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901.
Hexacyanoferrate(III) was used as a mediator in the determination of total iron, as iron(II)-1,10-phenanthroline, at a screen-printed carbon sensor device. Pre-reduction of iron(III) at −0.2 V versus Ag/AgCl (1 M KCl) in the presence of hexacyanoferrate(II) and 1,10-phenanthroline (pH 3.5-4.5), to iron(II)-1,10-phenanthroline, was complete at the unmodified carbon electrode surface. Total iron was then determined voltammetrically by oxidation of the iron(II)-1,10-phenanthroline at +0.82 V, with a detection limit of 10 μg l−1.In potable waters, iron is present in hydrolysed form, and it was found necessary to change the pH to 2.5-2.7 in order to reduce the iron(III) within 30 s. A voltammetric response was not found at lower pH values owing to the non-formation of the iron(II)-1,10-phenanthroline complex below pH 2.5.Attempts to incorporate all the relevant reagents (1,10-phenanthroline, potassium hexacyanoferrate(III), potassium hydrogen sulphate, sodium acetate, and potassium chloride) into a modifying coated PVA film were partially successful. The coated electrode behaved very satisfactorily with freshly-prepared iron(II) and iron(III) solutions but with hydrolysed iron, the iron(III) signal was only 85% that of iron(II). 相似文献
902.
Fungaloi P Waterman P Nigri G Statius-van Eps R Sluiter W van Urk H LaMuraglia G 《Photochemistry and photobiology》2003,78(5):475-480
Photodynamic therapy (PDT) is based on a photochemical reaction using a photosensitizer and light to produce reactive oxygen species that have biological effects. Although its application in some fields is largely based on thrombosis, in the vascular setting thrombosis must be prevented. In this study we examined the effects of PDT on the changes in activity of thrombomodulin (TM) and tissue factor (TF) as important regulators of the coagulation process of endothelial cells. Human umbilical vein endothelial cells were treated with PDT (chloro-aluminum-sulfonated phthalocyanine, lambda = 630 nm) at different light-energy doses, and TM and TF levels were measured using fluorescence spectroscopy. Microparticles (MP) were analyzed using flow cytometry analysis. PDT alters the thrombogenic state of endothelial cells by causing decreased expression of TM and increased expression of functional TF in a light-energy dose-dependent way. PDT-treated endothelial cells shed large numbers of MP containing high levels of TF. TF functionality of PDT-treated cells, measured by a Factor Xa-generating assay, was high. TF was located mostly intracellularly and in MP. The disturbed anticoagulant balance described in this study may explain the occurrence of thrombosis induced by PDT and, if not contained, dispute the suitability of PDT as an adjuvant modality to treat vascular restenosis. 相似文献
903.
Procelewska J Zahl A van Eldik R Zhong HA Labinger JA Bercaw JE 《Inorganic chemistry》2002,41(11):2808-2810
The reaction of the platinum(II) methyl cation [(N-N)Pt(CH(3))(solv)](+) (N-N = ArN[double bond]C(Me)C(Me)[double bond]NAr, Ar = 2,6-(CH(3))(2)C(6)H(3), solv = H(2)O (1a) or TFE = CF(3)CH(2)OH (1b)) with benzene in TFE/H(2)O solutions cleanly affords the platinum(II) phenyl cation [(N-N)Pt(C(6)H(5))(solv)](+) (2). High-pressure kinetic studies were performed to resolve the mechanism for the entrance of benzene into the coordination sphere. The pressure dependence of the overall second-order rate constant for the reaction resulted in Delta V(++) = -(14.3 +/- 0.6) cm(3) mol(-1). Since the overall second order rate constant k = K(eq)k(2), Delta V(++) = Delta V degrees (K(eq)) + Delta V(++)(k(2)). The thermodynamic parameters for the equilibrium constant between 1a and 1b, K(eq) = [1b][H(2)O]/[1a][TFE] = 8.4 x 10(-4) at 25 degrees C, were found to be Delta H degrees = 13.6 +/- 0.5 kJ mol(-1), Delta S degrees = -10.4 +/- 1.4 J K(-1) mol(-1), and Delta V degrees = -4.8 +/- 0.7 cm(3) mol(-1). Thus DeltaV(++)(k(2)) for the activation of benzene by the TFE solvento complex equals -9.5 +/- 1.3 cm(3) mol(-1). This significantly negative activation volume, along with the negative activation entropy for the coordination of benzene, clearly supports the operation of an associative mechanism. 相似文献
904.
