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221.
Enantioselective Self‐Assembly of Triangular Dy3 Clusters with Single‐Molecule Magnet Behavior 下载免费PDF全文
Three pairs of enantiopure chiral triangular Ln3 clusters, [Ln3LRRRRRR/SSSSSS(μ3‐OH)2(H2O)2(SCN)4]?xCH3OH?yH2O ( R ‐Dy3 , Ln=Dy, x=6, y=0; S ‐Dy3 , Ln=Dy, x=6, y=1; R ‐Ho3 , Ln=Ho, x=6, y=1; S ‐Ho3 , Ln=Ho, x=6, y=1; R ‐Er3 , Ln=Er, x=6, y=0; S ‐Er3 , Ln=Er, x=6, y=1), have been successfully synthesized by a rational enantioselective synthetic strategy. The core of triangular Ln3 is bound in the central N6O3 of the macrocyclic ligand, and the coordination spheres of Ln ions are completed by four SCN? anions and two H2O molecules in axial positions of the macrocycle. The circular dichroism (CD) and vibrational circular dichroism (VCD) spectra of the enantiomers demonstrate that the chirality is successfully transferred from the ligands to the resulting Ln3 clusters. Ac susceptibility measurements reveal that single‐molecule magnet behavior occurs for both enantiopure clusters of R ‐Dy3 and S ‐Dy3 . This work is one of the few examples of the successful design of a pair of triangular Dy3 clusters showing simultaneously slow magnetic relaxation and optical activity, and this might open up new opportunities to develop novel multifunctional materials. 相似文献
222.
Min-Jie Shi Sheng-Zhong Kou Bao-Shou Shen Jun-Wei Lang Zhi Yang Xing-Bin Yan 《中国化学快报》2014,25(6):859-864
Ionic liquid gel polymers have widely been used as the electrolytes in all-solid-state supercapacitors, but they suffer from low ionic conductivity and poor electrochemical performance. Arc discharge is a fast, low-cost and scalable method to prepare multi-layered graphene nanosheets, and as-made graphene nanosheets (denoted as ad-GNSs) with few defects, high electrical conductivity and high thermal stability should be favorable conductive additive materials. Here, a novel ionic liquid gel polymer electrolyte based on an ionic liquid (EM1MNTF2) and an copolymer (P(VDF-HFP)) was modified by the addition of ad-GNSs as an ionic conducting promoter. This modified gel electrolyte shows excellent thermal stability up to 400 ℃ and a wide electrochemical window of 3 V. An all-solid-state supercapacitor based on commercial activated carbon was fabricated using this modified ionic liquid gel polymer electrolyte, which shows obviously improved electrochemical behaviors compared with those of the corresponding all-solid-state supercapacitor using pure ionic liquid gel polymer electrolyte. Specially, smaller internal resistance, higher specific capacitance, better rate performance and cycling stability are achieved. These results indicate that the ionic liquid gel polymers modified by ad-GNSs would be promising and suitable gel electrolytes for high performance all-solid-state electrochemical devices. 相似文献
223.
Raluca Nicoleta Darie Eduard Lack Franz Lang Jr. Martin Sova Alexandra Nistor Iuliana Spiridon 《International Journal of Polymer Analysis and Characterization》2014,19(5):453-467
New materials were obtained by incorporating in polypropylene (PP) matrix 60% wood wastes resulting after extraction with supercritical carbon dioxide, water, and ethanol. Structural, mechanical, thermal, and rheological characterizations, as well as moisture uptake of the composites, were evaluated before and after accelerated weathering. It was found that the extraction method influenced the composite properties due to the hydrophilic-hydrophobic balance. The addition of extracted fibers results in an increase in hardness and tensile properties and a decrease of impact strength as compared to PP. 相似文献
224.
分别用稀土醋酸盐和稀土高氯酸盐与希弗碱配体和巯基烟酸配体反应得到了两例镝配合物[Dy2(OAc)6H2O]n(1)和{[DyL(H2O)4]ClO4·H2O}n(2)(L=2,2'-二硫代-二(3-吡啶甲酸)),并通过单晶X-射线衍射、元素分析、红外光谱和磁性测试对其进行了表征。结构研究和磁性测试表明:化合物1是羧基桥连的一维链结构,该化合物表现出慢磁弛豫性质,有效能垒为2 K;化合物2是通过原位生成的二硫键桥连的二维网状结构,表现出明显的铁磁相互作用和慢磁弛豫行为。 相似文献
225.
David Adner Marcus Korb Charles Lochenie Birgit Weber Heinrich Lang 《无机化学与普通化学杂志》2015,641(7):1243-1246
The synthesis and characterisation of the hexanuclear copper(II) carboxylate complex [Cu(O2CCHPhOC2H4OC2H4OCH3)2]6 ( 1 ) is described. Single‐crystal X‐ray structure analysis reveals that the copper(II) ions are arranged in a six‐membered ring which adopts a chair‐like conformation. The copper(II) ions are bridged by μ2‐ and μ3‐coordinating carboxylates. The magnetic behavior of 1 was measured between 2 and 300 K, revealing at low temperature a weak antiferromagnetic interaction. The χM(T) dependency was fitted mathematically with one coupling constant J1 and a paramagnetic impurity α. 相似文献
226.
