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41.
Chromatographic behaviour of six selected herbicides (chlortoluron, metoxuron, chloridazon, simazine, propazine and atrazine) was studied by reversed-phase (RP) high-performance liquid chromatography (HPLC) containing Genapol X-080 non-ionic surfactant as methanol/water mobile phase constituent. The concentration of methanol was changed from 50 to 0% (v/v) for constant 2% (v/v) concentration of the surfactant. The surfactant concentration in purely aqueous micellar mobile phase varied from 1 to 5% (v/v) what is approximately 360-1800 times above the CMC. Within this concentration range Genapol X-080 proves concentration dependent selectivity changes for chlortoluron/atrazine critical pair not occurred in hydro-methanolic mobile phases. Further studies revealed that this chromatographic system offers high compatibility with cloud-point extraction environmental sample pretreatment approaches using Genapol X-080 for the purpose, too. 相似文献
42.
Štefan Toma Anton Gáplovský Milan Hudeček Zuzanna Langfelderová 《Monatshefte für Chemie / Chemical Monthly》1985,116(3):357-364
The electronic absorption spectra of 22 arylferrocenes and their arylferricenium salts with pentacyanopropenide (PCNP) were recorded. The attemptedHammett correlation of max of the d-d transition bands of arylferrocenes revealed that this band is substituent dependent only for strong electron-withdrawing substituents. Excellent correlation of max of the d-d transition bands with + constants was found in the case of arylferricenium cations. Good correlations of max was also found with theE
1/2 oxidation potentials measured by cyclic voltametry.
Substituentenabhängigkeit des d-d-Überganges in den Elektronenabsorptions-Spektren von Arylferrocenen und entsprechenden Arylferricenium-Salzen
Zusammenfassung Elektronenabsorptions-Spektren von 22 Arylferrocenen und ihren Arylferricenium-Pentacyanopropenid-Salzen wurden gemessen. VersuchteHammett-Korrelationen des längstwelligen d-d-Überganges (max) zeigten, daß diese Bande nur von stark elektronenanziehende Substituenten abhängig ist. Im Fall der Arylferricenium-Kationen wurde eine ausgezeichnete Korrelation zwischen max der d-d-Bande und den +-Konstanten festgestellt. Eine gute Korrelation der max-Werte wurde auch mit denE 1/2 Oxidationspotentialen gefunden, die durch cyclische Voltametrie meßbar sind.相似文献
43.
Milan Kunz 《Journal of mathematical chemistry》1993,13(1):145-151
Differences between topological and geometrical distance matrices are examined. Some examples of geometrical distances when graphs are embedded in spaces of different dimensions are given. Relations of topological distance matrices to other graph matrices are shown. The topological distance matrices are defined in the Hilbert space and their elements are distances through the graph lattices. 相似文献
44.
The response of a single TE102 and double TE104 rectangular cavity to the insertion of samples contained in tubes with variable wall thickness and a quartz Dewar into the cavity has been analyzed. A direct, indirect, and concurrent (positive or negative) “lens effect” inside the double TE104 rectangular cavity is discussed. The experimental dependence of the EPR signal intensity on the wall thickness of the sample tube, δ, for the line-like samples with identical length of the sample material column, L=30 mm, recorded in the microwave cavity showed a directly proportional increase of the relative “lens effect” with the increase of the wall thickness of the tube in the interval, δ∈<0.1 mm, >0.5 mm. The insertion of the variable-temperature double-wall quartz Dewar (home-built, resonant frequency shift, ca. −300 MHz) into the single TE102 rectangular cavity showed the same relative “lens effect”, with ca. 1.5-time increase of the EPR signal intensity, for a point-like sample and the line-like samples with material columns of diameter of 1 and 1.3 mm, and wall thickness of the sample tubes, δ∈<0.1 mm, >0.5 mm. The increased effect of the Dewar arises because the active volume of the quartz Dewar tube walls is always much more larger than the active volume of the sample tube wall. In the case of the double TE104 rectangular cavity, the insertion of the quartz Dewar: (i) into the same cavity, in which the sample is present, caused a direct “lens effect”, with ca. 1.8-fold increase of the EPR signal intensity; however, (ii) into the complementary cavity, in which the sample is absent, caused an indirect “lens effect”, with ca. 0.6-fold decrease of the EPR signal intensity. With the Dewar and sample in one cavity and a large empty sample tube in the complementary cavity, a concurrent (positive or negative) “lens effect” can be observed. Thus, the possible increase/decrease of the EPR signal intensity depends on the volume ratio of the quartz Dewar tube walls and large sample tube wall inserted into the double TE104 rectangular cavity. Each of the above phenomena may be a significant source error in quantitative EPR spectrometry unless the samples to be compared in the quantitative EPR analysis are contained in sample tubes having the same wall thickness and each EPR spectra should be recorded inside an identical quartz Dewar. 相似文献
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48.
