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161.
Three novel Schiff base cadmium(II) complexes, derived from the end‐on (μ‐1,1‐N3) azide or end‐to‐end (μ‐1,3‐NCS) thio cyanate bridges and similar tridentate Schiff base ligands, have been synthesized under similar synthetic procedures and their crystal structures determined by X‐ray diffraction methods. They are the dinuclear double end‐on azide‐bridged [Cd2(L1)2(N3)2(μ‐1,1‐N3)2] ( 1 ), the dinuclear double end‐on azide‐bridged [Cd2(L2)2(N3)2(μ‐1,1‐N3)2] ( 2 ), and the dinuclear double end‐to‐end thiocyanate‐bridged [Cd2(L3)2(NCS)2(μ1,3‐NCS)2] ( 3 ), where L1, L2 and L3 are three similar tridentate Schiff bases obtained by condensation of 2‐pyridylaldehyde with N,N‐diethylethane‐1,2‐diamine, of 2‐pyridylaldehyde with N‐isopropylethane‐1,2‐diamine, and of 2‐pyridylaldehyde with N,N‐dimethylpropane‐1,3‐diamine, respectively. Each cadmium(II) centre in the complexes is in a distorted octahedral coordination. There is a crystallographic inversion centre in each of the complexes. The similar small ligands used as the secondary ligands in the preparation of the cadmium(II) complexes with similar Schiff bases can result in similar structures. 相似文献
162.
Three linear trinuclear Schiff base complexes, {Zn[Zn(CH3COO)(C17H16N2O2)]2} ( 1 ), {Zn[Zn(CH3COO)(C25H20N2O2)]2} ( 2 ), and {Cd[Cd(CH3COO)(C18H18N2O2)]2} ( 3 ), were synthesized for the first time under solvolthermal conditions. Their structures have been characterized by elemental analyses, X-ray single crystal determinations, and infrared spectroscopy. There are three bridges across the M-M atom pairs (M is Zn for 1 and 2 , or Cd for 3 ) in each complex, involving two O atoms of a Schiff base ligand (N,N′-bis(salicylidene)-1, 3-propanediaminate (SALPD2-) for 1 , N, N′-bis(2-hydroxy-naphthalmethenylimino)-1, 3-propanediaminate (NAPTPD2-) for 2 , and N,N′-bis-(salicylidene)-1,4-butanediaminate (SALBD2-) for 3 ), and an O-C-O moiety of a μ-acetato group. In each of the complexes, the central M2+ ion is located on an inversion center and has a distorted octahedral coordination involving four bridging O atoms from two Schiff base ligands in the equatorial plane and one O atom from each bridging acetate group in the axial positions. The coordination around the terminal M2+ ions is irregular square pyramidal, with two O atoms and two N atoms of the Schiff base ligand in the basal plane and one O atom from an acetate group in the apical position. The acetate bridges linking the central and terminal M2+ ions are mutually trans. The M…M distances are 3.050(3) Å in 1 , 3.139(2) Å in 2 , and 3.287(6) Å in 3 . 相似文献
163.
164.
Wen Weng Qing Le Zeng Bi Xia Yao Wen Shi Lin Qing Hua Wang Xiu Li You 《Chromatographia》2006,64(7-8):463-467
Five structurally related amino acid derivatives were enantioseparated by HPLC with a commercially available chiral stationary phase, Chiralcel OD-H. The chromatographic experiments were performed in the normal phase mode. n-Hexane/polar alcohol was used as mobile phase. Excellent baseline enantioseparations could be obtained for all these solutes. The effects of the concentration of polar alcohol and the column temperature on the retentions and enantioseparations were studied in detail. From the van't Hoff plots the corresponding apparent thermodynamic parameters were derived. Mechanism aspects of chiral recognition were discussed based on the relationship between the thermodynamic parameters and the structures of the solutes. It was found that the substituent of the phenyl group on the residual group of the amino acid derivatives was close relevant to thermodynamic origin of enantioseparation. Much better enthalpy–entropy compensation effect was obtained by plotting the differential, rather than the original, thermodynamic parameters. 相似文献
165.
