Extraction of U(VI) with N,N′-dimethyl-N,N′-dioctylmalonamide from nitrate media

The extraction of uranyl nitrate with the novel extractant N,N′-dimethyl-N,N′-dioctylmalonamide (DMDOMA) from aqueous sodium nitrate (and nitric acid) was investigated. The extraction mechanism was established and the stoichiometry of the main extracted species confirms to UO₂(NO₃)₂ · DMDOMA. The IR spectral study was also made of the extracted species. Methyl substituent improves the extraction ability of malonamide for U(VI) compared with that of N,N,N′,N′-tertrabutylmalonamide (TBMA).     

N，N′-二甲基-N，N′-二己基-3-氧戊二酰胺萃取镧系元素的研究

溶剂萃取因反应速度快,分离效果好,已成为国内外分离提纯稀土的主要方法[1～3].在稀土元素的萃取分离中,为了提高萃取效率,从高放废液中分离、除去锕系和镧系元素从而实现选择性分离,首要问题是选择结构合适的萃取剂和萃取条件[4].由于酰胺类萃取剂具有螯合性能,对Ln(Ⅲ)、An(Ⅲ,Ⅳ,Ⅵ)和碱土金属都有良好的萃取能力,而且此类化合物耐辐射,不易水解,能够燃尽,不产生二次污染,是～种比较有发展前途的萃取剂,在核燃料后处理方面展示较好的应用前景[5～7].     

N，N′-二甲基-N，N′-二辛基丙二酰胺萃取铀(Ⅵ)的研究

The novel unsymmetrical extractant N，N′-dimethyl-N，N′-dioctylmalonamide (DMDOMA) was prepared by reaction of diethyl malonate with N-methyl octanamine. The extraction mechanism and the behavior of uranyl nitrate with DMDOMA employed cyclohexane as diluent were studied. The effects of concentrations of nitric acid, sodium nitrate, extractant and also the temperature on the extraction were considered. The stoichiometry of the extracted species is and the coordination of extracted species was suggested based on the IR data. The value of ΔH of extraction is -26.9 ± 0.80 kJ·mol^-1. The value of the apparent extraction constant is 133.88 ± 17.92, which shows that the optimization of extractant structure improves the extractability of malonamide for uranyl nitrate.     

Theoretical study on the hydrolysis mechanism of N,N -dimethyl- N ′-(2′,3′-dideoxy-3′-thiacytidine)formamidine

The hydrolysis mechanisms of N,N-dimethyl-N′-(2′,3′-dideoxy-3′-thiacytidine)formamidine (FA-3TC) in the gas phase and in aqueous solution were studied by use of the density functional theory B3LYP/6-31+G(d, p) method. Two possible reaction pathways in the title reaction were considered. In one pathway water attacks the C=N double bond first (path A) while in the other water attacks the C-N single bond first (path B). The calculated results indicate that the first step in both pathways is the rate-limiting process and path A is more favorable than path B in the gas phase. The effect of solvent water on the title reaction was assessed at the B3LYP/6-31+G(d, p) level of theory based on the polarizable continuum model (CPCM). In water the first mechanism (path A) is also favored. Supported by the National Natural Science Foundation of China (Grant Nos. 20473055 and 20773089) and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (Grant No. 20071108-18-15)     

N，N′-二甲基-N，N′-二辛基-3-氧戊二酰胺从盐酸介质中萃取三价镧系金属的研究

以煤油/辛醇(7:3,V/V)为稀释剂,研究N,N′-二甲基-N,N′-二辛基-3-氧戊二酰胺(DMDODGA)从盐酸介质中萃取三价镧系金属的性能及反应机理;考察了水相盐酸浓度、萃取剂浓度及温度对其萃取性能的影响。结果表明分配比在所研究酸度范围内随盐酸浓度的增加先增大后减小;随萃取剂浓度的增加而增大;萃合物的组成为MCl3.2DMDODGA(M=Sm,Gd,Dy)或MCl3.DMDODGA(M=Er,Lu)。萃取过程为放热反应,升高温度不利于萃取。同时计算出了萃取反应的平衡常数及热力学函数。萃合物的红外光谱表明羰基氧、醚氧均与镧系离子配位。     

