Journal of Analytical Methods in Chemistry最新文献

In the scientific literature, it has been documented that electrochemical genosensors are novel analytical tools with proven clinical diagnostic potential for the identification of carcinogenic processes due to genetic and epigenetic alterations, as well as infectious diseases due to viruses or bacteria. In the present work, we describe the construction of an electrochemical genosensor for the identification of the k12p.1 mutation; it was based on use of Screen-Printed Gold Electrode (SPGE), Cyclic Voltammetry (CV), and Atomic Force Microscopy (AFM), for the monitoring the electron transfer trough the functionalized nanostructured surface and corresponding morphological changes. The sensitivity of the genosensor showed a linear response for the identification of the k12p.1 mutation of the K-ras gene in the concentration range of 10 fM to 1 μM with a detection limit of 7.96 fM in the presence of doxorubicin (Dox) as DNA intercalating agent and indicator of the hybridization reaction. Thus, the electrochemical genosensor developed could be useful for the identification of diseases related with the K-ras oncogene.

The determination of trace metals in seawater is an important project of marine environmental monitoring. However, the presence of many alkali metal ions with high concentration, such as sodium ion, seriously interferes with the detection limit and accuracy of atomic absorption spectrometry (AAS, flame/graphite furnace integrated). The conventional chemical methods for the enrichment of trace metals are complex, and low boiling point organic solvents are used. In this paper, a kind of commercial cross-linked polystyrene resin microspheres was chloromethylated and aminated to introduce EDTA-type amino polycarboxylic groups and then loaded in a column as the absorption filler. A set of seawater pretreatment and enrichment devices was designed and assembled. The enriching process and conditions of trace Cu, Zn, Pb, and Cd in standard seawater were studied. 10 g of the modified resin could enrich the equivalent seawater and remove successfully the light metal ions. pH = 5∼9 and 0.2 mL/min of the flow rate were the suitable conditions for preconcentration. The enriched metal ions in the eluent were analyzed on the AAS. Compared with the conventional solvent method, the novel material and enrichment device have high preconcentration efficiency, strong anti-interference ability, and low cost and could be directly applied for routine seawater detection.

This paper describes a capillary electrophoresis method for the determination of the cationic B-vitamins thiamine, nicotinamide, pyridoxine, pyridoxal, and pyridoxamine in untreated cell culture medium samples. The effects of the buffering capacity, the mobility of the coion, and the preconditioning solution on the robustness of the method were investigated. Using a 100 mM phosphoric acid and 55 mM triethanolamine background electrolyte at pH 2.3 and capillary preconditioning with 1 M NaOH, all five vitamins could be separated with good resolution. Preliminary method validation data over the range 10-110 µM for undiluted samples, with 10 μM being the lower range limit of quantification QL, showed accuracy recoveries of 94-104%, and migration time and peak area repeatabilities within 0.4% RSD and 2.6% RSD, respectively.

Diosgenin, a steroidal sapogenin, has attracted attention worldwide owing to its pharmacological properties, including antitumor, cardiovascular protective, hypolipidemic, and anti-inflammatory effects. The current diosgenin analysis methods have the disadvantages of long analysis time and low sensitivity. The aim of the present study was to establish an efficient, sensitive ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) approach for pharmacokinetic analysis of diosgenin amorphous solid dispersion (ASD) using tanshinone IIA as an internal standard (IS). Male Sprague-Dawley rats were orally administered diosgenin ASD, and orbital blood samples were collected for analysis. Protein precipitation was performed with methanol-acetonitrile (50 : 50, v/v), and the analytes were separated under isocratic elution by applying acetonitrile and 0.03% formic acid aqueous solution at a ratio of 80 : 20 as the mobile phase. MS with positive electron spray ionization in multiple reaction monitoring modes was applied to determine diosgenin and IS with m/z 415.2⟶271.2 and m/z 295.2⟶277.1, respectively. This approach showed a low limit of quantification of 0.5 ng/ml for diosgenin and could detect this molecule at a concentration range of 0.5 to 1,500 ng/ml (r = 0.99725). The approach was found to have intra- and inter-day precision values ranging from 1.42% to 6.91% and from 1.25% to 3.68%, respectively. Additionally, the method showed an accuracy of -6.54 to 4.71%. The recoveries of diosgenin and tanshinone IIA were 85.81-100.27% and 98.29%, respectively, with negligible matrix effects. Diosgenin and IS were stable under multiple storage conditions. Pharmacokinetic analysis showed that the C _max and AUC_0⟶t of diosgenin ASD were significantly higher than those of the bulk drug. A sensitive, simple, UPLC-MS/MS analysis approach was established and used for the pharmacokinetic analysis of diosgenin ASD in rats after oral administration.

To study the differences in phenolic compounds between tobacco smokers' saliva and mainstream smoke, a method was developed for the analysis of 12 phenolic compounds in saliva and mainstream smoke based on ultrahigh-performance liquid chromatography with fluorescence detection (UPLC-FLD). The contents and distributions of phenolic compounds in tobacco smokers' saliva and mainstream smoke were compared. The results were as follows: (1) Phenolic compounds were quantitatively analyzed by the internal standard method using 4-fluorophenol as an internal standard. For smokers' saliva samples, the limits of quantification (LOQs) ranged from 2.2 to 19.1 μg/L, and the recoveries were from 80.2% to 119.2% at the three spiked levels. For mainstream smoke samples, the LOQs ranged from 0.03 to 0.26 μg/cig, and the recoveries ranged from 84.9% to 107.0% at the three spiked levels. (2) The contents of phenolic compounds from 14 cigarettes in mainstream smoke and smokers' saliva were determined. In mainstream smoking, the main phenolic compounds were hydroquinone, catechol, phenol, meta- and para-Cresol, and o-methylhydroquinone. In smokers' saliva, the main phenolic compounds were phenol and meta- and para-Cresol and the contents of phenolic compounds in smokers' saliva from different cigarettes were significantly different. (3) The content distribution patterns of phenolic compounds in smokers' saliva differed from those in mainstream smoke. The predominant phenolic compound in mainstream smoke was dihydroxybenzene, while monophenols predominated in smokers' saliva. (4) The contents of phenolic compounds from five kinds of cigarettes were analyzed in the saliva of different smokers using principal component analysis, which indicated that cigarettes with different sensory effects were clearly distinguished by differences in the contents of phenolic compounds in saliva.

