Phase Extraction System Research Articles

Correlation between serum advanced glycation end-products and vascular complications in patient with type 2 diabetes

Advanced glycation end-products (AGEs) formation increases with metabolic disorders, leading to higher serum AGE levels in patients with progressive vascular complications. Measuring AGE levels in biological samples requires multiple pre-analytical processing steps, rendering analysis of multiple samples challenging. This study evaluated the progression of diabetic complications by analyzing AGE levels using a pre-analytical processing strategy based on a fully automated solid phase-extraction system. Serum samples from patients with diabetes, with or without macrovascular complications (Mac or non-Mac) or microvascular complications (Mic or non-Mic), were processed with the established methods. Free and total AGE levels in sera were measured using liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS). In patients with diabetes, both free and total AGE levels were elevated in those with complications compared to those without complications. In Mac and Mic groups, free and total AGE levels and z-scores (the sum of normalized AGE levels) also increased. AGE z-scores were markedly higher than those of single AGE levels in distinguishing each complication. Our study demonstrated that the free AGE z-score, measured using a new analytical method without hydrolysis, correlated with the presence of vascular complications and may serve as a marker of disease complications.

Flow analysis-solid phase extraction system and UHPLC-MS/MS analytical methodology for the determination of antiviral drugs in surface water

An automated flow analysis-solid phase extraction (FA-SPE) system and methodology of ultra-high-performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS) analysis were developed for the determination of selected antiviral drugs (acyclovir, amantadine, rimantadine, and oseltamivir) in water samples. The proposed FA-SPE approach enables the integration of various extraction stages and elimination of the sample evaporation step and offers individual customisation of SPE parameters, inter alia sample, and eluate flow rate and volume. Using the developed FA-SPE procedure, e.g. a 100-fold preconcentration of the target analytes in 1 h was achieved. A method for chromatographic analysis was also developed to determine the selected antiviral drugs in combination with the use of the FA-SPE system. The developed FA-SPE UHPLC-MS/MS method was validated including the determination of linearity of analytical graphs, limits of detection (5.5–99.9 pg mL−1) and quantification (18.3–329.8 pg mL−1), intra-day (1.8–8.3%) and inter-day (3.0–9.2%) precision, recovery (95.6–105.3%), and matrix effects (− 12.9 to 13.2%). The proposed method was successfully applied to analyse tap, drinking, and river water samples, revealing the presence of amantadine at a concentration of 40.1 pg mL−1 in one sample. The environmental impact of the developed FA-SPE sample preparation procedure was also assessed using the AGREEprep metric tool and compared with five other literature methods, achieving the most sustainable outcome.Graphical abstract

New fabric phase sorptive extraction for nondestructive analysis of heritage textile samples

Several types of pesticides used in museum collections over time become dangerous for people who may handle textile articles treated with such substances. In the case of the analysis of ancient, modern, and contemporary textile materials, it is particularly important to keep the artifacts intact, as they cannot be replaced. The need to use micro- or nondestructive techniques led to the development of methods such as solid-phase microextraction (SPME), liquid‒liquid dispersive microextraction (DLLME), and single-droplet microextraction (SDME). In this paper is described an optimized extraction method of three pesticides (malathion, methoxychlor, and permethrin) by creating a non-destructive solid phase extraction system on a textile support, abbreviated FPSE – 100 % cotton fabric coated with a sol-gel solution prepared from a polymer (PEG or PDMS). To obtain a suitable FPSE, the following parameters were evaluated: polymer selection (individual or mixture of polymers), acid catalyst (trifluoroacetic acid, acetic acid and hydrochloride acid), amount of polymer (1.0 g, 2.5 g or 5.0 g), polymerization time (30 min, 120 min and 240 min), ultrasonic bath temperature (40 °C and 70 °C), and type of bath to obtain the sol-gel (ultrasonic bath, water bath with stirring and mechanical stirrer). To complete the FPSE optimization, the influence of pesticide extraction time on FPSE and desorption from FPSE in ethyl acetate was also assessed.The pesticides extraction yields obtained for the laboratory textile samples are in the range of 52.7 %–128.0 %. The technique proposed in the manuscript proved to be effective as a nondestructive tool for evaluating and quantifying the presence of pesticides in textile museum collections. The approach described here reduces heritage object damage due to sampling compared to methods commonly employed and may represent a starting point for future research.

