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951.
A flow injection analysis of Ca(2+) and Mg(2+) using indirect potentiometric detection in natural waters is proposed, where Ca(2+) or Mg(2+) are injected into a buffer carrier containing phosphate, resulting in the formation of Ca(3)(PO(4))(2) or Mg(3)(PO(4))(2). The consequent reduction in free phosphate in the carrier solution is detected using a metallic cobalt wire electrode. Indirect electrode response was used and the experimental conditions affecting electrode response were optimized. Responses were linear in the concentration range 5x10(-4) to 5x10(-3) M with a detection limit of 1x10(-5) M in 20 mM phosphate buffer at pH 8.0. The relative standard derivation at 1 mM of Ca(2+) and Mg(2+) were 3.9 and 3.7% (n=10), respectively. EGTA and 8-hydroxyquinoline were used as the masking agents for Ca(2+) and Mg(2+), respectively. Concentrations of Ca(2+) and Mg(2+) in natural waters were successfully determined by the proposed method. 相似文献
952.
Singh J van Vlijmen H Lee WC Liao Y Lin KC Ateeq H Cuervo J Zimmerman C Hammond C Karpusas M Palmer R Chattopadhyay T Adams SP 《Journal of computer-aided molecular design》2002,16(3):201-211
The integrin VLA-4 (41) is involved in the migration of white blood cells to sites of inflammation, and is implicated in the pathology of a variety of diseases including asthma and multiple sclerosis. We report the structure-activity relationships of a series of VLA-4 antagonists that were based upon the integrin-binding sequence of the connecting segment peptide of fibronectin (Leu-Asp-Val), and of VCAM-1 (Ile-Asp-Ser), both natural ligands of VLA-4. We explore variation in the ligand derived peptide portion of these antagonists and also in the novel N-terminal cap, which have discovered through chemical optimization, and which confers high affinity and selectivity. Using the X-ray derived conformation of the Ile-Asp-Ser region of VCAM-1, we rationalize the structure-activity relationships of these antagonists using 3D QSAR (COMFA). The COMFA model was found to be highly predictive with a cross-validated R2
CVof 0.7 and a PRESS of 0.49. The robustness of the model was confirmed by testing the influence of various parameters, including grid size, column filtering, as well as the role of orientation of the aligned molecules. Our results suggest that the VCAM-1 structure is useful in generating highly predictive models of our VLA-4 antagonists. The COMFA model coupled with the knowledge that the peptide amides are tolerant to methylation should prove useful in future peptidomimetic design studies. 相似文献
953.
Infrared spectra of NaNO2 and KNO2 in the region of the anion internal modes have been obtained using a diamond anvil cell at pressures up to 65 kbar. At 39°C NaNO2 undergoes a phase transition at ca. 10.0 kbar, not at 14 kbar as reported from an earlier IR study. A similar transition was found at 6.3 kbar for KNO2. The symmetric modes lose intensity with increasing pressure, and all modes suffer blue-shifts. For KNO2 ν(NO)5 shifts much more than ν(NO)a. 相似文献
954.
McLain JL Poterya V Molek CD Jackson DM Babcock LM Adams NG 《The journal of physical chemistry. A》2005,109(23):5119-5123
A technique has been developed to simultaneously determine recombination rate coefficients, alpha e, and initial concentrations of ion types that coexist in a flowing afterglow plasma. This was tested using the H3(+) + allene reaction in which two different C3H3+ isomers are produced. Use of an electrostatic Langmuir probe enabled the C3H3+ isomer branching ratios for propargyl and cyclic C3H3+ from this allene reaction and their alpha e to be determined over the temperature range 172-489 K. The study showed that the cyclic C3H3+ to propargyl C3H3+ branching ratios from the allene reaction varied from 50/50 at 172 K to 18/82 at 489 K. Over this temperature range, the alpha e for both isomers change only slightly. The room temperature alpha e values for propargyl and cyclic C3H3+ are (1.15 +/- 0.2) x 10(-7) and (8.00 +/- 0.1) x 10(-7) cm3/s, respectively. The data are discussed relative to current theories and in relation to fuel-rich flame chemistry, interstellar molecular synthesis, and modeling of Titan's atmosphere. 相似文献
955.
Rao FV Houston DR Boot RG Aerts JM Hodkinson M Adams DJ Shiomi K Omura S van Aalten DM 《Chemistry & biology》2005,12(1):65-76
Family 18 chitinases play key roles in organisms ranging from bacteria to man. There is a need for specific, potent inhibitors to probe the function of these chitinases in different organisms. Such molecules could also provide leads for the development of chemotherapeuticals with fungicidal, insecticidal, or anti-inflammatory potential. Recently, two natural product peptides, argifin and argadin, have been characterized, which structurally mimic chitinase-chitooligosaccharide interactions and inhibit a bacterial chitinase in the nM-mM range. Here, we show that these inhibitors also act on human and Aspergillus fumigatus chitinases. The structures of these enzymes in complex with argifin and argadin, together with mutagenesis, fluorescence, and enzymology, reveal that subtle changes in the binding site dramatically affect affinity and selectivity. The data show that it may be possible to develop specific chitinase inhibitors based on the argifin/argadin scaffolds. 相似文献
956.
The first synthesis of a conjugated trihydroxy eicosatetraenoic acid, a possible structure for Lipoxin A is described. A biomimetic approach was utilized. 相似文献
957.
A data acquisition system and processing software for spark-source mass spectrometry (s.s.m.s.) with photographic detection is described. The distinctive feature of this system is that data integrity is maintained during the acquisition and real-time reduction. A microprocessor is used to decide whether or not to save the incoming plate blackening data on a digital tape. This results in the selective recording of spectral lines while relatively long fields with only background are neglected. The magnetic tape is then processed on a general-purpose computer. As the complete profile of each peak is recorded, significant improvements can be made for the blackening linearization, the traceback of interferences and the mass calibration. The off-line software makes it possible not only to obtain the elemental sample composition but also to control the instrumental parameters and the photoplate characteristics. This renders the system suitable for research purposes as well as for routine analysis. 相似文献
958.
959.
Adams Tidjani Yasushi Watanabe 《Journal of polymer science. Part A, Polymer chemistry》1995,33(9):1455-1460
γ-Oxidation of linear low-density polyethylene based on hexene and butene was investigated. Irradiation was performed at different dose rates in air (from 2 rad/s to 100 rad/s). Degraded samples were analyzed with IR combined with NO and SF4 derivatizations. Our results showed that the lower the dose rate, the higher the degree of oxidation in terms of γ-product formation. Ketone species appeared to be the dominant γ-products. The G values of γ-product formation were very dependent on the dose rate of initiation. Comparison of the G value ratio of different γ-products revealed stoechiometry differences. The complex appearance and disappearance of unsaturations was tentatively explained. The modifications of elongation at break induced by γ-irradiation were monitored by molecular changes in weight. This was not conclusive because changes in elongation at break are inconsistent with changes in Mw/Mn. © 1995 John Wiley & Sons, Inc. 相似文献
960.
Dehouck P Visky D Vander Heyden Y Adams E Kovács Z Noszál B Massart DL Hoogmartens J 《Journal of chromatography. A》2004,1025(2):189-200