Characterization of perfluorohexane sulfonate (PFHxS) isomers, a chemical proposed for listing under the Stockholm Convention, is important to elucidate its environmental behaviors and sources. Optimized chromatographic separation coupled with monitoring of the characteristic fragments enabled the identification of four mono-substituted and two di-substituted branched PFHxS isomers. The transitions of molecular ions m/z 399 to the fragments m/z 80 (n-), m/z 169 (iso-), m/z 319 (1m-), m/z 80 (2m-), and m/z 180 (3m-) were selected for quantifying the mono-substituted isomers. Method accuracy of the established LC-MS/MS was verified by comparing the results of technical products with those determined by ¹⁹F-nuclear magnetic resonance (NMR). The developed method was then used to quantify the isomeric compositions of PFHxS in the perfluorooctane sulfonate (PFOS) industrial products which contained PFHxS as an impurity, as well as in several kinds of water samples, with the limits of detection for all isomers in the range of 4 to 30 pg/L. For the first time, a liquid chromatography-tandem mass spectrometry method was established to separate and quantify the PFHxS isomers. The isomeric profiling of water samples suggested that PFHxS in the waters was mainly due to the direct contamination of PFHxS rather than from PFOS contamination.

The present study introduces a novel electrode for rapid, highly sensitive, and selective electrochemical sensor for cadmium(II) using 5% N¹-hydroxy-N¹,N²-diphenylbenzamidine (HDPBA) modified carbon paste electrode (CPE) (HDPBA‒CPE). Surface characterizations and structural analysis of the proposed HDPBA‒CPE were performed using several analytical techniques. The voltammetric measurements of Cd(II) were conducted by cyclic voltammetry (CV) and square wave anodic stripping voltammetry (SWASV). Several experimental conditions such as composition and pH of buffer solutions, HDPBA composition, accumulation potential and time, and other voltammetric conditions were optimized. Cd(II) was preconcentrated on the modified electrode surface for 270 s using Britton Robinson (B-R) buffer (0.1 M, pH 4) at -1.0 V versus Ag/AgCl, followed by electrochemical oxidation of the accumulated Cd(II) in the positive scan of SWASV after a quiet time of 10 s. Under optimized parameters, the proposed method showed a linear range of 0.3-100 nM Cd(II) with a detection limit of 0.032 nM. The fabricated HDPBA-modified carbon paste electrode exhibited excellent sensitivity, selectivity, stability, and reproducibility (with RSD of 3.8%). The developed HDPBA‒CPE was used for the quantification of Cd(II) in tobacco and environmental water samples, and it was found to be applicable for the determination of different types of real samples.

In this study, a microscopy apparatus that can switch between the fluorescence microscopy and ultralow-frequency Raman microscopy modes was developed. The apparatus can be easily constructed by equipping a standard epi-illumination microscope with an additional port featuring a removable half mirror. Owing to the switchability, fluorescence imaging, and spectroscopy, Raman spectroscopy in the frequency range down to ∼10 cm^-1 can be performed using the apparatus. To demonstrate the advantageous features of this apparatus, micron-sized crystals of perylene, which have two polymorphic forms, were analyzed. The two polymorphs were clearly identified based on their shapes, fluorescence spectra, and ultralow-frequency Raman spectra, all of which can be observed with our apparatus alone. These results indicate that the apparatus is a powerful tool for the analysis and characterization of various nano-/micron-sized crystals.

The primary objective of this study was to develop and validate an efficient and accurate ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) approach as a means to detect tropifexor plasma concentrations in beagle dogs and to study its pharmacokinetic profile in beagle dogs. The chromatographic separation of tropifexor and oprozomib (internal standard, ISTD) on the column, with the addition of acetonitrile for rapid precipitation and protein extraction, was achieved with 0.1% formic acid aqueous solution-acetonitrile for the mobile phase. A Xevo TQ-S triple quadrupole tandem mass spectrometer, under the selective reaction monitoring (SRM) mode, for the determination of the concentrations in the positive ion mode. The mass transfer pairs of tropifexor and oprozomib (ISTD) were m/z 604.08 ⟶ 228.03 and m/z 533.18 ⟶ 199.01, respectively. The profile displayed well linearity with calibration curves for tropifexor and oprozomib (ISTD) ranging from 1.0 to 200 ng/mL. In parallel, the lower limit of quantification (LLOQ) value for tropifexor could be measured with the aid of this novel technique at 1.0 ng/mL. In addition, the scope of intraday and interday for analyte accuracy was between -4.86% and 1.16%, with a precision of <7.31%. The recoveries of the analytes were >88.13% and were free of significant matrix effects. The stability met the requirements for the quantification of plasma samples under various conditions. Finally, the pharmacokinetic profile of tropifexor in beagle dog plasma following oral administration of 0.33 mg/kg tropifexor was determined by using the method facilitated in this work.