A gold-based nanobeacon probe for fluorescence sensing of organophosphorus pesticides

A nanomaterials-based novel molecular beacon has attracted growing attentions in fluorescent assays as many nanomaterials possess excellent quenching efficiency. In this work, a gold-based nanobeacon probe was established to detect organophosphorus pesticides for the first time. The constructed gold-based nanobeacon acted as a signal indicator and could display the decreasing of the intensity in the presence of targets, which competitively bound to single strand DNA. To achieve a high sensitive probe, some parameters including solution pH, temperature and reaction time were investigated and optimized. The gold-based nanobeacon probe assay was proved to be rapid and sensitive to achieve a detection limit of 0.035 μM for isocarbophos, 0.134 μM for profenofos, 0.384 μM for phorate and 2.35 μM for omethoate, respectively. The prepared nanobeacon effectively reduced the background and improved the detection sensitivity and selectivity. The probe is stable, easy to operate and does not need sophisticated instruments. These features makes the probe feasible for screening trace organophosphorus pesticides in real samples.     

Spectroscopic characterization of core and shell regions in monolayer protected gold nanoparticles

We report studies on the structure of the metallic core and the alkyl cap layer in monolayer protected gold nanoparticles having sizes down to 1.6 nm. These particles are obtained by laser ablating gold targets in alkane-thiol solutions at different concentrations. The electronic structure of gold core and the vibrational properties of the capping hydrocarbon chains reveal effects connected with the nanosized nature of the particles.     

Electrical behavior of the Au/MoS2 interface studied by light emission induced by scanning tunneling microscopy

Light emitted in the tunneling junction of a scanning tunneling microscope has been used to establish the electrical characteristics of nanojunctions made of Au islands deposited on flat MoS₂ surfaces. It is shown that these characteristics are those of rectifying contacts when the gold islands are isolated and that they evolve toward those of ohmic contacts when the island density increases. It is observed that the rectifying behavior also evolves over time as on infinite metal/semiconductor contacts. Using the STM tip, single gold islands can be manipulated on the MoS₂ surface so that their electrical behavior can be changed depending on their position with regard to the other islands.     

Transport of Neutrally Buoyant and Dense Variably Sized Colloids in a Two-Dimensional Fracture with Anisotropic Aperture

The transport of monodisperse as well as polydisperse colloid suspensions in a two-dimensional, water saturated fracture with spatially variable and anisotropic aperture is investigated with a particle tracking model. Both neutrally buoyant and dense colloid suspensions are considered. Although flow and transport in fractured subsurface formations have been studied extensively by numerous investigators, the transport of dense, polydisperse colloid suspensions in a fracture with spatially variable and anisotropic aperture has not been previously explored. Simulated snapshots and breakthrough curves of ensemble averages of several realizations of a log-normally distributed aperture field show that polydisperse colloids exhibit greater spreading than monodisperse colloids, and dense colloids show greater retardation than neutrally buoyant colloids. Moreover, it is demonstrated that aperture anisotropy oriented along the flow direction substantially increases colloid spreading; whereas, aperture anisotropy oriented transverse to the flow direction retards colloid movement.     

Study of adsorption of oxygen on β-Al2O3 + Au and β-Al2O3 + Pt: Work function measurements—proposition of a model

To improve the understanding of the electrochemical effects observed on an original potentiometric gas sensor, interactions of oxygen with the device were investigated. This gas sensor is made of a solid electrolyte (treated Na-β-alumina) associated with two metallic electrodes (gold and platinum) located in the same gas mixture. Adsorption of charged oxygen species, considered responsible for the electrical response developed by the sensor, was investigated by work function measurements. Results showed that charged oxygen species only form on partially gold or platinum covered solid electrolyte. Comparison of these results with those obtained in a previous calorimetric study of interactions between oxygen and the same materials suggests the existence of at least two different oxygen species adsorbed on the surface of the sensitive element. The first one, located on the solid electrolyte surface, is neutral and characterized by an endothermal reaction of formation. The second one is charged and probably produced at the gas/solid electrolyte/metallic electrode interface. A mechanism based on the concept of “three phase boundary” and similar to the “reverse spillover” phenomenon is proposed to account for the adsorption of these oxygen species.     

金催化化学发光新体系——苯并吡喃化学发光分析法测定金矿中的痕量金

本文提出了一种测定矿样中痕量金的化学发光分析法,氯化6,7-二羟基-2,4-二甲基苯并吡喃-H_2O_2化学发光体系,方法的检出限为7ppb。工作曲线线性范围是10～1000ppbAu,测定的相对标准偏差小于7％。应用本法测定矿样中的金,结果良好。     

Construction of self-assembled monolayer terminated with N-heterocyclic carbene-rhodium(I) complex moiety

Functionalization of self-assembled monolayer (SAM) of alkanethiolate with metal containing unit is one of the versatile methods to obtain functional surfaces such as heterogeneous catalysts. However, organic molecules that strongly bind to transition metals at SAM terminal are limited. Recently N-heterocyclic carbenes (NHCs) such as cyclic diaminocarbenes have emerged as strongly σ-donating ligands forming a robust bond with broad spectrum of transition metals. In the present study, for the purpose of establishment of a new robust basement for heterogeneous metal catalysts, a SAM of the alkanethiolate terminated with NHC-rhodium(I) complex moiety was prepared by utilizing a newly designed disulfide molecule bearing NHC-metal complex terminals. X-ray photoelectron spectroscopy (XPS) analysis and angle resolved XPS measurement revealed successful formation of the Rh-complex-terminated SAM on a gold substrate. Infrared reflection absorption spectroscopy (IRRAS) analysis suggested that the linker methylene chains connecting the rhodium complex moiety and the gold surface are in a loosely packed structure. This unique chemical species, NHC, would be a promising candidate as a basement for the construction of functional surface.     

Determination of gold in ore by flame atomic absorption spectrometry with flow-injection on-line sorbent extraction preconcentration

Gold in ores was determined by flame atomic absorption spectrometry following on-line preconcentration by sorbent extraction in a flow-injection system. The medium polarity adsorption resin Amberlite XAD-8 packed in a 220-μl micro-column was used to collect gold(III) from hydrochloric acid sample solutions for 40 s at 7.6 ml/min. Ethanol was used to elute the adsorbed analytes into the nebulizer. Optimization studies were made on sample loading rate, elution rate and sample acidity. Some possible interferences on the determination are discussed. A 35-fold enrichment was achieved at a sampling frequency of 60 h^?1 and with an RSD of 1.4%. The detection limit (3σ) and 2 μg l^?1. Results for gold in ore samples showed good agreement with those obtained using activated carbon adsorption preconcentration. The recoveries were 97–108%.     

Theoretical insight of adsorption thermodynamics of multifunctional molecules on metal surfaces

Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries.