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71.
A new potentially multidentate hexaprotic ligand H(6)[TETA-(PO)(2)] has been prepared by reaction of ethylenediamine-N,N'-diacetic acid (EDDA), paraformaldehyde, and phosphinic acid; its coordination properties with three lanthanide ions (La(3+), Gd(3+), and Lu(3+)) have been explored. The structures of the complexes were studied in aqueous solution by potentiometric pH titrations and by (31)P NMR spectroscopy. Four acidity constants were determined potentiometrically in the range 2.5 < pH < 14. The four measured pK(a) values can be divided into two groups, and within each group the initial deprotonation was found to have little effect on the second. Variable temperature (31)P and (31)P[(1)H] EXSY NMR spectra showed that, for [Lu(TETA-(PO)(2))](3-), the two phosphorus atoms exist in different chemical environments and undergo an exchange process which is very fast on the NMR time scale at room temperature. This result is consistent with one of the phosphinate residues coordinating the metal ion and exchanging with a free analogue. In the case of [La(TETA-(PO)(2))](3-), only one temperature invariant signal is observed in (31)P NMR spectra; it corresponds to both phosphinate residues remaining uncoordinated to La(3+). The stability of [Ln(TETA-(PO)(2))](3-) has an order of La(3+) > Gd(3+) > Lu(3+). The coordination of one phosphinate residue to Lu(3+) brings the metal ion closer to the plane of four nitrogens and farther from the four carboxylate arms, resulting in [Lu(TETA-(PO)(2))](3-) having a lower stability than the corresponding La(3+) and Gd(3+) complexes. A pM-pH distribution diagram showed that introducing two phosphinate groups into TETA renders [Gd(TETA-(PO)(2))](3-) more stable than [Gd(TETA)](-). The selectivity factor of the ligand for Gd(3+) vs Ca(2+), Zn(2+), and Cu(2+) has been calculated, and the hydration number for [Dy(TETA-(PO)(2))](3-) has been measured by (17)O NMR spectroscopy to be zero. 相似文献
72.
A chemiluminescence signal at 425 nm was observed when ferric state myoglobin was mixed with luminol in alkaline medium. Because the signal was remarkably enhanced in the presence of Fe(CN)6
4–, analytical applications were investigated in a flow-injection system. The increase in chemiluminescence was linearly dependent on myoglobin concentration in the range 0.1 to 100 nmol L–1, and the limit of detection was 0.04 nmol L–1 with relative standard deviation 3.2% (3). It was also found that binding of Mb with the ligands CN–, SCN–, and F– significantly inhibited the chemiluminescence reaction. The linear dynamic ranges for the ligands were 1.0–300.0, 0.1–3.0, and 0.5–100.0 nmol L–1, and the limits of detection (S/N=3) 0.4, 0.04, and 0.2 nmol L–1, for F–, CN–, and SCN–, respectively. The relative standard deviations were 5.32%, 6.13%, and 3.38% for 0.1 nmol L–1 CN–, 0.5 nmol L–1 SCN–, and 1.0 nmol L–1 F–, respectively. At a flow rate of 2.0 mL min–1 the assay could be accomplished in 1 min, including sampling and washing. The method has been successfully applied to the determination of myoglobin in human urine and F– in water samples. A possible mechanism of chemiluminescence production by myoglobin and luminol is presented. 相似文献
73.
草酰胺桥联大环二羰四胺铜(Ⅱ)-钴(Ⅱ)异双核配合物的合成、结构、表征和电化学性质 总被引:2,自引:0,他引:2
合成了一种具有草酰胺桥联大环二羰四胺结构的 Cu( ) -Co( )异双核配合物 ,用红外光谱、电子光谱、摩尔电导、热重分析、室温磁矩、循环伏安等对其进行了表征 .初步推定 Cu( ) -Co( )异双核配合物具有草酰胺桥联大环二羰四胺结构 .室温磁矩测定表明 ,通过草酰胺桥联配体金属离子间有一定的反铁磁性自旋偶合作用 .循环伏安法测定了配合物的半波电位 ,实验表明 ,此类配合物能够稳定高价态 Cu( ) ,外延桥基配位对大环内腔 Cu( )离子的氧化还原过程无影响 .单核配合物 X射线晶体衍射研究表明 ,其为单斜晶系 ,空间群 P2 1 /c,a=0 .73 861 (1 5 ) nm,b=2 .1 2 1 1 (4 ) nm,c=0 .95 2 5 0 (1 9) nm,β=94.70 (3 )°,R1 =0 .0 5 1 3 ,w R2 =0 .1 1 77,Z=4.Cu( )处于大环四胺平面正方中心上方 0 .0 3 nm,并具有外延草酰胺桥 相似文献
74.
