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81.
Benzenehexapyrrole‐α,ω‐dialdehyde, composed of a pair of formyltripyrrole units with a 1,3‐phenylene linker, was metallated to give dinuclear single‐stranded helicates. X‐ray studies of the bis‐nickel(II) complex showed a helical C2 form with a pair of helical–metal coordination planes of a 3N+O donor set. The terminal aldehyde was readily converted into the imine by optically active amines, whereby helix‐sense bias was induced. Bis‐nickel(II) and bis‐palladium(II) complexes of the benzenehexapyrrole‐α,ω‐diimines were studied to show that an enantiomer pair of the helical C2 form are interchanged by slow flipping of each coordination plane and fast rotation around the C(benzene)?C(pyrrole) bond. The helical screw in the bis‐nickel(II) complexes was biased to one side in more than 95 % diastereoselectivity, which was achieved by using a variety of optically active amines, such as (R)‐1‐cyclohexylethylamine, (S)‐1‐ phenylethylamine, L ‐Phe(OEt) (Phe=phenylalanine), and (R)‐valinol. The nickel complexes showed much better diastereoselectivity than the corresponding palladium complexes.  相似文献   
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We investigate the statistics of polymer capture by a nanopore using Brownian dynamics simulations. It is found that when the velocity flux is greater than a critical velocity flux, the capture picture is a random selection process, otherwise it tends to a statistical process governed by energetic considerations. In addition, the chain ends capture probability decreases as the chain length increases and satisfies a power-law scaling of P0(N)~N-0.8.  相似文献   
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Four kinds of red phosphorescent organic light-emitting devices were fabricated and compared to investigate the effect of interfacial layers for hole transport and electron injection. 1 nm-thick LiF in the device A and C and 1 nm-thick Cs2CO3 in the device B and D were deposited as an electron injection layer between the anode and the electron transport layer, and 5 nm-thick layer of dipyrazion[2,3-f:2′,2′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile[HATCN] was inserted as a hole transport interfacial layer between the hole injection layer and the hole transport layer only in the device C and D. Under a luminance of 1000 cd/m2, the power efficiencies were 7.6 lm/W and 8.5 lm/W in the device A and B, and 8.6 lm/W and 13.4 lm/W in the device C and D. The quantum efficiency of the device D was 15.8% under 1000 cd/m2 which was somewhat lower than those of the device A and C, but a little higher than that of the device B. The luminance of the device D was much higher than those of the other devices at a given votage. The luminance of the device D at 7 V was 23,710 cd/m2, which was 13.0, 3.4, and 4.0 times higher than those of the device A, B, and C at the same voltage, respectively.  相似文献   
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Total glucosides of paeony are the active constituents of Paeoniae Radix Alba. In this study, a novel strategy was proposed to find more metabolites and the differences between paeoniflorin, albiflorin and total glucosides of paeony (TGP). This strategy was characterized as follows: firstly, the animals were divided into three groups (paeoniflorin, albiflorin and TGP) to identify the source of TGP metabolites from paeoniflorin or albiflorin; secondly, a generic information‐dependent acquisition scan for the low‐level metabolites was triggered by the multiple mass defect filter and dynamic background subtraction; thirdly, the metabolites were identified with a combination of data‐processing methods including mass defect filtering, neutral loss filtering and product ion filtering; finally, a comparative study was used in the metabolism of paeoniflorin, albiflorin and TGP. Based on the strategy, 18 metabolites of TGP, 10 metabolites of paeoniflorin and 13 metabolites of albiflorin were identified respectively. The results indicated that the hydrolysis, conjugation reaction and oxidization were the major metabolic pathways, and the metabolic sites were the glycosidic linkage, the ester bond and the benzene ring. This study is first to explore the metabolism of TGP, and these findings enhance our understanding of the metabolism and the interactions of paeoniflrin and albiflorin in TGP. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   
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Zhenju antihypertensive compound (ZJAHC) is a combined Chinese–Western medicine formula including clonidine (CLO), hydrochlorothiazide (HCT), rutin, Chrysanthemum indicum extract and pearl powder. Compared with CLO preparations, ZJAHC shows improved activities and decreased adverse effects. It is believed that the side effects of CLO are caused by its high peak plasma concentration. Hence, study of the influence of ZJAHC on the pharmacokinetic behaviors of clonidine seems essential. In present study, the plasma concentrations of CLO were determined with a liquid chromatography–tandem mass spectrometry (LC‐MS/MS) method. The MS/MS transitions monitored for clonidine and internal standard were 230.2 → 213.1 and 152.2 → 110.2, respectively. The analyte was quantified in a single run within 3 min. The pharmacokinetic study showed that the area under the plasma concentration–time curve of CLO in ZJAHC (60 µg/kg CLO) was similar to that of CLO‐HCT‐high (120 µg/kg CLO) but the peak concentration was much lower than that in CLO‐HCT‐high. ZJAHC could enhance the bioavailability without greatly increasing peak concentration of clonidine. This comprehensive effect of enhancing the bioavailability and avoiding the high peak plasma concentration for CLO might mainly result from the co‐contribution of Western medicine and traditional Chinese medicine (TCM), while the effect of TCM was stronger than that of Western medicine. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   
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Western blotting is a highly valued method for protein identification and relative quantitation in complex samples. It combines size-based electrophoretic separation with immunoaffinity to identify specific proteins. This technique remains popular and has become a workhorse in biochemical research and clinical laboratories. Despite its utility and popularity, this method has many limitations including slow analysis, incompatibility with limited sample application, low throughput and low information content. Recently there has been significant success in improving different aspects of Western blotting. In this review, we provide an overview of the developments in the area of improving conventional Western blotting methods with a focus on recent developments in microfluidic Western blotting. We overview different separation platforms, and discuss studies on protein transfer methods as well as protein immobilization methods and chemistries. We also describe integrated miniaturized platforms that can perform rapid separations and immunodetections.  相似文献   
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