Rapid quality assessment of Gentianae Macrophyllae Radix based on near-infrared spectroscopy and capillary electrophoresis

The aim of this study was to establish a rapid quality assessment method for Gentianae Macrophyllae Radix (RGM) using near-infrared (NIR) spectra combined with chemometric analysis. The NIR spectra were acquired using an integrating sphere diffuse reflectance module, using air as the reference. Capillary electrophoresis (CE) analyses were performed on a model P/ACE MDQ Plus system. Partial least squares-discriminant analysis qualitative model was developed to distinguish different species of RGM samples, and the prediction accuracy for all samples was 91%. The CE response values at each retention time were predicted by building a partial least squares regression (PLSR) calibration model with the CE data set as the Y matrix and the NIR spectra data set as the X matrix. The converted CE fingerprints basically match the real ones, and the six main peaks can be accurately predicted. Transforming NIR spectra fingerprints into the form of CE fingerprints increases its interpretability and more intuitively demonstrates the components that cause diversity among samples of different species and origins. Loganic acid, gentiopicroside, and roburic acid were considered quality indicators of RGM and calibration models were built using PLSR algorithm. The developed models gave root mean square error of prediction of 0.2592% for loganic acid, 0.5341% for gentiopicroside, and 0.0846% for roburic acid. The overall results demonstrate that the rapid quality assessment system can be used for quality control of RGM.     

A simple and rapid CZE method for the analysis of mycophenolic acid and its phenol glucuronide metabolite in human serum

A simple and rapid capillary electrophoretic method was developed for simultaneous determination of mycophenolic acid and its metabolite, phenol glucuronide, in human serum. The sample preparation in the proposed method required only the precipitation by acetonitrile. Separation was performed by capillary zone electrophoresis using 75 mM phosphate buffer (pH 7.5) as running buffer, an applied voltage of 10 kV, and UV detection at 217 nm. Each serum sample analysis was completed within 15 min. The optimized method demonstrated good performance concerning specificity, linearity (r>0.9955), accuracy (95.9-113%), precision (<6.4%) and enough sensitivity for therapeutic drug monitoring. This method was successfully applied to measurements of mycophenolic acid and mycophenolic acid glucuronide in renal transplant patient samples and was a useful alternative to high-performance liquid chromatography-based methods.     

Analysis of amino acids in cell culture supernatant using capillary electrophoresis with contactless conductivity detection

CE-C⁴D methods for the analysis of amino acids (AAs) are presented. Combining the results from two methods with acetic acid and cyclodextrin-based BGEs, 20 proteinogenic AAs could be analyzed using CE. CE-C⁴D was also, for the first time, applied to analyze free AAs in samples of mammalian cell culture supernatant. After dilution as only sample preparation, combining the results of the two CE methods allowed monitoring the concentration changes of 17 AAs in samples taken during the cultivation of CHO cells.     

Disopyramide analysis using REMEDi: comparison with EMIT and conventional high performance liquid chromatographic methods.

REMEDi (Rapid EMErgency Drug identification; Bio-Rad) is an automated high performance liquid chromatographic (HPLC) system designed to detect, identify and measure a range of basic and neutral drugs in 0.5-1.0 mL of urine or plasma/serum. We have evaluated REMEDi in the analysis of the antiarrhythmic drug disopyramide in patient samples. The specimens were also analysed by a conventional HPLC method, based on solvent extraction and UV detection (254 nm), and by EMIT. There were good correlations between the results obtained with each method (r = 0.91 or greater). REMEDi gave a lower mean result than EMIT [means +/- SD (mg/L): REMEDi 2.64 +/- 1.10, EMIT 3.14 +/- 1.51; t = 4.0, p less than 0.01; n = 25], but there were no other significant differences in mean results. The principal disopyramide metabolite, mono-N-desalkyldisopyramide, did not interfere in any method. Clearly REMEDi can be used for therapeutic drug monitoring of disopyramide provided enough sample is available.     