采用双股并流共沉淀方法制备了SnO2含量从10%至90%的锡锆体系DeNOx催化剂,用XRD、微区电子衍射、FT-Raman及FT-IR等技术深入研究了锡锆体系氧化物的结构及其随组成的变化规律.结果表明,由于Sn4+与Zr4+离子半径接近,SnO2与ZrO2易于形成固溶体,并随组成变化表现出不同的结构特征.纯ZrO2为单斜相,当少量Sn4+(SnO2 ≤ 20%)进入ZrO2晶格时形成四方相富锆固溶体,Sn4+起到稳定ZrO2四方相的作用;随着SnO2含量的增大,结构从无定形或微晶态的富锆固溶体(含SnO2 30~50%)经富锆固溶体与金红石结构的富锡固溶体在55% SnO2含量的共存状态变化到具有金红石结构的富锡固溶体(SnO2 ≥ 60%).FT-Raman和FT-IR光谱测试证明,Zr进入SnO2晶格使得Sn-O键的结合减弱,Sn离子上的有效正电荷减小,降低了SnO2对丙烯的燃烧能力,从而提高了对NO的还原活性. 相似文献
166.
Summary A clean method without use of organic solvents has been developed for isolation and high-performance liquid chromatographic
(HPLC) determination of oxytetracycline (OTC) and sulphadimidine (SDD) in cow's milk. Isolation is rapid and simple—homogenization
with an inorganic acid solution by means of a handy ultrasonic homogenizer, which is easy-to-use and portable, followed by
centrifugation. Reversed-phase HPLC was performed on a C4 column, with 1.25 mmol L−1 succinic acid solution as mobile phase, and identification was by means of a photodiode-array detector. Separation of the
analytes was achieved in less than 8 min. Significant linearity was established over the concentration range of 0.1–1.0 μg
mL−1 for both target compounds (r>0.99,P<0.01). Average recoveries of OTC and SDD (each spiked at 0.1–1.0 μg mL−1) were ≥88.8, and inter- and intra-assay variability was ≤2.8%. The total time required for analysis of one sample was <20
min. The limits of quantitation of the method (μg mL−1 in milk) were 0.044 for OTC and 0.023 for SDD. No organic solvent was used at any stage of the analysis. 相似文献
167.
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
168.
Jayeon Hong Sangsub Kim Gyurim Park Yongmoon Lee Hyungchae Kim Sungjin Kim Tae-Woo Lee Changsoon Kim Youngmin You 《Chemical science》2021,12(25):8668
Polymer electroluminescence devices producing circularly polarized luminescence (CP PLEDs) have valuable photonic applications. The fabrication of a CP PLED requires a polymer host that provides the appropriate chiral environment around the emitting dopant. However, chemical strategies for the design of chiral polymer hosts remain underdeveloped. We have developed new polymer hosts for CP PLED applications. These polymers were prepared through a free-radical polymerization of 3-vinylcarbazole with a chiral N-alkyl unit. This chiral unit forces the carbazole repeat units to form mutually helical half-sandwich conformers with preferred (P)-helical sense along the polymer main chain. Electronic circular dichroism measurements demonstrate the occurrence of chirality transfer from chiral monomers to achiral monomers during chain growth. The (P)-helical-sense-enriched polymer interacts diastereoselectively with an enantiomeric pair of new phosphorescent (R)- and (S)-dopants. The magnitude of the Kuhn dissymmetry factor (gabs) for the (P)-helically-enriched polymer film doped with the (R)-dopant was found to be one order of magnitude higher than that of the film doped with the (S)-dopant. Photoluminescence dissymmetry factors (gPL) of the order of 10−3 were recorded for the doped films, but the magnitude of diastereomeric enhancement decreased to that of gabs. The chiral polymer host permits faster energy transfer to the phosphorescent dopants than the achiral polymer host. Our photophysical and morphological investigations indicate that the acceleration in the chiral polymer host is due to its longer Förster radius and improved compatibility with the dopants. Finally, multilayer CP PLEDs were fabricated and evaluated. Devices based on the chiral polymer host with the (R)- and (S)-dopants exhibit electroluminescence dissymmetry factors (gEL) of 1.09 × 10−4 and −1.02 × 10−4 at a wavelength of 540 nm, respectively. Although challenges remain in the development of polymer hosts for CP PLEDs, our research demonstrates that chiroptical performances can be amplified by using chiral polymer hosts.Polymer electroluminescence devices producing circularly polarized luminescence (CP PLEDs) have valuable photonic applications. 相似文献
169.
C12-s-C12•2Br和C12En混合水溶液的胶团化行为 总被引:3,自引:0,他引:3
季铵盐二聚表面活性剂C12 s C12•2Br(s=2、3、4、6)和非离子表面活性剂C12E10或C12E23在水溶液中生成混合胶团.其临界胶团总浓度cmcT值介于二元复配体系中各组分的临界胶团浓度和之间.当添加少量非离子型表面活性剂(在水溶液中的摩尔分数α2=0.1)时,混合胶团中C12E10或C12E23的摩尔分数均已超过0.35;随着溶液中非离子型表面活性剂含量的增大,混合胶团中逐渐以C12E10或C12E23成分为主. 相似文献
170.