Two heptadentate Co(III) and Mn(III) complexes with partially deprotonated cyclen derivative bearing four hydroxypropyl pendants: structure,DNA binding and DNA cleavage

Two new complexes, (Co^III)₂(H₃L^?)₂(0.5H₂O)₂(ClO₄)₄ (I) and (Mn^III)₂(H₃L^?)₂(0.5H₂O)₂ (ClO₄)₄ (II), were synthesized and crystallographically characterized [H₄L = 1,4,7,10‐tetra‐(2‐hydroxypropyl)‐l,4,7,10‐tetraazacyclododecane] using electrospray ionization mass spectrometry and X‐ray photoelectron spectrometery. The characterizations confirmed that the valences of the metal ions increased from divalent to trivalent due to deprotonation of one OH group (H₄L was in the form of H₃L^?). Owing to the instability of Co(III) and Mn(III) in both air and in solution, they preferred to exist in divalent form. The two heptadentate complexes are extraordinary in that the chiral pendants of the complexes are different in configuration. Spectroscopic studies, viscosity measurements, thermal denaturation experiments and circular dichroism spectra demonstrated that the complexes were prone to interact with DNA by groove binding. At micromolar concentrations and under physiological conditions, the two complexes were able to oxidatively cleave the supercoiled pUC19 plasmid DNA into its nicked and linear forms. Mechanistic studies using various additives suggest the complexes had structures different from those of other inorganic complexes. These are the first reported inorganic complexes not containing planar aromatic ligands and yet binding at the major groove. Copyright © 2012 John Wiley & Sons, Ltd.     

Facile and Practical Synthesis of (R)‐6‐Br‐2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl

A new enantiopure 6‐monobromo‐substituted BINAP has been prepared via a one‐step nickel‐catalyzed coupling reaction in moderate yield. It is an important intermediate for asymmetric 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl (BINAP) derivatives. Its structure was elucidated by NMR spectral and elemental analysis.     

Finite-time H ∞ control for a class of Markovian jump delayed systems with input saturation

This work considers the finite-time control problem for a class Markovian jump delayed systems with partially known transition rates subject to saturating actuators. By employing local sector conditions and an appropriate Lyapunov–Krasovkii function, an observer-based state feedback controller is designed to guarantee that the resulted closed-loop constrained system is mean-square locally asymptotically finite-time stabilizable. Some sufficient conditions for the solution to this problem are derived in terms of linear matrix inequalities. Finally, a numerical example is provided to demonstrate the effectiveness of proposed method.     

Solution-processable graphenes by covalent functionalization of graphene oxide with polymeric monoamines

We develop here a simple wet chemistry to prepare covalent functionalized graphenes(FGs) through epoxide aminolysis especially under alkaline aqueous condition. Remarkably, a series of typical monoamines, such as industrial Huntsman Jeffamine~ M-2070 and M-2005 polymer with hydrophilic or hydrophobic polyetheramine chains, positively-charged 2-amino-N,N,Ntrimethylpropanaminium,negatively-charged sulfanilic acid, even oligopeptide sequence, can be effectively grafted on the platelets of graphene oxide precursor with covalent functionalization and partially reduced features. This strategy provides the researchers a facile and convenient approach to design and synthesize solution processable, biocompatible and functionalized graphenes for the potent applications in electronic inks, drug carriers and biomedicines. Expansion of the current study is actively ongoing in our laboratory.     

Development and validation of UPLC‐MS/MS method for determination of domperidone in human plasma and its pharmacokinetic application

A sensitive, rapid and selective ultra‐performance liquid chromatography–tandem mass spectrometric (UPLC‐MS/MS) method was developed for the determination and pharmacokinetic study of domperidone in human plasma. Diphenhydramine was used as the internal standard. Plasma sample pretreatment involved a one‐step liquid–liquid extraction with a mixture of diethyl ether–dichloromethane (3:2, v/v). The analysis was carried out on an Acquity UPLC^TM BEH C₁₈ column. The mobile phase consisted of methanol–water containing 10 mmol/L ammonium acetate and 0.5% (v/v) formic acid (60:40, v/v). The detection was performed on a triple quadrupole tandem mass spectrometer in multiple reaction monitoring mode via electrospray ionizationsource with positive mode. Each plasma sample was chromatographed within 2.1 min. The standard curves for domperidone were linear (r² ≥ 0.99) over the concentration range of 0.030–31.5 ng/mL with a lower limit of quantification of 0.030 ng/mL. The intra‐ and inter‐day precision (relative standard deviation) values were not higher than 13% and accuracy (relative error) was from ?7.6 to 1.2% at three quality control levels. The method herein described was superior to previous methods and was successfully applied to the pharmacokinetic study of domperidone in healthy Chinese volunteers after oral administration. Copyright © 2012 John Wiley & Sons, Ltd.     

Adsorption of thorium(IV) on magnetic multi-walled carbon nanotubes

The influences of pH, contact time, solid-liquid ratio, temperature and C60(C(COOH)2)n on Th(IV) adsorption onto the magnetic multi-walled carbon nanotubes(MMWCNTs) were studied by batch technique. The dynamic process showed that the adsorption of Th(IV) onto MMWCNTs could reach equilibrium in 40 h and matched the pseudo-second-order kinetics model. The adsorption of Th(IV) onto MMWCNTs was significantly dependent on pH values, the adsorption ratio increased markedly at pH 3.0–5.0, and then maintained a steady state as pH values increased. At low pH, different C60(C(COOH)2)n content could enhance the adsorption content of Th(IV) onto MMWCNTs, but restrained it at higher pH. Through simulating the adsorption isotherms by Langmuir, Freundlich and Dubini-Radushkevich models, it could be seen respectively that the adsorption pattern of Th(IV) onto MMWCNTs was mainly surface complexation, and that the adsorption process was endothermic and irreversible.