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131.
Lutnaes BF Bruås L Kildahl-Andersen G Krane J Liaaen-Jensen S 《Organic & biomolecular chemistry》2003,1(22):4064-4072
The reaction between beta,beta-carotene and BF3-etherates has been investigated, leading to structural elucidation of the blue product, formed in appropriate organic solvents, as a symmetrical charge delocalised dication (lambda(max) 985 nm at room temperature in CHCl3) with considerable stability. The reaction, monitored by EPR studies at -25 degrees C, occurred via free radical intermediates. A C40H56BF3 intermediate was captured by EIMS. The detailed structure of the dication was established by COSY, HSQC, HMBC and 1D and 2D ROESY NMR techniques (600 MHz, CDCl3, -20 degrees C) leading to complete assignments of 1H and 13C chemical shifts and 3J(H,H) coupling constants. The effects of the two delocalised charges on chemical shift (charge distribution) and bond distance (3J(H,H)) were considered. The results are consistent with charge delocalisation mainly in the C-5-C-9 and C-5'-C-9' regions and with bond inversion to retro shifted double bonds in the central C-13-C-13' region. A convention for denoting the charge delocalisation and bond types is presented. The experimental results are discussed relative to previous theoretical calculations of the beta,beta-carotene dication structure. (All-E) and (15-Z)-beta,beta-carotene provided the same dication. The NIR spectra and stability of dications prepared in the same manner from the related carotenes 20,20'-dinor-beta,beta-carotene, heptapreno-beta,beta-carotene and nonapreno-beta,beta-carotene were examined for comparison. Reactions of the beta,beta-carotene dication with selected nucleophiles provided products including isocryptoxanthin, isocarotene and mutatochrome with H2O as nucleophile, and isocryptoxanthin methyl ether, 8-methoxy-7,8-dihydro-beta,beta-carotene and isocarotene with CH3ONa as nucleophile. The formation of these products is rationalised from the structure assigned to the dication. 相似文献
132.
All methionine aminopeptidases exhibit the same conserved metal binding site. The structure of this site with either Co2+ions or Zn2+ions was investigated using density functional theory. The calculations showed that the structure of the site was not influenced by the identity of the metal ions. This was the case for both of the systems studied; one based on the X-ray structure of the human methionine aminopeptidase type 2 (hMetAP-2) and the other based on the X-ray structure of the E. colimethionine aminopeptidase type 1 (eMetAP-1). Another important structural issue is the identity of the bridging oxygen, which is part of either a water molecule or a hydroxide ion. Within the site of hMetAP-2 the results strongly indicate that a hydroxide ion bridges the metal ions. By contrast, the nature of the oxygen bridging the metal ions within the metal binding site of eMetAP-1 cannot be determined based on the results here, due to the similar structural results obtained with a bridging water molecule and a bridging hydroxide ion. 相似文献
133.
A multivariate approach to the quantitative determination of 2-hydroxybenzaldehyde (salicylaldehyde), 3-hydroxybenzaldehyde, and 4-hydroxybenzaldehyde in their mixtures is described. The method is based on second order data generated in a flow injection analysis system with a pH gradient and photodiode-array detection. Each injection gave rise to an 89 (times) x 101 (wavelength) matrix, containing both the acidic and the basic characteristics of the sample injected. A least-squares algorithm based on Lambert-Beers law was used for the prediction of concentrations in unknown samples. No assumptions concerning the qualitative mixture composition of the hydroxybenzaldehydes were necessary to perform concentration predictions. The following four data types were used in the least-squares modelling: (1) unfolded raw data, (2) acidic spectra, (3) basic spectra, and (4) first spectral derivative of the raw data. The prediction errors obtained were comparable to literature results. A graphic method, based on the model residuals for detecting erroneous samples, was developed. 相似文献
134.
Petersson B Nielsen BB Rasmussen H Larsen IK Gajhede M Nielsen PE Kastrup JS 《Journal of the American Chemical Society》2005,127(5):1424-1430
The X-ray structure of a partly self-complementary peptide nucleic acid (PNA) decamer (H-GTAGATCACT-l-Lys-NH(2)) to 2.60 A resolution is reported. The structure is mainly controlled by the canonical Watson-Crick base pairs formed by the self-complementary stretch of four bases in the middle of the decamer (G(4)A(5)T(6)C(7)). One right- and one left-handed Watson-Crick duplex are formed. The two PNA units C(9)T(10) change helical handedness, so that each PNA strand contains both a right- and a left-handed section. The changed handedness in C(9)T(10) allows formation of Hoogsteen hydrogen bonding between C(9)T(10) and G(4)A(5) of a PNA strand in an adjacent Watson-Crick double helix of the same handedness. Thereby, a PNA-PNA-PNA triplex is formed. The PNA unit A(3) forms a noncanonical base pair with A(8) in a symmetry-related strand of opposite handedness; the base pair is of the A-A reverse Hoogsteen type. The structural diversity of this PNA demonstrates how the PNA backbone is able to adapt to structures governed by the stacking and hydrogen-bonding interactions between the nucleobases. The crystal structure further shows how PNA oligomers containing limited sequence complementarity may form complex hydrogen-bonding networks. 相似文献
135.
