedithiol monolayer. The surface density of single stranded DNA (ssDNA) on the gold nanoparticle modified gold electrode was 4.8?×?10¹⁴ molecules per square centimeter which was 12-fold higher than that on the bare gold electrode. Hybridization was induced by exposure of the target ssDNA gold electrode to the solution of ECL probe consisting of complementary ssDNA tagged with ruthenium complex. The detection limit of target ssDNA on a gold nanoparticle modified gold electrode (6.7?×?10^?12 mol L^?1) is much lower than that on a bare gold electrode (1.2?×?10^?10 mol L^?1). The method has been applied to the detection of the DNA sequence related to cystic fibrosis. This work demonstrates that employment of gold nanoparticles self-assembled on a gold electrode is a promising strategy for the enhancement of the sensitivity of ECL detection of DNA.     

Bimodal Size Distribution of Gold Nanoparticles under Picosecond Laser Pulses

The evolution of size distributions of gold nanoparticles under pulsed laser irradiation (Nd:YAG, lambda = 355 nm, pulse width 30 ps) was carefully observed by transmission electron microscopy. Interestingly, the initial monomodal size distribution of gold nanoparticles turned into a bimodal one, with two peaks in the number of particles, one at 6 nm and the other at 16-24 nm. The sizes for small particles depended very little on the irradiated laser energy. This change is attributed to laser-induced size reduction of the initial gold nanoparticles followed by the formation of small particles. In our analysis, we extracted a characteristic value for the size-reduction rate per one pulse and revealed that laser-induced size reduction of gold nanoparticles occurred even below the boiling point. When laser energy is insufficient for the boiling of particles, formation of gold vapor around liquid gold drops is thought to cause the phenomenon. With enough laser energy for the boiling, the formation of gold vapor around and inside liquid gold drops is responsible for the phenomenon. We also observed particles with gold strings after one pulse irradiation with a laser energy of 43 mJ cm(-2) pulse(-1), which is sufficient energy for the boiling. It is considered that such particles with gold strings are formed by the projection of gaseous gold from liquid gold drops with some volume of liquid gold around the bubble. On the basis of comparison with previous work, picosecond laser pulses are thought to be the most efficient way to cause laser-induced size reduction of gold nanoparticles.     

DFT and in situ EXAFS investigation of gold/ceria-zirconia low-temperature water gas shift catalysts: identification of the nature of the active form of gold

A combined experimental and theoretical investigation of the nature of the active form of gold in oxide-supported gold catalysts for the water gas shift reaction has been performed. In situ extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) experiments have shown that in the fresh catalysts the gold is in the form of highly dispersed gold ions. However, under water gas shift reaction conditions, even at temperatures as low as 100 degrees C, the evidence from EXAFS and XANES is only consistent with rapid, and essentially complete, reduction of the gold to form metallic clusters containing about 50 atoms. The presence of Au-Ce distances in the EXAFS spectra, and the fact that about 15% of the gold atoms can be reoxidized after exposure to air at 150 degrees C, is indicative of a close interaction between a fraction (ca. 15%) of the gold atoms and the oxide support. Density functional theory (DFT) calculations are entirely consistent with this model and suggest that an important aspect of the active and stable form of gold under water gas shift reaction conditions is the location of a partially oxidized gold (Audelta+) species at a cerium cation vacancy in the surface of the oxide support. It is found that even with a low loading gold catalysts (0.2%) the fraction of ionic gold under water gas shift conditions is below the limit of detection by XANES (<5%). It is concluded that under water gas shift reaction conditions the active form of gold comprises small metallic gold clusters in intimate contact with the oxide support.     

Gold(I)-coordination triggered multistep and multiple photochromic reactions in multi-dithienylethene (DTE) systems

The preparation, characterization, and photochromic properties of a mononuclear gold(I) complex (1oo) with two identical DTE-acetylides and a dinuclear gold(I) complex (2ooo) with both DTE-acetylide and DTE-diphosphine are described. Both gold(I) complexes exhibit multistep and multiple photocyclization/cycloreversion reactions. Particularly, four-state and four-color photochromic switch is successfully achieved for the dinuclear gold(I) complex upon irradiation with appropriate wavelengths of light. In contrast, fully ring-closed form is unattained through multiple photocyclization for the two corresponding model organic compounds coupling with the same DTE units as gold(I) complexes but without gold(I)-participation. It is demonstrated that coordination of gold(I) ion to DTE-acetylides exerts indeed a crucial role in achieving stepwise and selective photocyclization and cycloreversion reactions for both gold(I) complexes, in which the coordinated gold(I) atom acts as an effective "barrier" to prohibit intramolecular energy transfer between multi-DTE moieties.     

