综述并分析了三唑类抗真菌药物中间体(2R,3S)-2-(2,4-二氟苯基)-3-甲基-[(1H-1,2,4-三-氮唑-1-基)甲基]环氧乙烷的合成方法,对工业化生产的技术方法提出了建议.

A simple pulsed slow positron beam based on a Penning-trap has been designed and is being constructed in Wuhan University. The cooled positrons from the trap with very low energy dispersion are dumped and chopped to pulses of a few tens of ns in width. Positron pulses are bunched by adjusting the potential of drift tube using an arbitrary wave generator, then accelerated to the target. Influences of the pulse width, the energy dispersion of positrons etc. on the time resolution of bunched positron pulse are simulated. The result shows that lower energy dispersion of positrons leads to much narrower positron pulses, indicating that a trap-based slow positron beam has a great advantage in developing a pulsed slow positron beam.

We did some research on the surface structures of the NaY zeolite,USY zeolite and porous γ-Al2O3 by positron annihilation lifetime spectroscopy in low temperature of 20-300 K.We measured the positron lifetimes of the three dehydration samples in low temperature respectively,in which,the lifetime spectra of NaY and USY were resolved into five components,and that of the γ-Al2O3 were resolved into four components.The results showed that the shorter lifetimes were not relative to the measure temperature,but the longest lifetime(about 40 ns) was relative to the measure temperature.The different relativity of the lifetime-temperature means the different surface structures of the NaY zeolite from that of the porous γ-Al2O3.

A. series of the MoO3/-gamma-Al2O3 samples is prepared by mechanically mixing MoO3 with gamma-Al2O3 powder. The solid state dispersion of the MoO3 in to the porous gamma-Al2O3 is studied by SEM, XRD, XPS, TG/DTA, and positron annihilation spectroscopy. The positron annihilation lifetime spectra of the MoO3/-gamma-Al2O3 are measured as a function of the mass ratio of MoO3 heating temperature, heating time and in a way that the MoO3 is loaded gradually, separately. The experimental results show the process of the thermal dispersion of the MoO3 into the gamma-Al2O3 support. It is shown that the MoO3 disperses into the outer surface first, and then into the secondary pores and the micro pores. The gradual Loading can make MoO3 effectively dispersed into gamma-Al2O3. Grinding can also affecte the thermal dispersion process.

A series of the MoO3/γ-Al2O3 samples is prepared by mechanically mixing MoO3 with γ-Al2O3 powder. The solid state dispersion of the MoO3 in to the porous γ-Al2O3 is studied by SEM, XRD, XPS, TG/DTA, and positron annihilation spectroscopy. The positron annihilation lifetime spectra of the MoO3/γ-Al2O3 are measured as a function of the mass ratio of MoO3, heating temperature, heating time and in a way that the MoO3 is loaded gradually, separately. The experimental results show the process of the thermal dispersion of the MoO3 into the γ-Al2O3 support. It is shown that the MoO3 disperses into the outer surface first, and then into the secondary pores and the micro pores. The gradual Loading can make MoO3 effectively dispersed into γ-Al2O3. Grinding can also affecte the thermal dispersion process.

用XRD、XPS、TG/DTA及正电子湮没谱学研究以浸渍法将三价铁离子(Fe(Ⅲ))加载于多γ-Al2O3载体上后,Fe(Ⅲ)在载体中的分散过程.研究了Fe(Ⅲ)/y-Al2O3原样,经60℃脱水2h以及经500℃烘烤1h后正电子寿命随Fe(Ⅲ)含量的变化;高含量(9.6%)、低含量(1.8%)Fe(Ⅲ)/y-Al2O3样品与γ-Al2O3载体的TG/DTA及其正电子寿命随烘烤温度的变化.实验表明:浸渍法能使Fe(Ⅲ)均匀地分散于载体二次孔内表面,置换出部分羧基中的氮;只有在高于400℃烘烤后,Fe(Ⅲ)和载体才能发生明显的相互作用,表现出应有的活性.