Development of ion chromatography and capillary electrophoresis methods for the determination of Li in Li–Al alloy

Two methods were developed for determination Li content in Li–Al alloy by employing ion chromatography (IC) and capillary electrophoresis (CE) without any prior separation of Al matrix. In absence of suitable certified reference material the two methods were used to validate each other. Using a high capacity column and a weaker eluent methane sulphonic acid, it was possible to separate Li in IC without eluting strongly retained Al. The method showed good precision and sensitivity and was extended for analysis of routine samples. In the case of CE using imidazole as co-ion, Li was detected in CE by indirect detection. In view of no interference from Al, samples were analyzed without any matrix separation. The CE method was used successfully for sample analysis and results were compared with IC results.     

在线固相萃取净化-高效液相色谱法测定人血浆中的霉酚酸

建立了在线固相萃取净化-高效液相色谱法联用(Online SPE-HPLC)测定人血浆中霉酚酸浓度的分析方法。联用系统以Capcell PAK MF Ph-1为净化柱,Poroshell 120?EC-C18为分析柱,血浆样品经甲醇沉淀蛋白后,直接进样分析。结果表明,霉酚酸在0.20~50.00μg/mL范围内线性关系良好,相关系数(r)为0.9998,检出限和定量下限分别为0.07、0.20μg/mL。在0.39、25.00、50.00μg/mL 3个质量浓度下的平均回收率为96.2%~105%,日内和日间相对标准偏差(RSD)分别为2.6%~3.1%和2.9%~3.3%。该法操作简便、快速,可用于人血浆中霉酚酸浓度的分析。     

Development of a CE method for the determination of mycophenolic acid in human plasma: a comparison with HPLC

Mycophenolate mofetil (MMF) is a widely used drug for the maintenance of immunosuppressive therapy in renal-transplant recipients. MMF is rapidly metabolized in vivo to mycophenolic acid (MPA), a reversible, noncompetitive inhibitor of inosine monophosphate dehydrogenase, which represents a limiting enzyme in lymphocyte proliferation. MPA shows large interindividual pharmacokinetic variability: its monitoring is therefore of primary importance to achieve adequate immunosuppression with minimized risk of graft rejection or toxicity. We developed a CE method for the determination of total MPA (tMPA) in plasma, based on easy sample preparation; CE evaluation of tMPA was performed in 30 mmol/L sodium-borate with 10 mmol/L SDS (pH 10.00) at 25 degrees C using a 60 cm (54.5 to window) uncoated capillary with UV detection at 254 nm wavelength. MPA was readily detectable in plasma; the CE method was linear in the range of 0.7-120 microg/mL (r >0.992). Intra- and interassay imprecision was <7% except for the lowest spiked MPA concentration, which had an intra-assay RSD% of 14.7 compared to 18.3 interassay. Data by CE were compared with results obtained by a validated HPLC method. CE assay of tMPA exhibited a very good correlation (r(2) >0.988) with respect to HPLC; Bland-Altman difference versus average showed a mean of -0.18 microg/mL +/- 1.14 SD. CE determination of tMPA is a robust, sensitive and reproducible method with the advantage over HPLC of being fast, simple and unexpensive, also enabling quick assessment of MPA for pharmacokinetic studies.     

Rapid sample screening method for authenticity controlling vanilla flavors using a CE microchip approach with electrochemical detection

Five vanilla-related flavors of food significance, vanillic alcohol (VOH), ethyl maltol (EMA), maltol (MAL), ethyl vanillin (EVA) and vanillin (VAN), were separated using CE microchips with electrochemical detection (CE-ED microchips). A +2 kV driving voltage for both injection and separation operation steps, using a borate buffer (pH 9.5, 20 mM) and 1 M nitric acid in the detection reservoir allowed the selective and sensitive detection of the target analytes in less than 200 s with reproducible control of EOF (RSD(migration times)<3%). The analysis in selected real vanilla samples was focusing on VAN and EVA because VAN is a basic fragrance compound of the vanilla aroma, whereas EVA is an unequivocal proof of adulteration of vanilla flavors. Fast detection of all relevant flavors (200 s) with an acceptable resolution (R(s) >1.5) and a high accuracy (recoveries higher than 90%) were obtained with independence of the matrices and samples examined. These results showed the reliability of the method and the potential use of CE microchips in the food control field for fraudulent purposes.     