N，N′-苄基-1，2二胺合铜的合成和晶体结构及与DNA的相互作用

A ligand， (N，N′-dibenzylethane-1，2-diamine) (L)， and its complex with copper acetate was synthesized and characterized by some spectral analyses. The copper(Ⅱ) ion is six-coordinated and exhibites octahedral coordination geometry， the coordination atoms are four nitrogen atoms from two(L) ligands and two carboxyl oxygen atoms from two acetic acid groups， respectively. After studying the interaction of the complex with calf thymus DNA through UV and fluorescence spectra， we can find that there is a strong binding and a large affinity berween the complex and calf thymus DNA. CCDC: 649416.     

Platinum(II) extraction by N,N′-dipentylethylenediamine-N′-thiocarbaldehyde from hydrochloric acid solutions

Platinum(II) extraction by N,N′-dipentylethylenediamine-N′-thiocarbaldehyde from 0.1 M HCl into chloroform and toluene diluents was studied at 25°C and a phase contact time of 5 min. The extraction had a coordination mechanism with a Pt ← S bond formed in the extracted complex PtCl₂S₂. Concentration constants and thermodynamic parameters of the extraction reaction were calculated. Original Russian Text ? R.A. Khisamutdinov, Yu.I. Murinov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 1, pp. 156–162.     

N, N’-双(3-吡啶醛)-(1R, 2R)-环己二胺席夫碱Ag(Ⅰ)配合物的合成、结构和荧光性质研究

以3-吡啶醛和（1R,2R）-环己二胺进行缩合得到Schiff碱配体L¹,然后,用配体L¹和AgNO₃进行配位反应,得到配合物[Ag（L¹）（NO₃）]_n（1）,并用元素分析、FT-IR、X-射线单晶衍射、热重分析、粉末衍射对其进行了表征。晶体结构表明：配合物1属于单斜晶系,C2空间群,Ag（Ⅰ）的配位环境均为扭曲四面体,分别和硝酸根的氧原子,配体中的2个吡啶氮原子以及1个亚胺氮原子配位,配体L¹有2种配位模式,其中,1个配体用两臂的2个吡啶氮原子分别和2个Ag（Ⅰ）离子配位,另外1个配体用两臂的2个吡啶氮原子分别和2个Ag（Ⅰ）离子配位,同时2个亚胺氮原子也分别和2个Ag（Ⅰ）离子配位,这样配合物形成3D孔状结构。同时研究了配合物的固体荧光性质。     

Synthesis and crystal structure of a new tetradecker complex: Tetra(μ4-N,N′-Ethylen-bis(3-Methoxysalicylideneamine)-bis(μ2-perchlorato-O,O′)-tetranickel(II)-tripotassium perchlorate

The title tetradecker complex C₇₂H₇₂Cl₃K₃N₈Ni₄O₂₈ has been synthesized and structurally characterized. The four NiL (L = N, N-ethylene-bis(3-methoxysalicylideneiminate) segments were linked into a discrete tetradecker structure by three K⁺ cation coordinated to the phenolic oxygen atoms of the neighboring NiL units and the oxygen atom of the ClO₄⁻ anions acting as bridges. The two bicephalous K⁺ cations are nine-coordinated, while the middle one is involved in a distorted bipentagonal pyramid. For the Ni²⁺ ion, it is involved in a square planar coordination sphere formed by a N₂O₂ unit from the Schiff base ligand.     

