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31.
Mercedes de Frutos Alejandro Cifuentes Jose Carlos Diez-Masa 《Journal of separation science》1997,20(1):29-33
The behavior of bovine whey proteins in Reversed-Phase High Performance Liquid Chromatography (RP-HPLC) systems has been investigated. The Linear Solvent Strength (LSS) model has been applied to the separation of these proteins studying how their retention time and band broadening change when different gradient parameters are modified. From our results it is deduced that the LSS model describes the behaviour of the whey proteins in RP-HPLC. Also, it seems that ts (the retention time for non-retained solutes) depends on the size of these proteins. The good fit observed between experimental data and the equations deduced from the LSS model allows the prediction of a gradient shape that permits a rapid analysis of the above mentioned proteins. 相似文献
32.
New physically adsorbed polymer coating for reproducible separations of basic and acidic proteins by capillary electrophoresis 总被引:1,自引:0,他引:1
In this work, a new physically adsorbed coating for capillary electrophoresis (CE) is presented. The coating is based on a N,N-dimethylacrylamide-ethylpyrrolidine methacrylate (DMA-EPyM) copolymer synthesized in our laboratory. The capillary coating is simple and easy to obtain as only requires flushing the capillary with a polymer aqueous solution for 2 min. It is shown that by using these coated capillaries the electrostatic adsorption of a group of basic proteins onto the capillary wall is significantly reduced allowing their analysis by CE. Moreover, the DMA-EPyM coating provides reproducible separations of the basic proteins with RSD values for migration times lower than 0.75% for the same day (n = 5) and lower than 3.90% for three different days (n = 15). Interestingly, the electrical charge of the coated capillary wall can be modulated by varying the pH of the running buffer which makes possible the analysis of basic and acidic proteins in the same capillary. The usefulness of this coating is further demonstrated via the reproducible separation of whey (i.e. acidic) proteins from raw milk. The coating protocol should be compatible with both CE in microchips and CE-MS of different types of proteins. 相似文献
33.
34.
Ashok K. Ganguli Shalabh Gupta Jing-Tae Zhao E. Alejandro Leon-Escamilla 《Journal of solid state chemistry》2005,178(10):2959-2972
A particular pathology of certain W5Si3-type A5B3 structures (I4/mcm) appears to arise because of unduly close approaches of the A1-type atoms on the cell faces at , 0, () that occur with the larger and more electropositive A and/or in the presence of smaller B atoms. A structure refinement of binary Ba4.81Pb3 indicates such a marginal stability in that the Ba atoms in the facial Ba0.81 chains exhibit an extreme displacement ellipsoid along . Although Ca5Sn3 and La5Ga3 binaries are unknown in this structure type, five stable ternary derivatives of these have been synthesized via substitution reactions and characterized by single crystal X-ray diffraction means: Ca4Sn3.223(4)Mg0.777, Ca4Sn3Cu1.30(4), Ca4.66(6)Sn3Zn0.704(4), La4.81(1)Ga1.38(2)Al1.62, and La4.762(5)Ga1.5(1)Zn1.5. Only the Ca-Sn-Zn phase exhibits lower symmetry, P4/mbm. The problematic A1 sites exhibit diverse changes in these, whereas the surrounding B2 tetrahedra are largely unaltered. The Ca-Sn results are, respectively: direct Mg/Sn substitution at the Ca1 site; mixed fractional distribution of the smaller Cu at two sites around the A1 position with an unresolved disorder; a pair of apparently independent modes, fractional Ca in the normal position and fractional Zn rectangles thereabout. The two La-Sn phases contain normal Ga,Al (Ga,Zn) tetrahedral chains with pairs of fractional disordered La atoms along , 0, z. Each can be rationalized in terms of a reasonable incommensurate structure. Electronic effects may also be operable. 相似文献
35.
Freiría A Bastida R del Carmen Fernández-Fernández M Macías A Valencia L Vicente M 《Inorganic chemistry》2005,44(4):930-934
We report here the first pentanuclear Ba(II) complex of a new tri-aza, tri-oxa macrocycle with two carboxymethyl "arms" pending from two N atoms, H2L2. The crystal structure corresponds to the formula [Ba5(H0.375L2)4(ClO4)(CH3CH2OH)(H2O)2](ClO4)2.5 x 9.5H2O and reveals the presence of four molecules of the ligand surrounding five Ba(II) ions, giving rise to an unusual structure with the metal ions inside a spherical organic cavity. 相似文献
36.
