羧基化多壁碳纳米管修饰碳糊电极用于溶出伏安法测定铋(Ⅲ)量

将羧基化的多壁碳纳米管滴涂在碳糊电极表面上,应用羧基化的多壁碳纳米管修饰碳糊电极(MWCNT-COOH/CPE)测定铋(Ⅲ)时,将试液在0.1mol.L-1盐酸溶液中在-500mV处预富集120s,使铋(Ⅲ)与1-(4-磺酸基苯基)-3-[4-(苯基偶氮)-苯基]-三氮烯(SPAPT)生成络合物,然后在-500～500mV范围内扫描,使络合物中的铋(Ⅲ)从电极上溶出,实现了铋离子的溶出伏安法测定。在-32mV处可得铋离子的氧化峰电位,其峰电流值与铋(Ⅲ)浓度在1.0×10-9～4.0×10-7 mol.L-1范围内呈线性关系,检出限(3S/N)为3.0×10-10 mol.L-1。     

A dual control problem and application to marketing

The general approach to adaptive and dual control is to formulate an optimal stochastic control problem. However, for such an approach only mathematical representations of the solution are available which allow little insight into the structure of the optimal controller. Here, an alternative deterministic approach is presented based upon determining a control in which a disturbance attenuation function remains bounded for all allowable (L₂ functions) disturbances. The disturbance attenuation function is composed of the ratio of an L₂ function of the desired outputs over an L₂ function of the disturbance inputs. This disturbance attenuation problem is converted to a differential game. For this game, the optimal control law, in a closed-form, is obtained by performing a minmax operation with respect to a quadratic cost function subjected to a bilinear system. The resulting controller is time-varying and depends nonlinearly on the state and the parameter estimates vector, and on an associated Riccati-type matrix. We provide insights into the structure of the resulting dual controller and illustrate the method by two examples. One of the examples is an application to marketing, to set promotional spending of a company, considering that the effect of promotional effort on sales is unknown.     

Synthesis and Fluorescent and Magnetic Properties of a New Europium Complex Eu(C_(20)H_(14)O_3N)_3(2,2'-bipy)(H_2O)·H_2O

A new europium(Ⅲ) complex Eu(C_(20)H_(14)O_3N)_3(2,2?-bipy)(H_2O)·H_2O has been synthesized with2-diphenylanine carbonyl benzoic acid and 2,2?-bipyridine as ligands.Crystal data for the complex are as follows:triclinic,space group ■,a=11.3334(5),b=16.0883(7),c=17.0116(8)?,α=70.411(4)o,β=82.435(4)o,γ=85.095(4)o,V=2894.0(2)?~3,D_c=1.484 g/cm~3,Z=2,μ=1.15 mm~(-1),F(000)=1320 and the final R=0.0447 and w R=0.0578.The Eu(Ⅲ) ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu~(3+):~5D_0→~7F_1 (592 nm) and ~5D_0→~7F_2 (616 nm),respectively.Also reported is the magnetic property of the complex.The complex exhibits antiferromagnetism in the temperature range of 300～2 K.     

Syntheses,Structures and Antitumor Activities of Tri(o-bromobenzyl)tin Diethyldithiocarbamate and Tri(m-fluorobenzyl)tin Pyrrolidine Dithiocarbamate

Tri(o-bromobenzyl)tin diethyldithiocarbamate(1) and tri(m-fluorobenzyl)tin pyrrolidine dithiocarbamate(2) have been synthesized and characterized by elemental analysis, IR spectroscopy, NMR(~1 H, ¹³C and ¹¹⁹Sn), thermogravimetric analysis and single-crystal X-ray diffraction. The two complexes crystallize in the triclinic system space group P1. For complex 1, a = 0.9770(1), b = 1.1011(1), c = 1.4583(1) nm, α = 78.431(1)°, β = 86.307(1)°, γ = 69.712(1)°, V = 1.4417(2) nm^3, Z = 2, Dc = 1.790 g/cm^3, m(Mo Kα) = 52.04 cm–1, F(000) = 756, R = 0.0434 and wR = 0.0593. For complex 2, a = 0.7055(1), b = 1.3349(3), c = 1.3782(3) nm, α = 89.216(2)°, β = 82.044(2)°, γ = 84.637(2)°, V = 1.2799(5) nm^3, Z = 2, Dc = 1.537 g/cm^3, m(Mo Kα) = 11.98 cm^–1, F(000) = 596, R = 0.0313 and wR = 0.0333. The two complexes represent mononuclear structures with five-coordinated [SnC3S2] cores forming a distorted trigonal bipyramid. The quantum chemical calculations of 1 and 2 have been investigated. The antitumor activity shows that 1 and 2 have higher activities than cisplatinum against Colo205, HepG2, MCF-7, Hela and H460 cell line in vitro.     