Caffeine quantification in dietary supplements using high-throughput on-line solid phase extraction coupled to Venturi easy ambient sonic-spray ionization mass spectrometry.

Caffeine is present in a large number of beverages and is an additive used in dietary supplements. Therefore, the concern about its quality and safety for consumers has been increasing and hence requires faster and simpler analytical methods to determine the caffeine amount. The high-throughput analysis is an appropriate solution to pharmaceuticals, bioanalysis, forensic and food laboratory routines. In this sense, Venturi easy ambient sonic-spray ionization mass spectrometry (V-EASI-MS), a specific ambient ionization source, is suitable to enable direct analysis of sample solutions in real time and is appropriate to be coupled to liquid chromatography (LC). The development of an on-line solid phase extraction system coupled to V-EASI-MS optimizes the advantages of LC-MS hyphenation by enhancing the figures of merit of the analytical method according to AOAC guidelines and simultaneously minimizing the runtime analysis to 1.5 min per sample, as well as sample preparation steps and solvent consumption, which is currently a challenge for quantitative applications of ambient ionization MS.

Analytical quality by design using a D-optimal design and parallel factor analysis in an automatic solid phase extraction system coupled to liquid chromatography. Determination of nine PAHs in coffee samples

Optimizing a multi-residue analysis when using an automatic SPE (solid phase extraction) system and complex matrices becomes a difficult problem because of the large number of experimental factors that can influence the recovery of the analytes. Furthermore, in most cases, the conditions of the factors that enhance the response of one analyte are in conflict with those suitable for some others.In this work, AQbD (Analytical Quality by Design) is applied to the development of an analytical procedure based on automatic SPE coupled to HPLC-FLD in the determination of nine polycyclic aromatic hydrocarbons (PAHs) in coffee samples.Focussing on the SPE, the elution volume, the dry time, and volume in the wash stage, and the organic solvent (at two, three, three, and four levels, respectively) were considered.The first problem is to handle these four factors (control method parameters, CMPs) at different levels to optimize responses (critical quality attributes, CQAs). This task has been carried out using a D-optimal design that, starting from a full factorial design of four factors with 72 experiments, reduced this number to 19, maintaining the precision of the estimates, saving time and costs in the laboratory.The second problem is related to the choice of CQAs to apply the AQbD methodology. A complex matrix such as coffee contains impurities that interferes with the target analytes and may even coelute in the chromatographic determination. A PARAFAC decomposition allows avoiding this problem and uses the “second order advantage” to unequivocally identify each analyte. Then, the obtained sample loadings were used as responses. Specifically, each CQA is the difference between spiked and blank coffee samples. All these CQAs must be maximized.Once the experimental data were obtained, two alternatives were posed: on the one hand, the classical optimization based on the estimation of the effects of CMPs on the CQAs, and on the other hand, applying the AQbD methodology to construct the design space that allows to increase the knowledge of the automatic SPE system.Because the experimental domain of CMPs is discrete and the SPE system performs differently for each analyte, it is not possible to obtain the maximum of all CQAs at the same factor levels. Therefore, the design space of the CMPs is obtaining through the Pareto front of the non-dominated values of CQAs.The nine PAHs selected were phenanthrene (PHE), anthracene (ANT), fluoranthene (FLN), pyrene (PYR), chrysene (CHR), benzo[a]anthracene (BaA), perylene (PER), benzo[b]fluoranthene (BbF) and benzo[a]pyrene (BaP). European regulations amending foodstuff set maximum levels for BaP and the sum of the content of four compounds (PAH4): BaP, BaA, BbF and CHR.

Biohybrid adsorbent for the preconcentration of lead and its determination in fruit juices by electrothermal atomic absorption spectrometry.