The photochromic mechanism of 1-phenyl-3-methyl-4-(6-hydro-4-amino-5-sulfo-2,3- pyrazine)-pyrazole-5-one has been investigated using the density functional theory(DFT). The solvent effect is simulated using the polarizable continuum model(PCM) of the self-consistent reaction field theory. According to the crystal structure of the title compound, an intramolecular proton transfer mechanism from enol to keto form was proposed to interpret its photochromism. Bader's atom-in-molecule(AIM) theory is used to investigate the nature of hydrogen bonds and ring structures. Time-dependent density functional theory(TDDFT) calculation results show that the photochromic process from enol to keto form is reasonable. The conformation and molecular orbital analysis of enol and keto forms explain why only intramolecular proton transfer is possible. The results from analyzing the energy and dipole moments of enol form, transition state and keto form in the gas phase and in different solvents have been used to assess the stability of the title compound. 相似文献
227.
Amperometric l-glutamate biosensor based on bacterial cell-surface displayed glutamate dehydrogenase
A novel l-glutamate biosensor was fabricated using bacteria surface-displayed glutamate dehydrogenase (Gldh-bacteria). Here the cofactor NADP+-specific dependent Gldh was expressed on the surface of Escherichia coli using N-terminal region of ice nucleation protein (INP) as the anchoring motif. The cell fractionation assay and SDS-PAGE analysis indicated that the majority of INP-Gldh fusion proteins were located on the surface of cells. The biosensor was fabricated by successively casting polyethyleneimine (PEI)-dispersed multi-walled carbon nanotubes (MWNTs), Gldh-bacteria and Nafion onto the glassy carbon electrode (Nafion/Gldh-bacteria/PEI-MWNTs/GCE). The MWNTs could not only significantly lower the oxidation overpotential towards NAPDH, which was the product of NADP+ involving in the oxidation of glutamate by Gldh, but also enhanced the current response. Under the optimized experimental conditions, the current–time curve of the Nafion/Gldh-bacteria/PEI-MWNTs/GCE was performed at +0.52 V (vs. SCE) by amperometry varying glutamate concentration. The current response was linear with glutamate concentration in two ranges (10 μM–1 mM and 2–10 mM). The low limit of detection was estimated to be 2 μM glutamate (S/N = 3). Moreover, the proposed biosensor is stable, specific, reproducible and simple, which can be applied to real samples detection. 相似文献
228.
Dr. Christiane Lang Sebastian Bestgen Dr. Alexander Welle Rouven Müller Prof. Peter W. Roesky Prof. Christopher Barner‐Kowollik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14728-14731
A platform technology for the creation of spatially resolved surfaces encoded with a monolayer consisting of different metal complexes was developed. The concept entails the light‐triggered activation of a self‐ assembled monolayer (SAM) of UV‐labile anchors, that is, phenacylsulfides, and the subsequent cycloaddition of selected diene‐functionalized metal complexes at defined areas on the surface. The synthesis and characterization of the metal complexes for the UV‐light assisted anchoring on the surface and a detailed study of a short‐chain oligomer model system in solution confirm the high efficiency of the photoreaction. The hybrid materials obtained by this concept can potentially be utilized for the design of highly valuable catalytic or (opto‐)electronic devices. 相似文献
229.
Selective Permeability of Uranyl Peroxide Nanocages to Different Alkali Ions: Influences from Surface Pores and Hydration Shells 下载免费PDF全文
Yunyi Gao Fadi Haso Jennifer E. S. Szymanowski Jing Zhou Lang Hu Prof. Dr. Peter C. Burns Prof. Dr. Tianbo Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(51):18785-18790
The precise guidance to different ions across the biological channels is essential for many biological processes. An artificial nanopore system will facilitate the study of the ion‐transport mechanism through nanosized channels and offer new views for designing nanodevices. Herein we reveal that a 2.5 nm‐sized, fullerene‐shaped molecular cluster Li48+mK12(OH)m[UO2(O2)(OH)]60?(H2O)n (m≈20 and n≈310) ( U60 ) shows selective permeability to different alkali ions. The subnanometer pores on the water–ligand‐rich surface of U60 are able to block Rb+ and Cs+ ions from passing through, while allowing Na+ and K+ ions, which possess larger hydrated sizes, to enter the interior space of U60 . An interestingly high entropy gain during the binding process between U60 and alkali ions suggests that the hydration shells of Na+/K+ and U60 are damaged during the interaction. The ion selectivity of U60 is greatly influenced by both the morphologies of the surface nanopores and the dynamics of the hydration shells. 相似文献
230.
Influence of P‐Bonded Bulky Substituents on Electronic Interactions in Ferrocenyl‐Substituted Phospholes 下载免费PDF全文
Dominique Miesel Dr. Alexander Hildebrandt Marcus Korb Prof. Dr. Heinrich Lang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11545-11559
2,5‐Diferrocenyl‐1‐Ar‐1H‐phospholes 3 a – e (Ar=phenyl ( a ), ferrocenyl ( b ), mesityl ( c ), 2,4,6‐triphenylphenyl ( d ), and 2,4,6‐tri‐tert‐butylphenyl ( e )) have been prepared by reactions of ArPH2 ( 1 a – e ) with 1,4‐diferrocenyl butadiyne. Compounds 3 b – e have been structurally characterized by single‐crystal XRD analysis. Application of the sterically demanding 2,4,6‐tri‐tert‐butylphenyl group led to an increased flattening of the pyramidal phosphorus environment. The ferrocenyl units could be oxidized separately, with redox separations of 265 ( 3 b ), 295 ( 3 c ), 340 ( 3 d ), and 315 mV ( 3 e ) in [NnBu4][B(C6F5)4]; these values indicate substantial thermodynamic stability of the mixed‐valence radical cations. Monocationic [ 3 b ]+–[ 3 e ]+ show intervalence charge‐transfer absorptions between 4650 and 5050 cm?1 of moderate intensity and half‐height bandwidth. Compounds 3 c – e with bulky, electron‐rich substituents reveal a significant increase in electronic interactions compared with less demanding groups in 3 a and 3 b . 相似文献