Nanocomposite membranes containing positively polarized gold nanoparticles for facilitated olefin transport

Positively polarized gold nanoparticles have been demonstrated for use as stable olefin carriers for facilitated olefin transport membranes. The formation and size of gold nanoparticles stabilized by 4-dimethylaminopyridine (DMAP) were monitored using X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV–visible spectroscopy. Nanocomposite membranes that deliver high separation performance for olefin/paraffin mixtures were prepared by dispersing gold nanoparticles stabilized by DMAP in a polymer matrix, poly(vinyl pyrrolidone) (PVP). X-ray photoelectron spectroscopy (XPS) and zeta potential measurements revealed that gold nanoparticles stabilized by DMAP exhibited a high positive polarity, which is responsible for the reversible interaction between the gold nanoparticles and olefin molecules. Compared to neat PVP membranes, the composite membranes consisting of PVP and the polarized gold nanoparticles showed stable and enhanced separation of olefin/paraffin mixtures.     

Fabrication, characterisation and voltammetric studies of gold amalgam nanoparticle modified electrodes.

The tabrication, characterisation, and electroanalytical application of gold and gold amalgam nanoparticles on glassy carbon electrodes is examined. Once the deposition parameters for gold nanoparticle electrodes were optimised, the analytical utility of the electrodes was examined in CrIII electroanalysis. It was found that gold nanoparticle modified (Au-NM) electrodes possess higher sensitivity than gold macroelectrodes. In addition, gold amalgam nanoparticle modified (AuHg-NM) electrodes were fabricated and characterised. The response of those electrodes was recorded in the presence of important environmental analytes (heavy metal cations). It was found AuHg-NM electrodes demonstrate a unique voltammetric behaviour and can be applied for electroanalysis when enhanced sensitivity is crucial.     

Effects of gold nanoparticle and electrode surface properties on electrocatalytic silver deposition for electrochemical DNA hybridization detection

In this paper we report the catalytic effects of various gold nanoparticles for silver electrodeposition on indium tin oxide (ITO)-based electrodes, and successfully apply this methodology for signal amplification of the hybridization assay. The most widely used gold nanoparticle-based hybridization indicators all promote silver electrodeposition on the bare ITO electrodes, with decreasing catalytic capability in order of 10 nm gold, DNA probe-10 nm gold conjugate, streptavidin-5 nm gold, and streptavidin-10 nm gold. Of greater importance, these electrocatalytic characteristics are affected by any surface modifications of the electrode surfaces. This is illustrated by coating the ITO with an electroconducting polymer, poly(2-aminobenzoic acid)(PABA), as well as avidin molecules, which are promising immobilization platforms for DNA biosensors. The catalytic silver electrodeposition of the gold nanoparticles on the PABA-coated ITO surfaces resembles that on the bare surfaces. With avidin covalently bound to the PABA, it is interesting to note that the changes in electrocatalytic performance vary for different types of gold nanoparticles. For the streptavidin-5 nm gold, the silver electrodeposition profile is unaffected by the presence of the avidin layer, whereas for both the 10 nm Au and DNA probe-10 nm gold conjugate, the deposition profiles are suppressed. The streptavidin-5 nm gold is employed as the hybridization indicator, with avidin-modified (via PABA) ITO electrode as the immobilization platform, to enable signal amplification by the silver electrodeposition process. Under the conditions, this detection strategy offers a signal-to-noise ratio of 20. We believe that this protocol has great potential for simple, reproducible, highly selective and sensitive DNA detection on fully integrated microdevices in clinical diagnostics and environmental monitoring applications.     

Catalysis by gold dispersed on supports: the importance of cationic gold

There are many examples of catalysis in solution by cationic complexes of gold, and recent results, reviewed here in this critical review, demonstrate that cationic gold species on oxide and zeolite supports are also catalytically active, for reactions including ethylene hydrogenation and CO oxidation. The catalytically active gold species on supports are evidently not restricted to isolated mononuclear gold complexes, but include gold clusters, which for at least some reactions are more active than the mononuclear complexes and for some reactions less active. Fundamental questions remain about the nature of cationic gold in supported catalysts, such as the nature of the cationic gold clusters and the nature of gold atoms at metal-support interfaces (88 references).     

In situ GISAXS investigation of gold sputtering onto a polymer template

Microphase-separation structures in mixed diblock-triblock copolymer thin films are used for the incorporation of gold atoms inside the polymer matrix via sputtering of gold. Polystyrene (PS) spheres are arranged in a liquidlike type with a well defined nearest neighbor distance inside a polyisoprene matrix acting as a template for directing the gold atoms. Sputtering conditions are selected with a very low sputtering rate to avoid clustering in the atmosphere so that gold reaches the polymer surface in its atomic state. Due to the mobility of the gold atoms and the selective interaction with the PS parts of the microphase separation structure, gold is accumulated inside the polymer film in the PS spheres, as probed in situ with grazing incidence small-angle X-ray scattering (GISAXS). Nominally 4.3 A of gold is deposited, which by diffusion is spread out vertically over a thickness of 280 nm. UV-vis spectroscopy reveals a small blue shift for the gold sputtered polymer film. Atomic force microscopy proves the absence of gold clusters on the film surface. For low sputtering rate, GISAXS proves good sensitivity for gold migration inside the polymer film and opens new possibilities for studying polymer-metal interaction.     

