高分辨电感耦合等离子体质谱仪测定中亚山地冰川雪冰中超痕量元素

在超净实验条件下,利用高分辨电感耦合等离子体质谱仪直接测定雪冰样品中浓度在1ng/L~100μg/L之间的多种超痕量元素Al、Fe、Mn、Co、Cu、Zn、Sr、Sb、Cd、CsBa、Tl、Pb和Bi的实验方法进展。在测定过程中灵敏度的变化可通过监测ArAr质谱峰的变化进行校正,并建立了数学校正公式。以1%HNO3为空白溶液获得了各元素的检出限(ng/L)分别为:Al40、Mn6、Fe40、Co2.74、Cu9.6、Zn20、Sr0.03、Sb0.15、Cs0.04、Ba0.4、Tl0.07、Pb0.8和Bi0.05。利用标准参考物质SLRS-4对测试方法的准确度进行了评价。研究了在硝酸含量分别为0.5%、1%、2%和4%时雪冰中超痕量元素质谱信号强度的变化特点。测定结果发现,对于污化层样品,当硝酸的含量为1%时痕量元素的质谱信号强度最大;对于非污化层样品,痕量元素的质谱信号强度在硝酸含量为0.5%时较大,但与硝酸含量为1%时的质谱信号强度相比变化率小于10%。结合中亚山地冰川雪冰中痕量元素浓度差别大的特点,确定硝酸在样品中的含量为1%为合适的酸度。并对卓奥友峰和珠穆朗玛峰雪坑样品进行了分析方法的重复性研究。     

阴离子型层柱材料的插层组装

提出插层组装的概念,论述了阴离子型层状材料经插层组装出结构有序的层柱材料,包括层柱材料插层组装途径、插层组装的客体、插层组装的驱动力以组装客体在层间的定位,以及插层组装的发展前景。     

Synthesis of a new class of conformationally rigid phosphino-oxazolines: highly enantioselective ligands for Ir-catalyzed asymmetric hydrogenation

[reaction: see text] A new class of conformationally rigid phosphino-oxazoline ligands were synthesized from readily available enantiopure phenyl glycinol. Ir complexes with these ligands are air-stable and highly enantioselective catalysts for asymmetric hydrogenation of aryl alkenes and alpha,beta-unsaturated esters in up to 99% ee.     

膜渗透与离子色谱联用技术测定蔬菜中亚硝酸盐和硝酸盐

建立了膜渗析与离子色谱联用技术分析蔬菜等复杂基体中亚硝酸盐和硝酸盐的方法。蔬菜样品经沸水浴后,试样液通过膜渗析除去水溶性大分子杂质和颗粒,直接进入离子色谱分析。渗析池采用0.20μm的醋酸纤维为渗析膜,以水为接收液,分析柱为Metrosep A Supp4-250阴离子交换柱,以1.8mmol/L Na2CO3 1.7mmol/L NaHCO3为流动相,采用化学抑制电导检测。以20g称样计量,方法中NO2-、NO3-的检出限分别为0.075mg/kg和0.105mg/kg;实际样品的加标回收率分别为80.6%~98.7%和90.5%~114%;相对标准偏差(RSD)≤10%。本方法前处理简单,重现性好,准确度高。     

电子辐照诱发固态相变导致的氮化硼纳米结构生长

报道了N+离子轰击产生的氮化硼(BN)纳米结构,及在电子辐照时结构演化的高分辨透射电子显微镜的原位测定结果.应当强调的是,这种类富勒烯和发夹结构的演化,实际上是电子辐照诱发固态相变的发展,观察中发现的一些BN颗粒、卷曲物,可以被认为是类富勒烯等纳米结构形成的前体或早期阶段.提出了一种类富勒烯等结构的电子辐照动力学模型,并进行了讨论. 关键词： 氮化硼 电子辐照 透射电子显微镜 氮化硼纳米形成物     

DYNAMIC STRESS FIELD AROUND THE MODE Ⅲ CRACK TIP IN AN ORTHOTROPIC FUNCTIONALLY GRADED MATERIAL

The problem of a Griffith crack in an unbounded orthotropic functionally graded material subjected to antipole shear impact was studied. The shear moduli in two directions of the functionally graded material were assumed to vary proportionately as definite gradient. By using integral transforms and dual integral equations, the local dynamic stress field was obtained. The results of dynamic stress intensity factor show that increasing shear moduli’s gradient of FGM or increasing the shear modulus in direction perpendicular to crack surface can restrain the magnitude of dynamic stress intensity factor.     

