Synthesis, structural characterization and luminescent properties of a series of Cu(I) complexes based on polyphosphine ligands

A series of Cu(I) complexes with a [Cu(NN)(PP)](+) moiety, [Cu(phen)(pba)](BF(4)) (1a), [Cu(2)(phen)(2)(pbaa)](BF(4))(2) (2a), [Cu(2)(phen)(2)(pnaa)](BF(4))(2) (3a), [Cu(2)(phen)(2)(pbbaa)](BF(4))(2) (4a), [Cu(dmp)(pba)](BF(4)) (1b), [Cu(2)(dmp)(2)(pbaa)](BF(4))(2) (2b), [Cu(2)(dmp)(2)(pnaa)](BF(4))(2) (3b) and [Cu(2)(dmp)(2)(pbbaa)](BF(4))(2) (4b) (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, pba = N,N-bis((diphenylphosphino)methyl)benzenamine, pbaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)benzene-1,4-diamine, pnaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)naphthalene-1,5-diamine and pbbaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)biphenyl-4,4'-diamine), were rationally designed and synthesized. These complexes were characterized by (1)H and (31)P NMR, electrospray mass spectrometry, elemental analysis and X-ray crystal structure analysis. Introduction of different central arene spacers (phenyl, naphthyl, biphenyl) into ligands, resulting in the size variation of these complexes, aims to tune the photophysical properties of the complexes. Each Cu(I) ion in these complexes adopts a distorted tetrahedral geometry constructed by the chelating diimine and phosphine groups. Intermolecular C-H···π and/or π···π interactions are involved in the solid states. The dmp-containing complex exhibits better emission relative to the corresponding phen complex due to the steric encumbrance of bulky alkyl groups. Furthermore, for complexes with identical diimine but different phosphine ligands, the tendency of increased emission lifetime as well as blue-shifted emission in the solid state follows with the decrease in size of complexes. Intermolecular C-H···π interactions have an influence on the final solid state photophysical properties through vibrationally relaxed non-radiative energy transfer in the excited state. Smaller-sized complexes show better photophysical properties due to less vibrationally relaxed behavior related to flexible C-H···π bonds. Nevertheless, the tendency for increased quantum yield and emission lifetime, as well as blue-shifted emission in dilute solution goes with the increase in size of complexes. The central arene ring (phenyl, naphthyl or biphenyl) has an influence on the final photophysical properties. The larger the π-conjugated extension of central arene ring is, the better the photophysical properties of complex are. The rigid and large-sized complex 3b, with a high quantum yield and long lifetime, is the best luminophore among these complexes.     

Isolation and identification of 2-isopropyl-5-methylphenol from Stellera chamaejasme and its insecticidal activity against Aphis craccivora and Pieris rapae

In this study, the root powder of Stellera chamaejasme was extracted with chloroform. The crude extract thus obtained was chromatographed several times with silica gel columns and finally one pure natural product was obtained. This product was identified as 2-isopropyl-5-methylphenol (thymol), which was separated for the first time from S. chamaejasme root. The results of a laboratorial bioassay showed that it had good insecticidal activity against Aphis craccivora and Pieris rapae. Its median lethal concentrations (LC50) (24 h after treatment) were 14.81 and 47.68 mg L(-1), respectively. This is the first time that the insecticidal activity of thymol against A. craccivora and P. rapae has been reported.     

Establishment of A431 cell membrane chromatography-RPLC method for screening target components from Radix Caulophylli

We describe here an analytical method of A431 cell membrane chromatography (A431/CMC) (CMC, cell membrane chromatography) combined with RPLC for recognition, separation, and identification of target components from traditional Chinese medicines (TCMs) Radix Caulophylli. The A431 cells with high expressed epidermal growth factor receptor (EGFR) were used to prepare the stationary phase in the CMC model. Retention fractions on the A431-CMC model were collected using an automated fraction collection and injection module (FC/I). Each fraction was analyzed by RPLC under the optimized conditions. Gefitinib and erlotinib were used as standard compounds to investigate the suitability and reliability of the A431 cell membrane chromatography-RPLC method prior to screening target component from Radix Caulophylli total alkaloids. The results indicated that caulophine and taspine were the target component acting on the epidermal growth factor receptor. This method could be an efficient way in drug discovery using natural medicinal herbs as a source of novel compounds.     

MARKOV CHAIN-BASED ANALYSIS OF THE DEGREE DISTRIBUTION FOR A GROWING NETWORK

In this article, we focus on discussing the degree distribution of the DMS model from the perspective of probability. On the basis of the concept and technique of first-passage probability in Markov theory, we provide a rigorous proof for existence of the steady-state degree distribution, mathematically re-deriving the exact formula of the distribution. The approach based on Markov chain theory is universal and performs well in a large class of growing networks.     

The ergodicity of stochastic generalized porous media equations with lévy jump

In this article,we first prove the existence and uniqueness of the solution to the stochastic generalized porous medium equation perturbed by Lévy process,and then show the exponential convergence of(pt)t≥0 to equilibrium uniform on any bounded subset in H.     

The kernel method and systems of functional equations with several conditions

We generalize the kernel method to equation systems in which the number of unknowns is allowed to exceed the number of equations. With this generalization, we derive the generating functions for several kinds of sequences and generating trees whose recursions are dependent on the parity of the indices.     

Fast and simple methods for the optimization of kurtosis used as a projection pursuit index

As a powerful method for exploratory data analysis, projection pursuit (PP) often outperforms principal component analysis (PCA) to discover important data structure. PP was proposed in 1970s but has not been widely used in chemistry largely because of the difficulty in the optimization of projection indices. In this work, new algorithms, referred as "quasi-power methods", are proposed to optimize kurtosis as a projection index. The new algorithms are simple, fast, and stable, which makes the search for the global optimum more efficient in the presence of multiple local optima. Maximization of kurtosis is helpful in the detection of outliers, while minimization tends to reveal clusters in the data, so the ability to search separately for the maximum and minimum of kurtosis is desirable. The proposed algorithms can search for either with only minor changes. Unlike other methods, no optimization of step size is required and sphering or whitening of the data is not necessary. Both univariate and multivariate kurtosis can be optimized by the proposed algorithms. The performance of the algorithms is evaluated using three simulated data sets and its utility is demonstrated with three experimental data sets relevant to analytical chemistry.     

The influence of acid demineralization on surface characteristics of black carbon and its sorption for pentachlorophenol

Acid treatment is a routine demineralization process to obtain black carbon (BC), but there has been little systematic research about its influence on BC's characteristics. In this study, elemental analysis, SEM, FTIR, and Boehm titration were used to investigate that effect. Our results showed that the acid treatment had little influence on the sorption of fly ash and soot to pentachlorophenol (PCP), but it greatly increased the sorption of rice chars to PCP. There were two competing effects of acid demineralization on the adsorption capacity of BC. On one hand, it increased the amount of the acidic functional groups, which decreased the adsorption capacity. On the other hand, it increased the surface and pore volume of BC and caused the emergence of hidden carbon enclosed by minerals, which in turn increased the sorptivity significantly. Especially for rice chars (600°C), after acid treatment, their surface area increased from 3.52 to 235 m(2) g(-1) and the sorption capacity coefficient increased from 2.12 to 4.10.