湿法消解-氢化物发生-原子荧光光谱法测定土壤中的铅

应用AFS-230E型双道原子荧光光谱仪进行了氢化物发生-原子荧光法测定土壤中铅的研究.方法中采用硝酸做介质,将铁氰化钾直接加入硼氢化钠-氢氧化钠碱性溶液中,并对各种最佳分析条件进行了探讨和验证.铅的校准曲线在0-100μg/L浓度范围内呈线性,方法的检出限为0.14μg/L,相对标准偏差为2.1％,回收率为91.0％-95.0％.用标准物质进行对照,其测定值在给定的标准值范围之内.该方法操作简单、灵敏度高、高效,适合土壤样品中铅的测定.     

鸟苷发酵不同阶段发酵液紫外特征光谱的研究

研究了发酵不同阶段鸟苷发酵液的紫外吸收光谱,结果表明,鸟苷发酵不同阶段发酵液紫外吸收光谱会呈现相应的特征光谱。发酵前期除了275nm处的波峰外,在249nm又出现了一个新峰,并且随着发酵时间增加新峰逐渐升高成为主峰;发酵中期275nm处的波峰逐渐减弱并最后消失;发酵后期249nm处的波峰成为发酵液的特征波峰,并随时间的增加逐渐上升;发酵末期的显著特征为发酵液λmax的吸光值基本不变。鸟苷发酵不同阶段发酵液特征光谱研究为人们认识鸟苷发酵的动态过程提供了一种新的技术和途径,对于鸟苷发酵生产具有一定的指导意义。     

Synthesis and characterization of a poly(N‐isopropylacrylamide) with β‐cyclodextrin as pendant groups

A novel linear poly(N‐isopropylacrylamide) (PNIPA) with β‐cylodextrin (β‐CD) moiety (PNIPA‐β‐CD) was synthesized by the conjugation of β‐CD carrying amino groups (EDA‐β‐CD) onto PNIPA with epoxy groups (P(NIPA‐co‐GMA), M_n = 3.86 × 10⁴), and the related reaction conditions are investigated. PNIPA‐β‐CD was characterized by means of IR, NMR and UV spectroscopes, element analysis, and differential scanning calorimetry (DSC). The number‐average molecular weight (M_n) and the β‐CD content of the obtained PNIPA‐β‐CD are 4.87 × 10⁴ and 18.8 wt %, respectively. PNIPA‐β‐CD can not only respond to temperature stimuli but also include guest molecules. Lower critical solution temperature (LCST) of aqueous PNIPA‐β‐CD solution is similar to that of PNIPA. The association constant (K_a) for PNIPA‐β‐CD with methyl orange (MO) is 2.4 × 10³ L mol^?1 at pH 1.4, which is comparable to that of EDA‐β‐CD (K_a = 2.9 × 10³ L mol^?1). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3516–3524, 2005     

基于有序介孔碳/纳米金/L-半胱氨酸修饰电极测定铜(Ⅱ)

将纳米金(NG)电沉积在有序介孔碳(OMC)修饰玻碳电极表面,并将L-半胱氨酸(L-Cys)自组装至OM C/NG修饰电极表面,制备了OM C/NG/L-Cys修饰电极。采用透射电子显微镜考察了OM C的结构,扫描电子显微镜研究了OMC/NG/L-Cys修饰电极的表面形貌。考察了Cu2+在该修饰电极上的电化学行为,优化了Cu2+的测定条件。在最优条件下,溶出峰峰电流与Cu2+浓度在0.05~6.0μmol/L范围内呈良好线性关系,检出限为0.03μmol/L(S/N=3)。方法用于河水样品分析,其加标回收率在92.7%~101.6%之间。     

Density Functional Theory and Mass Spectrometry of Phthalate Fragmentations Mechanisms: Modeling Hyperconjugated Carbocation and Radical Cation Complexes with Neutral Molecules

