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21.
Lenka Novotna Tereza Emmerova Daniel Horak Zdenka Kucerova Marie Ticha 《Journal of chromatography. A》2010,1217(51):8032-8040
Magnetic non-porous hydrophilic poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) microspheres prepared by the dispersion polymerization and modified with iminodiacetic acid (IDA) were employed for the IMAC separation of phosphopeptides. Fe3+ and Ga3+ ions immobilized on IDA-modified magnetic microspheres were used for the enrichment of phosphopeptides from the proteolytic digests of two model proteins differing in their physico-chemical properties and phosphate group content: porcine pepsin A and bovine α-casein. The optimum conditions for phosphopeptide adsorption and desorption in both cases were investigated and compared. The phosphopeptides separated from the proteolytic digests were analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The ability of the prepared Fe3+- and Ga3+-IDA-modified magnetic microspheres to capture phosphopeptides from complex mixtures was shown on an example of bovine milk proteolytic digest. 相似文献
22.
The inhibition of the model enzyme, haloalkane dehalogenase from Sphingomonas paucimobilis, was investigated by a combination of electrophoretically mediated microanalysis with a partial filling technique, followed by indirect or direct detection. In this setup, part of the capillary is filled with a buffer suitable for the enzymatic reaction (20 mM glycine buffer, pH 8.6) whereas the rest of the capillary is filled with the background electrolyte optimal for separation of substrates and products. Two different background electrolytes and corresponding detection approaches were used to show the versatility of the developed method. The inhibition effect of 1,2-dichloroethane on the dehalogenation of brominated substrate 1-bromobutane was studied by means of 10 mM chromate - 0.1 mM cetyltrimethylammonium bromide (pH 9.2) in combination with indirect detection or 20 mM beta-alanine - hydrochloric acid (pH 3.5) in combination with direct detection. The method was used to estimate the inhibition constant K(I) (0.44 mM by indirect detection and 0.63 mM by of direct detection) and to determine the inhibition type. Compared to spectrophotometric and other discontinuous assays, the method is rapid, can be automated, and requires only small amount of reagents that is especially important in the case of enzymes and inhibitors. 相似文献
23.
Isolation and Crystallographic Characterization of the Labile Isomer of Y@C82 Cocrystallized with Ni(OEP): Unprecedented Dimerization of Pristine Metallofullerenes 下载免费PDF全文
Lipiao Bao Changwang Pan Prof. Zdenek Slanina Prof. Filip Uhlik Prof. Takeshi Akasaka Prof. Xing Lu 《Angewandte Chemie (International ed. in English)》2016,55(32):9234-9238
Although the major isomers of M@C82 (namely M@C2v(9)‐C82, where M is a trivalent rare‐earth metal) have been intensively investigated, the lability of the minor isomers has meant that they have been little studied. Herein, the first isolation and crystallographic characterization of the minor Y@C82 isomer, unambiguously assigned as Y@Cs(6)‐C82 by cocrystallization with Ni(octaethylporphyrin), is reported. Unexpectedly, a regioselective dimerization is observed in the crystalline state of Y@Cs(6)‐C82. In sharp contrast, no dimerization occurs for the major isomer Y@C2v(9)‐C82 under the same conditions, indicating a cage‐symmetry‐induced dimerization process. Further experimental and theoretical results disclose that the regioselective dimer formation is a consequence of the localization of high spin density on a special cage‐carbon atom of Y@Cs(6)‐C82 which is caused by the steady displacement of the Y atom inside the Cs(6)‐C82 cage. 相似文献
24.