Asymmetric synthesis of the natural erythro-(1R,2S)-8-O-4′-neolignan myrislignan

Abstract  

An efficient and practical asymmetric synthesis of erythro-(1R,2S)-8-O-4′-neolignan myrislignan was achieved by using vanillin and pyrogallic acid as the starting materials. Two key steps are involved: preparation of an enantiopure threo alcohol of predictable stereochemistry by dihydroxylation with AD-mix-β, and inversion of the absolute configuration from the threo to the erythro isomer using a Mitsunobu reaction. The route illustrates a new methodology for the synthesis of erythro-8-O-4′-neolignan.     

Extraction of europium and americium into phenyltrifluoromethyl sulfone by using hydrogen dicarbollylcobaltate in the presence of N,N′-diethyl-N,N′-diphenyl-2,6-dipicolinamide

Extraction of microamounts of europium and americium by a phenyltrifluoromethyl sulfone (FS 13) solution of hydrogen dicarbollylcobaltate (H⁺B⁻) in the presence of N,N,N′,N′-tetraethyl-2,6-dipicolinamide (TEtDPA, L) has been investigated. The equilibrium data have been explained assuming that the species HL⁺, \textHL ₂ ⁺ , {\text{HL}}_{ 2}^{ + } , \textML₂^{3 +} {\text{ML}_{2}^{3 +}} and \textML ₃ ³⁺ {\text{ML}_{ 3}^{ 3+}} (M³⁺ = Eu³⁺, Am³⁺) are extracted into the organic phase. The values of extraction and stability constants of the cationic complex species in FS 13 saturated with water have been determined. It was found that the stability constants of the corresponding complexes \textEuL_n ³⁺ {\text{EuL}}_{n}^{ 3+ } and \textAmL_n ³⁺ {\text{AmL}}_{n}^{ 3+ }, where n = 2, 3 and L is TEtDPA, in the mentioned FS 13 medium are comparable.     

Converting dipyrrinones to lactim ethers to fluorescent N,N′-difluoroboryl derivatives

A high-yield straightforward conversion of lactams to lactim ethers is shown by the conversion of (10H)-dipyrrin-1-ones to (11H)-dipyrrin-1-ol methyl and ethyl ethers in 90% yield from heating in neat trimethyl or triethyl phosphite at 160°C. Unlike the parent dipyrrinones, which form intermolecularly hydrogen-bonded dimers in CHCl₃, their lactim ethers are shown to be monomeric by vapor pressure osmometry. The latter react with boron trifluoride etherate to N,N′-bridged BF₂ derivatives that exhibit strong fluorescence (φ_F 0.6–0.8) near 535 nm. X-Ray crystal structures were obtained of the lactim ethyl ether of kryptopyrromethenone and the BF₂ derivative of the lactim ethyl ether 2,3-diethyl-7,8-dimethyl-(10H)-dipyrrin-1-one.     

基于吡啶多羧酸和N，N′-桥联混合配体的钴配合物的合成及结构分析

将吡啶-2,4,6-三羧酸(2,4,6-pytaH3),4-氨基-3,5-二(4-吡啶基)-1,2,4-三氮唑(4,4′-abpt)和CoCl2在不同的pH条件下发生水热反应,得到2个新的配位聚合物[Co(2,4,6-pytaH)(4,4′-abpt)(H2O)](1)和[Co1.5(2,4,6-pyta)(4,4′-abpt)(H2O)3].3.5H2O(2)。配合物1是在吡啶-2,4,6-三羧酸酸性环境下产生的,吡啶-2,4,6-三羧酸在水热条件下只脱去2个羧基上的质子变成2,4,6-pytaH2-,而配合物2是在NaOH碱性溶液下反应得到的,其中吡啶-2,4,6-三羧酸完全脱去3个羧基上的质子变成2,4,6-pyta3-。配合物1中包含一维Co-羧酸链,2中存在具有(4,4)拓扑网络的二维层。1和2中的一维链和二维层通过π-π堆积和丰富的氢键作用分别拓展成三维超分子网络。单晶结构分析表明,配合物1结晶于单斜晶系,P21/n空间群,a=0.961 30(10)nm,b=0.632 09(6)nm,c=3.372 9(4)nm,β=95.104(2)°,V=2.041 3(4)nm3,Z=4。而配合物2结晶于单斜晶系,P21/c空间群,a=1.795 2(2)nm,b=0.729 62(8)nm,c=2.078 7(2)nm,β=112.323(2)°,V=2.518 6(5)nm3,Z=4。     

