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121.
[structure: see text] The relative and absolute stereochemistry of the structurally unique 24-membered myxobacterial macrolides archazolid A and B, highly potent vacuolar-type ATPase (V-ATPase) inhibitors in vitro and in vivo, was determined on the basis of a combination of extensive high-field NMR studies, including J-based configuration analysis, molecular modeling, and chemical methods. 相似文献
122.
Hellman H Laitinen RS Kaila L Jalonen J Hietapelto V Jokela J Sarpola A Rämö J 《Journal of mass spectrometry : JMS》2006,41(11):1421-1429
The hydrolysis reactions of FeCl3 in 0.1 mM aqueous solutions were monitored by electrospray ionisation time-of-flight mass spectrometry (ESI-ToF-MS). In contrast to the other ionisation techniques, electrospray ionisation provides information on the composition of the elemental cores even in water and salt cluster ions. Therefore, the technique facilitates detection of the bonding of the chloride ions in the oxo-hydroxo-iron cores. A variety of mononuclear and polynuclear iron-oxohydroxo-chloride complexes were characterised from the cationic and anionic mass spectra of iron(III) solutions. Oxidation and reduction reactions of iron, as well as competition between OH- and Cl- ions within one iron core, were also observed. 相似文献
123.
Esa T. T. Kumpulainen Ari M. P. Koskinen Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(41):10901-10911
The influence of catalyst components in the copper–TEMPO (2,2,6,6‐tetramethylpiperidine N‐oxide) catalysed aerobic oxidation of alcohols was investigated. The type and amount of base greatly influences reactivity. The bipyridyl ligand concentration had no major influence on catalysis, but excessive amounts led to a decrease in activity for longer reaction times. The kinetic dependency for TEMPO was found to be 1.15, and for copper 2.25, which is an indication of a binuclear catalytic system. Optimised conditions with various allylic and aliphatic alcohols give good to excellent rapid oxidations. 相似文献
124.
Jorma Hölsä Marco Kirm Mika Lastusaari Janne Niittykoski Pavel Novák 《Journal of luminescence》2009,129(12):1560-1563
The electronic structures of the distrontium magnesium disilicate (Sr2MgSi2O7(:Eu2+)) materials were studied by a combined experimental and theoretical approach. The UV-VUV synchrotron radiation was applied in the experimental study while the electronic structures were investigated theoretically by using the density functional theory. The structure of the valence and conduction bands and the band gap energy of the material as well as the position of the Eu2+ 4f ground state were calculated. The calculated band gap energy (6.7 eV) agrees well with the experimental value of 7.1 eV. The valence band consists mainly of the oxygen states and the bottom of the conduction band of the Sr states. The calculated occupied 4f ground state of Eu2+ lies in the energy gap of the host though the position depends strongly on the Coulomb repulsion strength. The position of the 4f ground state with respect to the valence and conduction bands is discussed using the theoretical and experimental evidence available. 相似文献
125.
Hyppänen I Hölsä J Kankare J Lastusaari M Pihlgren L Soukka T 《Journal of fluorescence》2008,18(6):1029-1034
The up-converting ZrO2:Yb3+,Er3+ nanomaterials were prepared with the combustion and sol–gel methods. FT-IR spectroscopy was used for analyzing the impurities.
The crystal structures were characterized with X-ray powder diffraction and the mean crystallite sizes were estimated with
the Scherrer formula. Up-conversion luminescence measurements were made at room temperature with IR-laser excitation at 977 nm.
The IR spectra revealed the conventional and OH− impurities for the combustion synthesis products. The structure of the ZrO2:Yb3+, Er3+ nanomaterials was cubic except for the minor monoclinic and tetragonal impurities obtained with the sol–gel method. The materials
showed red (650–700 nm) and green (520–560 nm) up-conversion luminescence due to the 4F9/2→4I15/2 and (2H11/2, 4S3/2)→4I15/2 transitions of Er3+, respectively. The products obtained with the combustion synthesis exhibited the most intense luminescence intensity and
showed considerable afterglow. 相似文献
126.
