SIMULTANEOUS QUANTIFICATION OF NINE BIOACTIVE CONSTITUENTS IN DENGZHANXIXIN INJECTION BY UPLC-MS/MS

In this study, a rapid and comprehensive ultra-performance liquid chromatography/tandem mass spectrometry (UPLC-MS/MS) method was developed for simultaneous determination of nine major bioactive constituents in Dengzhanxixin injection. The chromatographic separations were obtained on an Acquity UPLC BEH C18 column (50 mm × 2.1 mm I.D., 1.7 μm) by a linear gradient elution with the mobile phase consisting of A (water and 0.6% acetic acid) and B (acetonitrile and 0.6% acetic acid). The total analytical run time was relatively short (14 min). The analytes and two internal standards (ISs) were all monitored in a selected-ion reaction (SIR) mode with a negative electrospray ionization (ESI^?) interface. The calibration curves of all analytes revealed good linear regression (r² ≥ 0.9972) within test ranges. This method provided good precision with RSD of intra- and interday variation less than 1.26% and 2.51%, respectively. The validated method was then applied to quantify the nine major constituents in six batches of Dengzhanxixin injection, and the results indicated that the established method could be considered as an improved tool for quality control of Dengzhanxixin Injection.     

CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION OF TRACE AMOUNTS OF ETHYLENEDIAMINETETRAACETIC ACID BASED ON ITS CATALYTIC EFFECT ON THE REACTION OF RHODAMINE B AND POTASSIUM DICHROMATE

A new method for the determination of trace ethylenediaminetetraacetic acid (EDTA) was developed using catalytic kinetic spectrophotometry based on the principle that in the medium of 0.10 mol/L sulfuric acid, trace EDTA has a catalytic effect on the oxidation of rhodamine B by potassium dichromate, and a suitable amount of 6.0 mol/L NaOH solution can inhibit the catalytic reaction. At the maximum absorption wavelength of 546 nm, the linear range for the determination of EDTA was shown over the concentration range 5.0 × 10^?5–7.0 × 10^?4 mol/L and the detection limit of this method for EDTA was 0.0501 mmol/L. The linear regression equation for the determination of EDTA and regression coefficient were ΔA = 512C (C: mol/L) + 0.0966, γ = 0.9993, respectively. The apparent activation energy of the catalytic reaction was 81.57 KJ/mol. The proposed method has been successfully applied to the determination of trace ethylenediaminetetraacetic acid in water and apple tinned foodstuff samples with satisfactory results. The relative standard deviation of 13 replicate determinations of EDTA was 1.15–2.37% and the recovery of the method was 99.90–102.7%, respectively. The determined results were in good agreement with that of established method Fe(III)-H₂O₂-bromothymol blue system inhibitory-kinetic spectrophotometry.     

STUDY ON THE INCLUSION INTERACTION BETWEEN SULFOBUTYLETHER-β-CYCLODEXTRIN AND CLOZAPINE BY FLOW INJECTION CHEMILUMINESCENCE

The inclusion interaction of sulfobutylether-β-cyclodextrin with clozapine was studied using flow injection chemiluminescence and molecular docking. By use of a homemade flow injection chemiluminescence model of lg[(I ₀?I _s)/I _s] = lgK + nlg[C _clozapine], the formation constant K, the stoichiometric ratio n, and thermodynamic parameters between sulfobutylether-β-cyclodextrin and clozapine were obtained. Results showed that the inclusion forming process of sulfobutylether-β-cyclodextrin/clozapine with a stoichiometric ratio of 1:1 was spontaneous through hydrophobic interaction. The molecular docking results showed that clozapine entered into the cavity of sulfobutylether-β-cyclodextrin with one hydrogen bond. Based on the good linear relationship of quenching of chemiluminescence intensity versus the logarithm of concentration between 0.07 and 50.0 ng mL^?1, a flow injection chemiluminescence method for clozapine was established for the first time with a detection limit of 0.02 ng mL^?1 (3σ). The proposed method was successfully applied for the determination of clozapine in spiked human urine and serum samples, with recoveries from 92.1–108.2% and relative standard deviations less than 2.7%.     

