Poster Presentation - Separation Techniques 2018
Ruslan Dedishov
SepSolve Analytical, United Kingdom
Dual-channel GC×GC-FID for routine TPH analyses
Ruslan Dedishov(Biography)
Ruslan Dedishov is Technical Sales Professional at Markes International GmbH. During the last 2 years he was focused on supporting and leading projects in the fi eld of trace analysis using GCMS technology. Before this role, Dedishov was developing and coordinating OEM business division at Knauer GmbH. Dedishov holds a degree in food chemistry from Julius Maximilians University of Wuerzburg, Germany
Ruslan Dedishov(Abstract)
The determination of aliphatic/aromatic compounds when performing Total Petroleum Hydrocarbon (TPH) analysis is typically a lengthy process – with solid phase extraction (SPE) to separate aliphatics into hexane and aromatics into dichloromethane, prior to two separate GC analyses per sample.The enhanced separation of comprehensive two-dimensional chromatography (GC×GC) negates the requirement for laborious sample fractionation, saving a significant amount of extraction and processing time, while also reducing consumable costs. Instead of two separate analyses, the traditional ‘boiling point’ separation is maintained in the first dimension while the aliphatic and aromatic compounds are separated in the second dimension. Fast and confident group-type quantitation is then performed, using simple data processing tools. Stencils are applied to group peaks into chemical classes (e.g. C8-C10, C10-C14 etc) based on their elution region. The use of flow rather than thermal modulation, ensures excellent retention time repeatability across large sample batches, enabling automated data processing to be performed with minimal operator intervention. Furthermore, here we demonstrate a dual-channel configuration, doubling the sample throughput per instrument - increasing productivity, reducing bench space and lowering installation costs, all while meeting the criteria set out in standard methods (e.g. TPH Criteria Working Group and Massachusetts Department of Environmental Protection).
Dedishov Ruslan
SepSolve Analytical, United Kingdom
Aroma profiling of pet food using high-capacity sorptive extraction and TD–GC×GC–TOF MS
Dedishov Ruslan(Biography)
Ruslan Dedishov is Technical Sales Professional at Markes International GmbH. During the last 2 years he was focused on supporting and leading projects in the fi eld of trace analysis using GCMS technology. Before this role, Dedishov was developing and coordinating OEM business division at Knauer GmbH. Dedishov holds a degree in food chemistry from Julius Maximilians University of Wuerzburg, Germany
Dedishov Ruslan(Abstract)
Pet food manufacturers place great importance on the aroma of their products, as off-odours may be unappealing to both the pets and their owners. Confident identification of the volatile organic compounds (VOCs) from pet food can help these companies better understand the factors governing the release of pleasant and unpleasant aromas. VOC aroma profiles are typically analysed by solid-phase micro-extraction (SPME), which although a fast and simple technique, can be limited in terms of sample capacity, reproducibility and sensitivity. An alternative to SPME is high-capacity probe-based sorptive extraction, which results in higher sample loadings because of the large volume of PDMS phase. Typically, a SPME fiber has a sorbent volume of just 0.5 µL, while the sorptive extraction probes used in this study contain 65 µL of sorbent. When used in conjunction with secondary refocusing by thermal desorption (TD), the result is greater sensitivity across a wide analyte range. Further analytical benefits can be achieved for analyte separation and detection, by using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC–TOF MS). The enhanced separation capacity of this approach is ideal for handling the complex aroma samples of pet food, because it allows the entire composition to be screened in a single analysis, with confident identification of compounds that would ordinarily co-elute. Here we demonstrate the value of high-capacity sorptive extraction with TD–GC×GC–TOF MS to investigate the volatile compounds present in the headspace of pet food, and discuss how these compounds might influence their aroma profiles.