Fruit juices are one of the most non-alcoholic beverages consumed in the world. Essential elements and other nutrients present in fruit juices play an important role in human well-being. However, fruit juices may also contain potentially toxic elements at trace levels, causing health risks. The objective of this work was to develop an analytical methodology based on the preconcentration of lead using a new biodegradable hybrid material composed of Rhodococcus erythropolis AW3 bacteria and Brassica napus hairy roots. The biodegradable hybrid material was implemented in an online solid phase extraction system for the determination of lead in fruit juices by electrothermal atomic absorption spectrometry. Effects of critical parameters on lead retention were studied. Under optimal experimental conditions, extraction efficiency higher than 99.9% and an enrichment factor of 62.5 were achieved. The dynamic capacity of the biodegradable hybrid material was 36 mg/g, which favored the reuse of the column to at least 8 biosorption-desorption cycles. The limit of detection and quantification for preconcentration of 5 mL of sample were 5.0 and 16.5 ng/L lead, respectively. The relative standard deviation was 4.8% (at 1 µg/L lead and n = 10). The developed method was suitable to be applied for lead determination in different types of fruit juices.

Identification of Turkish extra virgin olive oils produced in different regions by using NMR (1H and 13C) and IRMS (13C/12C)

AbstractIsotope ratio mass spectroscopy (IRMS) and nuclear magnetic resonance (NMR) spectroscopy techniques are two of the analytical methods that are used to characterize food products. The aim of this study is to classify extra virgin olive oil (EVOO) samples collected from different regions of Turkey based on 1H and 13C NMR spectra along with IRMS δ13C carbon isotope ratio data by using chemometrics multivariate data analysis methods. A total of 175 EVOO samples were analyzed in 2014/15 and 2015/16 harvest seasons. Multivariate classification and clustering models were used to identify geographical and botanical origins of the EVOOs. IRMS results showed that there was no significant difference in terms of δ13C values between the years in terms of harvest year (p > 0.05), only extraction phase and variety were statistically significant factors (p < 0.05). The interactions of the factors showed that the harvest year × variety interaction is important. The outcomes of this research clearly indicated that considering the partial least squares discriminant analysis result with NMR spectra, the percent success of the model in the South Marmara, North Aegean, and South Aegean region samples were 95%, 95.7%, and 96.4% in the model set, respectively. The results showed that by using classification and clustering models, geographic marking and labeling of these oils can be carried out regardless of differences in year and production systems (2 and 3 phase extraction system) according the NMR analysis.

Online micro solid phase extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry for trace analysis of endogenous plant hormones in Ulva linza.

Ulva linza (L.) is a species of green algae widely distributed in China. We aimed to establish a sensitive online analytical method for quantification of endogenous phytohormones in fresh minute seaweed samples. The method for quantification of endogenous plant hormones in fresh minute samples was developed based on a homemade online micro solid phase extraction (m-SPE) system coupled with an ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) platform. The online m-SPE instrument injected the eluent of m-SPE directly onto the LC separation column, improving the utilization of samples and saving time. The m-SPE column, of which the effective size was 9.6 × 2mm i.d., was filled with 19 mg of C18 (10μm). Under optimized conditions, the limits of detection were 0.002-0.060 ng ml-1 for five plant hormones. The actual sample recoveries of phytohormones were 76.4-103.4% and the coefficients of variance were below 14.1%. The temporal distribution of these endogenous plant hormones of U. linza during different growth periods is described. The proposed online m-SPE method was successfully applied to quantification of endogenous acidic and alkaline plant hormones in U. linza. It provides important information for the further study of the physiological and ecological effects of plant hormones in lower algal species.

Study of degradation of norfloxacin antibiotic and their intermediates by natural solar photolysis.