Amino acids: aspects of impurity profiling by means of CE

Quality control of active pharmaceutical ingredients (API) is commonly performed by means of HPLC. However, CE offers a suitable alternative, especially for the analysis of easily chargeable substances, i.e., amino acids. The article reviews, on the one hand, CE methods developed for impurity profiling of synthesized amino acid analogs. However, nowadays, production of amino acids/peptides is dominated by fermentation. Therefore, on the other hand, CE methods for the analysis of amino acids and small peptides are reported. The results of CE analysis of glutathione samples according to the monograph in the European Pharmacopoeia (Ph. Eur.) 5.7 and amino acid samples after derivatization with 9-fluorenylmethyl chloroformate (FMOC) and 3-(4-carboxybenzoyl)quinoline-2-carboxaldehyde (CBQCA) may pave the way for impurity profiling of fermentatively produced API by means of CE.     

Capillary electrophoresis for simultaneous analysis of heparin, chondroitin sulfate and hyaluronic acid and its application in preparations and synovial fluid

A simple and accurate capillary electrophoresis (CE) method was developed to simultaneously separate and quantify heparin, chondroitin sulfate and hyaluronic acid. The relative standard deviations (intra-day) of migration time, peak height and peak area for heparin, chondroitin sulfate and hyaluronic acid were lower than 1.11, 5.45 and 2.82%, respectively. The limits of detection of heparin, chondroitin sulfate and hyaluronic acid were 0.91, 0.12 and 9.04 × 10(-3) mg/mL, respectively. The developed electrophoretic method was successfully applied to the analysis of commercial drug products and biological samples containing chondroitin sulfate and/or hyaluronic acid. The recoveries for chondroitin sulfate and hyaluronic acid were in the range of 95.9 ~107.0%. This was the first time the content of hyaluronic acid in the synovial fluids from osteoarthritic rabbits was investigated by CE. The results suggested that hyaluronic acid in the synovial fluids from osteoarthritic rabbits may be further metabolized and the administration of chondroitin sulfate or hyaluronic acid could affect the content and metabolism of hyaluronic acid in the synovial fluids. The developed CE method was simple to implement without sample pretreatment such as depolymerisation, very repeatable and easily transferred from lab to lab.     

Capillary Electrophoresis for Detection and Quantitation of Domoic Acid in Mussels

Abstract

Capillary electrophoresis (CE) was utilized to quantitate the domoic acid content in mussel tissues. The analyses were conducted on samples obtained by aqueous extraction of the tissues. Lipids were removed from the extract in order to facilitate electroendomosis and to shorten analysis time. Satisfactory resolution of domoic acid was accomplished with 300 mM CAPS buffer at pH 10.25 or 10.30 and the electrophoresis time was less than 10 minutes per sample. A procedure was devised for quantitation of domoic acid in the mussel extracts. Application of this procedure on a sample of naturally contaminated mussel homogenate yielded results in close agreement with those reported in the literature.     

Capillary electrophoresis using a surfactant-treated capillary coupled with offline matrix-assisted laser desorption ionization mass spectrometry for high efficiency and sensitivity detection of proteins.

A method of combining capillary electrophoresis (CE) using a surfactant-modified capillary with matrix-assisted laser desorption ionization (MALDI) mass spectrometry (MS) is described for protein analysis. The CE-MALDI-MS coupling is based on CE fraction collection of nanoliter volume samples in less than 5 microl of dilute acid. This offline coupling does not require any special instrumentation and can be readily performed with commercial instruments. Protein adsorption during CE separation is prevented by coating the capillary with the surfactant didodecyldimethylammonium bromide. This surfactant binds strongly with the capillary wall, hence it does not desorb significantly to interfere with subsequent MALDI-MS analysis. It is shown that the use of a dilute acid for CE fraction collection is advantageous in lowering the detection limit of MALDI-MS compared to using an electrophoretic buffer. The detection limit for proteins such as cytochrome c is 23 fmol injected for CE, or 1.2 fmol spotted for MALDI-MS. This sensitivity is comparable to alternative CE-MALDI-MS coupling techniques using direct CE sample deposition on the MALDI target. In addition, the fraction collection approach has the advantage of allowing multiple reactions to be carried out on the fractioned sample. These reactions are very important in protein identification and structure analysis.     

