Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes

A first example of an Et₂Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.     

Investigation on Ochratoxin A stability using different extraction techniques

The stability of Ochratoxin A during its extraction using different extraction techniques has been evaluated. Microwave-assisted extraction and pressurised liquid extraction, in addition to two other reference methods of extraction, i.e. ultrasound-assisted and magnetic stirring-assisted extraction, were evaluated. The effect of extraction temperature using the cited techniques was checked.The results show that Ochratoxin A can be extracted using microwave-assisted extraction at temperatures up to 150 °C without degradation. Pressurised liquid extraction can be used at temperatures up to 100 °C, for extraction times of less than 30 min. Further, both ultrasound-assisted extraction and magnetic stirring extraction can be applied at temperatures up to 65 °C.High-performance liquid chromatography combined with fluorescence detection using a Chromolith RP-18e column at a flow rate of 5 mL min⁻¹ was used to quantify the Ochratoxin A. The retention time for the Ochratoxin A was 1.3 min. The limits of detection (LOD) and of quantification (LOQ) were 0.03 and 0.10 μg L⁻¹, respectively.     

Hydride generation atomic fluorescence spectrometric determination of ultratraces of selenium and tellurium in cow milk

A sensitive procedure has been developed for selenium and tellurium determination in milk by hydride generation atomic fluorescence spectrometry (HG-AFS) after microwave-assisted sample digestion. The method provides sensitivity values of 1591 and 997 fluorescence units ng⁻¹ ml⁻¹ with detection limits of 0.005 and 0.015 ng ml⁻¹ for Se and Te, respectively. The application of the developed methodology to the analysis of cow milk samples of the Spanish market evidenced the presence of concentration ranges from 11.1 to 26.0 ng ml⁻¹ for Se, and from 1.04 to 9.7 ng ml⁻¹ for Te having found a good comparability with data obtained after dry-ashing of samples.     

Microwave-accelerated derivatization processes for the determination of phenolic acids by gas chromatography-mass spectrometry

A rapid method for the derivatization of phenolic antioxidants using microwave irradiation has been developed. Six antioxidatively active phenolic components of wines and fruits, namely gallic acid, gentisic acid, vanillic acid, caffeic acid, ferulic acid and p-coumaric acid were used in the model study. The solution of phenolic acids was evaporated to dryness on a rotary evaporator followed by further drying under microwave irradiation (600 W, 30 s). The resultant residue was dissolved in pyridene and treated with bis(trimethylsilyl)acetamide while irradiated by microwave using high power for 30 s. Controlled reaction was carried out employing bis(trimethylsilyl)trifluoroacetamide under conventional heating for 30 min. The trimethylsilyl derivatives were identified and quantified on a gas chromatography/mass selective detector. The mass spectral fragmentation patterns of the derivatives obtained by microwave irradiation were identical to those prepared by heating. The yields of microwave-assisted silylation were comparable to those from conventional heating. The rsd were less than 8% for six replicates. The linearity in wine matrix was nearly perfect. This method is a useful protocol to examine the phenolic constituents in wines and agricultural products.     

微波辅助快速制备2D/1D ZnIn2S4/TiO2 S型异质结及其光催化制氢性能

The threat and global concern of energy crises have significantly increased over the last two decades. Because solar light and water are abundant on earth, photocatalytic hydrogen evolution through water splitting has been considered as a promising route to produce green energy. Therefore, semiconductor photocatalysts play a key role in transforming sunlight and water to hydrogen energy. To date, various photocatalysts have been studied. Among them, TiO₂ has been extensively investigated because of its non-toxicity, high chemical stability, controllable morphology, and high photocatalytic activity. In particular, 1D TiO₂ nanofibers (NFs) have attracted increasing attention as effective photocatalysts because of their unique 1D electron transfer pathway, high adsorption capacity, and high photoinduced electron–hole pair transfer capability. However, TiO₂ NFs are considered as an inefficient photocatalyst for the hydrogen evolution reaction (HER) because of their disadvantages such as a large band gap (~3.2 eV) and fast recombination of photoinduced electron–hole pairs. Therefore, the development of a high-performance TiO₂ NF photocatalyst is required for efficient solar light conversion. In recent years, several strategies have been explored to improve the photocatalytic activity of TiO₂ NFs, including coupling with narrow-bandgap semiconductors (such as ZnIn₂S₄). Recently, microwave (MW)-assisted synthesis has been considered as an important strategy for the preparation of photocatalyst semiconductors because of its low cost, environment-friendliness, simplicity, and high reaction rate. Herein, to overcome the above-mentioned limiting properties of TiO₂ NFs, we report a 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction synthesized through a microwave (MW)-assisted process. Herein, the 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction was constructed rapidly by using in situ 2D ZnIn₂S₄nanosheets decorated on 1D TiO₂ NFs. The loading of ZnIn₂S₄ nanoplates on the TiO₂ NFs could be easily controlled by adjusting the molar ratios of ZnIn₂S₄ precursors to TiO₂ NFs. The photocatalytic activity of the as-prepared samples for water splitting under simulated solar light irradiation was assessed. The experimental results showed that the photocatalytic performance of the ZnIn₂S₄/TiO₂ composites was significantly improved, and the obtained ZnIn₂S₄/TiO₂ composites showed increased optical absorption. Under optimal conditions, the highest HER rate of the ZT-0.5 (molar ratio of ZnIn₂S₄/TiO₂= 0.5) sample was 8774 μmol·g^-1·h^-1, which is considerably higher than those of pure TiO₂ NFs (3312 μmol·g^-1·h^-1) and ZnIn₂S₄nanoplates (3114 μmol·g^-1·h^-1) by factors of 2.7 and 2.8, respectively. Based on the experimental data and Mott-Schottky analysis, a possible mechanism for the formation of the S-scheme heterojunction between ZnIn₂S₄ and TiO₂ was proposed to interpret the enhanced HER activity of the ZnIn₂S₄/TiO₂heterojunctionphotocatalysts.      