In this work, the photolysis of the antibiotic norfloxacin (NOR) and the formation of its photodegradation products were studied using UV and solar radiation. Their extraction was also assessed in Milli-Q water and secondary effluents from a wastewater treatment plant. The photolysis of NOR was chromatographically monitored. The structure of each degradation product is related to the reaction of NOR with reactive oxygen species (ROS), as confirmed using radical quenchers and mass spectrometry. Additionally, the feasibility of extracting NOR and its degradation products was assessed using a commercial solid phase extraction system. Photolysis results showed the formation of five degradation products, generated under exposure to both types of radiation. The decays in NOR concentrations for the solar and UV treatments were adjusted to pseudo first-order kinetics with apparent constant values of ksolar = 1.19 × 10-3s-1 and kUV = 3.84 × 10-5s-1. Furthermore, the superoxide radical was the main participant species in the formation of the degradation products P3, P4, and P5. Species P1 and P2 do not need this radical for their formation. The presence of NOR in water opens the possibility of its photolysis by solar radiation. This work contributes to the understanding of the mechanisms that mediate its photodegradation, in addition to studying potential options for its determination and its photodegradation products in the sample treatment.

An aqueous-two phase extraction system for partitioning of anthocyanins from red cabbage

An aqueous-two phase extraction system for partitioning of anthocyanins from red cabbage

Effect-directed analysis of a hospital effluent sample using A-YES for the identification of endocrine disrupting compounds

An effect-directed analysis (EDA) approach was used to identify the compounds responsible for endocrine disruption in a hospital effluent (Basque Country). In order to facilitate the identification of the potentially toxic substances, a sample was collected using an automated onsite large volume solid phase extraction (LV-SPE) system. Then, it was fractionated with a two-step orthogonal chromatographic separation and tested for estrogenic effects with a recombinant yeast (A-YES) in-vitro bioassay. The fractionation method was optimized and validated for 184 compounds, and its application to the hospital effluent sample allowed reducing the number of unknowns from 292 in the raw sample to 35 after suspect analysis of the bioactive fractions. Among those, 7 of them were confirmed with chemical standards. In addition, target analysis of the raw sample confirmed the presence of mestranol, estrone and dodemorph in the fractions showing estrogenic activity. Predictive estrogenic activity modelling using quantitative structure-activity relationships indicated that the hormones mestranol (5840 ng/L) and estrone (128 ng/L), the plasticiser bisphenol A (9219 ng/L) and the preservative butylparaben (1224 ng/L) were the main contributors of the potential toxicity. Derived bioanalytical equivalents (BEQs) pointed mestranol and estrone as the main contributors (56 % and 43 %, respectively) of the 50 % of the sample's explained total estrogenic activity.

High-Resolution Demultiplexing (HRdm) Ion Mobility Spectrometry-Mass Spectrometry for Aspartic and Isoaspartic Acid Determination and Screening.

Isomeric peptide analyses are an analytical challenge of great importance to therapeutic monoclonal antibody and other biotherapeutic product development workflows. Aspartic acid (Asp, D) to isoaspartic acid (isoAsp, isoD) isomerization is a critical quality attribute (CQA) that requires careful control, monitoring, and quantitation during the drug discovery and production processes. While the formation of isoAsp has been implicated in a variety of disease states such as autoimmune diseases and several types of cancer, it is also understood that the formation of isoAsp results in a structural change impacting efficacy, potency, and immunogenic properties, all of which are undesirable. Currently, lengthy ultrahigh-performance liquid chromatography (UPLC) separations are coupled with MS for CQA analyses; however, these measurements often take over an hour and drastically limit analysis throughput. In this manuscript, drift tube ion mobility spectrometry-mass spectrometry (DTIMS-MS) and both a standard and high-resolution demultiplexing approach were utilized to study eight isomeric Asp and isoAsp peptide pairs. While the limited resolving power associated with the standard DTIMS analysis only separated three of the eight pairs, the application of HRdm distinguished seven of the eight and was only unable to separate DL and isoDL. The rapid high-throughput HRdm DTIMS-MS method was also interfaced with both flow injection and an automated solid phase extraction system to present the first application of HRdm for isoAsp and Asp assessment and demonstrate screening capabilities for isomeric peptides in complex samples, resulting in a workflow highly suitable for biopharmaceutical research needs.