液质联用法快速鉴定头孢丙烯及7-APRA的Z/E异构体

应用液相色谱-质谱联用技术建立了快速分离鉴定头孢丙烯及合成中间体7-氨基-3-[烯丙-1-基]-3-头孢环-4-羧酸（7-APRA）Z/E异构体的方法。7-APRA去氢离子在二级质谱中均发生丢失H₂S和OCNH的碎裂反应,产生碎片离子m/z 161和m/z 152。由于7-APRA Z异构体能发生氢转移,从而促使H₂S丢失,故Z异构体产物离子丰度比（I161/I152）明显高于E异构体,这一特征可以用于异构体的质谱识别。类似地,由于头孢丙烯Z异构体易断裂,因此更容易形成含有稳定苯酚基团的m/z 205碎片离子。为了给实验结果提供理论支持,使用密度泛函理论（DFT）量子计算对7-APRA异构体的构型进行优化,并对可能的碎裂机理进行探讨。     

A GREEN METHOD FOR THE DETERMINATION OF CHROMIUM(VI) AND IRON(III) IN WATER BY SEQUENTIAL INJECTION ANALYSIS AND SPECTROPHOTOMETRIC DETECTION

In this article, an organic-reagent-free method was described for the determination of Cr(VI) and Fe(III) by double-system double-wavelength sequential injection technique with a single sample injection. In this approach, the determination of Cr(VI) was based on the detection of a blue unstable intermediate compound resulting from the reaction of Cr(VI) with hydrogen peroxide, and the determination of Fe(III) was based on the color reaction of Fe(III) with thiocyanate in acidic medium. Sequential injection analysis (SIA) parameters, including spacer solution volume, aspiration order, aspiration volumes, flow rate, acid medium, solution acidity, and reagent concentrations, were optimized. The linear range for the determination was 3.0–60.0 μg mL^?1 for Cr(VI) and 1.0–40.0 μg mL^?1 for Fe(III), respectively. The limit of detection (LOD) was 0.6 μg mL^?1 for Cr(VI) and 0.2 μg mL^?1 for Fe(III), and the limit of quantitation (LOQ) was 2.0 μg mL^?1 for Cr(VI) and 0.67 μg mL^?1 for Fe(III). The total volume of the reagent consumed in each determination was only 0.11 mL. The proposed method was applied to the simultaneous determination of Cr(VI) and Fe(III) in electroplating wastewater and environmental waters. The results were in good agreement with those obtained by atomic absorption spectrometry. The recoveries were in the range of 97.5–101.1%.     

Evaluation of Halogen‐Specific Detector (XSDTM) for Trace Analysis of Chlorinated Fatty Acids in Fish

Abstract

The applicability of a halogen‐specific detector (XSD?, manufactured by OI Analytical) was evaluated for GC analysis of chlorinated fatty acid methyl esters (FAMEs) that are present at trace levels in transesterified fish extract, a complex matrix consisting of similar but nonchlorinated compounds. A characteristic of the XSD working principle is that thermal electron emission, negative surface ionization and positive surface ionization are all operative in a concerted manner. While the XSD is not superior to other GC detectors in terms of signal‐to‐noise, its merit is in its high selectivity (10⁶) and low detection limit (2 pg Cl) for chlorinated fatty acids, and ease of operation and maintenance. Its reasonably wide linear range (up to 10 ng Cl) is desirable for trace analysis of chlorinated FAMEs. A major drawback of this detector is a certain degree of peak broadening and peak tailing of eluted compounds with concentrations larger than ～1 ng Cl/µL in the injected solution even though this value does not exceed the upper limit of the XSD linear range. Nevertheless, in trace analysis of chlorinated compounds, the concentrations of analytes are usually well below 1 ng Cl/µL. Parallel use of the XSD and a universal detector such as FID in gas chromatography is useful for optimizing operation conditions for trace analysis and simultaneously analyzing nonchlorinated major components.     

1‐Pyrenemethanol,a Useful Fluorometric Reagent for the Detection and Determination of Carboxylic Acids in Atmospheric Samples

Abstract

A rapid fluorometric procedure for the selective and sensitive determination of carboxylic acids, based on pre‐column derivatization using 1‐pyrenemethanol, was optimized and applied to atmospheric sampling. The optimum conditions for derivatization were determined to be: reaction solvent–dichloromethane, temperature ?44°C, reaction time ?30 min, and reagent/total acid ratio ?15. Separation of the derivatives of acids up to twenty carbons by reversed‐phase (C₈) chromatography was achieved in 25 min using a water/acetonitrile gradient with a limit of detection for the derivatives of 20 pg for a 20 µL injection. A scanning detector with good spectral resolution allows qualitative identification of the components in complex samples. When used in atmospheric analysis, the recoveries of carboxylic acids from spiked samples were >80% with repeatabilities below 10% RSD. Low molecular weight acids were encountered predominantly in the vapor phase (0.20 to 92 ng/m³), whereas higher molecular weight acids were found mostly in particulate form (0.15–129 ng/m³).     

