Adsorptive Cathodic Stripping Voltammetry for Quantification of Alprazolam

A simple and highly sensitive electrochemical sensor was developed for adsorptive cathodic stripping voltammetry of alprazolam. Based on an electrochemically pretreated glassy carbon electrode, the sensor demonstrated good adsorption and electrochemical reduction of alprazolam. The morphology of the glassy carbon electrode and the electrochemically pretreated glassy carbon electrode were characterized by scanning electron microscopy/energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The electrochemical behaviors of alprazolam were determined by cyclic voltammetry, and the analytical measurements were studied by adsorptive cathodic stripping voltammetry. Optimized operational conditions included the concentration and deposition time of sulfuric acid in the electrochemical pretreatment, preconcentration potential, and preconcentration time. Under optimal conditions, the developed alprazolam sensor displayed a quantification limit of 0.1 mg L⁻¹, a detection limit of 0.03 mg L⁻¹, a sensitivity of 67 µA mg⁻¹ L cm⁻² and two linear ranges: 0.1 to 4 and 4 to 20 mg L⁻¹. Sensor selectivity was excellent, and repeatability (%RSD < 4.24%) and recovery (82.0 ± 0.2 to 109.0 ± 0.3%) were good. The results of determining alprazolam in beverages with the developed system were in good agreement with results from the gas chromatography–mass spectrometric method.     

New Strategy for Synthesis of the Disaccharide Moiety of the Highly Potent Anticancer Natural Product OSW-1

The facile synthesis of a partially protected OSW-1 disaccharide moiety, having a 2-O-p-methoxybenzoyl-β-D-xylopyranosyl-(1 → 3)-2-O-acetyl-L-arabinopyranoside structure, was elaborated by glycosylation in a β-stereoselective fashion. The xylopyranose donors were synthesized by a short synthetic approach via convenient selective 1,2-diacetal protection of 3,4-trans-diequatorial hydroxyl group. Regioselective ring opening of 1,2-diacetal-protected substrates efficiently led to the arabinopyranose acceptor with a free 3-hydroxyl group. Glycosylation of the xylopyranose donor with the arabinopyranose acceptor provided the β-disaccharide.     

Cationic NHC-Phosphine Iridium Complexes: Highly Active Catalysts for Base-Free Hydrogenation of Ketones

Novel bidentate N-heterocyclic carbene-phosphine iridium complexes have been synthesized and evaluated in the hydrogenation of ketones. Reported catalytic systems require base additives and, if excluded, need elevated temperature or high pressure of hydrogen gas to achieve satisfactory reactivity. The developed catalysts showed extremely high reactivity and good enantioselectivity under base-free and mild conditions. In the presence of 1 mol % catalyst under 1 bar hydrogen pressure at room temperature, hydrogenation was complete in 30 minutes giving up to 96 % ee. Again, this high reactivity was achieved in additive-free conditions. Mechanistic experiments demonstrated that balloon pressure of hydrogen was sufficient to form the activate species by reducing and eliminating the 1,5-cyclooctadiene ligand. The pre-activated catalyst was able to hydrogenate acetophenone with 89 % conversion in 5 min.     

Facile Synthesis of Pd Nanoparticle Modified Carbon Black for Electroanalysis: Application to the Detection of Hydrazine

Carbon black nanoparticles modified with palladium nanoparticles (Pd/CB) were prepared using a facile methodology. Stirring CB in an aqueous solution of palladium chloride was found to result in the spontaneous formation of Pd nanoparticles on the CB surface. The Pd/CB composite demonstrated high electrocatalytic activity towards hydrazine oxidation, with good stability and reproducibility. Three linear dynamic ranges of hydrazine determination were found between 5 µM and 50 mM. The limit of detection (LOD) for hydrazine was found to be 8.8 µM (based on 3σ). The sensitivity of unmodified CB to trace metal impurities present in certain common electrolytes is also noted.     

荧光胺电化学检测水溶液中的氨:荧光检测与伏安分析比较(英文)

荧光胺是一种非荧光剂,易与伯胺反应形成荧光产物,被普遍用于伯胺的荧光光谱定量分析.本文利用荧光胺与伯胺反应发展了一种新型灵敏的伏安法用于检测水溶液中的伯胺.首先,在有、无伯胺的0.1 mol.L-1PBS(pH 9.0)缓冲液中,研究了玻碳电极表面荧光胺的循环伏安电化学行为.荧光胺的不可逆氧化峰出现在0.70 V(vs.SCE),当加入伯胺时,在0.46 V(vs.SCE)出现另一不可逆的氧化峰,为荧光胺与伯胺反应的产物.继续加入氨水,荧光胺的氧化峰变弱,反应产物的氧化峰则由于荧光胺按反应化学计量比随氨消耗增多而随之增大.上述两个阳极峰分别对应于荧光胺及其反应产物,采用方波伏安和荧光光谱技术可实现水溶液中伯胺的定量检测.在0～60μmol.L-1氨浓度范围内,该反应产物方波伏安检测成线性响应.S/N=3或3σ时检测下限分别为0.71μmol.L-1和3.17μmol.L-1,与荧光法检测的结果相近.     

Electroanalytical Detection of n‐Butylamine at a Nickel/Carbon Nanotube Composite

We report the electroanalytical detection of n‐butylamine at a nickel/carbon nanotube (Ni/CNT) composite. Scanning Electron Microscopy (SEM) characterisation of the composite demonstrated that it consisted of bulk nickel particles ca. 2 μm in diameter entangled in CNT bundles. The spontaneous formation of Ni(OH)₂ was optimised, and comparison with a 3 mm nickel electrode showed that ca. 4 μg of the Ni/CNT composite cast on a 3 mm GC electrode possessed bulk nickel characteristics while also having higher activity and higher sensitivity towards the electrochemical detection of n‐butylamine. However, the Ni/CNT composite showed no response to ammonia, in contrast to the macro‐nickel‐electrode.     

One-step synthesis of fluorescein modified nano-carbon for Pd(II) detection via fluorescence quenching

Carbon black (CB) nanoparticles modified with fluorescein, a highly fluorescent molecule, were prepared using a facile and efficient methodology. Simply stirring CB in aqueous solution containing fluorescein resulted in the strong physisorption of fluorescein onto the CB surface. The resulting Fluorescein/CB was then characterised by means of X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), fluorescence microscopy and fluorescence spectroscopy. The optimum experimental conditions for fluorescence of Fluorescein/CB viz. fluorescence excitation and emission wavelengths, O(2) removal and the amount of Fluorescein/CB used, were investigated. The Fluorescein/CB was used as a fluorescent probe for the sensitive detection of Pd(II) in water, based on fluorescence quenching. The results demonstrated that the fluorescence intensity of Fluorescein/CB decreased with increasing Pd(II) concentration, and the fluorescence quenching process could be described by the Stern-Volmer equation. The limit of detection (LOD) for the fluorescence quenching of Fluorescein/CB by Pd(II) in aqueous solution was found to be 1.07 μM (based on 3σ). Last, approaches were studied for the removal of Fe(III) which interferes with the fluorescence quenching of Fluorescein/CB. Complexation of Fe(III) with salicylic acid was used to enhance and control the selectivity of Fluorescein/CB sensor towards Pd(II) in the presence of Fe(III).