N，N’-双（3-吡啶醛）-（1R，2R）-环己二胺席夫碱Ag（Ⅰ）配合物的合成、结构和荧光性质研究

以3-吡啶醛和(1R,2R)-环己二胺进行缩合得到Schiff碱配体L1,然后,用配体L1和AgNO3进行配位反应,得到配合物[Ag(L1)(NO3)]n(1),并用元素分析、FT-IR、X-射线单晶衍射、热重分析、粉末衍射对其进行了表征。晶体结构表明:配合物1属于单斜晶系,C2空间群,Ag(Ⅰ)的配位环境均为扭曲四面体,分别和硝酸根的氧原子,配体中的2个吡啶氮原子以及1个亚胺氮原子配位,配体L1有2种配位模式,其中,1个配体用两臂的2个吡啶氮原子分别和2个Ag(Ⅰ)离子配位,另外1个配体用两臂的2个吡啶氮原子分别和2个Ag(Ⅰ)离子配位,同时2个亚胺氮原子也分别和2个Ag(Ⅰ)离子配位,这样配合物形成3D孔状结构。同时研究了配合物的固体荧光性质。     

N，N′-二苄基-苯并咪唑四氯合铜(Ⅱ)化合物的合成、结构和性能研究(英)

A novel N，N′-dibenzyl-benzimidazolium tetrachlorocuprate(Ⅱ) complex, [C₂₁H₁₉N₂]₂[CuCl₄], was synthesized and its crystal structure was determined by X-ray diffraction. It crystallizes in monoclinic system, space group P2/c, a=1.203 9(2) nm, b=0.975 0(2) nm, c=1.878 2(6) nm, β=114.12(2)°, V=2.012 2(8) nm³. Its structure was identified by EA, IR and UV spectra and characterized by electrochemistry, thermal and magnetic property. The Cu(Ⅱ) atom of [CuCl₄]^2- has distorted tetrahedral coordination geometry. In the crystal structure, there are strong extensive C-H…Cl hydrogen bonds and π-π stacking interactions, which stabilized the crystal structure. CCDC: 221570.     

(1iR, 1iiR, 2iR, 2iiR)-Ni, Nii-(1,3-亚苯基双(亚甲基))环己烷-1,2-二胺作为配体的双核铂配合物的合成及其抗癌活性

以(1ⁱR,1ⁱⁱR,2ⁱR,2ⁱⁱR)-Nⁱ, Nⁱⁱ-(1,3-亚苯基双(亚甲基))环己烷-1,2-二胺(HL)作为配体,设计并合成了7种双核铂配合物,并利用IR,¹H NMR,¹³C NMR,ESI-MS和元素分析等进行了表征。通过MTT法测定目标双核铂配合物对人类HepG-2,A549,HCT-116和MCF-7四种癌细胞系的细胞毒性。结果表明,所有的化合物对HepG-2,A549和HCT-116细胞系均表现了良好的细胞毒活性,但对MCF-7细胞系均无活性。其中,以3-羟基环丁烷-1,1-二羧酸为离去基团的配合物P7对HepG-2和A549细胞系的活性优于卡铂,对HCT-116细胞系的活性接近于奥沙利铂。     

Studies on the radiolytic stability of N,N,N′,N′-tetra-2-ethylhexyl diglycolamide in n-dodecane solution containing different phase modifiers

