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1.
The paper advanced the theoretical procedures for quantitative design on selective stacking of zwitterions in full capillary sample matrix by a cathodic-direction moving reaction boundary (MRB) in capillary electrophoresis (CE) under control of electroosmotic flow (EOF). With the procedures, we conducted the theoretical computations on the selective stacking of two test analytes of L-histidine (His) and L-tryptophan (Trp) by the MRB created with 30 mM pH 3.0 formic acid-NaOH buffer and 2-80 mM sodium formate. The results revealed the following three predictions. At first, the MRB cannot stack His and Trp plugs if less than 12.5 mM sodium formate is used to form the MRB and prepare the sample matrix. Second, the MRB can stack His and/or Trp sample plugs completely if higher than 50 mM sodium formate is chosen to form the MRB. Third, the MRB can only focus His plug completely, but stack Trp plug partially if 20-50 mM sodium formate is used; this implied the complete MRB-induced selective stacking to His rather than Trp. All the three predictions were quantitatively proved by the experiments. With great dilution of sample matrix and control of EOF, controllable, simultaneous and MRB-induced selective stacking and separation of zwitterions were achieved. The theoretical results hold evident significances to the quantitative design of selective stacking conditions and the increase of detection sensitivity of zwitterions in CE. In addition, the control of EOF by cetyltrimethylammonium bromide (CTAB) can evidently improve the stacking efficiency to both His and Trp. 相似文献
2.
CE conditions for monitoring the unsaturated disaccharides of hyaluronic acid (di-HA) and chondroitin sulfate (di-CS) using an alkaline tetraborate buffer, electrokinetic sample injection, and UV absorption detection at 232 nm are reported. Separations were performed in an uncoated fused-silica capillary having reversed polarity and reversed electroosmosis generated with the addition of CTAB to the buffer. The influence of various separation parameters, including the concentration of CTAB, buffer pH, concentration of tetraborate, and applied voltage, on the resolution of the two disaccharides was investigated. Baseline separation was obtained with 25 mM tetraborate at pH 10.0 and having 0.05 mM CTAB. Chloride and phosphate in the sample are beneficial for the stacking of the disaccharides, with di-HA forming a much sharper peak than di-CS. Using samples prepared in 25 mM Tris-HCl (pH 7.5) and electrokinetic injection at the cathode at -10 kV for 40 s, linear relationships between the corrected peak area and the concentration of the disaccharides have been found in the ranges of 1.0-400.0 and 0.1-1.0 microg/mL (0.2-1.0 microg/mL for di-CS), with correlation coefficients being >0.9933 in all cases. The RSDs of detection times and corrected peak areas were between 1.13-1.24 and 1.57-2.13%, respectively. Applied to human serum samples that were prepared by ethanol precipitation and depolymerization of the two polysaccharides with chondroitinase ABC reveals comigration of endogenous compounds with di-HA and a sample-dependent detection time. The di-HA content in the serum sample can be estimated via subtraction of the blank peak that is obtained without enzymatic hydrolysis. 相似文献
3.
Yun Liu A.P. Whichello Valeska Ting John D. Fitz Gerald 《Journal of solid state chemistry》2005,178(11):3389-3395
A combined synthesis, diffraction and dielectric properties investigation of the dependence (and effect) of Mn2+/Nb5+ ordering in Ba3MnNb2O9 (BMN) upon annealing atmosphere and processing conditions has been carried out. Annealing in different atmospheres was not found to significantly alter either nominal stoichiometry or structure type. The obtained structure type (disordered metrically cubic or ordered trigonal) as well as the measured electrical properties (in particular, the dielectric loss) were, however, found to be sensitive to the synthesis route. Samples obtained via solid-state reaction were found to be predominantly of 1:2 Mn2+/Nb5+ ordered, trigonal structure type whereas samples obtained via an aqueous solution route were found to be of a Mn2+/Nb5+ ‘disordered’, metrically cubic structure type. All solid-state synthesized samples showed reasonable dielectric properties. The microwave dielectric constant and dielectric quality factor, Q, at 8 GHz of an as-synthesized BMN sample were 38 and 100, respectively. By contrast, the dielectric loss of the metrically cubic, Mn2+/Nb5+ ‘disordered’ samples obtained via an aqueous solution synthesis process were significantly worse. 相似文献
4.
In sample-stacking techniques, the detection limit cannot be improved by simply increasing the length of the sample solution, because the individual electrophoretic parameters must be optimized. In an attempt to increase the amount of sample injected, as well as to focus them onto a small zone, two novel methods are proposed. One of these employs an "ultra-high conductivity zone", which was inserted between the sample zone and background solution to build an unequal conductivity gradient. The other employs a "low temperature bath". A portion of the capillary (near the junction between the sample solution and the background solution) was immersed in a low temperature bath, which served as a "pseudo-high-conductivity zone" due to the fact that conductivity would increases when the temperature is decreased. As a result, a large volume of sample injection can be achieved. Using 3,4-methylenedioxymethamphetamine as a model compound, the detection limit was determined to be 1.6 x 10(-6) M (S/N = 3) by means of normal non-aqueous capillary electrophoresis (NACE). This could be improved to 3.0 x 10(-8) M, 4.8 x 10(-9) M and 5.0 x 10(-9) M, respectively, when the normal stacking, ultra-high conductivity zone NACE-stacking and the low-temperature zone NACE-stacking methods were applied. 相似文献
5.