A non-aqueous phase extraction system using tributyl phosphate for H3PO4 separation from wet-process superphosphoric acid: Extraction equilibrium and mechanism

A non-aqueous phase extraction system using tributyl phosphate for H3PO4 separation from wet-process superphosphoric acid: Extraction equilibrium and mechanism

Study on the Stability of Antibiotics, Pesticides and Drugs in Water by Using a Straightforward Procedure Applying HPLC-Mass Spectrometric Determination for Analytical Purposes

The stability of analytes is a critical point in chemical analysis, especially in the field of trace levels residue analysis. Nowadays, due to advances in analytical technology and in separation sciences, the analyses of water have been improved. Unfortunately, in this context, one of the most critical issues in water analysis include compound stability from sampling station to laboratory procedures. This study was carried out to explore the stability of several compounds in water from sampling to analysis concerning analytes reported in implementing decision 2018/840—Watch List. During method development and validation, the stability of compounds was investigated to detect the best operating conditions concerning sampling, extraction and analysis. In this paper, we report a study on the stability of antibiotics, pesticides and drugs in water determined using a straight-forward procedure applying mass spectrometric detection for analytical purposes. The laboratory tests were performed in Milli-Q water and surface water by analyzing samples through direct injection, solvent mixture (Water/ACN) and solid phase extraction system from time 0 to 168 h. All the analytes of the WL are stable in aqueous solutions with the addition of at least 25% ACN even after 168 h, and the analytes have shown a matrix effect on recovery of some analytes such as Famoxadone from sampling results (recovery in surface water 72%). For all the analytes investigated, recoveries were between 70 and 130% by using SPE procedures before UHPLC-MS/MS analysis, which is in good agreement with method validation procedures.

Ion-imprinted resin for use in an automated solid phase extraction system for determining 90Sr in environmental and human samples

In 90Sr analysis, determining its daughter 90Y improves the sensitivity of the radiometric methods. We found that to imprint a cavity made of [Y(6-(4-Vinylphenylcarbamoyl)pyridine-2-carboxylate)3] into a polystyrene skeleton yields a solid phase extraction resin with high selectivity for Y and Ln(III) over transition metals, alkaline, and alkaline-earth cations. We used this resin in an automated chromatography system to extract 90Y from milk, grass, vegetables, soil, sediments, water, human bones, and milk teeth samples. We found that the ion-imprinted resin could be used to separate light Ln(III) using a pH gradient, favoring the targeting of molecules used in nuclear medicine.

Behavior evaluation of freundlich and langmuir isotherms in cadmium preconcentration using solid phase extraction method for linear and nonlinear numerical computational patterns

Cadmium is naturally present in the mineral cadmium sulfide which is a rare form of this element and the highest amount of cadmium is obtained from the extraction process of other minerals such as lead, copper and zinc. The release of this metal into the environment leads to widespread epidemiological effects. Therefore, measuring small amounts of this metal is also of particular importance. Small amount measuring methods of this metal are such as,preconcentration using solid phase extraction system using adsorbents. The main part of the preconcentration process is achieved by adsorption processes. In this study, the behavior of Freundlich and Langmuir adsorption isotherms for the capacity of TMON and IMNM adsorbents in cadmium adsorption has been evaluated by Power and Rational statistical distributions. At the end of the study, the constant coefficients of the Freundlich and Langmuir models were compared in both linear and non-linear modes. The results showed; the linearization method for the Kf coefficient of the Freundlich isotherm can cause errors equal to 41.6% in TMON adsorbent and 39.3% in IMNM adsorbent. Also, in parameter b, errors of 66.66% are obtained in TMON adsorbent and 32.45% in IMNM adsorbent.

