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51.
Semi-empirical molecular orbital calculations were carried out for the compounds (C2H5)3As, (C2H5)3Ga and RAsH2 (R = C2H5, i-C3H7, i-C4H9, and t-C4H9) by using the CNDO/2-U program, and their capability of β-elimination reaction is compared on the basis of the torsion energy to the transition state, electrostatic interactions and orbital overlapping between the central atom and the β-hydrogen, and bond order of the metal-carbon, and carbon-hydrogen bond. In the comparison of (C2H5)3As with (C2H5)3Ga, we found that the β-elimination of (C2H5)3As could hardly be expected to take place in the thermal decomposition. The capability of β-elimination would be smaller in C2H5AsH2 than that in (C2H5)3As. Moreover when the ethyl group is replaced by a t-butyl group in RAsH2, the β-elimination reaction appears to become more difficult and a large possibility for a radical process is suggested. 相似文献
52.
Dextran-modified iron oxide nanoparticles 总被引:1,自引:0,他引:1
Dextran-modified iron oxide nanoparticles were prepared by precipitation of Fe(Ⅱ) and Fe(Ⅲ) salts with ammonium hydroxide by two methods. Iron oxide was precipitated either in the presence of dextran solution, or the dextran solution was added after precipitation. In the second method, the iron oxide particle size and size distribution could be controlled depending on the concentration of dextran in the solution. The nanoparticles were characterized by size-exclusion chromatography, transmission electron microscopy and dynamic light scattering. Optimal conditions for preparation of stable iron oxide colloid particles were determined, The dextran/iron oxide ratio 0-0,16 used in precipitation of iron salts can be recommended for synthesis of nanoparticles suitable for biomedical applications, as the colloid does not contain excess dextran and does not coagulate. 相似文献
53.
Rodrigo París José Luis de la Fuente 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3538-3549
Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), 1H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007 相似文献
54.
On‐line coupling of LC and ICP‐MS has been used for fractionation and detection of species of Cu, Fe, I, Se and Zn in human serum. It has been shown that anion exchange chromatography provided better separation capability (both intra‐ and inter‐element) than size‐exclusion chromatography. The mobile phases for ion exchange chromatography consisted of Tris–HNO3 buffer and ammonium salt (nitrate, acetate or formate). Formate was found to be the best mobile phase counter ion, enabling good chromatographic separation, and is acceptable for mass spectrometry too. The quantitative evaluation of element concentrations adhering to individual fractions was performed by the peak area normalization method. The repeatability of results ranged from 3 to 15% (depending on the element concentration level) and represented the main part of the result uncertainty. The accuracy of Cu and Zn fraction determinations was confirmed by comparison with the isotope dilution technique. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
55.
R. Németh 《Journal of statistical physics》1991,63(1-2):419-424
We calculate the site occupation probabilities of one-dimensional lattice gas models within the canonical and grand canonical ensembles. The appearing differences do not vanish if we increase the system size keeping the site energies discrete. In this way one can explain the surprising numerical results of Barszczak and Kutner. This effect in the single-site occupation number disappears in higher dimensions. 相似文献
56.
Pirjo Sainio Irma Mäkinen Jaap-Willem Hutter Theo den Ouden Mikael Krysell 《Accreditation and quality assurance》2006,11(3):116-121
The international joint project HYCREF (Contract No. G6RD-CT-2002-00854), funded by the European Commission in the 5th Framework programme, aimed to develop methods to prepare homogeneous and stable reference materials of water, soil, and waste contaminated with mineral oil hydrocarbons and to certify the mineral oil content by gas chromatographic methods. The results of a feasibility study for the preparation of three soil reference materials are discussed in this paper, and for the preparation of three waste reference materials in the second part (Koch et al., Accred Qual Assur submitted for publication). The soil materials were selected to represent different soil types and contamination levels. The project plan set three requirements for these reference materials: uncertainty in the mineral oil content resulting from the certification exercise <5%, a sample inhomogeneity of <3% and a minimum long-term stability of 5 years. For the most part, these requirements were met within this project. 相似文献
57.
Modulated
DSC for gas hydrates analysis 总被引:1,自引:0,他引:1
C. Giavarini F. Maccioni Maria Laura Santarelli 《Journal of Thermal Analysis and Calorimetry》2006,84(2):419-424
Modulated DSC has been applied to the study of methane,
ethane and propane hydrates at different hydrate and ice concentrations. The
reversing component of the TMDSC curves, makes it possible to characterize
such hydrates.
Methane and ethane hydrates show the melting-decomposition
peak at a temperatures higher than the ice contained in the sample, while
propane hydrate melts and decomposes at lower temperature than the ice present
in the sample. The hydrate peaks tend to disappear if the hydrate is stored
at atmospheric pressure. Guest size and cavity occupation fix the heat of
dissociation and stability of the hydrates, as confirmed by parallel tests
on tetrahydrofurane hydrates. 相似文献
58.
G. Gargaro F. Gasparrini D. Misiti G. Palmieri M. Pierini C. Villani 《Chromatographia》1987,24(1):505-509
Summary Enantiomers of several sulfoxides and some selenoxides can be easily separated by using a new chiral stationary phase (CSP-DACH-DNB)
containing the 3,5-dinitrobenzoyl derivative of R,R-(-)1,2-diamino-cyclohexane as selector, covalently bonded to the siliceous
matrix. The easy operative conditions and the high enantioselectivity values (α) allow a direct transfer of the analytical
separations to a semi-preparative and preparative scale. 相似文献
59.
Summary The gas chromatographic behaviour of crosslinked macroporous 2-hydroxyethyl methacrylate grafted with 2-methyloxazoline was
investigated and the range of applicability of the copolymer was assessed. Retention index values were measured on this copolymer
and compared with those obtained on the terpolymer 2-hydroxyethyl methacrylate-ethylene dimethacrylate-acrylonitrile. Rohrschneider
constants and efficiency data for selected sorbates are given. The use of this type of polymer in the separation of various
types of compounds is documented by various examples. 相似文献
60.