1-(水杨醛)-5-(香草醛)缩卡巴肼丁基锡配合物的合成、结构、谱学性质和除草活性

卡巴肼分别与水杨醛和香草醛缩合制备1,5-不对称二取代卡巴肼配体,在甲醇溶剂热中,正丁基三氯化锡与配体反应,合成1-(水杨醛)-5-(香草醛)缩卡巴肼丁基锡配合物(B1)和含N,N′-双水杨醛缩连氮分子的丁基锡配合物(B2),经元素分析,IR,1H、119Sn、13C NMR和X射线衍射晶体结构表征,配合物(B1)、(B2)晶体分别属单斜晶系、P21/n空间群和三斜晶系、P1空间群,中心锡与配基原子构成六配位畸形八面体构型,配合物(B1)在DMF-H2O溶剂体系中具有良好的荧光性质,当含水0~10%(V/V)时具有聚集荧光增强效应,含水量大于10%,随含水体积分数增加荧光强度减弱,以至最后淬灭。配体及其配合物(B1)对马齿苋、刺苋、决明子、四九菜心和苋菜5种靶标植物均具有一定生长抑制作用,尤其是配体对马齿苋、刺苋的生长有良好的抑制作用,配合物可以选择性抑制决明子的生长,可作为决明子除草剂的候选化合物。     

Unactivated C(sp3)–H functionalization via vinyl cations

Direct functionalization of inert C(sp³)–H bonds is a topic of immense contemporary interest and exceptional value in organic synthesis.The recent research has established a novel and practical protocol which features the engagement of vinyl cation species to functionalize C(sp³)–H bonds.The discussion of the topic is arranged by the strategies to generate the reactive intermediates,including ionization of vinyl triflates,addition of electrophiles to alkynes,tandem cyclization of enynes or diynes,and decomposition ofβ-hydroxy-α-diazo ketones.This review closes with a personal perspective on the dynamic research area of unactivated C(sp³)–H functionalization via vinyl cations.Hopefully,it will provide timely illumination and beneficial guidance for organic chemists who are interested in this area.Meanwhile continued development of the field is strongly anticipated in the future.     

Tuned C?H Functionalization to Construct Aza‐Podophyllotoxin/Aza‐Conidendrin Derivatives by Means of Domino Cyclization

An efficient domino cyclization method for the construction of aza‐podophyllotoxin/aza‐conidendrin derivatives has been established. Reactions of different dienes with aryl halides in the presence of a palladium catalytic system produced different kinds of podophyllotoxin derivatives through a highly regioselective C? H functionalization. Treatment of dienes with aryl halides that have electron‐withdrawing substituents on the phenyl ring created aza‐podophyllotoxin derivatives by means of the functionalization of the C? H bonds ortho to the C? halide bonds of the incoming aryl halides. The reaction of dienes with 1‐iodobenzene or aryl halides that incorporate electron‐donating groups produced aza‐conidendrin derivatives by means of the functionalization of both sp³ C? H and sp² C? H bonds. The regioselective C? H functionalization for the formation of different pseudo‐podophyllotoxin/‐conidendrin derivatives is proven by analyses of the ¹H NMR spectra of the products and selective X‐ray analyses of the structures of the products. Thus, the palladium‐catalyzed domino cyclization of 1,6‐dienes for the preparation of aza‐podophyllotoxin/aza‐conidendrin derivatives can be controlled by selectively controlling the C? H functionalization.     

一维链状三正丁基锡2,4-二氯苯氧乙酸酯的合成、结构和电化学性质研究

<正>有机锡化合物因具有抗癌活性和杀菌、杀螨作用,以及结构特点多变、反应性丰富,近年来引起了人们的高度关注,已合成出许多结构新颖和性能特殊的有机锡化合物[1-4]。研究发现,有机锡化合物中,中心锡原子的配位形式取决于与锡原子直接相连的     

三正丁基锡3-氨基-2-吡嗪甲酸酯聚合物的合成、结构和电化学性质研究

The tri(n-butyl)tin 3-amino-2-pyrazine formic ester polymer [n-Bu₃Sn(O₂CC₄H₂N₂NH₂-o)]_n has been synthesized and characterized by IR, ¹H NMR spectra and elemental analysis. Its crystal structure has been determined by X-ray diffraction. The crystal belongs to monoclinic space group P2₁/c with a=1.057 7(2) nm, b=1.083 6(2) nm, c=1.905 2(4) nm, β=100.604(3)°, Z=4, V=2.146 3(8) nm³, D_c=1.325 Mg·m^-3, μ(Mo Kα)=1.202 mm^-1, F(000)=880, R₁=0.039 3, wR₂=0.113 3. In the complex, tin atoms are five-coordinated distorted trigonal bipyramid configuration. Through the intermolecular N-H…N hydrogen bonds to form network structure with a “double bridge”. The result of analysis shows that the Sn(Ⅳ)/Sn(Ⅱ) electron transfer in electrode reaction is irreversible. CCDC: 779860.