Simultaneous determination of serotonin and creatinine in urine by combining two ultrasound-assisted emulsification microextractions with on-column stacking in capillary electrophoresis

This article describes the development of a rapid, simple, and sensitive analytical approach for the simultaneous determination of serotonin (5‐hydroxytryptamine) and creatinine in urine samples by combining two ultrasound‐assisted emulsification microextractions (USAEMEs) in series with on‐column stacking in CE. This serial USAEME procedure comprises analytes extraction from the donor solution (urine with K₂CO₃ additive) to an organic solvent followed by a back‐extraction from the organic phase into a small volume of hydrochloric acid. After 15 min of sample pretreatment, the acidic acceptor solution was analyzed directly on CE in the mode of capillary zone electrophoresis. The adoption of HCl as the acceptor phase not only provided effective back‐extraction but also facilitated pH‐mediated on‐column stacking in CE analysis. About 360‐fold sensitivity enhancement was achieved for serotonin detection. The limits of detection were 7.9 nM for serotonin and 13.3 μM for creatinine, respectively. Satisfactory results were obtained with respect to precision and recovery. The proposed method has been demonstrated to be convenient and effective for the analysis of real urine samples. We believe that two USAEMEs in series will find wide applications in simplified sample pretreatment prior to CE analysis.     

Highly efficient approach for characterizing nanometer-sized gold particles by capillary electrophoresis

This paper demonstrates that capillary electrophoresis (CE) can be employed for characterizing the sizes of nanometer-scale gold particles. We characterized the gold nanoparticles by effecting CE separation using a buffer of SDS (70 mM) and 3-cyclohexylamino-1-propanesulfonic acid (CAPS; 10 mM) at pH 11.0 and an applied voltage of 18 kV and obtained a linear relationship (R² > 0.99) between electrophoretic mobilities and size for nanoparticles whose diameters fall in the regime from 5.0 ± 0.5 to 41.2 ± 3.3 nm; the relative standard deviations of these electrophoretic mobilities are <0.8%. We evaluated the feasibility of employing these separation conditions for the size characterization by of gold nanoparticle samples that were synthesized by a rapid microwave heating method. We confirmed that this CE method is a valid one for size characterization by comparing the results obtained by CE with those provided by scanning electron microscopy (SEM); a good correlation exists between these two techniques. Our results demonstrate that CE can be employed to accelerate the analysis of the sizes of nanomaterials.     

Comparative analysis of the organic acid content of vinegar by capillary electrophoresis and ion-exclusion chromatography with conductimetric detection

Summary Ion-exclusion chromatography (IEC) and capillary electrophoresis (CE) have been compared for determination of organic acids in samples of Sherry wine vinegar. The accuracy of each technique was evaluated by use of the standard addition method. There were no differences between the techniques at a significance level of 5%, except for determination of malic acid by CE. Both analytical methods were used to analyse sixteen samples of Sherry wine vinegar supplied by different producers. The regression coefficients (r ²) for analysis by IEC and CE exceeded 0.94 for all acids. Results from both methods were in good agreement and the methods are sufficiently selective and sensitive to be applied directly to sherry wine vinegars.     

Effects of chain extender and uniaxial stretching on the properties of PLA/PPC/mica composites

Poly(lactic acid) (PLA)/poly(propylene carbonate) (PPC)/mica composites with different amount of chain extender (CE) were melt compounded and then processed via two routes (compression molding and uniaxial stretching) into sheets and films. The tensile, thermal, and oxygen barrier properties of all the samples were investigated. Tensile test showed that the tensile strength and elongation at break of all films were much higher than that of all sheets, especially for PLA/PPC/mica with 0.9‐wt% CE composite (CM₃(CE)_0.9) film. The crystallinity of all films increased significantly after uniaxial stretching of sheet samples. The Fourier transform infrared spectroscopy (FTIR) results proved the chemical reactions occurred between PLA/PPC and CE. Scanning electron microscope (SEM) analysis revealed that compatibility and interfacial adhesion of all samples were improved after adding mica and CE, and they were further enhanced after uniaxial stretching. The addition of CE was not favorable to improve the oxygen barrier performance of PLA/PPC/mica sheet samples. However, the oxygen barrier performance of film samples was significantly improved after uniaxial stretching. In particular, the CM₃(CE)_0.9 film had the lowest oxygen permeability coefficient (1.4 × 10^?15 cm³·cm/(cm²·s·Pa)), and this was the best oxygen barrier properties reported in the literature for PLA‐based composites, which was comparable with PA film. This study demonstrated the high efficiency of uniaxial stretching on improvement of properties of composites, which would promote the application of biodegradable polymers in oxygen sensitive food packaging.     

