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81.
Structural Manipulation of Ruthenium(II) Polypyridine Nitrone Complexes to Generate Phosphorogenic Bioorthogonal Reagents for Selective Cellular Labeling
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Tommy Siu‐Ming Tang Dr. Hua‐Wei Liu Prof. Kenneth Kam‐Wing Lo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9649-9659
We report a new class of ruthenium(II) polypyridine complexes functionalized with a nitrone group as phosphorogenic bioorthogonal probes. These complexes were very weakly emissive owing to rapid C=N isomerization of the nitrone moiety, but exhibited significant emission enhancement upon strain‐promoted alkyne–nitrone cycloaddition (SPANC) reaction with bicyclo[6.1.0]nonyne (BCN)‐modified substrates. The modification of nitrone with a dicationic ruthenium(II) polypyridine unit at the α‐C‐position and a phenyl ring at the N‐position led to remarkably accelerated reaction kinetics, which are substantially greater (up to ≈278 fold) than those of other acyclic nitrone–BCN systems. Interestingly, the complexes achieved specific cell membrane/cytosol staining upon specific labeling of an exogenous substrate, BCN‐modified decane (BCN‐C10), in live cells. Importantly, the in situ generation of the more lipophilic isoxazoline adduct in the cytoplasm resulted in increased cytotoxicity, highlighting a novel approach to apply the SPANC labeling technique in drug activation. 相似文献
82.
ShangZhongLIU QingXiaoLI 《中国化学快报》2004,15(7):771-773
New photoaffinity ligand candidates were synthesized based on 5-t-buty1-2-(4-(substituted-ethyny1)phenyl)-1, 3-dithiane for the noncompetitive blocker site on the gammaaminobutyric acid-gated chloride channel. Their half-maximal inhibition concentrations ranged from 4 to 32 nmol/L as measured by 4‘-ethyny1-4-n-[2,3-3^H2]-propylbicycloorthobenzoate (3^H EBOB) assay. 相似文献
83.
Five two-photon excitable dipyrrylmetheneboron difluoride labels (dipyrrylmethene-BF2 labels) with fluorescence emission maximum between 530 and 590 nm, and a frequently used rhodamine label, TAMRA, were conjugated to aminomodified oligonucleotides. The performance of the labeled oligonucleotides was studied in a separation-free nucleic acid hybridization assay using ArcDia™ TPX bioaffinity assay technology. The results show that oligonucleotide conjugates of dipyrrylmethene-BF2 labels provide higher two-photon excited fluorescence yield and better assay sensitivity than corresponding TAMRA conjugate. The effect of conjugation on photophysical properties of the labels and performance of the labeled oligonucleotides in separation-free hybridization assay is discussed. 相似文献
84.
Recently introduced bioaffinity assay technology, ArcDia TPX, is based on two-photon excited fluorescence (TPE) and it enables separation-free ultra-sensitive immunoassays from microvolumes. Here we present syntheses of novel two-photon excitable fluorescent labeling reagents which have been specially designed to be used as label molecules in the ArcDia TPX assay technique. The labeling reagents are based on dipyrrylmetheneboron difluoride (dipyrrylmethene-BF2) chromophore, which have been substituted with aryl, heteroaryl or arylalkenyl chemical groups to extend the pi-electron conjugation. These substitutions results in a series of dipyrrylmethene-BF2 fluorophores with different photophysical properties. Dipyrrylmethene-BF2 fluorophores have been further substituted with a dipeptide linker unit and finally activated as succinimidyl esters to enable specific coupling with primary amino groups. The dipeptide linker serves as a spacer arm between the label and a target, and enhances the solubility of the label in aqueous solutions. Study of the chemical and photophysical performance of the new labeling reagents is described. The new labeling reagents exhibit high fluorescence quantum yields, and molar absorption coefficients. The results show that the new labels with the hydrophilic dipeptide linker unit provide large two-photon excitation cross-sections, high fluorescence quantum efficiency and good solubility in aqueous solutions. The results suggest that the novel dipyrrylmethene-BF2 labels are highly applicable to bioaffinity assays based on two-photon excitation of fluorescence. 相似文献
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模糊最短路问题在许多领域有着广泛的应用,研究这一问题具有重要意义。根据多准则决策理论求非被支配路径集合,求最大效用模糊最短路以及利用模糊数排序方法求模糊最短路是常用的三种研究方法,本文利用OERI排序原理,使网络模糊边长具有线性可加性,对具有三角模糊数边权的网络给出了一种标号算法,该算法简单高效,且易于在计算机上实现,算法的时间复杂度为O(n^2)。 相似文献
87.
We describe a new experiment for measuring homonuclear-decoupled anisotropic chemical shift patterns in doubly 13C-labeled compounds under magic-angle spinning. The experiment combines a pair of selective and non-selective 180 degrees pulses to suppress the 13C-13C scalar and dipolar interactions. This is combined with the recently developed SUPER technique to recouple the chemical shift anisotropy. Demonstrations on 13Calpha and 13CO-labeled amino acids and peptides show that accurate chemical shift powder patterns can be obtained. This permits the use of chemical shift anisotropy for conformational studies of suitably extensively 13C-labeled peptides and proteins. 相似文献
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Stefan Felsner 《Order》2001,18(1):19-37
We define an analogue of Schnyder's tree decompositions for 3-connected planar graphs. Based on this structure we obtain: Let G be a 3-connected planar graph with f faces, then G has a convex drawing with its vertices embedded on the (f–1)×(f–1) grid. Let G be a 3-connected planar graph. The dimension of the incidence order of vertices, edges and bounded faces of G is at most 3.The second result is originally due to Brightwell and Trotter. Here we give a substantially simpler proof. 相似文献