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31.
Nielsen RD Che K Gelb MH Robinson BH 《Journal of the American Chemical Society》2005,127(17):6430-6442
Both the oxygen diffusion rate and the oxygen solubility vary with depth into the interior of biological membranes. The product of these two gradients generates a single gradient, a permeability gradient, which is a smooth continuous function of the distance from the center of the membrane. Using electron paramagnetic resonance and the spin-probe method, the relaxation gradient of oxygen, which is directly proportional to the permeability gradient, is the quantity that can be directly measured in membranes under physiological conditions. The gradient obtained provides a calibrated ruler for determining the membrane depth of residues either from loop regions of membrane-binding proteins or from the membrane-exposed residues of transmembrane proteins. We have determined the relaxation gradient of oxygen in zwitterionic and anionic phospholipid membranes by attaching a single nitroxide probe to a transmembrane alpha-helical polypeptide at specific residues. The peptide ruler was used to determine the depth of penetration of the calcium-binding loops of the C2 domain of cytosolic phospholipase A(2). The positions of selected residues of this membrane-binding protein that penetrate into the membrane, determined using this ruler, compared favorably with previous determinations using more complex methods. The relaxation gradient constrains the possible values of the membrane-dependent oxygen concentration and the oxygen diffusion gradients. The average oxygen diffusion coefficient is estimated to be at least 2-fold smaller in the membrane than that in water. 相似文献
32.
H. E. Hansen R. Talja H. Rajainmäki H. K. Nielsen B. Nielsen R. M. Nieminen 《Applied Physics A: Materials Science & Processing》1985,36(2):81-92
Molybdenum single crystals are irradiated at 20 K with 6 MeV protons. The radiation damage and lattice defect annealing is studied by positron lifetime spectroscopy in the temperature range from 15 to 720 K. Loss of vacancies due to recombination with mobile interstitials is observed at 40 K (Stage I) in agreement with resistivity measurements. This is the first time Stage I is observed by positrons below 77 K. The implanted hydrogen decorates the vacancies around 100 K, which is consistent with a hydrogen migration energy in molybdenum:E
M
H
= 0.3–0.4 eV. Clustering of spatially correlated vacancies takes place in a wide temperature region below the usual vacancy clustering stage (Stage III). Stage III is observed at rather low temperatures (400–480 K) due to the very high vacancy concentration. Hydrogen bound to vacancies and vacancy clusters is released above 540 K, which puts an upper limit to the hydrogen binding energy:E
B
H
1.4 eV. The present work emphasizes the advantage of employing a vacancy sensitive technique to study hydrogen in metals, where its intrinsic solubility is low. In such metals (as molybdenum) both the effective solubility and the effective mobility of hydrogen are strongly influenced by the presence of vacancies. 相似文献
33.
The infrared spectra of maleimide as a vapour (160°C), melt (100°C), oriented polycrystalline film, pellet and when dissolved in various solvents were recorded between 4000 and 400 cm?1. Also certain spectra in the far infrared region 400-40 cm?1 were obtained. Raman spectra of the crystalline solid, melt and as a saturated solution in acetonitrile were recorded and semiquantitative polarization measurements carried out. For N-D maleimide infrared and Raman spectra of the solid compound were recorded.The fundamental frequencies have been assigned in terms of C2v, symmetry on the basis of infrared vapour contours and dichroism of the oriented film as well as on Raman polarization data. A force field was derived for maleimide, by initially transferring force constants from maleic anhydride and subsequent refinement of the force constants. The agreement between observed and calculated frequencies for the in-plane modes was satisfactory whereas certain large discrepancies remained for the out-of-plane vibrations. 相似文献
34.
A method for the simultaneous determination of chromium(iii) and chromium(vi) in a flow system based on chemiluminescence was developed. A Dionex cation-exchange guard column was used to separate chromium(iii) from chromium(vi), and chromium(vi) was reduced by potassium sulfite, whereupon both species were detected by use of the luminol-hydrogen peroxide chemiluminescence system. Linear calibration for both species was established over the concentration range 1-1000 micrograms l-1. The precision at the 20 micrograms l-1 level was 3.5% for chromium(iii) and 3.3% for chromium(vi), respectively. The detection limit was 0.5 micrograms l-1 for both species. Data were in agreement with Zeeman-effect background corrected atomic absorption spectrometry measurements. 相似文献
35.
Nasser R.?El-Brollosy Claus?Nielsen Erik B.?PedersenEmail author 《Monatshefte für Chemie / Chemical Monthly》2005,136(7):1247-1254
Summary. A series of Emivirine and GCA-186 analogues substituted at N-1 with indan-1-yloxymethyl (6a–6c) and indan-2-yloxymethyl (6d–6f) were synthesized by reaction of the corresponding bis(indanyloxy)methans with uracils having 5-ethyl or 5-isopropyl and 6-benzyl or 6-(3,5-dimethylbenzyl) substituents. A route to the corresponding N-1 substituted 4-hydroxybut-2-enyloxymethyl analogue was also devised. All newly synthesized compounds showed potent activity against wild-type HIV-1, the most active compound being 5-ethyl-1-(indan-1-yloxymethyl)-6-(3,5-dimethylbenzyl)uracil (6b), which was 50-fold more active than Emivirine.Present address: Chemistry Department, Faculty of Science, Tanta University, Tanta, EgyptA research center funded by The Danish National Research Foundation for studies on nucleic acid chemical biology 相似文献
36.