37.
Jenny?ZevallosEmail author Alejandro?Toro-Labbé Otilia?Mó Manuel?Yá?ez 《Structural chemistry》2005,16(3):295-303
High level ab initio and density functional theory calculations have been carried out to investigate the relative stability of the different conformers of hyponitrous acid and its mono- and dithio-derivatives. Geometries and vibrational frequencies were obtained at the B3LYP/6-311+G(d,p) level and final energies through B3LYP/6-311++G(3df,2pd) single point calculations. The reliability of this theoretical scheme has been assessed by comparing these DFT results with those obtained at the G3 level of theory, for some suitable cases. The cis conformers of hyponitrous acid and its mono- and dithio-derivatives are systematically more stable than the
trans ones because in the cis conformation a dative interaction between the nitrogen-lone pairs and the σNX^* antibonding orbital is significantly favored. Quite interestingly, in general, the conformers presenting an intramolecular hydrogen bond (IHB) are not the global minima of the corresponding potential energy surfaces and only for hyponitrous acid the conformer with a OH ⋅s O IHB is slightly more stable than the cis conformer without IHB. The low stability of the tautomers with IHB is closely related with another weak intramolecular interaction which involves the lone-pairs of the chalcogen atoms and the πNN* antibondig orbital, and which is significantly perturbed when the IHB is formed. 相似文献
38.
39.
In this work, a simple, fast and reproducible method is presented for the determination of fibre/liquid-phase and fibre/gas-phase
partition coefficients of five chlorinated ethenes on a poly-(dimethylsiloxane), PDMS-coated, solid-phase microextraction
fibre, by employing a headspace HS-SPME coupled with gas chromatography. The partition coefficients were estimated by a numerical
method using a Level-I fugacity method coupled with parameter-estimation software. Dimensionless partition coefficients between
SPME fibre and liquid as well as gas phases were obtained at temperatures of 10 °C, 25 °C and 30 °C. The partition coefficients
of the fibre and the gas phase, K
fg, increase with decreasing temperature by a factor of ≈2 to 6, and they are directly proportional to the linear slope of the
regression line. The same tendency is observed for the partition coefficient of the fibre and liquid phase, K
fw, in a factor ≈1.2 to 2.0. The sorption enthalpy is higher in the gas phase; therefore, the sorption onto the fibre is favoured
at lower temperatures. The correlation of the log K
ow versus log K
fw and log K
oa versus log K
fg shows a linear relationship with the number of chlorine atoms in the C = C molecule. Long-term experiments resulted in sorption
to Teflon surfaces and possible losses in 43 mL vials, not observed in 250 mL Boston bottles. 相似文献
40.
Voltammetric behavior of zaleplon and its differential pulse polarographic determination in capsules
Larenas G Bollo S Rodriguez M Lemus I Nuñez-Vergara LJ Squella JA Alvarez-Lueje A 《Journal of AOAC International》2005,88(4):1135-1141
In this work both the electrochemical behavior and the analysis of the hypnotic pyrazolopyrimidine derivative zaleplon were studied. Zaleplon in ethanol-0.1M Britton Robinson buffer solution (30-70) showed 2 irreversible, well-defined cathodic responses in the pH range of 2-12 using differential pulse polarography (DPP), tast polarography, and cyclic voltammetry. From chronocoulometric studies, it was possible to conclude that one electron was transferred in each reduction peak or wave. For analytical purposes, the DPP technique working at pH 4.5 for peak I was selected, which exhibited adequate repeatability, reproducibility, and selectivity. The recovery was 99.97 +/- 1.52%, and the detection and quantitation limits were 5.13 x 10(-7)M and 1.11 x 10(-6)M, respectively. The DPP method was applied successfully to the individual assay of capsules in order to verify the content uniformity of zaleplon. Treatment of the sample is not required because the excipients do not interfere, the method is not time consuming, and it is less expensive than column liquid chromatography. 相似文献