Menglin Li
Institute of Materia Medica CAMS & PUMC, China
Profile proteins/peptides composition in zein excipient by silver staining SDS-PAGE and LC-MS/MS
Menglin Li(Biography)
Dr. Menglin Li is an assistant professor of National Research Center for Analysis of Drugs and Metabolites at PUMC&CAMS. I have many years of research experience in the field of proteomics. The projects which I performed include establishment of multidimensional chromatographic separation technique, in-depth identification of urinary proteome, and injury mechanism of triptolide in the rat model by using quantitative proteomics and targeted fatty acids analysis. At the same time, I participated in a variety of new drug research, including the anti-tumor mechanism of chlorogenic acid, the safety evaluation of pharmaceutical excipients and other projects. Research Interests: Proteomics, Lipodomics, Protein separation method
Menglin Li(Abstract)
Zein, one of the most critical protein products extracted from maize seeds, is extensively used in oral controlled drug and biomedical delivery systems as protein-based polymers. The commercial zein products usually form a mixture of zein types. According to the general idea, zein was differentiated into α, β, δ, and γ zein. However, zein being of protein origin, it still has limited application due to the possible immunogenicity. To ensure its safety, comprehensive analysis of its proteins/peptides component is necessary. Here we used proteomics analysis to uncover the proteins/peptides components in zein products. By using silver staining SDS-PAGE and in-gel digestion coupled with LC-MS/MS, we identified nine distinct proteins in zein products. The zein peptidome was also explored by MS and further analyzed by PEAKS Studio. In total 399 peptides originated from 69 proteins were discovered. Among of these, 70 peptides were predicted to have biological activity. Our research uncovered the complex component in zein excipient. Knowledge of these identified proteins/peptides has the potential to improve its safety and expand its application as a biomaterial.
Zhe Wang
Institute of Materia Medica CAMS & PUMC, China
A novel strategy to rapid characterization and quantification of commercial polysorbate 80 by high performance liquid chromatography with quadrupole time-of-flight mass spectrometry and computer-aided data analysis
Zhe Wang(Biography)
Dr. Zhe Wang is a research assistant in Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College. He has engaged in the research of pharmacuetical analysis and drug metabolism since 2009, including drug metabonomics, drug metabolic flux analysis, pharmacokinetics, drug metabolites discovery and identification, illegal adulterants detection in health foods, doping control. He has published 6 papers (first author), including: Journal of Chromatography B, 2017, 1040: 250; Phytomedicine, 2016, 23: 621; Journal of Separation Science, 2015, 38: 925, etc. Research Interests: Analytical method and strategy for discovery, identification and determination of target multiple compounds in complex matrix samples, such as plasma, urine and herbal medcine, using different effective separation techniques.
Zhe Wang(Abstract)
Polysorbate 80, as a nonionic surfactant with high surface activity and low toxicity, is widely used in the pharmaceutical, personal care and food industries. However, due to its complexity of composition and similarity of compound skeleton, it is difficult to be analyzed rapidly and comprehensively. In this work, a novel strategy was developed to characterize and quantify the commercial polysorbate 80 by high performance liquid chromatography with quadrupole time-of-flight mass spectrometry (HPLC-Q/TOF MS) and computer-aided data analysis. Firstly, a HPLC-Q/TOF MS method was established, and 143 compounds of 7 main high abundance groups in polysorbate 80 were discovered and identified, including: polyethylene oxide(PEO)- sorbitan, PEO-isosorbitan, PEO-sorbitan-monooleate, PEO-isosorbitan-monooleate, PEO-sorbitan-dioleate, PEO-isosorbitan-dioleate, positional isomers of PEO-sorbitan-dioleate and PEO-sorbitan-trioleate. Then their structures were further confirmed by 1H-NMR and 13C-NMR technology. In addition, 55 trace components in the polysorbate 80 were also identified, including: PEO, PEO-monooleate, PEO-sorbitan-monolinoleate, PEO-sorbitan-monostearate and PEO-sorbitan-monopalmitate. Secondly, colligative properties between the precise molecular weight and retention time of compounds in each group were found. Using these properties, compounds can be rapidly and accurately categorized and calculated the polymerization degree of PEO. Lastly, an automatic identification software of polysorbate 80 based on the above results was developed. After importing the LC-MS data into this software, compounds in commercial polysorbate 80 samples can be identified by molecular weight and retention time, further confirmed by fragment ions and relatively quantified by peak area, realizing rapid, accurate and comprehensive qualitative and quantitative analysis.
