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Properties of Analytes/Matrices in Selection of Chromatographic Methods and Detection Techniques

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Analytical Chemistry".

Deadline for manuscript submissions: closed (1 November 2020) | Viewed by 15533

Special Issue Editor


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Guest Editor
Department of Physical Chemistry, Medical University of Lublin, Chodźki 4a, 20-093 Lublin, Poland
Interests: liquid chromatography with modern detection techniques; sample preparation; analysis of xenobiotics in various biological samples; analysis of ionic compounds in plant extracts; biological activity of plant extracts
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Special Issue Information

Dear Colleagues,

Many modern analytical techniques are used in analyte residue analysis. The method selected depends on the complexity of the sample, the natures of the matrices and the analytes, and the analytical techniques available. The most efficient approach to analyte identification and quantitative analysis involves the use of chromatographic methods.

The following chromatographic methods are most frequently applied to the determination of analytes: high-performance liquid chromatography (HPLC), ultrahigh-performance liquid chromatography (UPLC), gas chromatography (GC) and multidimensional chromatographic techniques (GC x GC, LC x LC). These methods are used for the quantitative analysis of compounds in different matrices, e.g., environmental and biological samples, and food analysis.

The choice of an appropriate extraction and analytical method for separation and final determination is closely related to the properties of the target compounds and matrices. Common steps in the sample treatment for most of the analytical methods reported for mixtures of analytes include sample pretreatment, the extraction of analytes from the matrix, cleanup of the extracts to remove interference, and concentration to achieve the desired sensitivity. Incontestable progress has been made in the past years regarding the development of preparation techniques for sample analysis such as QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe), Solid Phase Extraction (SPE), Solid Phase Microextraction (SPME), Stir Bar Sorptive Extraction (SBSE), Hallow-Fiber Liquid Phase Microextraction (HFLPME), Dispersive Liquid-Liquid Microextraction (DLLME) or Focused Ultrasonic Solid-Liquid Extraction (FUSLE), and others.

The challenge for the analyst is to develop effective and validated analytical strategies for the analysis of hundreds of different analytes on hundreds of different sample types, quickly, accurately and at acceptable cost. HPLC or UPLC are the principal separation techniques in the analysis of almost all types of samples. For example, HPLC-DAD enables peak purity control and the group identification (or class identification) of analytes.

Sometimes the resolving power attainable with a single chromatographic system is insufficient for the analysis of complex mixtures. The coupling of chromatographic techniques is clearly attractive for the analysis of multicomponent mixtures of compounds. Analysis of the compounds present at low concentrations in complex mixtures is especially challenging because the number of interfering compounds present at similar or higher concentrations increases exponentially as the concentrations of target compounds decrease. Truly comprehensive 2-D hyphenation is generally achieved by frequent sampling from a first column into a second, which is a very rapid analysis. Multidimensional LC has long been seen as a potential solution to increase the resolution and improve the speed of analysis, particularly in the separation of complex mixtures, for example, pesticides in natural samples. Multidimensional LC methods are typically divided into two main groups: comprehensive separations (denoted LC × LC for a 2-D separation) concerned with the separation and quantification of large numbers (ca. tens to thousands) of constituents of a sample, and targeted “heart-cutting” or “coupled-column” methods (LC–LC for a 2-D separation) concerned with the analysis of a few (ca., 1–5) constituents of the sample matrix. In the past decade, research on the development of practically useful LC × LC has been particularly active. Multidimensional LC is a good alternative to multidimensional GC for polar or thermolabile compounds. Polar compounds need to be derivatized for GC analysis, and this is not necessary for LC.

This Special Issue will present in a properly structured manner up-to-date, state of the art information on the very important field of high-performance chromatographic techniques coupled with modern detection techniques (e.g., DAD, FLD, mass spectrometry (MS) or tandem mass spectrometry (MS/MS)). It is a well-established fact that chromatographic techniques with mass spectrometry (MS) or tandem mass spectrometry (MS/MS) find broad application in the separation, identification, and quantification of the majority of the important analytes.

I warmly invite colleagues to submit their original contributions to this Special Issue, which will be of interest to a wide range of our readers!

I would be delighted if you could respond to confirm your contribution and the proposed title by 30 June 2020 to assist in planning the whole project. In the cases of review articles an additional brief (1–2 pages) description of the topic including a draft index is required. This preliminary step is essential to avoid the overlapping of topics. The degree of novelty and the significance of the research will be scrutinized prior to the peer-reviewing process.