We report the synthesis and structural elucidation of two series of chiral cyclic squaramides, i.e. six-and twelve-membered ring squaramides 4 and 6, based on the cyclobutenedione structure, containing enantiomerically pure (1R,2R)-1,2-diphenylethylenediamine as the chiral element. Compounds 4a-d obtained from alkylation of 3, crystallize in space groups of monoclinic P2(1), monoclinic P2(1), monoclinic chiral P2(1)2(1)2(1), and the orthorhombic C222(1), respectively. For the first time the crystal structures of six-membered ring chiral cyclic squaramides are reported. These novel ligands have been tested in the enantioselective addition of diethylzinc to aryl aldehydes to give the corresponding alcohols in moderate yields, albeit with low enantioselectivity.

以浸渍法将不同浓度的钼酸铵水溶液加载于多孔γ-Al2O3,中,再经不同温度烘烤后制得Mo/γ-Al2O3样品.用热分析、XPS以及正电子湮没谱学对样品进行测试.实验表明浸渍法可使Mo均匀地分散在样品表面,当烘烤温度达到350.C后,Mo主要以取代氧化铝表面羟基中氢的方式与载体γ-Al2O3,发生相互作用,并以化学吸附的方式将钼离子固定于γ-Al2O3二次孔中.

用浸渍法制备了一系列不同担载量的负载型镍催化剂,并经不同温度下烘烤1小时后得到Ni/γ-Al2O3样品.分别用热分析(DTA/TG)、正电子湮没谱学等方法来表征镍在多孔氧化铝(γ-Al2O3)表面的分散特性.实验表明,在浸渍法制得的样品中,镍均匀分散于载体表面,在烘烤温度达到320℃时获得活性;在更高的烘烤温度下镍会向体内中扩散,使有效活性减少.

Co2+/γ-Al2O3 samples were prepared by incipient wetness impregnation of γ-Al2O3 with different concentration solution of CoCl2 and dried at 40 °C. We measured the positron lifetime spectra of the samples of different Co2+ mass fractions (0%–8.24%) heated at different temperatures (100–500°C). All lifetime spectra were resolved into four components, in which the third and the fourth components were related to the surface state of the micropores and the secondary pores of the γ-Al2O3. The experimental results showed that the Co2+ was mainly located in the micropores and the secondary pores near to the exterior of the support. For low Co2+ mass fraction samples, when the heating temperature was above 400 °C, dispersal was almost finished. When the Co2+ mass fraction was above 5.59%, Co2+ and Cl− were dispersed into the secondary pores in the form of multiple layers.

The samples were prepared from mechanical mixtures of Fe(NO3)3·9H2O with γ-Al2O3,and then the spontaneous dispersions of the Fe(Ⅲ) into the γ-Al2O3 support were studied by positron annihilation spectroscopy.We measured the positron annihilation lifetime spectra of the samples with different Fe(Ⅲ)(1.3%-4.2%) contents heated at different temperatures 100-600 ℃.It showed that with no heating,most of Fe(Ⅲ) was mainly located at the surface of the support.When the samples were heated,Fe(Ⅲ) would go to inner secondary pores and take the active-centres first,some went to the mircopores.When heated over 400 ℃,Fe(Ⅲ) could disperse evenly.

The reaction kinetics of positronium o-Ps on MoNi/Al2O3 hydrotreating catalyst was studied by using the positron annihilation spectroscopy for chemical analysis(PASCA).It was known from the experimental results that,under the temperature range of 20-100℃ and vacuum 1×10-5 Pa,the activation energy of o-Ps on MoNi/Al2O3 catalyst was 11.09 kJ/mol,reaction frequency factor A was 1.178×1010 kg/(mol·s) and reaction rate constant K was 1.344×108 kg/(mol·s)(25℃),respectively,on the basis of which,the kinetic equation was set up.The experiments were also carried out for the catalysts with various metal loading on the same support,and it was found that the characteristic correlative coefficient(k) is only related with the characteristics of support,but had nothing to do with the kinds of loading metals.The change of MSI could be shown by the change of k,to give some inspiration to the development of better catalyst.

