新型双苯甲酰基脲类化合物的合成

从原料百菌清出发,经过氟交换、氨解、水解、脱羧和酰化反应,合成得到12个新型双苯甲酰基脲类几丁质抑制剂衍生物,总收率超过30％-50％。     

昆虫几丁质抑制剂苯甲酰基苯脲类中苯甲酰基邻位取代基团对杀虫活性的影响

采用分子力学方法对苯甲酰基脲类昆虫几丁质抑制剂进行计算，发现苯甲酰基中的苯环与相连酰胺平面的夹角影响该类药物的杀虫活性，其中夹角在４０°左右杀虫活性最高。说明了分子中的构象影响杀虫活性。而这方面结果用传统的ＱＳＡＲ法难以得到，本计算结果较好的说明了苯甲酰基部分邻位取代基中２，６－二氟＞２－氯＞２，６－二氯＞２－氟的杀虫活性次序。     

1—（5‘—甲氧羰基—2’—羟基苯甲酰基（—1—（2‘—甲氧苯甲酰基）甲烷与Ac2O和HC...

邻羟基二苯甲酰基甲烷与Ａｃ２Ｏ和ＨＣ（ＯＥｔ）３反应通常是ＨＣ（ＯＥｔ）３作为酰化剂，得到３－苯甲酰基色酮。本文报道５－甲氧羰基－２－羟基苯甲酰基－（２＇－甲氧苯甲酰基）甲烷与Ａｃ２Ｏ和ＨＣ（ＯＥｔ）ｓ反应时，是Ａｃ２Ｏ而不是ＨＣ（ＯＥｔ）作为酰化剂，生成３－苯甲酰基－２－甲基色酮。其结构经ＮＭＲ、ＭＳ、ＩＲ和ＥＡ证实。并对其反应机理作了讨论。     

三苯甲酰基纤维素酯微珠的制备

以微晶纤维素为原料合成三苯甲酰基纤维素酯，将粉末状的三苯甲酰基纤维素酯转变成用于高效液相色谱手性填料的微珠，通过扫描电子显微分析考察了微珠的粒径分布。     

双（1—乙酰基—4—取代苯甲酰基氨基硫脲）及其衍生物的合成

由丁二酰肼Ⅰ与取代苯甲酰基异硫氰酯在无水CaCl_2处理过的乙腈溶剂中亲核加成,制得一系列未知的双(1-乙酰基-4-取代苯甲酰基氨基硫脲)衍生物Ⅱ,Ⅱ在碱性条件下环化为未知的双(3-亚甲基-4-取代苯甲酰基-1,2,4-三唑啉-5-硫酮)Ⅲ ,所有化合物结构均经鉴定,部分化合物对枯草芽孢杆菌和大肠杆菌有抑制作用。     

多卤代苯甲酰基脲类几丁质抑制剂的合成及杀虫活性多卤代苯甲酰基脲类几丁质抑制剂的合成及杀虫活性

从易得原料百菌清1出发, 经过氟交换、氨解、水解、脱羧和酰化反应, 合成得到10个新的多卤代苯甲酰基脲类几丁质抑制剂衍生物, 总收率为30%～50%. 所有化合物经¹H NMR, HREIMS, IR光谱证实. 对化合物进行了生物活性筛选, 结果表明该类化合物对粘虫和蚊幼虫均有一定的杀虫活性.     

双苯甲酰基脲类化合物的合成及杀虫活性

双苯甲酰基脲类化合物的合成及杀虫活性;双苯甲酰基脲;合成;百菌清;杀虫活性     

α（1,2,4—三唑—1—基）—α—苯甲酰基烯酮N,S;N,N;N,O和O,S…

以α（１，２，４三唑－１－基）－α－苯甲酰基烯酮二甲硫缩醛为反应中间体，与取代苯胺、邻苯二胺、乙二胺、乙醇胺和巯基乙醇反应，合成了２７个标题化合物，初步的生物活性测定表明，所合成的部分化合物具有抑菌及植物生长调节活性。     

3,3′—二苯甲酰基双酚—S及苯甲酰侧基聚芳醚腈的合成

利用双酚－Ｓ与苯甲酰氯形成的二元酚酯在ＡｌＣｌ３作用下进行Ｆｒｉｅｓ重排制备３，３′－二苯甲酰基双酚－Ｓ，以此与二氯苯甲腈进行缩聚反应合成了带苯甲酰基侧基的聚芳醚腈。     

具有生物活性有机磷化合物研究(ⅩⅪ)α-(取代苯甲酰胺基甲酰氧基)烃基膦酸酯衍生物的合成及性质

通过α－羟基烃基膦酸酯同取代苯甲酰基异氰酸酯的亲核加成反应合成了１６种含有取代苯甲酰胺基甲酰氧基烃基膦酸酯类化合物，收率８０～９０％。     

冠醚化Schiff 碱配合物金属胶束催化BNPP水解动力学

研究了两种新的冠醚化Schiff 碱过渡金属配合物与表面活性剂Brij35(聚氧乙烯(23)十二烷基醚)形成的金属胶束对BNPP（对硝基苯酚磷酸二酯）的催化水解反应. 探讨了催化反应机理, 建立了一种金属胶束催化BNPP水解的动力学数学模型; 计算了模拟酶催化反应的相关参数和表观活化能. 结果表明, 此类金属胶束作为模拟水解金属酶对BNPP水解反应表现出良好的催化活性.     

