20681-14-5Relevant academic research and scientific papers
Reduction of Gold(III) to Gold(I) by Dialkyl Sulphides. Evidence for an Atom-Transfer Redox Process
Annibale, Giuliano,Canovese, Luciano,Cattalini, Lucio,Natile, Giovanni
, p. 1017 - 1021 (1980)
A kinetic study of the reduction of gold(III) to gold(I) by dialkyl sulphides, in aqueous methanol, is reported.The reaction takes place in two steps.In the first step, substitution equilibria which are strongly dependent on the bulkiness of the entering sulphide are set up.In the second step, the gold(III) complexes react with an extra molecule of sulphide to give gold(I) species and sulphoxide; very likely the reductant attacks the substate at a chlorine and not at the metal centre, the halogen is then transferred from gold to sulphur leaving an electron pair on the metal.The reactivity of the gold(III) substrates increases with increasing substitution (-) (+) paralleling the increasing positive charge on the complex; on the other hand that of the sulphides parallels their basicity (SMe2 i2) indicating that in the redox step polar effects are more important than steric ones.The reaction rate also exhibits a marked solvent depedence, and increases with increasing percentage of water in the reaction medium, the relationship of log k1,2 to solvent polarity being linear.
Kinetic spectrophotometric method for o-phenylenediamine in the presence of gold(III)
Altun, Oezlen,Akbas, Halide,Doelen, Emre
, p. 499 - 502 (2007)
From the color developing reactions of o-phenylenediamine oxidizing agent and gold(III), the kinetic reactions between both of them in aquaeous solutions were studied using spectrophotometric and differential method. Light absorbances in the visible spectral range are measured as a function of mole fractions of phenylenediamine at a fixed gold(III) concentration and as a function of mole fraction of gold(III) at a fixed o-phenylenediamine concentration at periodic time internal. In the differential method, which was suggested by van't Hoff, one deals with the actual rates of reactions as determined by measuring the slopes of absorbance-time curves. Optimum condition of the reaction were established as pH 6 at λ = 466 nm and room temperature. When the oxidation of o-phenylenediamine by gold(III) was investigated, it was observed that the following rate formula and rate constant were found: v = k [ A u+ 3 ]1 / 2 [ o -phenylenediamine ]1 / 2, k = 2.33 × 10- 2 s- 1.
A simple and rapid colorimetric detection of serum lncRNA biomarkers for diagnosis of pancreatic cancer
Chen, Yangchao,Lou, Ut Kei,Wong, Chi Hin
, p. 8087 - 8092 (2020/03/18)
A colorimetric assay is developed for detection of lncRNA HOTTIP by one-step reverse transcription-loop-mediated isothermal amplification (RT-LAMP) coupled with positively-charged gold nanoparticles ((+)AuNP) for diagnosis of pancreatic cancer. This assay allows simple, rapid, and sensitive quantification of lncRNA down to 50 copies.
Cyanide and chloride exchange on homoleptic gold(III) square-planar complexes: Variable pressure kinetic investigation by heteronuclear NMR
Monlien, Florence J.,Helm, Lothar,Abou-Hamdan, Amira,Merbach, André E.
, p. 257 - 269 (2008/10/08)
Kinetic studies of X- exchange on [AuX4]- square-planar complexes (where X=Cl- and CN-) were performed at acidic pH in the case of chloride system and as a function of pH for the cyanide one. Chloride NMR study (330-365 K) gives a second-order rate law on [AuCl4]- with the kinetic parameters: (k2Au,Cl)298=0.56±0.03 s-1mol-1kg; ΔH2?Au,Cl=65.1±1 kJmol-1; ΔS2?Au,Cl=-31.3±3 Jmol-1K-1 and ΔV2?Au,Cl=-14±2 cm3mol-1. The variable pressure data clearly indicate the operation of an Ia or A mechanism for this exchange pathway. The proton exchange on HCN was determined by 13C NMR as a function of pH and the rate constant of the three reaction pathways involving H2O, OH- and CN- were determined: k0HCN,H=113±17 s-1, k1HCN,H=(2.9±0.7)×109 s-1mol-1kg and k2HCN,H=(0.6±0.2)×106 s-1mol-1kg at 298.1 K. The rate law of the cyanide exchange on [Au(CN)4]- was found to be second order with the following kinetic parameters: (k2Au,CN)298=6240±85 s-1mol-1kg, ΔH2?Au,CN=40.0±0.8 kJmol-1, ΔS2?Au,CN=-37.8±3 Jmol-1K-1 and ΔV2?Au,CN=+2±1 cm3mol-1. The rate constant observed varies about nine orders of magnitude depending on the pH and HCN does not act as a nucleophile. The observed rate constant of X- exchange on [AuX4]- are two or three orders of magnitude faster than the Pt(II) analogue.