The crystal structures of molybdocene‐amino acid compounds of the type [Cp2MoIV(κN, κO‐AA)]+Cl—·xH2O with AA = D ‐phenylalaninato (x = 1.5), DL ‐leucinato (x = 2) and DL ‐valinato (x = 1) have been determined (Cp = η5‐C5H5). The compounds feature an almost planar, five‐membered chelate ring of the aminocarboxylate moiety (deprotonated amino acid) with the molybdenum atom. In the phenylalaninato complex π‐stacking between the phenyl rings is found. The complexes were proven kinetically stable at pH < 1 for at least 24 h. 相似文献
6.
We have performed Monte Carlo simulations of hard spheres under gravity. Vertical boundaries are hard walls, which are well separated with each other. On the other hand, the periodic boundary condition is imposed in the horizontal direction. While we previously reported enhancement of crystallinity as well as crystallization due to gravity, we present here the results that demonstrate the succession of a defect. In case that the crystal formed at the bottom of the system includes kinds of stacking disorders for the (0 0 1) growth, twin band structure develops as mediated by a stacking disorder succeeded in the crystal formed in the fluid region which lies on the bottom crystal. In case that the stacking structure along horizontal direction changes from the (1 1 1) stacking to the (0 0 1) stacking, twin band structure in the (0 0 1) stacking region develops as succeeded in the crystal transformed. The twin band structure also becomes large with its upward growth. 相似文献
7.
A new pyrenemethylamine substituted l-Boc-tyrosine derivative was synthesized and characterized. UV-vis, FL, CD, and light scattering experiments proved that the chiral molecules were able to self-assemble for formation of new aggregate structure. The SEM and AFM images indicated that the helical wires could be fabricated by π-π stacking interaction between adjacent pyrene molecules. 相似文献
8.
Two new mixed‐anion zinc(II) and cadmium(II) complexes of 3‐(2‐pyridyl)‐5,6‐diphenyl‐1,2,4‐triazine (PDPT) ligand, [Zn(PDPT)2Cl(ClO4)] and [Cd(PDPT)2(NO3)(ClO4)], have been synthesized and characterized by elemental analysis, IR‐ and 1H NMR spectroscopy. The single crystal X‐ray analyses show that the coordination number in these complexes is six with four N‐donor atoms from two “PDPT” ligand and two of the anionic ligands, ZnN4ClOperchlorate, CdN4OnitrateOperchlorate. Self‐assembly of these compounds in the solid state via π–π‐stacking interactions is discussed. 相似文献
9.
Xian‐Zhong Sun Zhen‐Li Huang He‐Zhou Wang Bao‐Hui Ye Xiao‐Ming Chen 《无机化学与普通化学杂志》2005,631(5):919-923
Two new coordination polymers [Cd(tdc)(bpy)(H2O)]n ( 1 ) and [Cd(tdc)(phen)]n ( 2 ) (H2tdc = thiophene‐2,5‐dicarboxylic acid, bpy = 2,2′‐bipyridine and phen = 1,10‐phenanthroline) have been synthesized under hydrothermal condition. Their crystal structures have been established by X‐ray single‐crystal diffraction. Complex 1 crystallizes in the orthorhombic space group Fdd2 with a = 14.757(7), b = 45.38(2), c = 10.518(5) Å, V = 7044(6) Å3, Z = 16; 2 in the monoclinic space group P21/c with a = 7.262(1), b = 21.970(2), c = 10.051(1) Å, β = 105.01(1)°, V = 1548.8(2) Å3, Z = 4. Both of them are double‐stranded chains and further assembled into three‐dimensional networks by π‐π stacking interactions. 1 and 2 are stable in air, and show blue photoluminescence at 415 nm and 410 nm, respectively. 相似文献
10.
Peter D. Battle Jonathan C. Burley Clare P. Grey 《Journal of solid state chemistry》2004,177(1):119-125
Polycrystalline samples of the n=2 Ruddlesden-Popper phase La3LiMnO7 have been prepared and characterized. X-ray and neutron diffraction suggest that the structure is tetragonal with a disordered distribution of Li and Mn cations over the octahedral sites, but 6Li MAS NMR shows that the Li and Mn are 1:1 ordered locally. Electron microscopy shows that the stacking of the cation-ordered, perovskite-like bilayers along the crystallographic z-axis is disordered on the distance scale sampled by X-ray and neutron diffraction. Magnetometry data and neutron diffraction data collected at 2 K together suggest that the Mn cations within each structural domain order antiferromagnetically at 14 K, but that the disorder along z prevents the establishment of long-range magnetic order. 相似文献