CERIUM(IV)-BASED CHEMILUMINESCENCE OF FELODIPINE SENSITIZED BY RHODAMINE 6G

A simple, rapid, and sensitive flow injection chemiluminescence (FI-CL) method was proposed for the determination of felodipine. The method was based on the CL-emitting reaction between the studied drug and cerium(IV) in a nitric acid medium and measurement of the CL intensity produced by rhodamine 6G used as a sensitizer. Under the optimum conditions, the proposed procedure had a linear range between 5.0 × 10^?9 and 7.0 × 10^?6 g mL^?1, with a detection limit of 2.0 × 10^?9 g mL^?1. The relative standard deviation was 2.3% for 1.0 × 10^?7 g mL^?1 felodipine solution (n = 11). It was applied to the determination of felodipine in pharmaceutical preparations and biological fluids with satisfactory results. The possible mechanism of the chemiluminescence reaction was also discussed briefly.     

The Finite Element Method in Tribological Studies of Polymer Materials in Tribo-Pair with the Oxide Layer

We present an approach to the analysis of mechanisms of the tribological contact of a thin Al₂O₃ oxide layer formed under hard anodizing conditions on a plate made of the aluminium alloy EN AW-5251. The oxidation of the 50-μm ceramic layer was carried out for 60 min in a three-component electrolyte (SAS), a three-component electrolyte consisting of adipic, sulphuric and oxalic acid, at a temperature of 298.15 K and a current density of 3 A/dm². A three-dimensional oxide coating model, based on the computer analysis of images from a scanning electron microscope, is proposed. Tribological tests of stresses, strains and dislocations formed in the oxide layer and in the sample material (a block) were conducted. Modified polytetrafluoroethylene (TG15, TGK20/5, TMP12) and polyetheretherketone with carbon fibre and graphite were used as samples for tests in the tribological couple rider-plate of a linear reciprocating friction tester. A tribological couple modelled in the Solid Edge CAD programme was subjected to numerical analyses using the finite element method in the Autodesk Simulation Multiphysics programme under conditions consistent with actual conditions for contact pressures of 0.25, 0.50, and 1.0 MPa.     

SURFACTANT MEDIATED EXTRACTION OF TRITERPENES AND THEIR DIRECT HPLC ANALYSIS FROM THE MICELLAR SYSTEM

The pentacyclic triterpenes oleanolic acid (OA) and ursolic acid (UA) in Salvia triloba are attractive ingredients for cosmetic and pharmaceutical formulations. These triterpenoids are constitution isomers and differ only in the position of one methyl group in their chemical structures. Therefore it is difficult to achieve a baseline separation by standard RP-HPLC systems. Another challenge is that the complex plant contains a large variety of similar compounds. To achieve precise results for the target molecules, these compounds should be removed prior to analysis. Due to the large application of these two triterpenes, a fast quantification method is favored. If the triterpenes are extracted with aqueous two-phase systems, the target substances are enriched in a surfactant-rich phase. For this application, it is desirable to develop a method that is capable of quantifying both triterpenes directly by RP-HPLC without additional purification steps.

The optimal chromatographic conditions for pure substances as well as for crude surfactant-containing extracts were accomplished on a Nucleodur C18 ISIS column by isocratic elution with methanol/water/acetic acid/triethanolamine (90:10:0.04:0.02 v/v) as the mobile phase and a column temperature of 10°C. The flow rate was 0.6 mL/min, and the detection wavelength was 210 nm. With these parameters, a baseline separation was achieved and the calibration curve showed a very good linearity (R² > 0.999 for OA and UA) within the test range. The method is simple, rapid, and reliable for the quantification of crude extracts from plant material.     