Gas-phase studies of group-11 cation (Cu+, Ag+, and Au+) reactions with 2-propanol in a supersonic beam-expansion source
Huang,Su,Yeh
, p. 677 - 688 (2007/10/03)
The gas-phase reactions of group-11 ions (Cu+,Ag+, and Au+) with 2-propanol were investigated using laser vaporization combined with supersonic beam expansion in a time-of-flight mass spectrometer. A number of reaction pathways, including assoication, dehydrogenation, and dehydration, were observed. Among these metal ions, Au+ is highly reactive toward 2-propanol. The experimental results are parallel to studies by Wilkins et al. using an FT-ICR mass spectrometer (J. Am. Chem. Soc., 107, 7316 (1985)). The geometries and binding energies of all complexes M+-L, where M+ = Cu+, Ag+, and Au+, L = 2-propanol, acetone, propene, and H2O, were estimated using Moller-Plesset perturbation (MP2) and density functional theory (BLYP). The bond strengths of the complex ions involving gold revealed the strongest bonding, due to a relativistic effect. The energetic relationship between the reactants and the products facilitated an interpretation of the observed exit channels. Because of the supersonic beam source employed, larger clusters containing metal ions were generated as well. Because the cluster sizes with solvent molecules were ≥ 2, the reactivities were apparently limited to Cu+ and Ag+ clusters, while the reactive nature changed in Au+ along with the formation of acetone, lacking in the bare Au+ reactions. For larger clusters, calculations on Ag+ - (2-propanol)2 and Ag+ - (2-propanol)(acetone) complexes using BLYP were performed to obtain their energetics.
Reaction of carbon monoxide in the superacid HSO3F-Au(SO3F)3 and the gold(I) bis(carbonyl) cation [Au(CO)2]+. Isolation and characterization of gold(I) carbonyl fluorosulfate, Au(CO)SO3F
Willner, Helge,Aubke
, p. 2195 - 2200 (2008/10/08)
Solutions of gold tris(fluorosulfate), Au(SO3F)3, in fluorosulfuric acid, HSO3F, behave as superacids and will dissolve up to ~3.5 mol of CO/mol of Au(SO3F)3. During the CO uptake, Au(III) is reduced to Au(I), with Au+(solv) stabilized by CO to give the cation [(OC)Au(CO)]+(solv). The linear five-atom cation is characterized by its vibrational spectrum with CO stretching frequencies observed at 2251 (Raman) and 2211 (IR) cm-1. The cation is stable in solution, but solvent removal in vacuo leads to the formation of a new gold(I) monocarbonyl derivative, Au(CO)SO3F, in quantitative yield as a white solid. Au(CO)SO3F is thermally stable up to 190°C. The CO stretch is found at 2198 and 2195 cm-1 in the Raman and IR spectra, respectively, well above the value of free CO.
Formation of small negative and positive cluster ions of gold, silver, and copper by direct laser vaporization
Moini, Mehdi,Eyler, John R.
, p. 5512 - 5515 (2007/10/02)
Direct laser vaporization techniques have been employed to produce small cluster cations and anions of gold, silver, and copper in a Fourier transform ion cylotron resonance mass spectrometer using pure metal samples.Aunp (p = +1 and -1, n = 1-6), Agn+ (n = 1-3 ), Ag-, Cun+ (n = 1-3), and Cun- (n = 1-2) were observed, using two different experimental configurations.In one configuration ions were produced by Nd:YAG laser irradiation directed collinear with the magnetic field in the FTICR mass spectrometer while in the second laser light directed perpendicularly to the magnetic field was used.Relative kinetic energies of the aggregates, the relative intensities of positive vs negative ions, and the nature of the neutrals in the plasma formed by direct laser vaporization are discussed.