Ting Hu
Institute of Materia Medica CAMS & PUMC, China
A novel UPLC/MS/MS method for comprehensive profiling and quantification of fatty acid esters of hydroxy fatty acids in white adipose tissue
Ting Hu(Biography)
Fatty acid esters of hydroxy fatty acid (FAHFA) is a novel lipid class with antidiabetic and anti-inflammatory effects. In this paper, a novel UPLC/MS/MS method was developed for comprehensive profiling and quantification of FAHFAs. Through optimization of the chromatographic conditions, FAHFA isomers can be efficiently separated and quantified in 29 min with excellent peak shapes and good robustness. Ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight (UPLC/Q-TOF-MS) was employed for FAHFAs identification based on the high resolution m/z values and the fragmentation rules. The specific precursor-product ions of FAHFAs identified by UPLC/Q-TOF-MS were further transmitted to the UPLC/MS/MS instrument for their quantification under the multiple reaction monitoring (MRM) scan mode. A total of 64 FAHFAs, belonged to 17 different family members, was identified in white adipose tissue (WAT) of golden hamsters. Nine of the 17 FAHFA family members were newly discovered in this paper. And linoleic acid and linolenic acid are newly found building blocks of FAHFAs in WAT. The total FAHFA number detected from WAT were far larger than any of the previously reported works. Finally, this method was employed to investigated the disturbance of FAHFAs under the pathological condition of hyperlipidemia and the fenofibrate regulation effects of FAHFA.
Ting Hu(Abstract)
Ting Hu, PhD student of the Institute of Materia Medica, Peking Union Medical College & Chinese Academy of Medical Sciences. Her research focused on lipidomics research, mainly the development of new analytical method for lipid molecules, which are endogenously low abundances and difficult to detect. Research Interests: LC-MS method development
Soon Uk Chae
The Catholic University of Korea, South Korea
Determination of cyaniding 3-glucoside in rat plasma using LC-MS/MS and its application to a pharmacokinetic study of aronia extracts
Soon Uk Chae(Biography)
Soon Uk Chae is a graduate student with major in pharmacology/pharmacokinetics of The Catholic University of Korea. Research Interests: Bioanalysis, Non-clinical pharmacokinetics, In vivo drug-drug interaction study
Soon Uk Chae(Abstract)
Cyanidine-3-glucoside(C3G) is the most abundant in the aronia extract and has an excellent antioxidation, antidiabetic activity and excellent anti-inflammatory and antipruritic effects. Thus it has been increasingly utilized as health functional foods and materials. A simple and rapid LC‒MS/MS method was developed and validated to determine the levels of cyanidine-3-glucoside in rat plasma. Cyanidine-3-glucoside was extracted from 50 μL of plasma treated with 25 μL of 1 M HCl, stored on ice after protein precipitation with 20% trifluoroacetic acid. Chromatographic separation was performed on Agilent Poroshell 120 EC- C18 column (4.6 x 50 mm id, 2.7 μm). The mobile phase consisted of 0.1% formic acid in water - methanol (6:4, v/v) and the flow rate was 0.3 mL/min. The total chromatographic run time was 5.0 min. Detection was performed on a triple quadrupole mass spectrometer equipped with positive-ion electrospray ionization by selected reaction monitoring of the transitions at m/z 449.05 > 287.2. The lower limit of quantification was 2.5 ng/mL and the linear range was 2.5‒500 ng/mL (r ≥ 0.9966). Cyanidine-3-glucoside All validation data, including selectivity, precision, accuracy, matrix effect, recovery, dilution integrity, and stability, were well within acceptance limits. This newly developed bioanalytical method was simple, highly sensitive, required only a small volume of plasma (50 μL), and was suitable for application in pharmacokinetic studies after oral administration of a standardized aronia extracts in rat that used serial blood sampling.
