CM⁃Phos配体在钯催化交叉偶联反应中的应用

本文综合评述了近年来2-[2-(二环己膦基)苯基]-1-甲基-1H-吲哚(CM-Phos)膦配体及其衍生物在钯催化的交叉偶联反应中的应用, 主要根据不同种类的交叉偶联反应进行系统性分述, 并对该领域的发展前景进行了展望.     

具有性质cr+1=3,ar+1=3a+1或 4a的(a+1,3)型距离正则图

设г是直径为d且型为(a 1,3)的距离正则图,其中a≥2.用l(c,a,b)表示交叉阵列ι(г)中列(c,a,6)t的个数,记r=r(г)=l(c1,a1,b1),8=8(г)=l(Cr 1,ar 1,br 1)及t=t(г)=l(cr s 1,ar s 1,br s 1).那末,若Cr 1=3,ar 1=4a或3a 1,则d=r t 2.     

Design of luminescent iridium(III) and rhenium(I) polypyridine complexes as in vitro and in vivo ion,molecular and biological probes

Many luminescent transition metal polypyridine complexes display intense and long-lived triplet charge-transfer and intraligand transition emission with a large Stokes’ shift. These properties render them promising candidates as luminescent probes for ions, DNA, peptides, proteins and other biological entities. In this review article, we have summarised recent reports on ion, molecular and biological probes derived from luminescent rhenium(I) and iridium(III) polypyridine complexes. These complexes have been appended with different recognition moieties that interact with ions and biological molecules. The recognition is reflected by a change of spectroscopic and/or photophysical properties of the probes. The use of these complexes as cellular probes and imaging reagents has also been discussed.     

带有相依重尾冲击的Poisson噪音过程尾的一致渐近性质

本文考虑了带有某种相依重尾冲击的Poisson噪音过程尾的一致渐近性质.当冲击是二元上尾渐近独立的非负随机变量具有长尾和控制变化尾分布且噪音函数具有正的上下界时,得到了过程尾概率的一致渐近公式.进而,当冲击具有连续的一致变化尾分布时,去除了噪音函数具有正的下界的限制.对于噪音函数不一定具有正的上界的情形,当冲击具有两两负象限相依结构时,也得到了一致渐近性结果.     

On Bayes inference for a bathtub failure rate via S-paths

A class of semi-parametric hazard/failure rates with a bathtub shape is of interest. It does not only provide a great deal of flexibility over existing parametric methods in the modeling aspect but also results in a closed-form and tractable Bayes estimator for the bathtub-shaped failure rate. Such an estimator is derived to be a finite sum over two S-paths due to an explicit posterior analysis in terms of two (conditionally independent) S-paths. These, newly discovered, explicit results can be proved to be Rao–Blackwell improvements of counterpart results in terms of partitions that are readily available by a specialization of James’ work (Ann Stat 33:1771–1799, 2005). Both iterative and non-iterative computational procedures are introduced for evaluating the hazard estimates. Two applications of the proposed methodology are discussed, of which one is about a Bayesian test for bathtub-shaped failure rates and the other is related to modeling with covariates.     

Nonlinear Exact Solutions of the 2-Dimensional Rotational Euler Equations for the Incompressible Fluid

In this paper, the Clarkson–Kruskal direct approach is employed to investigate the exact solutions of the2-dimensional rotational Euler equations for the incompressible fluid. The application of the method leads to a system of completely solvable ordinary differential equations. Several special cases are discussed and novel nonlinear exact solutions with respect to variables x and y are obtained. It is of interest to notice that the pressure p is obtained by the second kind of curvilinear integral and the coefficients of the nonlinear solutions are solitary wave type functions like tanh(kt/2)and sech(kt/2) due to the rotational parameter k = 0. Such phenomenon never appear in the classical Euler equations wherein the Coriolis force arising from the gravity and Earth's rotation is ignored. Finally, illustrative numerical figures are attached to show the behaviors that the exact solutions may exhibit.     