This is the first ab initio study of the energetics of the fragmentation mechanisms of phthalate, by mass spectrometry, leading to protonated phthalic anhydride (m/z 149). Phthalates fragment by two major pathways; namely, the McLafferty + 1 rearrangement and the loss of alkoxy. Both pathways involve a carbonyl oxygen attack to the ortho-carbonyl carbon leading to structures with tetrahedral carbon intermediates that eventually give m/z 149. These pathways were studied by collision induced dissociation (CID) using triple quadrupole mass spectrometry. The proposed McLafferty + 1 pathway proceeds through a distonic M^•+, leading to the loss of an allylic-stabilized alkene radical. The McLafferty rearrangement step proceeds through a six-membered ring transition state with a small activation energy ranging 0.4–6.2 kcal/mol; the transfer of a second H from the distonic ion of the rearrangement step proceeds through a radical cation molecule complex. Based on quantum chemical modeling of the cation molecule complexes, two kinds of cation molecule complexes were identified as radical cation molecule complex and hyperconjugated cation molecule complex. This distinction is based on the cation and simplifies future modeling of similar complexes. Optimization of important fragments in these pathways showed cyclized and hydrogen-bonded structures to be favored. An exception was the optimized structure of the protonated phthalic anhydride (m/z 149) that showed a structure with an open anhydride ring.     

Neutron-induced defects in the lithium tetraborate single crystals

The X-band ( x ; 9.4 v GHz) electron spin resonance (ESR) spectra of the un-doped isotopically enriched lithium tetraborate (LTB) Li 2 B 4 O 7 single crystals, irradiated by thermal neutrons (fluences | n =2.74 ‐ 10 15 1 1.79 v ‐ 10 18 v cm m 2 ) were investigated at 300 and 77 v K. The LTB crystals of high chemical purity and optical quality with different isotope compositions ( 6 Li 2 10 B 4 O 7 , 6 Li 2 11 B 4 O 7 , 7 Li 2 10 B 4 O 7 and 7 Li 2 11 B 4 O 7 ) were grown by Czochralski technique. The thermal neutrons (the total quantity >90%) with fluence near 10 18 v cm m 2 induce at least 4 different types of stable paramagnetic centers in the Li and B isotopically enriched LTB crystals. The ESR spectra, electron structure and efficiency of generation for centers, induced by thermal neutrons, essentially depend on neutron fluence and isotope composition of the LTB crystals. The local symmetry and the spin Hamiltonian parameters of the observed paramagnetic centers were determined and their electron structure were established. The possible models and formation mechanism of the radiation defects, induced by thermal neutrons in the LTB lattice, are proposed.     

Fluctuation theory of hydrogen bonding applied to vibration spectra of HOD molecules in liquid water. I. Raman spectra

Statistical distributions of the frequencies of OH vibrations calculated from the experimental Raman spectra of HOD molecules over the temperature range of 10–200 C using the recently developed deconvolution technique have been analysed in the framework of fluctuation theory of hydrogen bonding. Two temperature independent functions that are the basis of the Zhukovsky theory for describing the temperature transformation of frequency distribution functions of OH vibrations in a statistical ensemble of O—H…O bonds were established and analytically approximated. This made it possible to reconstruct the entire set of initial spectra and to extrapolate their forms to a wider temperature range. These results support the continuum model of liquid water structure.     

Biserial Incidence Algebras

Let K be an algebraically closed field and A be a finite dimensional algebra over K. In this paper we give a classification of biserial incidence algebras with quiver methods.     

非谐环盘及变幅杆组成的变幅器动力学特性研究

为了解决齿轮超声加工振动系统的设计问题,将齿轮简化为环盘,根据环盘及变幅杆的力耦合条件、边界条件及动力学方程,推导了非谐环盘及变幅杆组成的变幅器的频率方程,并利用其设计了变幅器,实验证明:变幅器的谐振频率与理论设计结果基本一致.该理论方法使变幅器由全谐振设计拓展到非谐振设计.     

雷公滕碱乙,碱庚和碱己的结构

Wilforine, wilformine (I), wilforgine, and wilforzine were identified from T. wilfordii. IR, NMR, and mass spectrometry were used to identify the structures of these alkaloids.