A novel method for the non-derivatization liquid chromatographic determination of metals (potassium, aluminium, calcium and magnesium) and organic compounds (ascorbate and aspartate) was developed and validated based on evaporative light scattering detection (ELSD). Separation of calcium, magnesium and aluminium was achieved by the cation exchange column Dionex CS-14 and an aqueous TFA mobile phase according to the following time program: 0-6 min TFA 0.96 mL L−1, 6-7 min linear gradient from TFA 0.96-6.4 mL L−1. Separation of potassium, magnesium and aspartate was achieved by the lipophilic C18 Waters Spherisorb column and isocratic aqueous 0.2 mL L−1 TFA mobile phase. Separation of sodium, magnesium, ascorbate and citrate was also achieved by the C18 analytical column, according to the following elution program: 0-2.5 min aqueous nonafluoropentanoic acid (NFPA) 0.5 mL L−1; 2.5-3.5 min linear gradient from 0.5 mL L−1 NFPA to 1.0 mL L−1 TFA. In all cases, evaporation temperature was 70 °C, pressure of the nebulizing gas (nitrogen) 3.5 bar, gain 11 and the flow rate 1.0 mL min−1. Resolution among calcium and magnesium was 1.8, while for all other separations was ≥3.2. Double logarithmic calibration curves were obtained within various ranges from 3-24 to 34-132 μg mL−1, and with good correlation (r > 0.996). Asymmetry factor ranged from 0.9 to 1.9 and limit of detection from 1.3 (magnesium) to 17 μg mL−1 (ascorbate).The developed method was applied for the assay of potassium, magnesium, calcium, aluminium, aspartate and ascorbate in pharmaceuticals and food-supplements. The accuracy of the method was evaluated using spiked samples (%recovery 95-105%, %R.S.D. < 2) and the absence of constant or proportional errors was confirmed by dilution experiments. 相似文献
25.
Liao JH Chen CT Chou HC Cheng CC Chou PT Fang JM Slanina Z Chow TJ 《Organic letters》2002,4(18):3107-3110
[structure: see text] A push-pull conjugated molecule, 2,7-bis(1H-pyrrol-2-yl)ethynyl-1,8-naphthyridine (BPN), has been designed to bind selectively with octyl glucopyranoside (OGU). The BPN/OGU quadruple hydrogen-bonding complex adopts a rigid BPN conformation in which the proton donor (d) and acceptor (a) relays (daad) are resonantly conjugated through the ethynyl bridge, inducing pi-electron delocalization, i.e., a charge transfer effect. The excellent photophysical properties make BPN a highly sensitive probe for monitoring glucopyranoside to a detection limit of approximately 100 pM. 相似文献
26.
A comparison of spin-orbit coupling calculated [CASSCF(6,6)/(cc-pVDZ on C,H and VDZ+P on Br] for bromomethylcarbene and methylcarbene predicts a highly unusual inverse heavy-atom effect by the Br substituent, particularly at geometries near the syn conformation. This behavior is due to a vacant 4d orbital on the Br atom acting as a weak pi-electron acceptor and overwhelming the even weaker effect of the pi-symmetry lone pair donor 4p orbital, which in itself would cause a small normal heavy-atom effect. 相似文献
27.
Layered nanoscale amorphous solid films of methanol and ethanol undergo complete intermixing prior to the onset of measurable desorption at 120 K. This intermixing precedes and inhibits crystallization. Subsequent desorption of the film is described quantitatively by a kinetic model describing evaporation from a continuously mixed ideal binary liquid solution. This occurs at temperatures below the melting point of the binary mixture, indicating ideal behavior for the supercooled liquid solution. This approach provides a new method for preparing and examining deeply supercooled solutions. 相似文献
28.
29.
Time-of-flight spectra were collected for 2.5 keV 7Li+ backscattered from Fe surfaces covered with submonolayers of iodine. Li singly scattered from the adatoms has a consistently larger neutral fraction than for scattering from the substrate, implying a region of positive charge atop the iodine. The neutral fraction decreases for off-normal exit angles, indicating a nonuniform charge distribution around the polarizable adsorbates. This demonstrates that ion scattering can image the internal electronic structure of an adatom and provides an explanation for anomalous work function changes. 相似文献