An improved LC–MS/MS method for determination of docetaxel and its application to population pharmacokinetic study in Chinese cancer patients

Because of its unpredictable side effects and efficacy, the anticancer drug docetaxel (DTX) requires improved characterisation of its pharmacokinetic profiles through population pharmacokinetic studies. A sensitive and rugged LC–MS/MS method for the detection of DTX in human plasma was developed and optimised using paclitaxel as an internal standard (IS). The plasma samples underwent rapid extraction using hybrid solid-phase extraction-protein precipitation. The analyte and IS were separated with an isocratic system on a Zorbax Eclipse Plus C₁₈ column using water containing 0.05% acetic acid along with 20 μM of sodium acetate and methanol (30/70, v/v) as the mobile phase. Quantification was performed using a triple quadrupole mass spectrometer through multiple reaction monitoring in positive mode, using the m/z 830.3 → 548.8 and m/z 876.3 → 307.7 transitions for DTX and paclitaxel, respectively. The range of the calibration curve was 1–500 ng/mL for DTX, and the linear correlation coefficient was >0.99. The accuracies ranged from −4.6 to 4.2%, and the precision was no higher than 7.0% for the analytes. No significant matrix effect was observed. Both DTX and the IS showed considerable recovery. This method was finally applied to the establishment of a population pharmacokinetic model to optimise the clinical use of DTX.     

Bimetallic Covalent Organic Frameworks for Constructing Multifunctional Electrocatalyst

Covalent organic frameworks (COFs) are a new class of crystalline porous polymers comprised mainly of carbon atoms, and are versatile for the integration of heteroatoms such as B, O, and N into the skeletons. The designable structure and abundant composition render COFs useful as precursors for heteroatom-doped porous carbons for energy storage and conversion. Herein, we describe a multifunctional electrochemical catalyst obtained through pyrolysis of a bimetallic COF. The catalyst possesses hierarchical pores and abundant iron and cobalt nanoparticles embedded with standing carbon layers. By integrating these features, the catalyst exhibits excellent electrochemical catalytic activity in the oxygen reduction reaction (ORR), with a 50 mV positive half-wave potential, a higher limited diffusion current density, and a much smaller Tafel slope than a Pt-C catalyst. Moreover, the catalyst displays superior electrochemical performance toward the hydrogen evolution reaction (HER), with overpotentials of −0.26 V and −0.33 V in acidic and alkaline aqueous solution, respectively, at a current density of 10 mA cm⁻². The overpotential in the catalysis of the oxygen evolution reaction (OER) was 1.59 V at the same current density.     

Electrical and Thermal Transport Properties of n-type Bi6Cu2Se4O6 (2BiCuSeO + 2Bi2O2Se)

New thermoelectric materials, n-type Bi₆Cu₂Se₄O₆ oxyselenides, composed of well-known BiCuSeO and Bi₂O₂Se oxyselenides, are synthesized with a simple solid-state reaction. Electrical transport properties, microstructures, and elastic properties are investigated with an emphasis on thermal transport properties. Similar to Bi₂O₂Se, it is found that the halogen-doped Bi₆Cu₂Se₄O₆ possesses n-type conducting transports, which can be improved via Br/Cl doping. Compared with BiCuSeO and Bi₂O₂Se, an extremely low thermal conductivity can be observed in Bi₆Cu₂Se₄O₆. To reveal the origin of low thermal conductivity, elastic properties, sound velocity, Grüneisen parameter, and Debye temperature are evaluated. Importantly, the calculated phonon mean free path of Bi₆Cu₂Se₄O₆ is comparable to the interlayer distance for BiO─CuSe and BiO─Se layers, which is ascribed to the strong interlayer phonon scattering. Contributing from the outstanding low thermal conductivity and improved electrical transport properties, the maximum ZT ≈0.15 at 823 K and ≈0.11 at 873K are realized in n-type Bi₆Cu₂Se_3.2Br_0.8O₆ and Bi₆Cu₂Se_3.6Cl_0.4O₆, respectively, indicating the promising thermoelectric performance in n-type Bi₆Cu₂Se₄O₆ oxyselenides.     

Metabolic profiles of dioscin in rats revealed by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry

Dioscin (DIS), one of the most abundant bioactive steroidal saponins in Dioscorea sp., is used as a complementary medicine to treat coronary disease and angina pectoris in China. Although the pharmacological activities and pharmacokinetics of DIS have been well demonstrated, information regarding the final metabolic fates is very limited. This study investigated the in vivo metabolic profiles of DIS after oral administration by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry method. The structures of the metabolites were identified and tentatively characterized by means of comparing the molecular mass, retention time and fragmentation pattern of the analytes with those of the parent compound. A total of eight metabolites, including seven phase I and one phase II metabolites, were detected and tentatively identified for the first time. Oxidation, deglycosylation and glucuronidation were found to be the major metabolic processes of the compound in rats. In addition, a possible metabolic pathway on the biotransformation of DIS in vivo was proposed. This study provides valuable and new information on the metabolism of DIS, which will be helpful for further understanding its mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd.     

三能级钾原子气体三维傅里叶变换频谱的解析解

利用投影切片定理、傅里叶位移定理和误差函数给出三能级钾原子气体三维傅里叶变换频谱在T=0界面的解析解.固定均匀线宽,非均匀展宽和对角线相关系数可以定量地识别,通过在适当方向上拟合三维傅里叶变换频谱谱峰的切片来确定.结果表明,非均匀展宽增大,频谱图沿着对角线方向延伸,对角线相关系数增大,频谱图逐渐变圆,振幅也逐渐变小.     

Surface Modification of Cu-SSZ-13 with CeO2 to Improve the Catalytic Performance for the Selective Catalytic Reduction of NO with NH3

Kinetics and Catalysis - A series of Cu-SSZ-13@CeO2 catalysts with surface modification with CeO2 was prepared by the modified self-resemble method based on the one-pot synthesized Cu-SSZ-13...     

Utilizing the Space‐Charge Region of the FeNi‐LDH/CoP p‐n Junction to Promote Performance in Oxygen Evolution Electrocatalysis

The modulation of electron density is an effective option for efficient alternative electrocatalysts. Here, p‐n junctions are constructed in 3D free‐standing FeNi‐LDH/CoP/carbon cloth (CC) electrode (LDH=layered double hydroxide). The positively charged FeNi‐LDH in the space‐charge region can significantly boost oxygen evolution reaction. Therefore, the j at 1.485 V (vs. RHE) of FeNi‐LDH/CoP/CC achieves ca. 10‐fold and ca. 100‐fold increases compared to those of FeNi‐LDH/CC and CoP/CC, respectively. Density functional theory calculation reveals OH^? has a stronger trend to adsorb on the surface of FeNi‐LDH side in the p‐n junction compared to individual FeNi‐LDH further verifying the synergistic effect in the p‐n junction. Additionally, it represents excellent activity toward water splitting. The utilization of heterojunctions would open up an entirely new possibility to purposefully regulate the electronic structure of active sites and promote their catalytic activities.