DETERMINATION AND SEPARATION MECHANISM OF ACRYLAMIDE BY HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY

High-performance liquid chromatography using the negative peak method was developed for the determination and separation of acrylamide in food with methanol-water containing a background reagent of 0.01 mmol L^?1 5-sulfosalicylic acid (15/85, v/v) as the mobile phase with an ultraviolet-visible detector (λ_sig = 320 nm, λ_ref = 210 nm). The method was simple, the correlation coefficients exceeded 0.9990, and the limit of detection for acrylamide was 0.07 μg kg^?1. The concentrations of acrylamide in food were between 81 and 910 μg kg^?1. The recoveries were greater than 81.0% and the relative standard deviation was between 0.24 and 3.6%. The results showed that this method was suitable for the determination of acrylamide in food.     

DETERMINATION OF PICOMOLE CONCENTRATIONS OF ALUMINUM (III) IN HUMAN SALIVA AND URINE BY A LUMINOL-CARBOXYMETHYL CHITOSAN CHEMILUMINESCENCE SYSTEM

A luminol–carboxymethyl chitosan (CMCS) system was established using flow injection chemiluminescence (CL) based on the enhancing effect of CMCS on the luminol–dissolved oxygen reaction. The CL intensity was linear with the CMCS concentration ranging from 0.01–30.0 µM. Al(III) was shown to quench the CL of the luminol–CMCS reaction, and the decrease of CL intensity was linear with the logarithm of Al(III) concentration over the range from 10–1000 pM with a detection limit of 3.5 pM (3σ). At a flow rate of 2.0 mL min^?1, the analysis was performed within 30 s. The proposed CL method was successfully applied to the determination of picomole levels Al(III) in human saliva and urine after oral intake of two aluminum hydroxide tablets, with recoveries from 90.6–108.7% and relative standard deviations <3% (n = 5). The results indicated that the excreted Al(III) in saliva and urine reached its maximum values at 3 hr and 2 hr, and the total excretive ratio were 1.24 × 10^?3% and 3.45% in 6 hr and 12 hr, respectively. The elimination rate constant k and the half–life time t _1/2 in human saliva and urine were 0.3747 hr^?1, 1.8495 hr, 0.7132 hr^?1, and 0.9717 hr, respectively. The possible CL mechanism of the luminol–CMCS–Al(III) reaction is discussed.     

Novel determination of caffeine in human urine by direct analysis in real time mass spectrometry

Determination of caffeine is necessary for clinical research. A new method for the determination of caffeine in human urine was established by direct analysis in real time mass spectrometry using multiple reaction monitoring. The m/z 195.1 to 138.1 amu transition was employed in positive ionization mode. The preparation and analysis conditions were systemically optimized. The calibration curve was linear from 0.5–50 µg/mL with a limit of detection limit of 0.2 µg/mL. Intra-day and inter-day accuracy and precision were within the acceptable limits of ±15% at all concentrations. Moreover, the matrix effects for the determination of caffeine were evaluated. In conclusion, a simple, rapid, and reliable method without complex sample preparation and chromatographic separation was developed and validated for the determination of caffeine in human urine.     

A PORTABLE FLOW INJECTION ANALYZER FOR THE IN SITU DETERMINATION OF FILTERABLE REACTIVE PHOSPHORUS (FRP) IN FRESHWATER

The development and deployment of a portable flow injection analyzer for continuous, real-time monitoring of filterable reactive phosphorus (FRP) in the Tamar catchment is described. The optimized method can be used for the determination of FRP in freshwater systems (4–150 μg L^?1 P) and is capable of sampling with high temporal resolution (up to 15 samples h^?1). The analyzer, fitted with a pre-filter and an in-line membrane filter (0.45 μm, cellulose acetate), was used in situ (bank-side and shipboard deployment) to provide real-time FRP data and in the laboratory to determine FRP in freshwater samples. The portable FRP analyzer was reproducible (RSD < 5%; n = 3) over the range 4–150 μg L^?1 P and accurate, achieving good agreement with a laboratory based air-segmented continuous flow analyzer reference method for a range of freshwater samples from the Tamar catchment in SW England.     

Spectrophotometric Determination of Silicon in Rice and Alloy Steel Samples

Abstract

In the medium of 0.128 mol/L nitric acid and 0.450 mol/L sulfuric acid, silicon(IV) and ammonium molybdate form molybdosilicate blue blue complex in the presence of ascorbic acid. The maximum absorption wavelength of the complex locates at 810 nm. The apparent molar absorptivity is ε_810 nm = 3.18 × 10⁴ L · mol^?1 · cm^?1. Beer's law is followed over the range of 0 ～ 1.0 µg/mLof silicon(IV). The present method has been successfully applied to the determination of silicon in rice and alloy steel samples.     

