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In The Name Of God

In The Name Of God. Sanja Risticevic and Janusz Pawliszyn. Solid-Phase Microextraction in Targeted and Nontargeted Analysis: Displacement and Desorption Effects. Supervisor: Dr.M.Saraji. Mohammad Javad Hosseinishahi. Introduction Experimental section Results and discussion Conclusions

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In The Name Of God

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  1. In The Name Of God

  2. Sanja Risticevic and Janusz Pawliszyn Solid-Phase Microextraction in Targeted and Nontargeted Analysis:Displacement and Desorption Effects Supervisor: Dr.M.Saraji Mohammad Javad Hosseinishahi

  3. Introduction Experimental section Results and discussion Conclusions Reference

  4. Introduction • Solid-phase microextraction (SPME) was introduced in 1990 • This nonexhaustive and environmentally friendly technique integrates sampling, extraction, concentration, and sample introduction into a simple solvent-free procedure • SPME involves the use of a fibre coated with an extracting phase, that can be a liquid (Polymer) or a solid (Sorbent) • After extraction, the SPME fibre is transferred to the injection port of separating instruments, such as a GC

  5. Introduction Initial concentration of analyte in the sample volume of the extraction phase fiber coating/sample matrix distribution constant of the analyte the extracted amount at equilibrium

  6. Introduction volume of the extraction phase fiber coating/sample matrix distribution constant of the analyte fiber constant

  7. Experimental section A) Chemicals and Materials B) Sample Preparation C) SPME Procedure D) Instrument

  8. Chemicals and Materials HPLC-grade methanol and acetone Analyte standards were all of >97% purity (except for >95% purity for heptanal, nonanal, citral isomers, farnesol isomers, dodecanal, tridecanal, and linalool) Commercial SPME fiber assemblies in 23-gauge needle sizes and automated formats (100 μm PDMS), 85 μm (PA), 60 μm (CW) [metal], 65 μm PDMS/ (DVB), 85 μm (CAR)/PDMS, 50/30 μm DVB/CAR/PDMS, and 16 μm of Carbopack Z/PDMS [metal]) were obtained from Supelco The automated SPME holder and10 and 20 mL screw cap vials were purchased from Supelco

  9. Sample Preparation 3ml 250 ml Water 100 g of apple tissue 250 ml NaCl

  10. SPME Procedure The aqueous extraction standards and apple samples were analyzed fresh by HS-SPME at 30 °C using a 500 rpm agitation speed and 60 min extraction time t test was used to determine whether extraction equilibrium was reached for a particular component. To compare DVB/CAR/PDMS and PDMS/DVB coatings interms of extraction kinetics and desorption efficiency, extraction time profiles were performed with 5, 30, 60, and 120 min points. Interanalyte displacements were examined by analyzing aqueous calibration standards with 30 and 60 min extraction times and apple samples with 1, 5, 15, 30, 60, 120, and 180 min extraction times. All samples were analyzed at 30 °C

  11. Instrumental GC × GC/ToFMS Details: Primary dimension columns employed (30 m × 0.25 mm i.d. × 0.25 μm) Secondary dimension columns employed (1.15 m × 0.10 mm i.d. × 0.10 μm)

  12. Results and Discussions A) Trends in Coating Selectivity and Sensitivity B) Desorption Efficiency of Commercial Coatings C) Determination of the Linear Dynamic Range and Interanalyte Displacements

  13. Trends in Coating Selectivity and Sensitivity DVB/CAR/PDMS PDMS/DVB PDMS PDMS, PDMS/DVB, and DVB/CAR/PDMS coatings extracted all of the investigated metabolites

  14. Trends in Coating Selectivity and Sensitivity Carbopack Z/PDMS CAR/PDMS CW PA while only 47, 50, 44 and 39 peaks were extracted with PA, CAR/PDMS, CW, and Carbopack Z/PDMS coatings, respectively

  15. Trends in Coating Selectivity and Sensitivity Some nonpolar components such as: a) octane b) nonane Not detected PA Moderately polar such as: a) 2-hexanone b) Hexanal c) ethyl butanoate Nonpolar analytes octane to undecane Not detected CW Moderately polar Analytes such as: a) 2-hexanone b) Hexanal c) ethylbutanoate d) α-pinene e) eucalyptol This extraction phase was found to be unsuitable for the extraction of small molecular weight analytes Carbopack Z/PDMS Pore size is 100 Å

  16. Trends in Coating Selectivity and Sensitivity Fiber constants are reported for PDMS, PA, DVB/CAR/PDMS, and PDMS/DVB coatings, since the implementation of these coatings in spiked water analysis resulted insatisfactory reproducibility. In the worst-case scenario, for the PA coating, RSD ranged from 0.9% for linalool to 25.4% for ethyl stearate This result is attributed to the difference in the average sizes of the micropore diameter between Carboxen 1006 in DVB/CAR/PDMS and CAR/PDMS coatings and DVB in PDMS/DVB and DVB/CAR/PDMS coatings (12 and 16 Å, respectively).

