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991.
A study on a novel oxonia [3,3]-sigmatropic rearrangement as competitive alternative pathway to the acetylenic Prins cyclization on the addition of secondary homopropargylic alcohols to aldehydes catalyzed by iron(III) is described. ‘Ab initio’ theoretical calculations of the species involved on the rearrangement supports the in situ formation of 2,3-allenolates. The domino process involves three consecutive chemical events in one-pot format reaction (∼70% average). 相似文献
992.
Summary High-performance size exclusion chromatography has been applied to the analysis and separation of a range of biological products — substances and preparations used in human medicine that cannot be completely defined by chemical and physical means. A variety of proteins and polysaccharides have been examined and results are described for a number of blood products, and polysaccharides of bacterial origin. This method is superior to conventional size esclusion for characterization of such substances and permits their isolation for further examination, without work-up, by biological and immunological techniques. The selection of appropriate column supports is considered. The limitations are considered of this procedure for studying the interaction between antithrombin III and heparin as the basis of a non-biological assay method.Presented at the 14th International Symposium on Chromatography London, September, 1982 相似文献
993.
Duralí Mendíl Ahmet Bílgín Yaşar Gök H. Basrí Şentük 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(3-4):265-270
A new N,N'-substituted diaminoglyoxime (H
2
L) containing a diazatetraoxamacrobicycle [2.2.2B] has been synthesized from an aromatic primary amine attached to the cryptand moiety and cyanogen-di-N-oxide. The BF2
+-capped Co(III) and heterotri-nuclear complexes of thevic-dioxime were prepared. The new compounds werecharacterized by a combination of elemental analysis and 1H NMR,13C NMR, IR and MS spectral data. 相似文献
994.
Spectroscopic investigations have been undertaken on the effects of lanthanide ions on the spectrum of the anticancer agent, daunomycin. The visible spectral perturbations due to the metal ions resulted in hypochromic effects in the 480 nm region and in shifts towards longer wavelength. The different metal ions investigated did not give any significant difference in the, spectral character. Data analysis according to the methods of molar ratio, continuous variation and graphical approaches based on simplex matrix theory indicated the presence of predominantly a ML2 species at metal to ligand ratios, less than one. Data also suggested the presence of ML and ML3 as well. 相似文献
995.
Themistoclis Kabanos Spyros P. Perlepes Vaggelis Hondrellis John M. Tsangaris 《Monatshefte für Chemie / Chemical Monthly》1986,117(8-9):955-967
New complexes of the general formulae CoL
2
X·nH2O (X=Cl, Br, I, NCS, NO3 andn=0, 1, 2 or 3), Co2
L
2
X
3·EtOH (X=Cl, Br, I, NCS), Co(DH)X
2 (X=NCS, NO3) and Co(DH)2
X
2 (X=NCS, I) have been prepared, whereLH=N-(2-aminophenyl)pyridine-2-carboxamide andDH=N-(3-aminophenyl)pyridine-2-carboxamide. The compounds were characterized by X-ray powder patterns, conductivity measurements, thermogravimetric analysis, magnetic properties as well as by IR, ligand field and1H-NMR spectroscopy. In the presence of oxygen,LH undergoes a cobalt(III) ion promoted amide hydrogen ionization in thepH region 4–6.
Koordinationsverbindungen von N-(2-aminophenyl)- und N-(3-aminophenyl)pyridin-2-carboxamid mit Cobalt(II) und Cobalt(III). Die Natur der Deprotonierung von Amiden induziert von Cobalt(III) in saurem Medium
Zusammenfassung Neue Komplexe der allgemeinen Formeln CoL 2 X·nH2O (X=Cl, Br, I, NCS, NO3 undn=0, 1, 2, 3), Co2 L 2 X 3·EtOH (X=Cl, Br, I, NCS), Co(DH)X 2 (X=NCS, NO3) und Co(DH)2 X 2 (X=NCS, I) wurden dargestellt mit LH=N-(2-aminophenyl)pyridin-2-carboxamid undDH=N-(3-aminophenyl)pyridin-2-carboxamid. Die Verbindungen wurden mittels Röntgenstrukturanalyse, Leitfähigkeitsmessungen, thermogravimetrischen Analysen, magnetischen Eigenschaften sowie mit IR-, Ligandenfeld- und1H-NMR-Spektroskopie charakterisiert. In Gegenwart von Sauerstoff unterliegtLH einer Cobalt(III)ion-induzierten Amidwasserstoffionisierung impH-Bereich 4–6.相似文献
996.