A HYDROGEN PEROXIDE SENSOR BASED ON PRUSSIAN BLUE AND DNA-MODIFIED ELECTRODE

The polyvinylpyrrolidone (PVP) protected Prussian blue (PB) nanoparticles were prepared for use as a sensor for the catalytic reduction of hydrogen peroxide. The nanoparticles were used to modify a gold electrode, which was applied to detect hydrogen peroxide. Impedance spectra and differential pulse voltammetry were applied to detect the performance of the novel electrode and its response to H₂O₂ and Ramos cell smash fluid. Under the optimized experimental conditions, hydrogen peroxide was detected in a linear range of 6.25 × 10^?7 to 1.0 × 10^?5 mol · L^?1, and the detection limit was 7.12 × 10^?8 mol · L^?1 according to 3σ rule. Under the same conditions, hydrogen peroxide was determined in Ramos cell smash fluid with a linear range from 400–80000 mol mL^?1, with a detection limit of 114 mL^?1 according to 3σ rule. The modified electrode with Prussian blue nanoparticles displayed high sensitivity, good reproducibility, and long-term stability to hydrogen peroxide.     

DETERMINATION OF FLAVONES IN LOPHATHERUM GRACILE BY LIQUID CHROMATOGRAPHY TANDEM MASS SPECTROMETRY

Lophatherum gracile Brongn. (L. gracile) has been used for food and medicine in China for thousands of years. Flavonoids are one of the main bioactive components of this herb. A reliable method was established using liquid chromatography with tandem mass spectrometry to determine the concentrations of seven flavonoids. The separation was performed using a C₁₈ column at 40°C and the mobile phase was a mixture of methanol and 0.3% formic acid (v/v) in water in gradient elution mode at a flow rate of 1 mL/min. Quantification was performed through tandem mass spectrometry with negative electrospray ionization and multiple reaction monitoring at m/z [M-H]^?. The method was validated using calibration curves, limits of detection and quantification, precision, repeatability, stability, and accuracy. Seven compounds in eleven samples were determined, and there were significant differences in the concentrations of isoorientin, swertiajaponin, afzelin, luteolin-7-O-β-D-glucoside, vitexin, isovitexin, and swertisin. The established method is suitable for quality control for the analysis of L. gracile, as well as to provide necessary information for the rational utilization of L. gracile resources.     

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Determination of Ammonia in Seawater by Multichannel Flow Injection Analysis

An analytical method that uses multichannel flow injection is reported to determine ammonia in seawater. The sample throughput was twenty-eight samples per hour. The linear dynamic range for ammonia was from 20.0–1000.0 μg N · L^?1 with a limit of detection of 0.27 μg N · L^?1, and recovery values between 98.1% and 104.6%. The relative standard deviation values for nitrogen as ammonia were 2.15–3.33% (n = 6). Statistical t-test analysis indicated that analysis by the flow injection method provided results that were statistically the same as standard procedures. The reported method was suitable for the determination of ammonia in seawater.     

KINETIC SPECTROPHOTOMETRIC DETERMINATION OF TRACE AMOUNT OF EUROPIUM BASED ON ITS INHIBITORY EFFECT OF THE OXIDATION OF SWITZERLAND PIGMENT BY POTASSIUM BROMATE

In 4.0 × 10^?3 mol/L of hydrogen chloride medium, a trace of europium(III) plays a good inhibitory role in the fading reaction of Switzerland pigment oxidized by potassium bromate. Based on this principle, an inhibitory kinetic spectrophotometric method for the determination of trace europium was developed. A maximum absorption wavelength locates at 600 nm and a good linear range is presented over 0 – 0.18 µg/mL of europium(III) under the optimum conditions. The regression equation for the determination of europium(III) is ΔA = 4.495C(C:μg/mL) + 0.0278 with a correlation coefficient of 0.9965. The detection limit of the method was 19 ng/mL. The apparent activation energy of the inhibitory reaction and the reaction half-life period were 5.76 KJ/mol and 15.61 min, respectively. This method has been successfully used in the determination of europium in molecular sieve samples.