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991.
Reddy BM Lakshmanan P Khan A Loridant S López-Cartes C Rojas TC Fernandez A 《The journal of physical chemistry. B》2005,109(28):13545-13552
Ce(x)Zr(1)(-)(x)O(2) solid solutions deposited over silica surface were investigated by X-ray diffraction (XRD), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HREM) techniques in order to understand the role of silica support and the temperature stability of these composite oxides. For the purpose of comparison, an unsupported Ce(x)Zr(1)(-)(x)O(2) was also synthesized and subjected to characterization by various techniques. The Ce(x)Zr(1)(-)(x)O(2)/SiO(2) (CZ/S) (1:1:2 mole ratio based on oxides) was synthesized by depositing Ce(x)Zr(1)(-)(x)O(2) solid solution over a colloidal SiO(2) support by a deposition precipitation method and unsupported Ce(x)Zr(1)(-)(x)O(2) (CZ) (1:1 mole ratio based on oxides) was prepared by a coprecipitation procedure, and the obtained catalysts were subjected to thermal treatments from 773 to 1073 K. The XRD measurements disclose the presence of cubic phases with the composition Ce(0.75)Zr(0.25)O(2) and Ce(0.6)Zr(0.4)O(2) in CZ samples, while CZ/S samples possess Ce(0.75)Zr(0.25)O(2), Ce(0.6)Zr(0.4)O(2), and Ce(0.5)Zr(0.5)O(2) in different proportions. The crystallinity of these phases increased with increasing calcination temperature. The cell a parameter estimations indicate contraction of ceria lattice due to the incorporation of zirconium cations into the CeO(2) unit cell. Raman measurements indicate the presence of oxygen vacancies, lattice defects, and displacement of oxygen ions from their normal lattice positions in both the series of samples. The HREM results reveal, in the case of CZ/S samples, a well-dispersed nanosized Ce-Zr-oxides over the surface of amorphous SiO(2). The structural features of these crystals as determined by digital diffraction analysis of experimental images reveal that the Ce-Zr-oxides are mainly in the cubic geometry and exhibit high thermal stability. Oxygen storage capacity measurements by a thermogravimetric method reveal a substantial enhancement in the oxygen vacancy concentration of CZ/S sample over the unsupported CZ sample. 相似文献
992.
Constable EC Handel RW Housecroft CE Farràn Morales A Ventura B Flamigni L Barigelletti F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(13):4024-4034
A new series of V-shaped trinuclear metallorods and X-shaped pentanuclear metallostars has been prepared by the reaction of metal complexes bearing pendant phenolic functionalities with complexes containing electrophilic ligands. Specifically, {M(tpy)2} motifs (M=Ru or Os; tpy=2,2':6',2'-terpyridine) bearing one or two pendant 3,5-dihydroxyphenyl substituents at the 4-position of the central ring of the tpy have been reacted with the complexes [Ru(tpy)(Xtpy)]2+ (X=Cl or Br) to form new ether-linked species. The energy transfer from ruthenium to osmium in these complexes has been investigated in detail and the efficiency of transfer shown to be highly temperature dependent; the energy transfer is highly efficient at low temperature, whereas at room temperature nonradiative and nontransfer deactivation of the excited {Ru(tpy)2}* domains is most significant. 相似文献
993.
Laure Gouriou Štěpán Vysko?il Pavel Ko?ovský 《Journal of organometallic chemistry》2003,687(2):525-537
The reaction of iso-cinnamyl acetate with NaC(Me)(CO2Me)2, catalysed by Pd-‘MOP’ (MOP=2-methoxy-2′-diphenylphosphino-1,1′-binaphthalene) is known to proceed with a regiochemical memory effect that results in the predominant generation of the branched alkylation product. The analogous reaction employing ‘MAP’ as ligand (MAP=2-N,N-dimethylamino-2′-diphenylphosphino-1,1′-binaphthalene) proceeds with ‘normal’ regioselectivity to generate predominantly the linear isomer of product. A 2H-NMR based analysis, employing quadrupolar coupling in a chiral liquid crystal matrix, has been developed to facilitate the simultaneous study of the regiochemical and stereochemical outcome of the reaction of both enantiomers of iso-cinnamyl ester substrates in 2H-labelled but racemic samples. The analysis allows the comparison of relative rates of two competing isomerisation processes occurring in the π-allyl intermediates in the Pd-catalysed reaction, one of which facilitates asymmetric induction, the other resulting in loss of regiochemical memory. It is demonstrated that the two processes are partially coupled and that this then limits the attainment of high global enantiomeric excess in the branched product to reactions that proceed with low regiochemical retention. A key factor for the observation of high regiochemical memory is found to be the nucleophilicity of the malonate anion and the electrophilicity of the Pd-π-allyl intermediate with reduction in the reactivity of either partner resulting in the onset of substantial loss of memory. 相似文献
994.
Horst Müller 《Analytical and bioanalytical chemistry》1969,247(3-4):145-149
The ions ReBrnCl 6?n 2? (0?n?6) and OsBrnCl 6?n 2? , respectively, ReO4 ? and Br? have been separated on cellulose using the thin-layer chromatographic technique with 3.2 M sulphuric acid as the mobile phase. 相似文献
995.