Comparison of slurry sampling and microwave-assisted digestion for calcium, magnesium, iron, copper and zinc determination in fish tissue samples by flame atomic absorption spectrometry

The development of a slurry sampling method for the determination of calcium, copper, iron, magnesium and zinc in fish tissue samples by flame atomic absorption spectrometry is described. In comparison with microwave-assisted digestion, the proposed method is simple, requires short time and eliminates total sample dissolution before analysis. Suspension medium was optimized for each analyte to obtain quantitative recoveries from fish tissue samples without matrix interferences. Nevertheless, iron recoveries higher than 46% were not found. Treatment of samples slurried in nitric acid by microwave irradiation for 15-30 s at 75-285 W permitted to achieve efficient recoveries for calcium, iron, magnesium and zinc. Further improvement in the matrix effects for iron determination was accomplished by the use of an additional step of short microwave-assisted suspension treatment. However, standard addition method was required for calcium and copper determination, being necessary hydrochloric acid as suspension medium for the last one. Although copper could not be determined in the certified reference material using microwave-assisted digestion, the accuracy of the slurry sampling method was verified for all the investigated analytes. Detection limits were 22.8 ± 8.0, 0.884 ± 0.092, 5.07 ± 0.76, 35.5 ± 0.7 and 1.17 ± 0.04 μg g⁻¹ for calcium, copper, iron, magnesium and zinc, respectively. The standard deviations obtained using slurry sampling method and microwave-assisted digestion were not significantly different, and the mean relative standard deviation of the over-all method (n = 3) of the slurry sampling method for different concentration levels was below 12%.     

Effect of HF addition on the microwave-assisted acid-digestion for the determination of metals in coal by inductively coupled plasma-atomic emission spectrometry

The microwave-assisted acid-digestion for the determination of metals in coal by ICP-AES was investigated, especially focusing on the necessity of adding HF. By testing five certified reference materials, BCR-180, BCR-040, NIST-1632b, NIST-1632c, and SARM-20, it was found that the two-stage digestion without HF (HNO₃ + H₂O₂ was used) was very effective for the pretreatment of ICP-AES measurement. Both major metals (Al, Ca, Fe, and Mg) and minor or trace metals (Co, Cr, Cu, Mn, Ni, Pb, and Zn) in coal gave good recoveries for their certified or reference values. The possibility of ‘HF-memory effect’ was cancelled by the use of a set of vessels which had been never contacted with HF. Twenty-four Japanese standard coals (SS coals) were analyzed by the present method, and the concentrations of major metals measured by the present method provided very high accordance with those from the authentic JIS (Japanese Industrial Standard) method.     

Novel visible-light-driven photocatalyst of NiO/Cd/g-C3N4 for enhanced degradation of methylene blue

Novel NiO/Cd/g-C₃N₄ photocatalysts were synthesized using a green and straightforward microwave-assisted method and characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), the Brunauer–Emmett–Teller (BET) method, transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and ultraviolet–visible spectroscopy (UV–Vis). The ternary NiO/Cd/g-C₃N₄ nanocomposites were evaluated for the degradation of methylene blue (MB) at room temperature under the visible light irradiation. Experimental results revealed that the weight percent of cadmium had a remarkable effect on the photodegradation efficiency. The NiO/Cd/g-C₃N₄ (0.1%) sample exhibited superior activity in the degradation reaction. The activity of this nanocomposite was about 4.5 and 3.25 fold higher than those of the pure g-C₃N₄ and NiO/g-C₃N₄ samples in the degradation of MB, respectively. The enhanced photocatalytic activity was attributed to the low energy gap, increased absorption capacity of the visible light, and efficient suppression of the recombination of photogenerated electron-hole pairs. A detailed photocatalytic mechanism over the nanocomposite of NiO/Cd/g-C₃N₄ (0.1%) was proposed with superoxide radical anion O₂^– as the main reactive species. The stability of the nanocomposite was confirmed after four consecutive runs as well.     

Synthesis of phosphorus (silicon,tin)-containing derivatives of mercaptoketenes and some of their properties

Some newS-phosphorylated,S-silylated, andS-stannylated derivatives of -mercaptoketones were obtained. The reactions of some of these compounds induced by the temperature and by molecular oxygen as well as the phosphorylation of the Si- and Sn-containing derivatives were studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 353–357, February, 1995.     

Chemistry of <Emphasis Type="Italic">N,N</Emphasis>-bis(silyloxy)enamines 7. Quaternization of tertiary amines and nitrogen-containing heterocycles by <Emphasis Type="Italic">N,N</Emphasis>-bis(silyloxy)enamines

Coupling of N,N-bis(silyloxy)enamines with tertiary amines and nitrogen-containing heterocycles affording the corresponding functionalized ammonium or iminium salts was studied. The area of its application was determined, and optimal procedures for the synthesis of the target products were proposed. The mechanism including the formation of conjugated nitroso alkene or a silylnitrosonium cation as key intermediates is discussed.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2137–2143, October, 2004.