Dr. Tomasz Tuzimski (Ph.D., Adjunct Professor)
Guest Editor

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Keywords

  • analytes (basic, acidic, neutral, ionic, nonionic and others)
  • extraction techniques (QuEChERS/d-SPE, SPE, SPME, SBSE, HFLPME, DLLME, FUSLE, and others)
  • chromatographic methods (HPLC, UPLC, LC x LC, LC-LC, GC, GC x GC, GC-GC, and others)
  • detection techniques (DAD, FLD, MS, MS/MS, and others).

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Published Papers (4 papers)

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Research

22 pages, 2173 KiB  
Article
Development and Application of a Novel QuEChERS Method for Monitoring of Tributyltin and Triphenyltin in Bottom Sediments of the Odra River Estuary, North Westernmost Part of Poland
by Dawid Kucharski, Przemysław Drzewicz, Grzegorz Nałęcz-Jawecki, Kamila Mianowicz, Artur Skowronek and Joanna Giebułtowicz
Molecules 2020, 25(3), 591; https://doi.org/10.3390/molecules25030591 - 29 Jan 2020
Cited by 10 | Viewed by 3193
Abstract
A Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction method combined with Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) for determination of organotin compounds (OTC) has been newly developed. The novel analytical method was validated and the quality of the results was tested by [...] Read more.
A Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction method combined with Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) for determination of organotin compounds (OTC) has been newly developed. The novel analytical method was validated and the quality of the results was tested by the use of certificate reference material of freshwater sediment BCR 646. The method was applied in determination of OTC concentration in real samples of bottom sediments collected from the Polish part of Odra River Estuary. The samples came from locations with different anthropogenic impact. Additionally, the extraction recovery of OTC and matrix effect on MS signal response was investigated based on those real environmental samples. It was found that organic compounds and anthropogenic contaminations present in bottom sediments may affect extraction efficiency of the organotin compounds (OTC) and change the matrix effect on MS signal response. The highest concentrations of tributyltin were found in bottom sediments collected from locations in vicinity of the Szczecin harbor and shipyards. The presence of triphenyltin above limit of detection (5 ng TPhT/g of sediment) was observed only in two samples and its concentration was several times lower compared to concentration of tributyltin (from 58 ng/g to 5263 ng/g). In spite of the fact that, the application of TBT-based paints on hull of vessel entering EU ports has been banned by European Commission regulation No. 782/2003 since 2008, the OTC compounds are still present in bottom sediment and pose significant threat to the environment. This threat should be taken into account during dredging of waterways and other hydrotechnical works. Full article
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11 pages, 2497 KiB  
Article
Matrix-Induced Sugaring-Out: A Simple and Rapid Sample Preparation Method for the Determination of Neonicotinoid Pesticides in Honey
by Wenbin Chen, Siyuan Wu, Jianing Zhang, Fengjie Yu, Jianbo Hou, Xiaoqing Miao and Xijuan Tu
Molecules 2019, 24(15), 2761; https://doi.org/10.3390/molecules24152761 - 30 Jul 2019
Cited by 19 | Viewed by 3954
Abstract
In the present work, we developed a simple and rapid sample preparation method for the determination of neonicotinoid pesticides in honey based on the matrix-induced sugaring-out. Since there is a high concentration of sugars in the honey matrix, the honey samples were mixed [...] Read more.
In the present work, we developed a simple and rapid sample preparation method for the determination of neonicotinoid pesticides in honey based on the matrix-induced sugaring-out. Since there is a high concentration of sugars in the honey matrix, the honey samples were mixed directly with acetonitrile (ACN)-water mixture to trigger the phase separation. Analytes were extracted into the upper ACN phase without additional phase separation agents and injected into the HPLC system for the analysis. Parameters of this matrix-induced sugaring-out method were systematically investigated. The optimal protocol involves 2 g honey mixed with 4 mL ACN-water mixture (v/v, 60:40). In addition, this simple sample preparation method was compared with two other ACN-water-based homogenous liquid-liquid extraction methods, including salting-out assisted liquid-liquid extraction and subzero-temperature assisted liquid-liquid extraction. The present method was fully validated, the obtained limits of detection (LODs) and limits of quantification (LOQs) were from 21 to 27 and 70 to 90 μg/kg, respectively. Average recoveries at three spiked levels were in the range of 91.49% to 97.73%. Precision expressed as relative standard deviations (RSDs) in the inter-day and intra-day analysis were all lower than 5%. Finally, the developed method was applied for the analysis of eight honey samples, results showed that none of the target neonicotinoid residues were detected. Full article
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16 pages, 2826 KiB  
