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1.
During nitroxide-mediated polymerization (NMP) in the presence of a nitroxide R2(R1)NO*, the reversible formation of N-alkoxyamines [P-ON(R1)R2] reduces significantly the concentration of polymer radicals (P*) and their involvement in termination reactions. The control of the livingness and polydispersity of the resulting polymer depends strongly on the magnitude of the bond dissociation energy (BDE) of the C-ON(R1)R2 bond. In this study, theoretical BDEs of a large series of model N-alkoxyamines are calculated with the PM3 method. In order to provide a predictive tool, correlations between the calculated BDEs and the cleavage temperature (T(c)), and the dissociation rate constant (k(d)), of the N-alkoxyamines are established. The homolytic cleavage of the N-OC bond is also investigated at the B3P86/6-311++G(d,p)//B3LYP/6-31G(d), level. Furthermore, a natural bond orbital analysis is carried out for some N-alkoxyamines with a O-C-ON(R1)R2 fragment, and the strengthening of their C-ON(R1)R2 bond is interpreted in terms of stabilizing anomeric interactions. 相似文献
2.
According to the experiment results of X-ray diffraction and IR, the reduced partition function ratio (RPFR) and the contribution of various related vibration modes of uranium-crown ether complex (DCH18C6·H_3O)_2UO_2Cl_4 were theoreticallv calculated in detail. The equilibrium constant K_(eq) (that is, the single stage isotopic separation factor α) of exchange reaction for uranium isotopic chemical exchange system UO_2~(2+)(H_2O)_5—(DCH18C6.H_3O)_2UO_2Cl_4 is estimated to be 1.000746 at 12℃ and 1.000672 at 29℃, respectively, which are quite close to the experimental values 1.0010±0.0002 arid 1.0012±0.0004. Theoretical analysis shows that in the course of forming the complex of uranium with crown ether, the coordinated water of uranium is stripped, which performs a key action on the remarkable isotope effect for this system. 相似文献
3.
不对称亚砜与1,10—双(1‘苯基—3’—甲基—5‘氧化吡唑—4’—基)癸二酮—[1,10]对… 总被引:1,自引:0,他引:1
4.
Ultra-trace analysis of U,Th, Ca and selected heavy metals in high purity refractory metals with isotope dilution mass spectrometry 总被引:1,自引:0,他引:1
A method for the determination of trace impurities (U, Th, Ca, Fe, Cr, Ni, Cu, and Cd) in the refractory metals molybdenum and tungsten with isotope dilution mass Spectrometry (IDMS) has been developed. This method enables determinations of uranium and thorium down to the lowest pg/g level with high precision and accuracy. Selective chromatographic, extractive and electrolytic methods for the trace-matrix separation were combined with positive thermal ionization mass spectrometry. Different samples of high purity (4N) and of ultra high purity (UHP) materials for advanced technologies were analysed. The detection limits reached are (in ng/g): U 0.006, Th 0.008, Ca 10, Fe 19, Cr 0.5, Ni 0.6, Cu 2.7, and Cd 0.12. A comparison of results with other sensitive analytical methods (ICP-MS, GDMS, SIMS) makes obvious the urgent necessity of a reliable calibration method like IDMS because the analytical results obtained by the other methods often spread over a wide range. 相似文献
5.
研究了由4,4'-癸二酰-双-(1-苯基-3-甲基-5-吡唑啉酮)(DBPMP,简作H2A),氧化三辛基膦(TOPO),吡啶(Py)组成的三元体系从硝酸溶液中对铀的协同萃取,斜率法确定萃合物组成为UO2A.TOPO.Py,制取了固体协萃配合物,并用元素分析、IR及HNMR等进行了表征。 相似文献
6.
Ejnik JW Todorov TI Mullick FG Squibb K McDiarmid MA Centeno JA 《Analytical and bioanalytical chemistry》2005,382(1):73-79
Urine uranium concentrations are the best biological indicator for identifying exposure to depleted uranium (DU). Internal exposure to DU causes an increased amount of urine uranium and a decreased ratio of 235U/238U in urine samples, resulting in measurements that vary between 0.00725 and 0.002 (i.e., natural and depleted uraniums 235U/238U ratios, respectively). A method based on inductively coupled plasma dynamic reaction cell mass spectrometry (ICP-DRC-MS) was utilized to identify DU in urine by measuring the quantity of total U and the 235U/238U ratio. The quantitative analysis was achieved using 233U as an internal standard. The analysis was performed both with and without the reaction gas oxygen. The reaction gas converted ionized 235U+ and 238U+ into 235UO2+ (m/z=267) and 238UO2+ (m/z=270). This conversion was determined to be over 90% efficient. A polyatomic interference at m/z 234.8 was successfully removed from the 235U signal under either DRC operating conditions (with or without oxygen as a reaction gas). The method was validated with 15 urine samples of known uranium compositions. The method detection limit for quantification was determined to be 0.1 pg U mL–1 urine and an average coefficient of variation (CV) of 1–2% within the sample measurements. The method detection limit for determining 235U/238U ratio was 3.0 pg U mL–1 urine. An additional 21 patient samples were analyzed with no information about medical history. The measured 235U/238U ratio within the urine samples correctly identified the presence or absence of internal DU exposure in all 21 patients.The opinions and assertions expressed herein are those of the authors and are not to be construed as official or as representing the views of the Armed Forces Institute of Pathology, the Department of the Army, or the Department of Defense 相似文献
7.