(E)-beta-Trialkylstannyl-alpha,beta-unsaturated ketones are readily available from secondary propargylic alcohols via a two-step sequence involving highly regio- and stereoselective Pd(0)-catalyzed hydrostannation followed by mild oxidation (TPAP). The methodology has been applied to the synthesis of enantiomerically pure enone 12 which is a key intermediate for the total synthesis of zoanthamine, a structurally complex marine natural product. 相似文献
37.
Qingjiang Chen H. Dahlgaard S. P. Nielsen A. Aarkrog 《Journal of Radioanalytical and Nuclear Chemistry》2002,253(3):451-458
A procedure has been developed using 242Pu as tracer for simultaneous determination of 237Np and 239,240Pu in environmental samples. The validity of the method has been demonstrated by ICPMS and a-spectroscopy for up to 10 gram soil and sediment, seawater up to 200 litres. The paper describes a suitable chemical procedure for Np and Pu including a quantitative pre-concentration of neptunium and plutonium, preparation of Np4+ and Pu4+, Np(NO3)6
2- and Pu(NO3)6
2-. The ratio of 237Np/242Pu (or 237Np/239Pu) before and after the procedure has been determined using 10 g soil (free from Np and Pu) R
before/R
after = 1.004±3.3% (S.D n = 20) and 1 litre seawater R
before/R
after = 1.019±1.9% (S.D., n = 12). Results from the intercomparison samples IAEA-135, IAEA-381 and from environmental samples are presented. 相似文献
38.
J. W. Petersen G. Weyer S. Damgaard H. L. Nielsen 《Zeitschrift für Physik B Condensed Matter》1980,38(4):313-326
Single crystalline and polycrystalline -tin has been implanted at room temperature with 80-keV ions of radioactive119m
Sn,119Sb, and119m
Te. The radioactive nuclei decay to the Mössbauer level of119Sn. Mössbauer spectra of the emitted 24-keV radiation have been measured for different source temperatures by resonance counting techniques. Five individual lines in the spectra are characterized mainly by their isomer shifts and Debye temperatures. From these parameters the radiogenic119Sn atoms are concluded to be located in regular substitutional and interstitial lattice sites and in defect complexes. Simple models for the defects are proposed: A Sn-vacancy pair consists of Sn atoms on (nearly) substitutional sites with a dangling bond into an adjacent vacancy. In a complex oxygen-containing defect the Sn atoms have approximately a 5s
2 configuration withp-bonds to two nearest neighbour atoms. Sn atoms, having an atomic 5s
2 5p
2 configuration and large vibrational amplitudes, are concluded to be in non-bonding regular interstitial sites. For special implantation conditions minor fractions of SnO2 molecules are formed in the bulk. The interstitial119Sn and the119Sn-vacancy pairs are proposed to represent elementary point defects in -tin. Conclusions are also drawn concerning the lattice location and the defects created in the implantation process of the implanted parent isotopes. 相似文献
39.
The addition of stannylcuprate reagents such as (Bu3Sn)(PhS)CuLi to alkynones has been found to proceed in high yield and with excellent stereoselectivity for the Z isomer of the product (>95%). The behavior of the stannylcuprates is thus very different from that of their "carbocuprate" counterparts such as Me2CuLi or Me2Cu(CN)Li2 which are nonstereoselective. Furthermore, in contrast to the reactions of (R3Sn)(PhS)CuLi with the corresponding alkynoates, the presence of a proton source in the reaction medium has no effect on the stereoselectivity of the reaction of alkynones. 相似文献
40.
S. P. Nielsen A. Aarkrog P. A. Colgan E. McGee H. J. Synnott K. J. Johansson A. D. Horrill V. H. Kennedy N. Barbayiannis 《Journal of Radioanalytical and Nuclear Chemistry》1993,171(2):303-317
An intercomparison of sampling procedures used by five laboratories for the determination of radiocaesium in vegetation and peaty soil was carried out at two locations in Cumbria. The multiple sampling has given information on the homogeneity of the parameters studied at each location. The parameters comprise soil bulk densities, total deposition of137Cs, deposition of137Cs in three soil layers, biomass densities, concentrations of137Cs in pasture, and activity ratios (134Cs/137Cs) in soil and vegetation. The determination of total deposition of137Cs gave no indication of differences between the laboratories. The results from the soil profiles do indicate significant differences between laboratories. One laboratory using a coring technique observed difficulties during sampling due to compression of the soil. The coring technique should thus be avoided or applied with extreme care for the sampling of depth profiles in peaty soil. The results from the sampling of pasture show no indication of differences between the laboratories. For the parameters studied the observed variabilities across soil depths and locations range from 10% to 81% in terms of relative standard deviations. A comparison across all results at the two locations indicate a 50% higher field variability at one of the sites relative to the other. 相似文献