The radiolytic stability of a branched diglycolamide extractant, namely N,N,N′,N′-tetra-2-ethylhexyl diglycolamide (T2EHDGA) dissolved in n-dodecane containing several phase modifiers, viz. N,N-dihexyloctanamide (DHOA), tri-n-butyl phosphate (TBP), 1-decanol and iso-decanol has been investigated. The distribution ratio of Am(III) decreased with increased radiation dose studied up to 1000 kGy. Nevertheless, all the composition of extractants showed satisfactory results up to 500 kGy, beyond which the extractants degraded drastically. The stripping behaviour of Am(III) with 0.2 M HNO₃ was found to be unaffected even with the ligand solution irradiated up to 1000 kGy. Extraction of fission product and structural elements was also investigated using the irradiated solvents and was found to be not significantly affected with increasing absorbed dose with the exception of Mo which showed sharp rise in the distribution coefficient values. Loading of Nd in the organic phase decreased with the irradiated solvent due to degradation of the carrier. The effect of the absorbed dose on physical parameters such as density, viscosity and interfacial tension of the solvents has also been investigated.     

(1iR,1iiR,2iR,2iiR)-Ni,Nii-(1,3-亚苯基双(亚甲基))环己烷-1,2-二胺作为配体的双核铂配合物的合成及其抗癌活性

以(1ⁱR,1ⁱⁱR,2ⁱR,2ⁱⁱR)-Nⁱ,Nⁱⁱ-(1,3-亚苯基双(亚甲基))环己烷-1,2-二胺(HL)作为配体,设计并合成了7种双核铂配合物,并利用IR,¹H NMR,¹³C NMR,ESI-MS和元素分析等进行了表征。通过MTT法测定目标双核铂配合物对人类HepG-2,A549,HCT-116和MCF-7四种癌细胞系的细胞毒性。结果表明,所有的化合物对HepG-2,A549和HCT-116细胞系均表现了良好的细胞毒活性,但对MCF-7细胞系均无活性。其中,以3-羟基环丁烷-1,1-二羧酸为离去基团的配合物P7对HepG-2和A549细胞系的活性优于卡铂,对HCT-116细胞系的活性接近于奥沙利铂。     

CH3SOx (x＝0, 1)与三线态Oy (y＝1, 2, 3)反应机理的理论研究

采用B3LYP方法和6-311G(d, p)基组对CH₃S及其氧化后继物CH₃SO与O_y (y＝1, 2, 3)反应形成酸雨的微观机理进行了理论研究. 对反应势能面上的各驻点进行几何构型全优化. 振动分析和IRC计算证实了中间体和过渡态的真实性和相互连接关系. 找到了7条生成SO₂的反应途径, 其中CH₃S与O直接反应得到产物CH₃和SO最容易进行; CH₃S先与O₃反应, 其产物再与O₃反应得到CH₃SO₂, CH₃SO₂最后分解得到CH₃S和SO₂较容易进行, 其它的反应较难进行.     

The synthesis, characterization and antimicrobial activity of N,N′-bis(2-thiophenecarboxamido)-1,3-diaminopropane and N,N′-bis (2-furancarboxamido)-1,3-diaminopropane and their Cu(II), Zn(II), Co(III) complexes

Metal complexes derived from amides; N,N′-bis(2-thiophenecarboxamido)-1,3-diamino propane (1) and N,N′-bis(2-furancarboxamido)-1,3-diaminopropane (2) were characterized by elemental analysis, spectral (NMR, FT-IR, LC-MS) methods, magnetic moment, molar conductance, and TGA/DTA studies. The complexes were dimeric and have the general formula [ML.Cl_m.(H₂O)_n]2Cl₂ where M=Cu(II), Zn(II), Co(III); m = 1, 2; n = 0, 1. The antimicrobial activities of the amides and their complexes were studied against the bacteria; Escherichia coli (ATCC 11230), Yersinia enterocolitica (ATCC 1501), Bacillus magaterium (RSKK 5117), Bacillus cereus (RSKK 863), Bacillus subtilis (RSKK 863) and yeast; Candida albicans (ATCC 10239).