采用氨吸附-程序升温脱附(NH3-TPD)、低温N2吸附(BET)、压汞法以及加氢精制活性评价等技术,探索SiO2-Al2O3载体在制备过程中孔结构和表面性质的变化.实验结果表明,采用特殊扩孔剂制备载体,当焙烧温度为700℃时,平均孔径可达到17.3nm,其中孔径大于20 nm的孔占总孔体积的13.2%;同时载体表面上的中、强酸中心也全部丧失,均为弱酸中心.采用该载体制备的MoNiP/SiO2-Al2O3石蜡加氢精制催化剂,在MoO3用量减少了约1/4的情况下,比目前工业上使用的催化剂具有更高的脱金属能力和加氢精制活性.

The effects of cephanone on the surface activity and aggregation behavior of Triton X-100 molecule were studied by the methods of surface tension and fluorescence, respectively. The binding constant between cephanone and Triton X-100 micelles was determined by the method of steady state fluorescence. The location of cephanone in Triton X-100 micelles was investigated through nuclear magnetic spectroscopy(NMR). The results showed that the surface activity of Triton X-100 decreased with the increase of cephanone concentration. With the increase of Triton X-100 concentration, the binding constant between cephanone and Triton X-100 micelles decreased, but the distribution coefficient of cephanone between Triton X-100 micelles and water continuous phase kept to be invariable. The results of H-1-NMR showed that cephanone was located around the polar group of Triton X-100 micelle.

In this article,we firstly report combination use of the two initiators for synthesizing monodispersed poly(methyl methacrylate)(PMMA) microspheres.Under gravity and surface tension of the liquid,PMMA microspheres was self-organized into an ordered structure-photonic crystals.Result from that,the ratio of refractive index and limitation in photonic crystals can influence the location of photonic gap,which is in accord with Bragg-Snell law.Also we report the deviation of photonic gap was observed between the experimental value and the theoretical value which was caculated by translight software based on the transfer matrix method(TMM).We also got PMMA/ TiO_2 photonic crystals by filling TiO_2 nanocrystals into PMMA photonic crystals.Due to the larger ratio of refractive index,the photonic gap display red shift.

A series of samples of rare-earth NaY zeolite (RE-NaY), prepared from mechanical mixtures of rare-earth chloride with NaY zeolite, were studied by positron annihilation spectroscopy. We measured the positron lifetime spectra as a function of the rare-earth chloride content in the RE-NaY heated at 500 degreesC for 1 h, as a function of the heating temperature with heating time of 1 h, and as a function of the heating time at 500 degreesC for RE-NaY (5%) respectively. All lifetime spectra were resolved into five components, in which the third, the fourth and the fifth components are related to the ortho-positronium annihilation in sodalite cage, supercage and interface void, respectively. The experimental results showed that positron annihilation spectroscopy was sensitive to the change of the dispersion of rare earth in NaY zeolite.

The positron annihilation lifetime spectra were measured as a function of the content of the nano-nickel, of temperature, as well as of the heating time for the supported nano-nickel catalyst that was prepared by mechanical mixture nano-metal nickel particles with gamma-alumina (γ-Al2O3). The lifetime spectra were well resolved into four lifetime components. The longest lifetime τ4 was assigned to ortho-positronium annihilating in the secondary pore of the γ-Al2O3. The results showed that part of the nano-nickel had entered into γ-Al2O3 by thermal diffusion at heating above 200°C and had interacted with the face of the γ-Al2O3, but the length of diffusion is not very large.

A series of samples, prepared from mechanical mixtures of NaCl with NaY zeolite and resulting in the dispersion of NaCl in NaY, was studied by position annihila tion spectroscopy. We measured the positron lifetime spectroscopy as a function of the weight ratio of the NaCl-NaY zeolite heated at 500℃ for 1h, as a function of the heating temperature held for 1h, and as a function of the heating duration at 500℃ for NaCl/NaY(15%). All the lifetime spectra were resolved into five components, in which the third, fourth and fifth components are related to the positron annihilation in β cage, supercage and interface void respectively. The experimental results showed that position annihilation spectroscopy is sensitiv e to the change of the dispersion of NaCl in NaY zeolite.