Gerhard Bringmann Markus Rückert Jan Schlauer Markus Herderich 《Journal of chromatography. A》1998,810(1-2):231-236
The atropodiastereomeric dimeric naphthylisoquinoline alkaloids, michellamines A (1a), B (1b) and C (1c), together with their monomers, korupensamines A (2a) and B (2b), were investigated using electrospray ionization tandem mass spectrometry coupled to liquid chromatography (LC–ESI-MS–MS). From the spectra obtained, characteristic product ions were chosen to monitor the chromatographic separation achieved on an RP-18 column. Under acidic conditions required for chromatographic analysis, the monomeric alkaloids 2a and 2b yielded protonated molecules [M+H]+, while the dimers, the michellamines, exhibited doubly protonated [M+2H]2+ molecules. In addition, the coeluting alkaloids 1b and 2b were identified unambiguously by means of tandem mass spectrometry. Thus, together with the retention times of the alkaloids, the product ion spectra allowed us the identification of michellamines in the presence of their presumed biogenetic monomeric precursors. Application of the HPLC–MS–MS method successfully proved the enzymatic formation of michellamine C (1c) by in vitro dimerization of korupensamine B (2b). 相似文献
905.
DC-plasma-polymerized pyrrole (PP-Py) films deposited on metals were extensively characterized by Time-of-Flight Secondary
Ion Mass Spectrometry (TOF-SIMS), Reflection-Absorption IR Spectroscopy (RAIR), X-ray Photoelectron Spectroscopy (XPS), Scanning
Tunneling Microscopy (STM), Glow Discharge Optical Spectroscopy (GDOS), electrical conductivity (ASTM Franklin test), and
contact angle measurements. TOF-SIMS and RAIR showed no spectroscopic evidence of the presence of the pyrrole ring structure
in any of the plasmadeposited films. The major parameter that affected their composition was found to be the pressure. Films
deposited at low pressure were less hydrogenated than those polymerized at high pressure or in remote plasma conditions. Although
all deposits oxidized slowly in air, their surface energy remained low over an extended period of time. The electrical conductivity
of the PP-Py films was in the range of 10−3–10−4 S/cm, i.e., higher than that of amorphous carbon films. 相似文献
906.
Multivariate classification methods are needed to assist in extracting information from analytical data. The most appropriate method for each problem must be chosen. The applicability of a method mainly depends on the distributional characteristics of the data population (normality, correlations between variables, separation of classes, nature of variables) and on the characteristics of the data sample available (numbers of objects, variables and classes, missing values, measurement errors). The CLAS program is designed to combine classification methods with evaluation of their performance, for batch data processing. It incorporates two-group linear discriminant analysis (SLDA), independent class modelling with principal components (SIMCA), kernel density estimation (ALLOC), and principal component class modelling with kernel density estimation (CLASSY). Most of these methods are implemented so as to give probabilistic classifications. Multiple linear regression is provided for, and other methods are scheduled. CLAS evaluates the classification method using the training set data (resubstitution), independent test data, and pseudo test data (leave-one-out method). This last method is optimized for faster computation. Criteria for classification performance and reliability of the given probabilities, etc. are determined. The package contains flexible possibilities for data manipulation, variable transformation and missing data handling. 相似文献
907.
