Electrochemical and electronic properties of LiCoO2 cathode investigated by galvanostatic cycling and EIS

The processes of extraction and insertion of lithium ions in LiCoO(2) cathode are investigated by galvanostatic cycling and electrochemical impedance spectroscopy (EIS) at different potentials during the first charge/discharge cycle and at different temperatures after 10 charge/discharge cycles. The spectra exhibit three semicircles and a slightly inclined line that appear successively as the frequency decreases. An appropriate equivalent circuit is proposed to fit the experimental EIS data. Based on detailed analysis of the change in kinetic parameters obtained from simulating the experimental EIS data as functions of potential and temperature, the high-frequency, the middle-frequency, and the low-frequency semicircles can be attributed to the migration of the lithium ions through the SEI film, the electronic properties of the material and the charge transfer step, respectively. The slightly inclined line arises from the solid state diffusion process. The electrical conductivity of the layered LiCoO(2) changes dramatically at early delithiation as a result of a polaron-to-metal transition. In an electrolyte solution of 1 mol L(-1) LiPF(6)-EC (ethylene carbonate)?:DMC (dimethyl carbonate), the activation energy of the ion jump (which is related to the migration of the lithium ions through the SEI film), the thermal activation energy of the electrical conductivity and the activation energy of the intercalation/deintercalation reaction are 37.7, 39.1 and 69.0 kJ mol(-1), respectively.     

Recent progress on switchable rotaxanes

Switchable rotaxanes are currently attracting considerable attention from chemists, physicists and materials scientists because of their potential to perform relative inter-component positional changes in response to external stimuli and the potential applications in the fields such as molecular machines, molecular switches, molecular logic gates and memory devices. This tutorial review summarizes recent work on switchable rotaxanes and their potential applications.     

基于光谱成像技术对中药黄柏煎煮实验的研究

煎煮中药的目的在于使药材中的活性成分充分析出,从而最大发挥中药治疗疾病的功效。为了检测药材在煎煮过程中活性成分的溶出度变化情况,运用光谱成像技术,以中药材黄柏为例,检测了其在煎煮过程中不同时刻的荧光强度,分析结果从侧面反映了黄柏活性成分的溶出度规律。     

Investigating the binding interaction of azur A with hyaluronic acid via spectrophotometry and its analytical application

The interaction between azur A (AA) and hyaluronic acid (HA) at AA concentrations from 3.430×10^–5 to 8.575×10^–5 M and sodium chloride concentrations from 0 to 0.01 M was investigated spectrophotometrically at 620 nm at temperatures from 0 to 50 °C. AA was shown to be a useful spectroscopic probe for detecting carboxyl groups in HA macromolecules. The interaction between AA and HA was temperature sensitive and little AA–HA interaction was observed at temperatures higher than 30 °C. The interaction of HA with AA was seen to be electrostatic in nature. The maximum binding number decreased with decreasing NaCl concentration, and the absorbance sensitivity decreased with increasing NaCl concentration in aqueous solution. Self-interference from the AA in the AA–HA interaction caused an overestimate of the molar mass of hyaluronic acid. An improved method was proposed to estimate the molar mass of HA, and a molar mass of 1.219×10⁶ Da was obtained with this improved method for HA.     

Highly regioselective synthesis of 2,3,4-trisubstituted 1H-pyrroles: a formal total synthesis of lukianol A

A combined use of alpha-lithiation and nucleophilic substitutions of N,N-dimethyl 3,4-bis(trimethylsilyl)-1H-pyrrole-1-sulfonamide 8c led to several 2-substituted 3, 4-bis(trimethylsilyl)-1H-pyrrole-1-sulfonamides. Utilizing the beta-effect of a trimethylsilyl group, a highly regioselective synthesis of 2,3,4-trisubstituted 1H-pyrroles 23 and 34 was accomplished. The marine natural product lukianol A (3) was prepared utilizing this strategy.     

Large-scale identification of human biliary proteins from a cholesterol stone patient using a proteomic approach

Gallbladder bile, one of the most important body fluids, is composed of water, inorganic ions, conjugated bile salts, phospholipids, cholesterol, bilirubin, mucin and proteins. The separation and identification of bile proteins remain difficult due to the complexity of this matrix. In the present study, human gallbladder bile was obtained from a cholesterol stone patient, and the proteins were isolated and purified by dialysis, precipitation and delipidation procedures. The resulting proteins were divided into several aliquots. One aliquot was subjected to two-dimensional gel electrophoresis (2DE). The protein spots were then in-gel digested and analyzed by liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). Another aliquot was directly digested and analyzed by a combination of strong cation-exchange (SCX) and reversed-phase (RP) chromatography prior to tandem mass spectrometry (2D-LC/MS/MS). Eventually, 48 and 218 unique proteins were identified from 2DE/MS and 2D-LC/MS/MS, respectively, resulting in a total of 222 unique identified proteins. Of the 218 proteins identified by 2D-LC/MS/MS, 92 were identified based on more than one unique tryptic peptide, and, of the total 222 proteins, 98 were identified based on more than one unique tryptic peptide.     