Milan Melník Peter Mikuš Ivan Malík 《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):1015-1019
AbstractIn this review structural parameters of forty complexes with an inner coordination sphere of Pt(η2-P2L)(η2-S2L) are analyzed and classified These complexes crystallize in three crystal systems: orthorhombic (four examples), triclinic (six examples) and monoclinic (thirty examples). The organodiphosphines create four- (PCP), five- (PC2P), six- (PC3P) and seven- (PC4P) membered metallocyclic rings with mean P-Pt-P bite angle values of 72.5° (PCP) < 85.3° (PC2P) < 93.0° (PC3P) < 97.4° (PC4P). The dithiolates create four- (SCS), five- (SC2S), six- (SC3S; SCSCS; SPNPS; SPCPS) and seven- (SC4S) membered metallocyclic rings with mean S-Pt-S bite angle values of 74.5° (SCS) < 85.8° (SCSCS) < 87.0° (SPNPS) < 89.0° (SC2S) < 92.3° (SC4S) < 93.5° (SC3S) < 97.5° (SPCPS). The mean Pt-P and Pt-S bond distances are 2.257 and 2.328?Å, respectively. The data are compared with those found in complexes with inner coordination spheres of Pt(PL)2(SL)2, Pt(PL)2(η2-S2L) and Pt(η2-P2L)(SL)2. 相似文献
49.
Violeta Marković Svetlana Marković Ana Janićijević Marko V. Rodić Vukadin M. Leovac Nina Todorović Snežana Trifunović Milan D. Joksović 《Structural chemistry》2013,24(6):2127-2136
A study on the synthesis and mechanistical aspects of formation of 3-methyl-5-oxo-3-pyrazolin-1-carboxamide (MOPC) starting from S-methylisothiosemicarbazide hydrogen iodide and methyl acetoacetate was performed. In the alkaline aqueous solution, the intermediate methyl acetoacetate S-methylisothiosemicarbazone undergoes substitution of CH3S? anion by hydroxide anion, cyclization, carbanion formation, and elimination of methanol, thus yielding corresponding Na-enolate salt of pyrazol-5-one derivative. The structure of the compound obtained after protonation of the formed enolate salt was determined by means of spectroscopic techniques and single-crystal X-ray diffraction analysis. The mechanism of conversion of methyl acetoacetate S-methylisothiosemicarbazone into MOPC was investigated by means of the B3LYP functional, and it was found that the reaction is thermodynamically controlled. 相似文献
50.
Tomas Bertok Pavol Gemeiner Milan Mikula Peter Gemeiner Jan Tkac 《Mikrochimica acta》2013,180(1-2):151-159
We report on an ultrasensitive label-free lectin-based impedimetric biosensor for the determination of the sialylated glycoproteins fetuin and asialofetuin. A sialic acid binding agglutinin from Sambucus nigra I was covalently immobilised on a mixed self-assembled monolayer (SAM) consisting of 11-mercaptoundecanoic acid and 6-mercaptohexanol. Poly(vinyl alcohol) was used as a blocking agent. The sensor layer was characterised by atomic force microscopy, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy. The biosensor exhibits a linear range that spans 7 orders of magnitude for both glycoproteins, with a detection limit as low as 0.33 fM for fetuin and 0.54 fM for asialofetuin. We also show, by making control experiments with oxidised asialofetuin, that the biosensor is capable of quantitatively detecting changes in the fraction of sialic acid on glycoproteins. We conclude that this work lays a solid foundation for future applications of such a biosensor in terms of the diagnosis of diseases such as chronic inflammatory rheumatoid arthritis, genetic disorders and cancer, all of which are associated with aberrant glycosylation of protein biomarkers. Figure
Key aspects of the biosensor: 1) mixed SAM formation, 2) immobilisation of lectin & blocking and 3) a glycoprotein recognition. 相似文献