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51.
Two new C18-norditerpenoid alkaloids from Aconitum delavayi 总被引:2,自引:0,他引:2
Shan Hao Jiang Hai Qing Wang Yi Ming Li Shuang Jun Lin Jun Jie Tan Da Yuan Zhu 《中国化学快报》2007,18(4):409-411
Further phytochemical investigation of the unique C18-norditerpenoid alkaloids from the roots of Aconitum delavayi Franch ledto the isolation of two new norditerpenoid alkaloids,delavaconitine F 1 and delavaconitine G 2.Their structures were determinedfrom spectroscopic evidence. 相似文献
52.
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
53.
With the rapid development of human society, clean energy forms are imperative to sustain the normal operations of various mechanical and electrical facilities under a cozy environment. Hydrogen is considered among the most promising clean energy sources for the future. Recently, electrochemical water splitting has been considered as one of the most efficient approaches to harvest hydrogen energy, which generates only non-pollutant water on combustion. However, the sluggish anodic oxygen evolution reaction significantly restricts the efficiency of water splitting and requires a relatively high cell voltage to drive the electrolysis. Therefore, seeking a thermodynamically favorable anodic reaction to replace the sluggish oxygen evolution reaction by utilizing highly active bifunctional electrocatalysts for the anodic reaction and hydrogen evolution are crucial for achieving energy-efficient hydrogen production for industrial applications. Nevertheless, it is known that the oxygen evolution reaction can be replaced with other useful and thermodynamically favorable reactions to reduce the electrolysis voltage for realizing energy-efficient hydrogen production. Therefore, in this study, we present a bifunctional nickel nanoparticle-embedded carbon (Ni@C) prism-like microrod electrocatalyst synthesized via a two-step method involving the synthesis of a precursor metal-organic framework-74 and subsequent carbonization treatment for methanol oxidation and hydrogen evolution. The interfacial structure consisting of a nickel and carbon skeleton was realized via in situ carbonization. However, the dispersed nickel nanoparticles do not easily aggregate owing to the partition by the surrounding carbon as it would sufficiently expose the active Ni sites to the electrolytes, ensuring fast charge transfer between the catalyst and electrolytes by accelerating the electrochemical kinetics. In the anodic methanol oxidation, the products were detected as carbon dioxide and formate with faradaic efficiencies of 36.2% and 62.5%, respectively, at an applied potential of 1.55 V. Meanwhile, the Ni@C microrod catalyst demonstrated high activity and durability (2.7% current decay after 12 h of continuous operation) toward methanol oxidation, which demonstrates that methanol oxidation precedes oxidation under voltage forces. Notably, the bifunctional catalyst not only exhibits excellent performance toward methanol oxidation but also yields a low overpotential of 155 mV to drive 10 mA∙cm−2 toward hydrogen evolution in 1.0 mol∙L−1 KOH aqueous solution with 0.5 mol∙L−1 methanol at room temperature, which guarantees the hydrogen production efficiency. More importantly, the constructed two-electrode electrolyzer produced a current density of 10 mA∙cm−2 at a low cell voltage of 1.6 V, which decreased by 240 mV after replacing the oxygen evolution reaction with methanol oxidation. 相似文献
54.
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
55.
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
56.
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
57.
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
58.
59.
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
60.
Xianhao Lv Mizhen Sun Lei Xu Runzhe Wang Huayi Zhou Yuyu Pan Shitong Zhang Qikun Sun Shanfeng Xue Wenjun Yang 《Chemical science》2020,11(19):5058
Designing a donor–acceptor (D–A) molecule with a hybridized local and charge transfer (HLCT) excited state is a very effective strategy for producing an organic light-emitting diode (OLED) with a high exciton utilization efficiency and external quantum efficiency. Herein, a novel twisting D–π–A fluorescent molecule (triphenylamine–anthracene–phenanthroimidazole; TPAAnPI) is designed and synthesized. The excited state properties of the TPAAnPI investigated through photophysical experiments and density functional theory (DFT) analysis reveal that its fluorescence is due to the HLCT excited state. The optimized non-doped blue OLED using TPAAnPI as a light-emitting layer exhibits a novel blue emission with an electroluminescence (EL) peak at 470 nm, corresponding to the Commission International de L''Eclairage (CIE) coordinates of (0.15, 0.22). A fabricated device termed Device II exhibits a maximum current efficiency of 18.09 cd A−1, power efficiency of 12.35 lm W−1, luminescence of ≈29 900 cd cm−2, and external quantum efficiency (EQE) of 11.47%, corresponding to a high exciton utilization efficiency of 91%. Its EQE remains as high as 9.70% at a luminescence of 1000 cd m−2 with a low efficiency roll-off of 15%. These results are among the best for HLCT blue-emitting materials involved in non-doped blue fluorescent OLEDs. The performance of Device II highlights a great industrial application potential for the TPAAnPI molecule.A new pure fluorescent blue HLCT-emitter was designed and synthesized. Highly efficient non-doped blue OLEDs with low efficiency roll-off were achieved. 相似文献