苯并氮杂冠醚-15-冠-5 Schiff碱钴(Ⅱ)配合物在胶束中催化BNPP水解研究

在催化磷酸二酯水解的模拟酶模型中,配合物配体结构扮演了非常重要的角色[1-2]。由于冠醚环具有主客体识别功能,在酶学理论中把它作为模拟酶的第一代生物有机体。镶嵌有过渡金属离子的冠醚配合物对催化磷酸二酯水解具有很好的活性[3];Schiff碱过渡金属离子配合物对催化磷酸二酯水解也具有很好的活性[4]。因此,冠醚Schiff碱过渡金属离子配合物对催化磷酸二酯水解也应具有很好的活性,这已有所报道[5]。但冠醚结构和过渡金属离子相同而取代基不同的配合物作为模拟酶催化磷酸二酯水解还未见报道。本文按文献设计合成了三种冠醚结构相同而取代基…     

Catalytic Kinetics of the Schiff Base Metal Complexes Bearing Side Chain of Cyclic morpholine in Carboxylic Ester Hydrolysis

It has been reported that two Schiff base transition metal complexes bearing the side chain of the morpholine ring were synthesized and characterized, and two complexes with the same base agent but different metal ions were used as a simulant hydrolase in the catalytic hydrolysis of p-nitrophenyl picolinate in this paper. The mechanism of PNPP catalytic hydrolysis is proposed and supported by the results of the spectral analysis and the kinetic calculation. A kinetic mathematical model, applied to the calculation of the kinetic and thermodynamics parameters of PNPP catalytic hydrolysis, has been established on the foundation of the mechanism proposed. The result of the study shows that the two complexes have a good catalytic activity in PNPP catalytic hydrolysis, and the rate of the PNPP catalytic hydrolysis was increased with the increase of the pH values in the buffer solution and affected by the polarization effect of metal ion of the complexes.     

Secretory immunoglobulin a from health y human mothers' milk catalyzes nucleic acid hydrolysis

The human milk secretory immune system is known to be the first line of protection for the newborn infant against various pathogens. Secretory IgA (sIgA), the typical immunoglobulin found in secretions, can fight infections through many mechanisms. Using different methods, we have shown that sIgA from the milk of healthy women possesses DNAse and RNAse activities. The catalytic center is localized in the light chain of catalytic sIgA, while the DNA-binding center is predominantly formed by its heavy chain. The enzymic properties and substrate specificity of catalytic sIgA distinguish it from other known DNases and RNases. It is reasonable to assume, that the milk DNA- and RNA-hydrolyzing antibodies are capable not only of neutralizing viral and bacterial nucleic acids by binding these antigens as well as by hydrolyzing them. The DNA-hydrolyzing activity of Abs raises the possibility that these catalytic Abs may provide protective functions for the newborn through the hydrolysis of viral and bacterial nucleic acids.     

Phosphate Diester Cleavage Promoted by the Metallomicelles of Ce(III) Complexes of Aza-Crown Ether with Different Numbers of Nitrogen Atoms

The design of artificial hydrolase has attracted extensive attention due to their scientific significance and potential application in the field of gene medicine and molecular biology. This work reports the catalytic activation of two aza-crown ether Ce(III) complexes and their metallomicelles as artificial hydrolase in bis(4-nitrophenyl) phosphate ester (BNPP) hydrolysis. The chemical composition of two complexes was determined by the fluorescence spectra and the mole ratio method for electronic absorption spectra. The bonding effect of BNPP and solubilizing effect of the complexes were proved by a method of fluorescence spectroscopy. The catalytic activity of different catalytic systems in BNPP hydrolysis was measured with UV-vis spectrophotometric method. These catalytic systems showed high catalytic activity for promoting BNPP hydrolysis at the almost physiological conditions. BNPP hydrolysis rate in these catalytic system is about 10⁷- to 10⁹-fold faster than that of the BNPP spontaneous hydrolysis in aqueous solution at the same conditions. The metallomicelle systems exhibited higher catalytic activity compared with the complex solution systems in BNPP hydrolysis, and hexadecyltrimethyl ammonium bromide micelle provides a useful catalytic environment for reaction. The acid effect of the catalytic system is ascribed to the formation of metal-bound hydroxide serving as a better kind of nucleophile.     