  17. Trends in Coating Selectivity and Sensitivity The trends in extraction efficiencies obtained with PDMS/DVB and CAR/PDMS coatings are also illustrated in Figure Contour plots of extracted ion chromatograms (the x- and y-axes represent the retention times in the first and second dimensions) corresponding to 60 min HS-SPME extraction of an aqueous sample spiked with 52 metabolites and obtained with (A) PDMS/DVB and (B) CAR/PDMS coatings. S1Table Page 2 - 3

  18. Trends in Coating Selectivity and Sensitivity The largest improvement in extraction sensitivity was achieved with DVB /CAR /PDMS for analytes having molecular weights of <185 g/mol. Likewise, since the ability of an adsorbent to extract a particular analyte is strongly dependent on the average size of the micropore diameter, KfsVf improvements of 11-fold for 2-pentanol and 4-fold for α-pinene, 1-pentanol, e2-hexanone, and 2-hexanol were detected when DVB /CAR /PDMS was compared to PDMS/DVB Above this molecular weight threshold, the performance of the two coatings was similar across the hydrophobicity and volatility range PDMS/DVB performed slightly better only for the latest eluting members of each homologous series. A – < 100 g/mol B – between 100 and 120 g/mol C – between 180 and 215 g/mol

  19. Desorption Efficiency of Commercial Coatings Memory Effect For DVB /CAR /PDMS & CAR/PDSM

  20. Desorption Efficiency of Commercial Coatings 5, 30, 60 and 120 min extraction A – 1-nonanol, B – 1-undecanol, C – 1-pentadecanol and D-1-heptadecanol

  21. Determination of the Linear Dynamic Range and Interanalyte Displacements Determination of linear dynamic range (LDR, 9-point calibration curve, each point run in triplicates) and method repeatability for actual spiked metabolite concentrations employed in coating evaluation study for experimental design involving DVB/CAR/PDMS coating and 60 min HS-SPME extraction S3Table Page 15-16

  22. Determination of the Linear Dynamic Range and Interanalyte Displacements Figure 2. SPME calibration curves for 2-pentanol (A; 60 and 30 min extraction times employed) and 2-heptadecanone (B) for aqueous samples spiked with 52 metabolites and analyzed with DVB /CAR /PDMS fiber coating at 30 °C

  23. Determination of the Linear Dynamic Range and Interanalyte Displacements Extraction time (1−180 min) uptakes of major components in the apple matrix exhibiting high HS-SPME sensitivity and selectivity: (A) ethyl butanoate, (B) ethyl 2-methylbutanoate, (C) hexylhexanoate.

  24. Determination of the Linear Dynamic Range and Interanalyte Displacements DVB/CAR/PDMS extraction time profiles of nonane (plot A), nonanal (plot B) and 1-nonanol (plot C)

  25. Determination of the Linear Dynamic Range and Interanalyte Displacements HS-SPME extraction time profiles of representative low S/N and low KfsVf polar compounds in the apple matrix: (A) (2Z)-2-penten-1-ol and (B) (3Z)-3-hexen-1-ol

  26. Determination of the Linear Dynamic Range and Interanalyte Displacements HS-SPME extraction time profiles of selected compounds in apple homogenate for which the occurrence of interanalyte displacement was detected: (A) 1-methoxybutane, (B) 2-methylpropanol

  27. Determination of the Linear Dynamic Range and Interanalyte Displacements HS-SPME extraction time profiles of selected compounds in apple homogenate for which the occurrence of interanalyte displacement was detected: (A) 1-methoxybutane, (B) 2-methylpropanol

  28. Conclusions the results obtained in this study clearly demonstrate that nonpolar high Henry’s constant compounds that have high Kfs are not displaced The wide volatility, hydrophobicity, polarity, and molecular weight ranges of compounds considered in this systematic study allowed for a comprehensive evaluation of performance characteristics of commercially available SPME−GC fiber coatings in terms of extraction sensitivity, desorption efficiency, and feasibility in complex sample analysis The investigation of complex mixtures with DVB/CAR/PDMS revealed that interanalyte displacements are infrequent. The only analytes that were affected by interanalyte competition for adsorption sites included small molecular weight and early-eluting compounds with medium to high polarity and low fiber constants

  29. References (1) Arthur, C. L.; Pawliszyn, J. Anal. Chem. 1990, 62, 2145−2148. (2) Pawliszyn, J. In Handbook of Solid Phase Microextraction; Pawliszyn, J., Ed.; Chemical Industry Press: Beijing, China, 2009; pp. 54-1 (3) Risticevic, S.; Niri, V. H.; Vuckovic, D.; Pawliszyn, J. Anal. Bioanal. Chem. 2009, 393, 781−795. (4) Risticevic, S.; Chen, Y.; Kudlejova, L.; Vatinno, R.; Baltensperger, B.; Stuff, J. R.; Hein, D.; Pawliszyn, J. Nat. Protoc. 2010, 5, 162−176. (5) Pawliszyn, J. In Solid Phase Microextraction: Theory and Practice; Pawliszyn, J., Ed.; Wiley-VCH: New York, 1997; pp 11−96. (6) Baltussen, E.; Cramers, C. A.; Sandra, P. J. F. Anal. Bioanal. Chem. 2-3 , 373 , 2002 (7) Nongonierma, A.; Cayot, P.; Quéré, J. L.; Springett, M.; Voilley, A. Food Rev. Int. 2006, 22, 51−94. (8) Musteata, F. M.; Pawliszyn, J. J. Proteome Res. 2005, 4, 789−800. (9) Günther, C. S.; Matich, A. J.; Marsh, K. B.; Nicolau, L. Food Res. Int. 2011, 44, 1331−1338. (10) Robinson, A. L.; Boss, P. K.; Heymann, H.; Solomon, P. S.; Trengove, R. D. J. Chromatogr., A 2011, 1218, 504−517. (11) Harrigan, G. G.; Martino-Catt, S.; Glenn, K. C. Metabolomics. 272-2759 , 3 , 2007 (12) Fiehn, O.; Wohlgemuth, G.; Scholz, M.; Kind, T.; Lee, D. Y.; Lu, Y.; Moon, S.; Nikolau, B. Plant J. 2008, 53, 691−704. (13) Lόpez, R.; Lapeña, A. C.; Cacho, J.; Ferreira, V. J. Chromatogr., A. 15-8 , 1143 ,2007

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  31. Thanks a lot for attention

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