纳米氧化铜的制备及常温脱硫效能研究

采用硝酸铜为原料、氢氧化钠溶液为沉淀剂、使用体积比为1∶1的乙醇-水溶液为分散剂的直接沉淀法制备，通过改变工艺条件得到了三种纳米氧化铜产品，平均粒径分别为25.63，10.74和7.57 nm。采用TG-DTA、FIR、XRD和TEM等对纳米氧化铜进行表征。对产品的常温脱硫活性进行了穿透试验，并与已开发的其他常温精脱硫产品进行了比较，结果表明纳米氧化铜应用于H₂S脱硫，可在常温条件下具有优异的脱硫活性，对H₂S的脱除精度可以达到0.05 mg·m^-3以下。经过优选，产品在3 000 h^-1空速下穿透硫容达到25.3%，高于同类型的其他脱硫剂产品。     

A Novel Green Preparation of a, a''''-Bis (substituted benzylidene)-cycloalkanones Promoted by FeCl_3 6H-2O in Ionic Liquid

a, a'-Bis(substituted benzylidene)cycloalkanones were efficiently prepared from cycloalkanones and benzaldehydes in [bmim][BF4] by using iron(III) chloride hexahydrate as a catalyst. It is shown that [bmim][BF4] and iron(III) chloride hexahydrate can be quantitatively recovered and be reused effectively for many times. Compared with the known methods, this novel process has the advantage of being an envkonmentally benign process together with good yields and mild reaction conditions.     

Underpotential deposition of tin(II) on a gold disc electrode and determination of tin in a tin plate sample

This work describes a study of the underpotential deposition (UPD) of Sn²⁺ on a polycrystalline gold disc electrode using cyclic voltammetry (CV) and chronocoulometry (CC). Sn²⁺ ions showed well-defined peaks from UPD and UPD stripping (UPD-S) in 1 mol/L HCl solutions, while bulk deposition (BD) and BD stripping (BD-S) of the ions were also observed. The measured UPD shifts, E_UPD, between the UPD-S and the BD-S peaks were more than 200 mV. The UPD charge and the surface coverage of tin were measured by CC. A new method for determining Sn²⁺ was therefore developed, based on the excellent electrochemical properties of the Au/Sn UPD system. A plot of the UPD-DPASV (differential pulse anodic stripping voltammetry) signal versus the Sn(II) concentration was obtained for [Sn(II)] of 1.98×10^–7 to 3.64×10^–5 M. The method developed here has been applied to determine the tin in a tin plate sample.     

Solvent-free Synthesis of Dihydrofuran-fused [60]Fullerene Derivatives by High-speed Vibration Milling

Solvent-free organic reactions have been attracting great interest of chemists due to the elimination of the usage of harmful organic solvents,low costs,and simplicity in the procedure1.Solvent-free mechanochemical reactions of fullerenes were explored and are significant for the reactions of fullerenes because the low solubility of fullerenes in common organic solvents requires large quantity of organic solvents and some novel fullerene reactions could only occur in the solid-state reaction2.…     

Spectroscopic characterization of effective components anthraquinones in Chinese medicinal herbs binding with serum albumins

The interactions of serum albumins such as human serum albumin (HSA) and bovine serum albumin (BSA) with emodin, rhein, aloe-emodin and aloin were assessed employing fluorescence quenching and absorption spectroscopic techniques. The results obtained revealed that there are relatively strong binding affinity for the four anthraquinones with HSA and BSA and the binding constants for the interactions of anthraquinones with HSA or BSA at 20 degrees C were obtained. Anthraquinone-albumin interactions were studied at different temperatures and in the presence of some metal ions. And the competition binding of anthraquinones with serum albumins was also discussed. The Stern-Volmer curves suggested that the quenching occurring in the reactions was the static quenching process. The binding distances and transfer efficiencies for each binding reactions were calculated according to the F?ster theory of non-radiation energy transfer. Using thermodynamic equations, the main action forces of these reactions were also obtained. The reasons of the different binding affinities for different anthraquinone-albumin reactions were probed from the point of view of molecular structures.     