Evaluation of inhibitors of the arachidonic acid cascade with intact platelets using an on-line dilution and on-line solid phase extraction HPLC–MS method

An automatic on-line dilution/on-line solid phase extraction (SPE) system has been developed for the detection of metabolites of the arachidonic acid cascade in platelets. The method allows the direct injection of larger quantities of centrifugates from cell suspensions previously treated with an equal volume of an acetonitrile/methanol mixture for protein precipitation. The method was used to study the effect of inhibitors of platelet arachidonic acid cascade enzymes (cytosolic phospholipase A2α, cyclooxygenase-1, thromboxane synthase, 12-lipoxygenase) and related targets (cyclooxygenase-2, microsomal prostaglandin E synthase-1, 5-lipoxygenase) in intact platelets after stimulation with calcium ionophore A23187. In addition to enzyme inhibition, the cell-damaging properties of the test compounds was determined by measuring the release of serotonin from the platelets into the incubation buffer.

A semi‐automatic solid phase extraction system based on MIL‐101(Cr) foam‐filled syringe for detection of triazines in vegetable oils

In this study, several metal-organic framework-melamine foam columns were first developed and used as a laboratory-made semi-automatic solid phase extraction packed in syringe adsorber for the extraction of six triazine herbicides from vegetable oil samples coupled to high-performance liquid chromatography-tandem mass spectrometry. The metal-organic framework-foam columns were prepared using a simple approach by embedding the solid particles in melamine foam using polyvinylidene difluoride physical encapsulation. The method was applicable to a wide variety of metal-organic framework materials, and the incorporated materials retained their unique properties. Key factors that affect the extraction efficiency, including the MIL-101(Cr) amount, sample flow rate, type and volume of the eluting solvent, and flow rate of eluting solvent, were investigated. Under optimum conditions, the proposed method exhibited low limits of detection (0.017-0.096ng/mL, S/N=3) for six triazines. The relative standard deviations calculated for all herbicides ranged from 0.2 to 14.9%. This study demonstrated that the MIL-101(Cr)-foam column can be used as a high-quality adsorption material for the detection of triazines in vegetable oils.

A Novel Glass Fiber Coated with Sol-Gel Poly-Diphenylsiloxane Sorbent for the On-Line Determination of Toxic Metals Using Flow Injection Column Preconcentration Platform Coupled with Flame Atomic Absorption Spectrometry.

A novel simple and sensitive, time-based flow injection solid phase extraction system was developed for the automated determination of metals at low concentration. The potential of the proposed scheme, coupled with flame atomic absorption spectrometry (FAAS), was demonstrated for trace lead and chromium(VI) determination in environmental water samples. The method, which was based on a new sorptive extraction system, consisted of a microcolumn packed with glass fiber coated with sol–gel poly (diphenylsiloxane) (sol–gel PDPS), which is presented here for the first time. The analytical procedure involves the on-line chelate complex formation of target species with ammonium pyrrolidine dithiocarbamate (APDC), retention onto the hydrophobic sol–gel sorbent coated surface of glass fibers, and finally elution with methyl isobutyl ketone prior to atomization. All main chemical and hydrodynamic factors, which affect the complex formation, retention, and elution of the metal, were optimized thoroughly. Furthermore, the tolerance to potential interfering ions appearing in environmental samples was also explored. Enhancement factors of 215 and 70, detection limits (3 s) of 1.1 μg·L−1 and 1.2 μg·L−1, and relative standard deviations (RSD) of 3.0% (at 20.0 μg·L−1) and 3.2% (at 20.0 μg·L−1) were obtained for lead and chromium(VI), respec tively, for 120 s preconcentration time. The trueness of the developed method was estimated by analyzing certified reference materials and spiked environmental water samples.

Digitally enhanced molecular dispersion spectroscopy.

A frequency and intensity noise immune fiber dispersion spectrometer with a digitally enhanced homodyne phase extraction system is presented. A hydrogen cyanide (H13CN) vapor cell is placed in a digitally enhanced Sagnac interferometer, and the anomalous dispersion at the 1550.515 nm P11 transition is interrogated with a tunable laser. An analytical model of the dispersion induced phase readout shows close agreement with the experimentally obtained phase signal. Immunity to frequency and intensity noise confers sub-microradian phase sensitivity, corresponding to a spectroscopic detection limit of 77ppb×m/Hz.