Wei Y Guo X Shuang S Dong C Sun X Wong M 《Journal of photochemistry and photobiology. B, Biology》2005,81(3):190-194
Novel dimeric capsules are generated from the noncovalent assembly of 5, 10, 15, 20-tetrakis(4-N-ethylpyridiniurmyl)prophyrin (TEPyP) and tetracarboxyl-phenyl calix[4]arene. The self-assembly system was investigated based on UV-Vis absorption and fluorescent spectra. The factors affecting the interaction process including pH and concentration were examined in detail. The association constants between TEPyP and calix[4]arene were determined by the nonlinear least squares fit. The results showed that the basic medium is favourable to the interaction and electrostatic interaction was determinate in the processes of self-assembly process. The related mechanism was discussed. 相似文献
75.
Ya Wen TANG Shuang CAO Ling Ling ZHANG Jian Chun BAO Ping ZHOU Tian Hong LU 《中国化学快报》2006,17(12):1623-1626
The performance of the direct formic acid fuel cell (DFAFC) is considerably higher than the direct methanol fuel cell (DMFC) because of some characteristics of formic acid1. For example, formic acid is non-toxic. Formic acid has two orders of magnitude smaller crossover flux through a Nafion membrane than methanol2. In DFAFC, the concentration of formic acid can be as high as 20 mol/L, while the best concentration of methanol in DMFC is only about 2 mol/L3. Thus, the power density of … 相似文献
76.
77.
Shuang Zhang 《K-Theory》1992,6(1):1-27
We first determine the homotopy classes of nontrivial projections in a purely infinite simpleC*-algebraA, in the associated multiplier algebraM(A) and the corona algebraM
A/A in terms ofK
*(A). Then we describe the generalized Fredholm indices as the group of homotopy classes of non-trivial projections ofA; consequently, we determine theK
*-groups of all hereditaryC*-subalgebras of certain corona algebras. Secondly, we consider a group structure of *-isomorphism classes of hereditaryC*-subalgebras of purely infinite simpleC*-algebras. In addition, we prove that ifA is aC*-algebra of real rank zero, then each unitary ofA, in caseA it unital, each unitary ofM(A) and ofM(A)/A, in caseA is nonunital but -unital, can be factored into a product of a unitary homotopic to the identity and a unitary matrix whose entries are all partial isometries (with respect to a decomposition of the identity).Partially supported by a grant from the National Science Foundation. 相似文献
78.
Pb(Zr0.25Ti0.75)O3 (PZT25) thin films were prepared on LaNiO3-coated thermally oxidized silicon substrates by chemical solution deposition method, where LaNiO3 electrodes were also prepared by a chemical solution deposition technique. The dielectric constant and dielectric loss of
the PZT25 thin films were 570 and 0.057, respectively. The remanent polarization and coercive field were 20.11 μC/cm2 and 60.7 kV/cm, respectively. The PZT25 thin films on LaNiO3-coated thermally oxidized silicon substrates showed improved fatigue characteristics compared with their counterparts on
plantium-coated silicon substrates. 相似文献
79.
80.
H. Abramowicz F. Dydak J. G. H. de Groot J. Knobloch J. May P. Palazzi F. Ranjard W. D. Schlatter J. Steinberger H. Taureg W. von Rüden H. Wahl J. Wotschack P. Buchholz F. Eisele H. P. Klasen K. Kleinknecht B. Pszola B. Renk H. J. Willutzki T. Flottmann C. Geweniger J. Krolikowski K. Tittel C. Guyot J. P. Merlo A. Para B. Peyaud J. Rander J. Rothberg J. P. Schuller R. Turlay J. T. He T. Z. Ruan W. M. Wu 《Zeitschrift fur Physik C Particles and Fields》1982,12(3):225-227
Right handed weak quark currents coupled to the usual left handed weak lepton current would be seen in inclusive antineutrino scattering on nuclei as a contribution at largey with the quark (not antiquark) structure function. We do not see such a term, and can therefore put an upper limit on the relative strengths of such right handed currents: \(\varrho ^2 = \frac{{\sigma _R }}{{\sigma _L }}< 0.009\) , 90% confidence. This measurement puts limits on the mixing angle of left-right symmetric models. In distinction to similar limits derived from muon decay or β decay, our limits are also valid if the right handed neutrino is heavy. 相似文献