随着地浸采铀矿山的退役,特别是应现代绿色矿山建设的要求,地下水修复越来越被重视,如何制定酸法地浸采铀矿山地下水修复法规,采用哪种修复技术才能获得更好的效果,这些问题一直困扰着环境保护部门和项目执行者。本研究针对酸法浸出矿山特点,提出了地下水修复法规的制定原则,并实践了地下水修复综合技术、自然净化、迁移净化、冲洗、弱酸浸出等方法,并在应用中获得较好的效果。在总结地浸采铀矿山地下水修复现场试验和退役矿山实际应用的基础上,充分分析影响地下水修复的矿床自然条件、地下水质量和用途、修复技术、修复费用和时间等因素,给出了推荐的酸法地浸采铀矿山地下水修复策略。 相似文献
8.
在过量碳酸盐存在的U(Ⅵ)溶液中,U(Ⅵ)的化学状态与溶液的pH值有关,当pH>8时,U(Ⅵ)以[UO2(CO3)3]4-离子存在.吸附于树脂相的U(Ⅵ)的化学状态也与供吸附的料液的pH值有关,当pH>9时,U(Ⅵ)才完全以[UO2(CO3)3]4-吸附于树脂相.当pH在6.5~8.0范围时,U(Ⅵ)在溶液中还可能以[UO2(CO3)2]2-或Hn[UO2(CO3)3]n-4形式存在,而U(Ⅵ)以[UO2(CO3)2]2-形式吸附于树脂相的可能性很小,它主要以U2O2-7的形式吸附于树脂相. 相似文献
9.
O. I. Artyushin E. V. Sharova I. L. Odinets S. V. Lenevich V. P. Morgalyuk I. G. Tananaev G. V. Pribylova G. V. Myasoedova T. A. Mastryukova B. F. Myasoedov 《Russian Chemical Bulletin》2004,53(11):2499-2507
An efficient method for the synthesis of secondary alkylamides of phosphorylacetic acids (APA) was proposed. The method involves amidation of ethyl phosphorylacetates with primary aliphatic amines. The scope of reaction was determined. Reactions with ethylenediamine and 1,4-diaminobutane yield the corresponding bisamides; in the case of 1,3-diaminopropane, N-(3-aminopropyl)diphenylphosphorylacetamide or N,N-propylenebis(diphenylphosphorylacetamide) was obtained, depending on the reaction conditions. The extraction of americium(III) complexes and the sorption of uranium(VI) by sorbents with physically sorbed APA from nitric acid solutions were studied. There is no correlation between the partition coefficient of americium(III) and the structure of APA; in the sorption of uranium(VI), the degree of extraction depends on the complexone structure.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2394–2402, November, 2004. 相似文献
10.
Binary zirconium orthophosphates R1/3Zr2(PO4)3 and M1/4Zr2(PO4)3, where R = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu; M = Th, U, have been synthesized and studied by IR spectroscopy [structural family of NaZr2(PO4)3 (NZP)]. Vibrational analysis for the PO4 tetrahedron and investigation of symmetry relations among trigonal NZP phases showed that ordering of lanthanide atoms in structures of NaZr2(PO4)3 type with space group R
c leads to symmetry reduced to P
c. The lanthanide atoms occupy the 2b sites. The phosphorus atoms occupy two independent sites: 6f with C
2 symmetry and 12g with C
1 symmetry. Factor group analysis admits that the IR spectrum can contain eight v3 bands and two v1 bands of the stretching vibrations of the PO4 ions. The M atoms of actinides occupy statistical positions in the structure, and space group R
c is retained.Original Russian Text Copyright © 2004 by V. S. Kurazhkovskaya, D. M. Bykov, and A. I. Orlova__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1013–1019, November–December, 2004. 相似文献