Metal complexes formed by metal-assisted solvolysis of di-pyridylketone azine: structures and magnetic properties

A series of metal complexes were achieved from the metal-assisted solvolysis reaction of di-pyridylketone azine (dpka). The tetranuclear nickel cluster , [Ni(2)[dpk(O)(OH)][dpk(O)(OCH(3))](N(3))(2)](2), is centrosymmetric with a central core described as an edge-shared triangle core. Neighboring Ni(II) ions are alternately bridged by (micro(2)-N(3), micro(3)-O) and (micro(2)-O, micro(3)-O) double bridges. Complex , [Cu(4)[dpk(O)(OCH(3))](4)(N(3))(2)](CuCl(2))(2) contains a tetranuclear cluster and two identical [CuCl(2)]M(-) anions. The tetranuclear structure has two crystallographically imposed twofold axes, in which the four copper ions are arranged to be rhombic shape. The neighboring copper(ii) ions along the lateral are bridged by single micro(2)-O from the ligand dpk(O)(OCH(3)) and the short diagonal copper ions are bridged by two symmetric end-on azides. In dinuclear Cu(ii) complex [Cu(2)[dpka(OCH(2)CH(3))]Cl(2)](ClO(4)) (3), the metal centers are coordinated in a planar configuration and bridged by a -N-N- bridge. It is also observed that the Cl atom coordinated to one Cu(II) center is also weakly coordinated to another inversion related Cu(II) to generate a centrosymmetric dimer. The metal centers in one-dimensional polymeric Cu(ii) complex [Cu(2)[dpka(OCH(3))](N(3))(2)(ClO(4))](n) (4), however, are bridged by a -N-N- bridge and an end-to-end azide bridge, alternately. Magnetic susceptibility measurements indicate that shows ferromagnetic interaction within the tetranuclear cluster, and that displays moderately strong antiferromagnetic interaction (J = -56.7 cm(-1)) for the bis(micro-N(3)) bridge. For compound , it shows strong antiferromagnetic coupling (J = -286 cm(-1)) between the intradinuclear Cu(II) ions mediated by the single N-N bridge and negligible magnetic interactions between the adjacent dinuclear Cu(II) ions mediated by the single end-to-end azide bridge. The mechanism of the metal-assisted solvolysis reaction was also discussed.     

大蒜对硒的吸收及硒对大蒜生长的影响

在培养液中添加不同浓度的Ｎａ２ＳｅＯ３研究大蒜对硒的吸收以及吸收的硒对大蒜生长的影响。结果表明，大蒜对硒具有很强的生物富集作用，总硒含量为对照的６２２倍，当添加１ｍｍｏｌ／ＬＮａ２ＳｅＯ３时，有机化程度最主达７８．２４％，另外吸收的硒影响大蒜的生长，低浓度硒促进大蒜生长，１ｍｍｏｌ／ＬＮａ２ＳｅＯ为最适的促进生长浓度，并能提高大蒜中的蛋白质，可溶性糖，ＤＮＡ，ＲＮＡ含量，大蒜可作为补硒和高营养价值     

A Facile Method of Synthesis of a Calix[4]arene Amide and the Crystal Structure of a Self-assembled Calix[4]arene Amide via van Der Waals Interaction

A new facile method of synthesis of calix[4]arene amide via the aminolysis of the calix[4]arene esters was reported. One ethyl ester of the compound (2) was aminolysized byn-butylamine. The crystal structure of compound (1)shows that one ethyl ester of compound (1) enters into thecavity of another compound (1) forming a long chainhost-guest supramolecule. From the 2D NMR data, the compound(1) does not assemble in THF or CHCl₃ solution. The CH- interaction and crystallization energy might be theimportant driving forces for forming the self-assembledcalix[4]arene.     

Discrete global descent method for discrete global optimization and nonlinear integer programming

A novel method, entitled the discrete global descent method, is developed in this paper to solve discrete global optimization problems and nonlinear integer programming problems. This method moves from one discrete minimizer of the objective function f to another better one at each iteration with the help of an auxiliary function, entitled the discrete global descent function. The discrete global descent function guarantees that its discrete minimizers coincide with the better discrete minimizers of f under some standard assumptions. This property also ensures that a better discrete minimizer of f can be found by some classical local search methods. Numerical experiments on several test problems with up to 100 integer variables and up to 1.38 × 10¹⁰⁴ feasible points have demonstrated the applicability and efficiency of the proposed method.