F U Erko? S Ozsar B Güven G Kalkandelen E U?rar 《Journal of chromatographic science》1989,27(2):86-90
In the present work, a practical, rapid, reliable and isocratic reversed-phase high-performance liquid chromatographic (HPLC) method is described for the qualitative and quantitative analysis of estriol, estradiol-17 beta, estrone, testosterone, and progesterone. Chromatographic separation is complete in 16 min using a mobile phase of 50% acetonitrile (v/v) in water. The order of elution is estriol, testosterone, estradiol-17 beta, estrone, and progesterone; retention times are 2.5, 5.5, 5.6, 6.9, 16.3 min, respectively. Absorbance maxima of individual steroids is the limiting factor in quantitative determination. The recommended wavelengths for UV monitoring are E3 214, E2 280, T 254, E1 214, and P4 254 nm. 相似文献
996.
Hourdin M Gouhier G Gautier A Condamine E Piettre SR 《Journal of combinatorial chemistry》2005,7(2):285-297
Ten cross-linked polystyrene-supported, protected chiral amines featuring both a spacer, comprising from 5 to 15 atoms, and a fluorinated linker have been successfully prepared. The development of the monitoring technique by gel-phase 19F NMR spectrometry on cross-linked polystyrene derivatives proved to be of high value in four steps of the process, as shown by the comparison of data gathered from both a classic NMR spectrometer and elemental analysis. Gel-phase 19F NMR spectrometry, thus, constitutes a useful technique that complements IR and 13C NMR spectrometries for the qualitative monitoring of reactions. In addition, quantitative determination of the conversion in a given transformation is possible, provided that 19F chemical shifts of the substrate and the product be different enough (Deltadelta>base width), as illustrated by the Mitsunobu coupling process (16-->17). The technique is nondestructive, and the samples used to monitor the reactions may be returned to the reaction medium. Deprotection of the above amines was achieved and furnished eight of the final resins in good to acceptable purity for future applications. 相似文献
997.
[reaction: see text] A short synthesis of intermediates possessing the tricyclic core of natural madangamines, bioactive alkaloids found in marine sponges, is described. The key reaction entails the condensation of the sodium salt of diethylacetonedicarboxylate with a dihydropyridinium salt derivative. This new approach is modeled on a biogenetic proposal linking madangamines to ircinals, related alkaloids occurring in sponges of the same order. 相似文献
998.
Storsberg J Yao ML Ocal N de Meijere A Adam AE Kaufmann DE 《Chemical communications (Cambridge, England)》2005,(45):5665-5666
The first example of a pi,sigma domino-Heck reaction under concomitant rearrangement of the tetracyclic allylcyclopropane endo,exo-bishomobarrelene (5) is reported; the stereoselective reaction proceeds via an intramolecular insertion of a primarily-formed carbopalladation intermediate into a strained cyclopropane C-C sigma-bond, giving 9. 相似文献
999.
Montserrat Barquín María J. Gonzlez Garmendia Liher Larrínaga Elena Pinilla María R. Torres 《无机化学与普通化学杂志》2005,631(11):2210-2214
The complexes of copper formato with pyrazine and dimethylpyrazines: Cu(HCOO)2(pyrz) ( 1 ), Cu2(HCOO)4(pyrz) ( 2 ), Cu2(HCOO)4(2,3‐Me2pyrz) ( 3 ), Cu2(HCOO)4(2,5‐Me2pyrz) ( 4 ), and Cu2(HCOO)4(2,6‐Me2pyrz)2 ( 5 ) have been synthesized and characterized by chemical analysis and IR and electronic spectro scopies. The three‐dimensional structure of compound 1 consists of –Cu–pyrz–Cu–pyrz– chains joined by bridging formate groups coordinated, in configuration syn‐anti, to two copper atoms. The coordination around the copper atom is orthorhombic with two Cu–O distances of 2.374(1) Å, two Cu–O of 1.952 Å and two Cu–N of 2.080 Å. Compound 5 is formed by molecular dimers with the [Cu2(μ‐HCOO)4] unit, two copper atoms and four syn‐syn fomate groups, and two ligands coordinated to the copper atoms in the axial positions. In compounds 2 and 3 chains of [Cu2(μ‐HCOO)4] dimers with pyrz or 2,3‐Me2pyrz as bridging ligands are formed. The EPR signal of 1 is orthorhombic (g = 2.23, 2.20 and 2.06). In the EPR spectra of 2 – 5 compounds the triplet (S = 1) signals are observed. The g?, g∥ and D values are been calculated. 相似文献
1000.
S. Küppers 《Accreditation and quality assurance》1997,2(1):30-35
Any analytical data is used to provide information about a sample. The "possible error" of the measurement can be of extreme
importance in order to have complete information. The measurement uncertainty concept is a way to achieve quantitative information
about this "possible error" using an estimation procedure. On the basis of the analytical result, the chemist makes a decision
on the next step of the development process. If the uncertainty is unknown, the information is not complete; therefore this
decision might be impossible. The major problem for the in-process control (IPC) procedure is that not only the repeatability
but also the intermediate precision (which expresses the variations within laboratories related to different days, different
analysts, different equipment, etc.) has to be good enough to make a decision. Unfortunately, the statistical information
achieved from one single analytical run only gives information about the repeatability. This paper shows that the estimation
of the measurement uncertainty for IPC is a way to solve the problem and gives the necessary information about the quality
of the procedure. An example demonstrates that an estimate of uncertainty based on the standard deviations of an analytical
method gives a value similar to one based on the standard deviations obtained from a control chart. Therefore, the estimation
is both a very useful and also a very cost-effective tool. Though measurement uncertainty cannot replace validation in general,
it is a viable alternative to validation for all methods that will never be used routinely.
Received: 24 May 1996 Accepted: 10 August 1996 相似文献