Sensitive determination of anions in saliva using capillary electrophoresis after transient isotachophoretic preconcentration

A transient isotachophoresis-capillary electrophoresis (tITP-CE) system for the determination of minor inorganic anions in saliva is described. The complete separation and quantification of bromide, iodide, nitrate, nitrite, and thiocyanate has been achieved with only centrifugation and dilution of the saliva sample. In-line tITP preconcentration conditions, created by introduction of the plugs of 5 mM dithionic acid (leading electrolyte) and 10 mM formic acid (terminating electrolyte) before and after the sample zone, respectively, allowed the limits of direct UV absorption detection (at 200 nm) to be up to 50-fold improved as compared with CE without tITP. As a result, nitrate and thiocyanate were still detectable at 4.6 and 3.8 μg l⁻¹, respectively, in 1000 times diluted saliva. The daily variations of anionic concentrations in saliva samples taken from a smoking health volunteer were discussed based on the results of tITP-CE analysis. It was confirmed that the thiocyanate concentration in saliva noticeably increased after smoking. This is apparently the first report on simultaneous quantification of more than four anionic salivary constituents using CE.     

Analysis of low molecular weight aldehydes in air samples by capillary electrophoresis after derivatization with 4-hydrazinobenzoic acid

This work reports the analysis of selected aldehydes in air samples using capillary electrophoresis (CE). The method is based on the reaction of aldehydes with 4-hydrazinobenzoic acid (HBA) to give the corresponding hydrazones with maximum absorbance at 290 nm. Under optimized CE conditions, the HBA derivatives of four carbonyls (formaldehyde, acetaldehyde, propionaldehyde, and acrolein) were completely separated from one another, in less than 6 min, using a pH 9.3 tetraborate buffer at 0.040 mol L(-1) concentration as background electrolyte. A few method validation parameters were determined revealing good migration time repeatability (< 1.5% CV) and area repeatability (< 2% CV), excellent linearity (50-300 microg/L, r > 0.996) and adequate sensitivity for environmental applications. The limits of detection with respect to each single aldehyde were in the range of 2.7-8.8 ng L(-1). The methodology was applied to the determination of aldehydes indoors. Samples were collected in HBA impregnated octadecylsilica cartridges, at different times during the day. The most abundant carbonyls in the samples were acetaldehyde followed by formaldehyde, with estimated peak concentrations of 4.3 and 2.9 ppbv, respectively.     

Routine determination of major anions in atmospheric aerosols by capillary electrophoresis

Capillary electrophoresis (CE) with indirect UV detection utilizing a pyromellitate-based electrolyte was used for the routine analysis of major anions in atmospheric aerosols collected on filters with high-volume (Hi-Vol) samplers. The long-term reliability of the CE system was checked over an 8-month period during which over 2900 samples were analyzed. In addition, approximately 1100 samples were analyzed in parallel by ion chromatography (IC). It has been shown that acceptable analytical performance can be routinely obtained. The agreement between the CE and IC results is good, generally better than 20% at concentrations larger than 1 mg l⁻¹.     

Analytical separation of Au/Ag core/shell nanoparticles by capillary electrophoresis

This paper demonstrates that capillary electrophoresis (CE) can be employed for characterizing the sizes of a series of Au/Ag core/shell nanoparticles (NPs). We effected the CE separation of Au/Ag core/shell NPs using a mixed buffer of sodium dodecyl sulphate (SDS) (40 mM) and 3-(cyclohexylamino)propanesulfonic acid (10 mM) at pH 9.7 and an applied voltage of 20 kV. A linear relationship (R(2)>0.99) existed between the electrophoretic mobilities and the sizes of the Au/Ag core/shell NPs within the diameter range from 25 to 90 nm; the relative standard deviations of these electrophoretic mobilities were <0.9%. From the good correlation between the results obtained by CE and those provided by scanning electron microscopy, we confirmed that this CE method is a valid one for characterizing the sizes of Au/Ag core/shell NP samples. In addition, when the Au/Ag core/shell NPs were separated through CE and detected using an on-line photodiode array detector, this approach allowed the chemical characterization of the NP species. This CE approach should allow the rapid and cost-effective characterization of a number of future nanomaterials.