Simultaneous catalytic hydrolysis of carbonyl sulfide and carbon disulfide over Al2O3-K/CAC catalyst at low temperature

In this work, a series of coal-based active carbon(CAC) catalysts loaded by Al2O3were prepared by sol-gel method and used for the simultaneous catalytic hydrolysis of carbonyl sulfide(COS) and carbon disulfide(CS2) at relatively low temperatures of 30-70 ℃. The influences of calcinations temperatures and operation conditions such as: reaction temperature, O2concentration, gas hourly space velocity(GHSV) and relative humidity(RH) were also discussed respectively. The results showed that catalysts with 5.0 wt% Al2O3calcined at 300 ℃ had superior activity for the simultaneous catalytic hydrolysis of COS and CS2. When the reaction temperature was above 50 ℃, catalytic hydrolysis activity of COS could be enhanced but that of CS2was inhibited. Too high RH could make the catalytic hydrolysis activities of COS and CS2decrease. A small amount of O2introduction could enhance the simultaneous catalytic hydrolysis activities of COS and CS2.     

Hydrolysis of BNPP Catalyzed by the Crowned Schiff Base Co(II) Complex Containing Benzoaza‐15‐Crown‐5 in Micellar Solution

It has been reported that three aza crowned Schiff base cobalt (II) complexes were synthesized and characterized, and the metallomicelle made up of the cobalt (II) complexes and surfactants(Brij35, CTAB, LSS), as mimic hydrolytic metalloenzyme, was used in catalytic hydrolysis of bis(4‐nitrophenyl) phosphate (BNPP). The analysis of specific absorption spectrums of the hydrolytic reaction systems indicated that key intermediates made up of BNPP and Co (II) complexes are formed in the reaction process of BNPP catalytic hydrolysis. The mechanism of BNPP catalytic hydrolysis proposed is based on the analytic result of specific absorption spectra. Based on the mechanism proposed, a kinetic mathematical model for the calculation of the kinetic parameter of BNPP catalytic hydrolysis has been established. The acid effect of reaction system, structure effect of the complexes, effect of temperature and effect of micelles on the rate of BNPP hydrolysis catalyzed by the complexes have been discussed.     

Studies on PNPP Hydrolysis Catalyzed by Schiff Base Cobalt（Ⅱ） Complexes Containing Benzoaza-15-crown-5

Three novel Schiff base cobalt（Ⅱ） complexes containing benzoaza-15-crown-5, CoL^1, CoL^2 and CoL^3 were synthesized and characterized, and these complexes were used in catalytic hydrolysis of carboxylic ester （PNPP, p-nitrophenyl picolinate） as mimic hydrolytic metalloenzyme. The analysis of specific absorption spectra of the hydrolytic reaction systems indicated that the catalytic hydrolysis involved the key intermediates formed by PNPP with cobalt（Ⅱ） complexes. The CoL^3 bearing the electron withdrawing group shows better catalytic activity due to its stabilization effect on active species MLS^-. The catalytic mechanism of PNPP hydrolysis was also proposed. The kinetic parameter of PNPP catalytic hydrolysis has been calculated and the activation energy for the catalytic hydrolysis is 43.69, 39.76 and 35.44 kJ·mol^-1, respectively.     

Hydrolysis of BNPP Catalyzed by the Crowned Schiff Base Co(II) Complexes in Micellar Solution

Two symmetrical double aza‐crowned Schiff base cobalt(II) complexes were synthesized and characterized, and the metallomicelle made up of the cobalt(II) complexes and surfactant, as mimic hydrolytic metalloenzyme, was used in catalytic hydrolysis of bis(4‐nitrophenyl) phosphate (BNPP). The analysis of specific absorption spectrums of the hydrolytic reaction systems indicated that key intermediates made up of BNPP and Co(II) complexes are formed in reaction processes of the BNPP catalytic hydrolysis. In this article, the mechanism of BNPP catalytic hydrolysis has been proposed based on the analytic result of specific absorption spectrum. A kinetic mathematical model, for the calculation of the kinetic parameter of BNPP catalytic hydrolysis has been established based on the mechanism proposed. The acid effect of reaction system, the structural effect of the complexes, the effect of surfactant micelles and the effect of temperature on the rate of BNPP hydrolysis catalyzed by the complexes have been discussed.     

聚醚桥连二异羟肟酸单核和双核过渡金属配合物催化PNPP水解

Two polyether bridged dihydroxamic acids and their mono-and binuclear manganese(Ⅱ), zinc(Ⅱ) complexes have been synthesized and employed as models to mimic hydrolase in catalytic hydrolysis of p-nitrophenyl picolinate (PNPP). The reaction kinetics and the mechanism of hydrolysis of PNPP have been investigated. The kinetic mathematical model for PNPP cleaved by the complexes has been proposed. The effects of the different central metal ion, mono-and binuclear metal, the pseudo-macrocyclic polyether constructed by polyethoxy group of the complexes, and reactive temperature on the rate for catalytic hydrolysis of PNPP have been examined. The results showed that the transition metal dthydroxamates exhibited high catalytic activity to the hydrolysis of PNPP, the catalytic activity of binuclear complexes was higher than that of mononuclear ones, and the pseudo-macrocyclic polyether might synergetically activate H20 coordinated to metal ion with central metal ion together and promote the catalytic hydrolysis of PNPP.