The equilibrium composition of the vapor above thorium nitrate-nitric acid-water mixtures has been studied as a function of the concentrations of thorium nitrate and nitric acid using a transpiration technique. At 25°C, the thorium nitrate concentrations m
T
ranged from 0.1 to 2.5 molal and the nitric acid concentrations m
N
from 0.3 to 25 modal. The vapor pressure of the nitric acid was found to increase with increasing thorium nitrate concentration for a constant molality of nitric acid in aqueous solution. At constant m
T
, the nitric acid vapor pressure was particularly enhanced at low nitric acid concentrations. The water vapor pressures decreased regularly with increasing concentrations of both nitric acid and thorium nitrate. The experimental data were fitted to Scatchard's ion-component model, and to empirical multiparameter functions. From the fitting parameters, and available literature data for the nitric acid-water and thorium nitrate-water systems at 25°C, expressions were calculated for the variation of water and thorium nitrate activities, as functions of the nitric acid and thorium nitrate concentrations, using the Gibbs-Duhem equation. Calculated values for the thorium nitrate activities were strongly dependent on the form of the function originally used to fit the vapor pressure data.Issued as AECL-7461. 相似文献
997.
R. Schmid Liang-feng Han K. Kirchner V. N. Sapunov 《Monatshefte für Chemie / Chemical Monthly》1993,124(5):493-509
Summary The kinetics of outer-sphere oxidation of Fe(Xphen)
3
2+
ions (X=H or several methyl substituents) in acetonitrile (MeCN) solution by iron(III), introduced as Fe(tmp)6(ClO4)3 (tmp=trimethylphosphate), have been investigated at 25°C. The reactions are very complex because of solvation equilibria betweentmp andMeCN coordinated at Fe3+, with a reduction potential difference of 0.20 V for the replacement of onetmp byMeCN. This makes the various solvate species highly different in driving force. The second essential feature is the high charge-type of +2/+3. This brings about strong acceleration by salt because of ion association reducing the work necessary to overcome the Coulombic repulsion in forming the precursor complex.The task was to deconvolute two kinds of speciation: the ionic and the solvate speciations. The analysis suggests the concurrent existence of five Fe(tmp)
n
3+
(n=2–6) species among which four species (n=2–5) are reacting, with an additional mono and bis perchlorate ion pair for eachn. Extra complications arise as some of the solvation equilibria are not always fast compared to the redox reactions, leading to non-first order rate constants.Although the rate constants could not be defined with the desired precision, at least two results are worth noting: (i) The relative effects of driving force and charge are highlighted in controlling overall reactivity. (ii) The stronger the reducing power of the Fe(Xphen)
3
2+
moiety, the less it can distinguish between the various solvate species (reactivity-selectivity relationship).