Simultaneous quantitation of dexmedetomidine and glucuronide metabolites (G-Dex-1 and G-Dex-2) in human plasma utilizing liquid chromatography with tandem mass spectrometric detection

Dexmedetomidine (Dex) (Precedex) is a novel lipophilic imidazole derivative with a high affinity for alpha-2 adrenergic receptors, which exhibits sedative, analgesic-sparing, and sympatholytic properties. The pharmacological effects and therapeutic benefits of this drug have drawn continued interest from the medical community. Here we report a liquid chromatography/tandem mass spectrometry (LC/MS/MS) method to simultaneously measure the concentrations of dexmedetomidine and its glucoronide metabolites, G-Dex-1 and G-Dex-2, in human plasma samples. A solid-phase extraction method was developed to effectively extract Dex, G-Dex-1, and G-Dex-2 from plasma matrices. An isocratic chromatographic method was developed to achieve baseline separation of G-Dex-1 and G-Dex-2. The linear dynamic range evaluated was 19.08-1908.56 pg/mL for Dex, 65.17-6518.17 pg/mL for G-Dex-1, and 29.42-2943.28 pg/mL for G-Dex-2. The linear correlation coefficient (r) ranged from 0.9944-0.9979 for Dex, from 0.9966-0.9984 for G-Dex-1, and from 0.9939-0.9966 for G-Dex-2. The intra-assay coefficient of variation (CV) was between 2.5-12.5% for Dex, between 5.2-11.0% for G-Dex-1, and between 3.5-12.1% for G-Dex-2. The inter-assay precision of QC samples give % CV ranges from 6.5-9.3% for Dex, from 7.1-10.6% for G-Dex-1, and from 8.2-10.2% for G-Dex-2. The inter-assay accuracies ranged from 102.0-109.3% for Dex, from 95.4-105.6% for G-Dex-1, and from 98.7-115.0% for G-Dex-2.     

LC-MS/MS determination of 2-(4-((2-(2S,5R)-2-Cyano-5-ethynyl-1-pyrrolidinyl)-2-oxoethylamino)-4-methyl-1-piperidinyl)-4-pyridinecarboxylic acid (ABT-279) in dog plasma with high-throughput protein precipitation sample preparation

As an effective DPP-IV inhibitor, 2-(4-((2-(2S,5R)-2-Cyano-5-ethynyl-1-pyrrolidinyl)-2-oxoethylamino)-4-methyl-1-piperidinyl)-4-pyridinecarboxylic acid (ABT-279), is an investigational drug candidate under development at Abbott Laboratories for potential treatment of type 2 diabetes. In order to support the development of ABT-279, multiple analytical methods for an accurate, precise and selective concentration determination of ABT-279 in different matrices were developed and validated in accordance with the US Food and Drug Administration Guidance on Bioanalytical Method Validation. The analytical method for ABT-279 in dog plasma was validated in parallel to other validations for ABT-279 determination in different matrices. In order to shorten the sample preparation time and increase method precision, an automated multi-channel liquid handler was used to perform high-throughput protein precipitation and all other liquid transfers. The separation was performed through a Waters YMC ODS-AQ column (2.0 x 150 mm, 5 microm, 120 A) with a mobile phase of 20 mm ammonium acetate in 20% acetonitrile at a flow rate of 0.3 mL/min. Data collection started at 2.2 min and continued for 2.0 min. The validated linear dynamic range in dog plasma was between 3.05 and 2033.64 ng/mL using a 50 microL sample volume. The achieved r(2) coefficient of determination from three consecutive runs was between 0.998625 and 0.999085. The mean bias was between -4.1 and 4.3% for all calibration standards including lower limit of quantitation. The mean bias was between -8.0 and 0.4% for the quality control samples. The precision, expressed as a coefficient of variation (CV), was < or =4.1% for all levels of quality control samples. The validation results demonstrated that the high-throughput method was accurate, precise and selective for the determination of ABT-279 in dog plasma. The validated method was also employed to support two toxicology studies. The passing rate was 100% for all 49 runs from one validation study and two toxicology studies.     

A highly organocatalytic stereoselective double Michael reaction: efficient construction of optically enriched spirocyclic oxindoles

An effective double Michael reaction has been disclosed to access spirocyclic oxindoles in high yields (up to 98%) and excellent enantioselectivities (up to 98% ee).