Luminescent rhenium(I) polypyridine fluorous complexes as novel trifunctional biological probes

We present the synthesis, characterization, and photophysical properties of three luminescent rhenium(I) polypyridine fluorous complexes [Re(Me(2)bpy)(CO)(3)(L)](PF(6)) (Me(2)bpy = 4,4'-dimethyl-2,2'-bipyridine; L = 3-amino-5-(N-((3-perfluorooctyl)propyl)aminocarbonyl)pyridine (py-Rf-NH(2)) (1), 3-isothiocyanato-5-(N-((3-perfluorooctyl)propyl)aminocarbonyl)pyridine (py-Rf-NCS) (2), 3-ethylthioureidyl-5-(N-((3-perfluorooctyl)propyl)aminocarbonyl)pyridine (py-Rf-TU-C(2)H(5)) (3)). The isothiocyanate complex 2 has been used to label bovine serum albumin (BSA) and glutathione (GSH). The photophysical properties of the resultant bioconjugates have been studied. The isolation of the luminescent fluorous rhenium-GSH conjugate from a mixture of 20 amino acids has been demonstrated using fluorous solid-phase extraction (FSPE). Additionally, the cytotoxicity of complexes 1 and 3 toward HeLa cells has been examined by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) assay. The cellular uptake properties of complex 3 have also been investigated by laser-scanning confocal microscopy.     

Rhenium(I) polypyridine biotin isothiocyanate complexes as the first luminescent biotinylation reagents: synthesis, photophysical properties, biological labeling, cytotoxicity, and imaging studies

We report here the design of the first class of luminescent biotinylation reagents derived from rhenium(I) polypyridine complexes. These complexes [Re(N-N)(CO)(3)(py-biotin-NCS)](PF(6)) (py-biotin-NCS = 3-isothiocyanato-5-(N-((2-biotinamido)ethyl)aminocarbonyl)pyridine; N-N = 1,10-phenanthroline (phen) (1a), 3,4,7,8-tetramethyl-1,10-phenanthroline (Me(4)-phen) (2a), 4,7-diphenyl-1,10-phenanthroline (Ph(2)-phen) (3a)), containing a biotin unit and an isothiocyanate moiety, have been synthesized from the precursor amine complexes [Re(N-N)(CO)(3)(py-biotin-NH(2))](PF(6)) (py-biotin-NH(2) = 3-amino-5-(N-((2-biotinamido)ethyl)aminocarbonyl)pyridine; N-N = phen (1c), Me(4)-phen (2c), Ph(2)-phen (3c)). To investigate the amine-specific reactivity of the isothiocyanate complexes 1a-3a, they have been reacted with a model substrate ethylamine, resulting in the formation of the thiourea complexes [Re(N-N)(CO)(3)(py-biotin-TU-Et)](PF(6)) (py-biotin-TU-Et = 3-ethylthioureidyl-5-(N-((2-biotinamido)ethyl)aminocarbonyl)pyridine; N-N = phen (1b), Me(4)-phen (2b), Ph(2)-phen (3b)). All the rhenium(I) complexes have been characterized, and their photophysical properties have been studied. The avidin-binding properties of the thiourea complexes 1b-3b have been examined by the 4'-hydroxyazobenzene-2-carboxylic acid (HABA) assay. Titration results indicated that the complexes exhibited emission enhancement by ca. 1.4-1.5-fold upon binding to avidin, and the lifetimes were elongated to ca. 0.8-2.0 micros. Additionally, we have biotinylated bovine serum albumin (BSA) with the isothiocyanate complexes. All the resultant rhenium-BSA bioconjugates displayed intense and long-lived orange-yellow to greenish-yellow emission upon irradiation in aqueous buffer under ambient conditions. The avidin-binding properties of the bioconjugates have been investigated using the HABA assay. Furthermore, the cytotoxicity of the thiourea complexes 1b-3b toward the HeLa cells has been examined by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) assay. The IC50 values were determined to be ca. 17.5-28.5 microM, which are comparable to that of cisplatin (26.7 microM) under the same conditions. The cellular uptake of complex 3b has been investigated by fluorescence microscopy, and the results showed that the complex was localized in the perinuclear region after interiorization.