The structure of 5-hydroxy-trans-2, trans-4-pentadienal acetate has been determined, using three-dimensional diffractometercollected X-ray data. The compound has the all-trans configuration with the atoms C-1 to C-5 in a plane. The charge distribution in the acetate and in the glutacondialdehyde anion have been calculated using the CNDO/2 approximation. In both compounds higher negative charges were found on carbon atoms C-2 and C-4 than on C-1, C-3 and C-5. 相似文献
136.
H. E. Bjørnstad H. N. Lien Yu-Fu Yu B. Salbu 《Journal of Radioanalytical and Nuclear Chemistry》1992,156(1):165-173
Low level90Sr in environmental and biological samples is determined using a combined HDEHP solvent extraction-liquid scintillation procedure. Yttrium-90 is selectively extracted from nitric acid solution into 5% di(2-ethylhexyl) phosphoric acid (HDEHP) in toluene, and90Y in the organic phase is measured directly using an ultra low level liquid scintillation spectrometer.The working program of the Quantulus counter has been optimized. As the counting efficiency using liquid scintillation counting is high and the stripping and precipitation of Yttrium-90 oxalate is omitted, this procedure is simpler and more timesaving than traditional methods. The chemical recoveries of90Y were 85.1% for soil, 75.7% for milk and 65.3% for bone. The detection limit is 8 mBq. 相似文献
137.
H.?J.?M.?BouwmeesterEmail author M.?W.?Den?Otter B.?A.?Boukamp 《Journal of Solid State Electrochemistry》2004,8(9):599-605
The surface exchange coefficient and chemical diffusion coefficient of oxygen for the perovskites La0.6Sr0.4Co1–yFeyO3– (y=0.2, 0.5 and 0.8) were measured using the conductivity relaxation technique. Measurements were performed between 600 and 800 °C in an oxygen partial pressure range between 10–4 and 1 bar. Both transport coefficients decrease markedly with decreasing oxygen partial pressure below about 10–2 bar at all temperatures. This is attributed to ordering of oxygen vacancies. Implications for using La0.6Sr0.4Co1–yFeyO3– as an oxygen separation membrane are discussed.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10-12 April 2003 相似文献
138.
I. Espe B. Skaali P. O. Tjøm S. M. Lee M. Rozkoš B. Elbek 《Czechoslovak Journal of Physics》1979,29(11):1208-1214
Highly excited compound nuclei of74Kr have been formed by bombardment of58Ni with 70 MeV16O ions. The spectra of protons and -particles resulting from the decay of the compound nucleus (and several daughter nuclei) have been recorded at laboratory angles from 30° to 155°. The CM differential cross sections corresponding to definite energies for the particles emitted were calculated from the data. The charged particle spectra and the angular distributions show that evaporation processes are dominant. A study of spectral shapes and angular distributions has to some extent made it possible to distinguish primary particles from those evaporated after the emission of one or several particles.On leave fromFaculty of Mathematics and Physics, Charles University, Prague, Czechoslovakia. 相似文献
139.
Rational approximations to the exponential function with real poles only are studied with respect to stability at infinity and maximal order. Along each half line in the parameter space it is shown that these two properties occur in an alternating way (or do not occur at all). As an application of the general results the special approximations withq-fold poles at ±
–1 only, real, are studied. A short proof of the superconvergence for collocation methods is also given.Dedicated to W. Gröbner on the occasion of his 80th birthday. 相似文献
140.
P. Hájíček 《Foundations of Physics》2012,42(4):555-581
In our previous work, a new approach to the notorious problem of quantum measurement was proposed. Existing treatments of
the problem were incorrect because they ignored the disturbance of measurement by identical particles and standard quantum
mechanics had to be modified to obey the cluster separability principle. The key tool was the notion of separation status.
Changes of separation status occur during preparations, registrations and scattering on macroscopic targets. Standard quantum
mechanics does not provide any correct rules that would govern these changes. This gives us the possibility to add new rules
to quantum mechanics that would satisfy the objectification requirement. The method of the present paper is to start from
the standard unitary evolution and then introduce minimal corrections. Several representative examples of registration and
particle scattering on macroscopic targets are analysed case by case in order to see their common features. The resulting
general Rule of Separation Status Changes is stated in the Conclusion. 相似文献