Article
Combination of Three Functionalized Temperature-Sensitive Chromatographic Materials for Serum Protein Analysis
by Weiwei Sun, Rongji Dai, Bo Li, Guoxin Dai, Di Wang, Dandan Yang, Pingping Chu, Yulin Deng and Aiqin Luo
Molecules 2019, 24(14), 2626; https://doi.org/10.3390/molecules24142626 - 19 Jul 2019
Cited by 2 | Viewed by 2888
Abstract
We have developed a methodology to capture acidic proteins, alkaline proteins, and glycoproteins separately in mouse serum using a combination of three functionalized temperature-responsive chromatographic stationary phases. The temperature-responsive polymer poly(N-isopropylacrylamide) was attached to the stationary phase, silica. The three temperature-responsive [...] Read more.
We have developed a methodology to capture acidic proteins, alkaline proteins, and glycoproteins separately in mouse serum using a combination of three functionalized temperature-responsive chromatographic stationary phases. The temperature-responsive polymer poly(N-isopropylacrylamide) was attached to the stationary phase, silica. The three temperature-responsive chromatographic stationary phase materials were prepared by reversible addition–fragmentation chain transfer polymerization. Alkaline, acidic, and boric acid functional groups were introduced to capture acidic proteins, alkaline proteins, and glycoproteins, respectively. The protein enrichment and release properties of the materials were examined using the acidic protein, bovine serum albumin; the alkaline protein, protamine; and the glycoprotein, horseradish peroxidase. Finally, the three materials were used to analyze mouse serum. Without switching the mobile phase, the capture and separation of mouse serum was achieved by the combination of three temperature-responsive chromatographic stationary phase materials. On the whole, 313 proteins were identified successfully. The number of different proteins identified using the new method was 1.46 times greater than the number of proteins that has been identified without applying this method. To our knowledge, this method is the first combinatorial use of three functionalized temperature-responsive chromatographic stationary phase silica materials to separate proteins in mouse serum. Full article
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20 pages, 2121 KiB  
Article
Comparison of Various Chromatographic Systems for Analysis of Cytisine in Human Serum, Saliva and Pharmaceutical Formulation by HPLC with Diode Array, Fluorescence or Mass Spectrometry Detection
by Karol Wróblewski, Anna Petruczynik, Tomasz Tuzimski, Dominika Przygodzka, Grzegorz Buszewicz, Patrycjusz Kołodziejczyk and Piotr Tutka
Molecules 2019, 24(14), 2580; https://doi.org/10.3390/molecules24142580 - 16 Jul 2019
Cited by 9 | Viewed by 4795
Abstract
Background: Identification and quantitative determination of cytisine, especially in biological samples and pharmaceutical formulations, is still a difficult analytical task. Cytisine is an alkaloid with a small and very polar molecule. For this reason, it is very weakly retained on reversed phase (RP) [...] Read more.
Background: Identification and quantitative determination of cytisine, especially in biological samples and pharmaceutical formulations, is still a difficult analytical task. Cytisine is an alkaloid with a small and very polar molecule. For this reason, it is very weakly retained on reversed phase (RP) stationary phases, such as commonly used alkyl-bonded phases. The very weak retention of cytisine causes it to be eluted together with the components of biological matrices. Objective: Comparison and evaluation of various chromatographic systems for analysis of cytisine in different matrices—serum, saliva and pharmaceutical formulation—by high performance liquid chromatography (HPLC) with diode array (DAD), fluorescence (FLD) and mass spectrometry (MS) detection. Methods: The analyses were performed using HPLC in reversed phase (RP), hydrophilic interaction liquid chromatography (HILIC) and ion exchange chromatography (IEC) modes. Different sample pre-treatment methods were tested: Protein precipitation (with acetone, methanol (MeOH) or acetonitrile (ACN), and solid phase extraction (SPE) using cartridges with octadecyl (C18), hydrophilic-lipophilic balanced copolymer (HLB) or strong cation exchange sorbents (Strata X-C). Conclusion: Significant differences were observed in retention parameters with a change of the used chromatographic system. The various properties of stationary phases resulted in differences in analyte retention, peaks’ shape and systems’ efficiency. The weakest retention was observed using RP systems; however, the use of the Polar RP phase can be an alternative for application in green chromatography. In the strongest retention was observed using a strong cation exchange (SCX) phase. The most optimal systems were chosen for the analysis of cytisine in the pharmaceutical preparation, serum and saliva after sample pre-treatment with the new SPE procedure. Due to the sensitivity, the use of HPLC-DAD or HPLC-FLD is the most optimal for drug analysis in pharmaceutical preparations, whereas HPLC-MS is suitable for analysis of cytisine in biological samples. Full article
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