A novel intramolecular cyclization reaction is reported, in which various 1,2-bis(amidinohydrazone)s are converted into 3-amino-1,2,4-triazine or its substituted analogues. The reaction is easily carried out at microscale as well as ordinary scale level by heating the appropriate bis(amidinohydrazone) to roughly 200°C in an inert atmosphere or in vacuo. No solvents or other reagents are needed. The products are easily isolated, being sublimed off from the starting material and forming single crystals. A microscale procedure employing glass ampoules as the reaction vessel is described. The reaction is rapid and offers a facile way of preparing large series of substituted 3-amino-1,2,4-triazines individually in crystalline form for screening purposes. Because large numbers of bis(amidinohydrazone)s have been synthesized for biochemistry and drug development and libraries exist, the present method may be more practical than combinatorial approaches for the production of 3-amino-1,2,4-triazines, as it allows simultaneous individual syntheses. As the reaction is intramolecular, it is probable that the method can also be used also for mixtures of bis(amidinohydrazone)s to produce several triazines in one ampoule. The structure of the products was confirmed by mass, NMR and IR spectroscopy, elemental analyses and comparison with authentic samples. The reaction was studied using five bis(amidinohydrazone)s of aliphatic glyoxals, phenylglyoxal bis(amidinohydrazone) as well as the bis(amidinohydrazone) of 1,2-cyclohexanedione as starting materials. From the compound mentioned last a bicyclic product was obtained. In the case of the unsymmetric starting material ethylglyoxal bis(amidinohydrazone), both possible isomers were formed. The safety of heating the nitrogen-rich starting materials in large-scale syntheses has not been verified. 相似文献
127.
Veli Hietaniemi Auli Kostamo Jorma Kumpulainen Juha-Matti Pihlava 《Fresenius' Journal of Analytical Chemistry》1995,352(1-2):40-42
Strawberry and cabbage candidate reference materials (RMs) have been prepared by our laboratory during 1992–1993. Fresh materials have been homogenized and spiked with known concentrations of pesticides representing compounds commonly used for strawberries and cabbages. The candidate RMs have been then freeze-dried, homogenized, bottled under a stream of nitrogen and stored frozen at –20°C. Homogeneity and stability of the candidate RMs have been studied during the storage period. Homogeneity of the candidate RMs for 5 g samples has been within 10%. Homogeneity and stability studies have been carried out using the conventional multiresidue method of Luke et al. [1]. Instrumental analysis have been performed by gas chromatography mass spectrometry (GC-MS) employing selected ion monitoring (SIM). 相似文献
128.
Summary The analytical quality control program employed by the ongoing FAO study on 14 trace elements in nationally representative staple foods of European countries is presented. The analytical quality control used is based on: 1) precautions taken to avoid trace element contaminations or losses during sampling and sample handling; and, 2) on methods used to guarantee that the actual determinations yield correct results. The precautions are presented. A number of certified biological reference materials (RMs) were used to validate the analytical methods employed. The following staple food RMs were also prepared: wheat flour, potato powder, animal muscle (pork) and milk powder. They were tested for homogeneity and subjected to an interlaboratory comparison study on the basis of which recommended values for trace element concentrations were defined. Further, the mean relative standard deviation for the 95% confidence limits of the medians in all RMs was below 5% for Ca, Mg and Zn; below 10% for Mn; below 15% for Fe, Cu and Se; and below 25% for Mo and Ni. These RMs were used to control the analytical quality of the trace element determinations in the actual samples. It is concluded that important contaminations were avoided in sampling and sample handling and that use of the RMs described was necessary to guarantee the analytical quality of the results. 相似文献
129.
S. Juutinen R. Julin P. Ahonen C. Fahlander J. Hattula J. Kumpulainen A. Lampinen T. Lönnroth D. Müller J. Nyberg A. Pakkanen M. Piiparinen I. Thorslund S. Törmänen A. Virtanen 《Zeitschrift für Physik A Hadrons and Nuclei》1990,335(4):475-476
A comparison of the experimental and theoretical K/L conversion-intensity ratios of E0 transitions in the lead region is presented. No major differences were found, the overall agreement being better than 7%. However, with the present data, a systematic 5% deficiency of the measured values, as compared with the calculated ones, can not be ruled out. 相似文献
130.
Bounds for various functions of the eigenvalues of a Hermitian matrix A, based on the traces of A and A2, are improved. A technique is presented whereby these bounds can be improved by combining them with other bounds. In particular, the diagonal of A, in conjunction with majorization, is used to improve the bounds. These bounds all require O(n2) multiplications. 相似文献