Redox-Kinetik von Metallkomplexe in nicht-wäßrigen Lösungsmitteln: Oxidation einer Serie von Tris(1,10-phenanthrolin)eisen(II)-Ionen mit Hexakis(trimethylphosphat)eisen(III) in Acetonitril-eine Reaktivitäts-Selektivitäts-Beziehung
Zusammenfassung Es wurde die Kinetik der Outer-sphere Oxidation einer Reihe von Fe(Xphen) 3 2+ Ionen (X=H oder verschiedene Methylsubstituenten) mit Eisen(III), eingeführt als Fe(tmp)6(ClO4)3 (tmp=Trimethylphosphat), bei 25°C in Acetonitril (MeCN) untersucht. Diese Reaktionen sind sehr komplex, da gebundenestmp teilweise durchMeCN ausgetauscht wird, wobei der Ersatz einestmp-Moleküls durchMeCN das Redoxpotential um 0.2 V verschiebt. Deshalb sind die verschiedenen Solvatkomplexe in ihrer Reaktivität sehr unterschiedlich. Ein zweites wesentliches Merkmal der untersuchten Reaktionen ist der hohe Ladungstyp von +2/+3. Das bringt eine starke Erhöhung der Reaktionsgeschwindigkeit durch Elektrolytzusatz infolge von Ionenassoziation mit sich, die die Coulombsche Arbeit für die Bildung des Precursorkomplexes reduziert. Die Aufgabe bestand demnach in der Aufklärung von zwei Speziationsarten, der Solvations- und Ionenassoziationsgleichgewichte. Die Analyse weist auf das gleichzeitige Vorliegen von fünf Fe(tmp) n 3+ Species (n=2–6) hin, wobei vier von ihnen (n=2–5) reagieren. Zusätzlich gibt es für jedesn noch Ionenpaare und Ionentriplets mit Perchlorat. Eine zusätzliche Komplizierung ergibt sich, weil bestimmte Solvationsgleichgewichte nicht immer schnell sind im Vergleich zu den Redoxreaktionen, die dann nicht mehr pseudo-erster-Ordnung sind.Wenn auch die Geschwindigkeitskonstanten nicht mit der üblicherweise gewünschten Präzision angegeben werden können, sind zumindest zwei Ergebnisse nennenswert: (a) Es wird die relative Bedeutung der driving force und der Reaktantenladung für die Gesamtreaktivität hervorgehoben und (b) Je stärker die Reduktionskraft des Fe(Xphen) 3 2+ Ions, desto weniger kann es die verschiedenen Solvatspezies unterscheiden (Reaktivitäts-Selektivitäts-Beziehung).相似文献
998.
《Electroanalysis》2006,18(18):1763-1770
Poly(L ‐lactide) stabilized gold nanoparticles (designated as PLA–AuNP) with an average particle size of ca. 10 nm were used to modify a disposable screen‐printed carbon electrode (SPE) for the detection of As(III) by differential pulse anodic stripping voltammetry. Gold modification was evaluated by cyclic voltammetry, whereas scanning electron microscopy and transmission electron microscopy revealed the size and distribution of gold nanoparticles. The PLA–AuNP/SPE was applied effectively to detect toxic As(III) in HCl medium. Under the optimal experimental conditions, a linear calibration curve up to 4 ppm with a detection limit (S/N=3) of 0.09 ppb was obtained. The sensitivity was good enough to detect As(III) at levels lower than the current EPA standard (10 ppb). Most importantly, the PLA–AuNP/SPE can be tolerable from the interference of Cu, Cd, Fe, Zn, Mn, and Ni and hence provides a direct and selective detection method for As(III) in natural waters. Practical utility of the PLA–AuNP/SPE was demonstrated to detect As(III) in “Blackfoot” disease endemic village groundwater from southwestern coast area of Taiwan (Pei‐Men). 相似文献
999.
An artificial neural network (ANN) model is developed for simultaneous determination of Al(III) and Fe(III) in alloys by using chrome azurol S (CAS) as the chromogenic reagent and CCD camera as the detection system. All calibration, prediction and real samples data were obtained by taking a single image. Experimental conditions were established to reduce interferences and increase sensitivity and selectivity in the analysis of Al(III) and Fe(III). In this way, an artificial neural network consisting of three layers of nodes was trained by applying a back-propagation learning rule. Sigmoid transfer functions were used in the hidden and output layers to facilitate nonlinear calibration. Both Al(III) and Fe(III) can be determined in the concentration range of 0.25-4 μg ml−1 with satisfactory accuracy and precision. The proposed method was also applied satisfactorily to the determination of considered metal ions in two synthetic alloys. 相似文献
1000.
Two procedures are proposed for the potentiometric determination of Ag(I), Pd(II) and Au(III) in binary mixtures, by titration with potassium iodide solution, and use of a commercial iodide electrode as sensor. In the first procedure, two aliquots of the mixture are titrated, at pH 2.0 ± 0.2 and 9.0 ± 0.2, adjusted with dilute sulphuric acid and ammonia solution. At pH 2.0, the titrant reacts with both metals, whereas at pH 9.0, Ag(I) is the only reactant. The second procedure utilizes titration of two aliquots of the mixture in the presence and absence of a selective masking agent. The methods have been applied to the determination of these metals in some jewellery alloys. 相似文献