The reaction of gold and dithizone

On thermodynamic grounds gold(III) and gold(I) are likely to oxidize dithizone rather than to form complexes. Conditions are described to obtain all the spectra previously ascribed to “gold dithizonate” both in a single system and separately. Oxidation products are responsible for several of the peaks, and it is unlikely that any of the species obtained is a gold dithizonate except possibly that giving the transitory peak at 490 nm. Analytical processes based on the reaction of gold and dithizone should be recognised as involving oxidation and treated with extreme caution.     

二丁基卡必醇萃淋树脂吸萃金的性能及其机理的研究

研究了二丁基卡必醇（ＤＢＣ）萃淋树脂吸萃金的机理，溶液酸效应、吸附等温线、吸附速炫、盐析剂应柱操作条件等，将该树脂用于矿样中金含是珠测定，结果与７１７离子交换树脂吸附法一致。     

Nanostructured gold hollow microspheres prepared on dissolvable ceramic hollow sphere templates

Fifty and one-hundred micrometer diameter nanostructured gold hollow microspheres (GHSs), in >98% purity, have been prepared by using ceramic hollow spheres, CHSs, as templates. Tennanometer diameter gold nanoparticles were covalently linked to the thiol moiety of (3-mercaptopropyl)trimethoxysilane, which had been self-assembled onto the CHSs. Greater structural strength was obtained by the generation of additional gold nanoparticles, in situ on the gold nanoparticle coated CHSs (by immersing the gold nanoparticle coated CHSs into an aqueous mixture of hydroxylamine and gold chloride). GHSs were obtained by dissolving the CHSs templates. The sizes, shapes, surface areas (185.3 m2/g for CHSs and 182.9 m2/g for GHSs), pore diameters (7.7 nm for CHSs and 7.8 nm for GHSs), and pore volumes (0.41 cm3/g for CHSs and 0.36 cm3/g for GHSs) of GHSs were quite similar to their CHSs counterparts. Significantly, GHSs showed surface plasmon bands whose maximum (644 nm) shifted from that observed for the parent 10-nm gold nanoparticles (522 nm).     

Kinetics of gold nanoparticle aggregation: experiments and modeling

We investigate the aggregation kinetics of gold nanoparticles using both experimental techniques (i.e., quasi-elastic light scattering, UV-visible spectroscopy, and transmission electron microscopy) and mathematical modeling (i.e., constant-number Monte Carlo). Aggregation of gold nanoparticles is induced by replacing the surface citrate groups with benzyl mercaptan. We show that the experimental results can be well described by the model in which interparticle interactions are described by the classical DLVO theory. We find that final gold nanoparticle aggregates have a fractal structure with a mass fractal dimension of 2.1-2.2. Aggregation of approximately 11 initial gold nanoparticles appears to be responsible for the initial color change of suspension. This kinetic study can be used to predict the time required for the initial color change of a gold nanoparticle suspension and should provide insights into the design and optimization of colorimetric sensors that utilize aggregation of gold nanoparticles.     

Facile synthesis of chlorophyll analog possessing a disulfide bond and formation of self-assembled monolayer on gold surface

A chlorophyll analog forming self-assembled monolayers (SAMs) on a gold surface was synthesized for the first time. 13(2)-(Demethoxycarbonyl)pheophorbide-a, which was converted from naturally occurring chlorophyll-a, was condensed with 2-hydroxyethyl disulfide to give a chlorin dyad linked by a disulfide bond. The chlorin analog was spontaneously immobilized on a gold substrate by soaking in an acetone solution of the dyad for 24 h. The resulting gold plate exhibited a visible absorption spectrum with about 420- and 675-nm maxima as the Soret and Qy peaks, respectively, indicating that chlorin pi-conjugates were modified on the gold substrate through Au-S bonding. Both visible absorption and fluorescence emission bands of the chlorin chromophores on the gold substrate were red-shifted compared with those of the synthesized chlorin dyad in a homogeneous acetone solution. The measured absorbance at the Soret maximum suggests that the chlorin chromophores on the gold plate were densely packed on a gold surface to form a SAM. Cathodic photocurrents were generated from SAMs of the chlorins on a gold substrate with irradiation of visible-lights above 400 nm. Photoinduced electron transfer from chlorins on the gold substrate to oxygen molecules in an electrolyte solution were attributed to the cathodic photocurrent generation.     

Reactions of Cationic Gold(I) with Allenoates: Synthesis of Stable Organogold(I) Complexes and Mechanistic Investigations on Gold‐Catalyzed Cyclizations

The reaction of allenoates with cationic gold(I)—generated in situ from a phosphine gold chloride and a silver salt—formed unusual, room temperature stable vinyl gold(I) lactones under very mild conditions. The scope and limitations for the synthesis of this novel organogold complex was investigated. DFT calculations on the highest occupied molecular orbitals (HOMOs) of allenoates and the natural bond orbital (NBO) charge densities provided an explanation for the limitations. A plausible mechanism for its formation was proposed based on in situ ¹H and ³¹P NMR spectroscopic analyses. Controlled experiments for the cleavage of the gold–carbon bond by electrophiles indicated that this vinyl gold(I) complex is the likely intermediate in the gold‐catalyzed reaction of carbon–carbon multiple bonds.