Maarten Honing Dami Barcel Ben L. M. van Baar Udo A. Th. Brinkman 《Trends in analytical chemistry : TRAC》1995,14(10):496-504
Column liquid chromatography with mass spectrometric detection (LC-MS) has been widely accepted as the preferred technique for the identification and quantification of polar and thermally labile compounds at trace levels. Over the last decade many different types of LC-MS interfacing techniques have been used for the determination of carbamate pesticides and especially for the N-methylcarbamate carbofuran. This article addresses the difficulties encountered with the various types of LC-MS interface and discusses recent alternatives for the determination of carbofuran. With thermospray and particle beam interfaces the quantification of carbofuran is affected by both the ion source pressure and temperature, whereas quantification using the recently developed atmospheric pressure ionization interfaces, atmospheric pressure chemical ionization, electrospray, and ionspray, is less dependent on these parameters. 相似文献
908.
Barroso B Dijkstra R Geerts M Lagerwerf F van Veelen P de Ru A 《Rapid communications in mass spectrometry : RCM》2002,16(13):1320-1329
An on-line high-performance liquid chromatography/mass spectrometry (HPLC/MS) method is described for the rapid characterization of any type of oligosaccharide released from glycoproteins. The procedure can be applied without further manipulation to fractions collected from a high-performance anion-exchange chromatography-pulse amperometric detection (HPAEC-PAD) system commonly used for glycosylation mapping of glycoproteins, or to a pool of oligosaccharides directly released from glycoproteins. The system consists of a porous graphitized high-performance chromatography column (Hypercarb) coupled to a quadrupole time-of-flight (TOF) mass spectrometer. Oligosaccharides are eluted from the column with a gradient of ammonium acetate/acetonitrile and directly identified following in-source fragmentation. Some applications of the method are presented, as well as information about the spectra and fragmentation behavior observed for N- and O-linked oligosaccharides released from some recombinant glycoproteins. Low femtomole limits of detection are achieved using proper miniaturization. 相似文献
909.
Radmila Krupkov Jan Fbry Ivana Císaov Pemysl Vank 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(5):i66-i68
The title room‐temperature phase of (NH4)2(PO3F) is orthorhombic (Pna21) and is related to the β‐K2SO4 structure family. The title structure consists of ammonium cations, NH4+, and fluorophosphate anions, (PO3F)2?. These ions are connected by N—H?O hydrogen bonds. Two‐centre N—H?F hydrogen bonds are not present in the structure. Phase transitions were detected at 251±2 and 274±2 K during cooling and heating, respectively. 相似文献
910.
Fluorescence imaging and spectroscopy of ethyl nile blue A in animal models of (pre)malignancies 总被引:4,自引:0,他引:4
van Staveren HJ Speelman OC Witjes MJ Cincotta L Star WM 《Photochemistry and photobiology》2001,73(1):32-38
Discrimination between normal and premalignant tissues by fluorescence imaging and/or spectroscopy may be enhanced by a tumor-localizing fluorescent drug. Ethyl Nile Blue A (EtNBA), a dye with no phototoxic activity, was investigated for this purpose. The pharmacokinetics and tissue-localizing properties were investigated in a rat palate model with chemically induced premalignant mucosal lesions (0.5 mg/kg EtNBA intravenous [i.v.]), a hairless mouse model with UVB-induced premalignant skin lesions (1 mg/kg EtNBA intraperitoneal) and in a rat skin-fold observation chamber model on the back of a rat with a transplanted solid tumor (2.5 mg/kg EtNBA i.v.). Fluorescence images and spectra were recorded in vivo (600 nm excitation, 665-900 nm detection) and in frozen tissue sections at several time points after EtNBA administration. In the rat palate the EtNBA fluorescence was maximum almost immediately after injection, whereas in the mouse skin and the observation chamber the fluorescence maximum was reached between 2 and 3 h after injection. EtNBA cleared from tissues after 8-24 h. EtNBA localizes in the transplantable solid tumor, but is not targeted specifically to the dysplastic location in the rat palate and mouse skin. However, in the rat palate the EtNBA fluorescence increased significantly with increasing dysplasia, apparently due to the increasing thickness of the upper keratinized layer of the epithelium where the dye was found to localize. Localization in this layer occurred both in the rat palate and in hairless mouse skin. 相似文献