硫代钼酸盐和硫代钨酸盐的合成性质和取代反应的研究

本文提出了在水或水/醇溶液中[NH_4]_2[MO_nS_(4-n)](M=Mo、W,n=0-2)进行取代反应的方法。用该方法合成出[X]_2[MO_nS_(4-n)](X=(n-Bu)_4N、Ph_4P、py—C_(16)H_(33)共18个化合物,其中11个为新化合物,并采用元素分析、红外光谱、电子光谱和X-粉末衍射等方法对这些化合物进行了表征。     

A microfluidic device using a green organic light emitting diode as an integrated excitation source

A simply fabricated microfluidic device using a green organic light emitting diode (OLED) and thin film interference filter as integrated excitation source is presented and applied to fluorescence detection of proteins. A layer-by-layer compact system consisting of glass/PDMS microchip, pinhole, excitation filter and OLED is designed and equipped with a coaxial optical fiber and for fluorescence detection a 300 microm thick excitation filter is employed for eliminating nearly 80% of the unwanted light emitted by OLEDs which has overlaped with the fluorescence spectrum of the dyes. The distance between OLED illuminant and microchannels is limited to approximately 1 mm for sensitive detection. The achieved fluorescence signal of 300 microM Rhodamine 6G is about 13 times as high as that without the excitation filter and 3.5 times the result of a perpendicular detection structure. This system has been used for fluorescence detection of Rhodamine 6G, Alexa 532 and BSA conjugates in 4% linear polyacrymide (LPA) buffer (in 1 x TBE, pH 8.3) and 1.4 fmol and 35 fmol mass detection limits at 0.7 nl injection volume for Alexa and Rhodamine dye have been obtained, respectively.     

Stereo- and enantioselective determination of pesticides in soil by using achiral and chiral liquid chromatography in combination with matrix solid-phase dispersion

The separation of enantiomers and diastereomers of 8 commonly used pesticides was investigated by liquid chromatography (LC) using a Chiralcel OD column (cellulose tris-3,5-dimethylphenylcarbamate as the chiral stationary phase) and a Pirkle-type Chirex 3020 column (urea derivative from the reaction of (R)-1-(alpha-naphthyl)ethylamine with (S)-tert-leucine, chemically bonded to 3-aminopropylsilanized silica as the chiral stationary phase). The pesticides studied included one organophosphorus insecticide (phenthoate), 3 triazole fungicides (uniconazole, diniconazole, and propiconazole), and 4 pyrethroids (fenpropathrin, beta-cypermethrin, beta-cyfluthrin, and alpha-fenvalerate). The enantiomers were separated within 20 min with a resolution of > or = 1.5 using a mixture of n-hexane and 2-propanol as the mobile phase for all the pesticides studied except propiconazole, for which only the 2 diastereomers were baseline separated. This method allows determination of the enantiomers or stereoisomers of the above pesticides in soil. The strategy was as follows: (1) First, the total concentration(s) of the enantiomer pair(s) of a chiral pesticide in soil was (were) determined by a newly developed matrix solid-phase dispersion (MSPD) procedure, followed by silica-based LC quantification. The recoveries ranged from 76.5 to 93.6% with relative standard deviations of 6.0%. (2) Second, the enantiomeric ratio(s) (ER(s)) of the chiral pesticide was (were) determined by LC with a chiral stationary phase after fractionation of the MSPD extract by silica-based LC. The determined ERs or stereoisomeric ratio(s) (SR(s); for propiconazole, only the SR of the 2 diastereomers was determined) in soil samples spiked with the above 8 racemic pesticides agreed with those of the corresponding standard solutions. (3) Third, based on the total concentrations and the corresponding ERs, the concentration of each enantiomer in soil was calculated. The proposed method is rapid, precise, and sensitive, and is appropriate for the investigation of the stereo- and enantioselective degradation of pesticides in environmental media.     

A spectroscopic study on the 12-heteropolyacids of molybdenum and tungsten (H3PMo12−nWnO40) combined with cetylpyridinium bromide in the epoxidation of cyclopentene

The epoxidation of cyclopentene with hydrogen peroxide catalyzed by 12-heteropolyacids of molybdenum and tungsten (H₃PMo_12−nW_nO₄₀, n = 1–11), 12-tungstophosphoric acid and 12-molybdophosphoric acid combined with cetylpyridinium bromide as a phase transfer reagent was carried out in acetonitrile. Among 13 heteropolyacids investigated, catalyst of H₃PMo₆W₆O₄₀ showed the highest activity, giving a conversion of 60% and a selectivity of 95% in the epoxidation of cyclopentene. The fresh catalysts and the catalysts under reaction condition were characterized by UV–vis, FT-IR and ³¹P NMR spectroscopy, which has revealed that all of the molybdotungstophosphoric acids were degraded in the presence of hydrogen peroxide to form a considerable amount of phosphorus-containing species. The active species resulted from H₃PMo₆W₆O₄₀ are new kinds of phosphorus-containing species, which is different from {PO₄[WO(O₂)₂]₄}³⁻.     

Synthesis of polypiperazine-amide thin-film membrane on PPESK hollow fiber UF membrane

A new interfacial polymerization (IP) procedure is developed in order to synthesize polypiperazine-amide thin-film membrane on the inner surface of poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber ultrafiltration (UF) membrane.A hollow fiber composite membrane with good performance was prepared and studied by FT-IR and scanning electron microscopy.