Chae Bin Lee
The Catholic University of Korea, South Korea
Quantitation of spinosin in mouse plasma by liquid chromatography‒tandem mass spectrometry and its application to a pharmacokinetic study
Chae Bin Lee(Biography)
A highly sensitive and rapid LC‒MS/MS method was developed and validated to determine the levels of spinosin, a flavone-C-glycoside, is a bioactive ingredient isolated from Zizyphi Spinosi Semen, in mice plasma by using theobromine as an internal standard. Spinosin and theobromine were extracted from 8 μL of plasma after protein precipitation with methanol. Chromatographic separation was performed on Phenomenex Luna C18 column (50 × 2.0 mm id, 3 μm). The mobile phase consisted of 0.1% formic acid in acetonitrile -0.1% formic acid in water (20:80 v/v) and the flow rate was 0.4 mL/min. The total chromatographic run time was 3.0 min. Detection was performed on a triple quadrupole mass spectrometer equipped with positive-ion electrospray ionization by selected reaction monitoring of the transitions at m/z 609.25 > 327.10 (for spinosin) and m/z 180.90 > 108.30 (for the internal standard). The lower limit of quantification was 1 ng/mL and the linear range was 1‒200 ng/mL (r ≥ 0.9991). All validation data, including selectivity, precision, accuracy, matrix effect, recovery, dilution integrity, stability, and incurred sample reanalysis, were well within acceptance limits. This newly developed bioanalytical method was simple, highly sensitive, required only a small volume of plasma (8 μL), and was suitable for application in pharmacokinetic studies after oral administration of a standardized Zizyphi Spinosi Semen extracts in mice that used serial blood sampling.
Chae Bin Lee(Abstract)
Chae Bin Lee is a graduate student with major in pharmacology/pharmacokinetics of The Catholic University of Korea. Research Interests: Bioanalysis, Mouse plasma; Small volume; LC‒MS/MS; Pharmacokinetics
Mustafa Tuzen
Gaziosmanpasa University, Turkey
Arsenic speciation by using new syntheses polymeric material and solid phase microextraction and its graphite furnace atomic absorption spectrometric determination
Mustafa Tuzen(Biography)
Dr. Mustafa Tuzen is Professor in Chemistry Department, Gaziosmanpasa University in Turkey. He administrated seven masters and five doctoral theses under his supervision. He completed several national and international projects. He is member of Turkish Academy and Sciences. He is well known specialist in analytical environmental chemistry. He is working on analytical chemistry, trace element analysis, enrichment and separation, speciation analysis, adsorption, biosorption, green extraction techniques, sample preparation methods, microextraction of trace organic and inorganic species. He has got 243 papers in SCI journals, cited papers in SCI journals: 10316, H factor: 62 according to Web of Science. Acknowledgements Jamshed Ali is grateful to the TUBITAK (Scientific and Technological Research Council of Turkey) for being awarded Research Fellowship Program of 2216 and providing financial support. Dr. Mustafa Tuzen thanks to Turkish Academy of Sciences for financial support.
Mustafa Tuzen(Abstract)
Total concentration does not give enough information about toxicity and bioavailability of arsenic in water and environmental samples. Arsenic present in different oxidation states in aqueous solution but it mostly exist in As(III) and As(V). The toxicity of As(III) is higher than As(V). So, As(III) and As(V) speciation in water samples is very important for environmental studies (1,2). New syntheses polystyrene polydimethyl siloxane polymer was loaded into the micropipette tip of the syringe system for solid phase microextraction of arsenic(III) and arsenic(V) speciation. Various analytical parameters such as pH, eluent type and its volume, polymer amount, sample volume, etc. were optimized. Effect of some cations, anions and transition metal ions were also investigated. While the recovery of As(V) was found quantitative in the pH range of 6-8, As(III) recovery was found below 5% in all pH values. The total concentration of arsenic was obtained by the addition of oxidizing agent potassium permanganate. The accuracy of the developed method was confirmed by using certified reference materials. The relative standard deviation was found lower than 5 %. Low detection limit and high preconcentration factor were obtained according to literature values. Optimized method was successfully applied to natural water samples for the speciation of As(III) and As(V). Graphite furnace atomic absorption spectrometry was used for the determination of arsenic concentration
Aymen Khalid AL-Suwailem
King Saud University, Saudi Arabia
Stereoselective high-performance liquid chromatographic (HPLC) method
Aymen Khalid AL-Suwailem(Biography)
Prof Aymen Khalid AL-Suwailem PhD pharmaceutical analytical chemistry Prince Sultan Cardiac Center
Aymen Khalid AL-Suwailem(Abstract)
stereoselective high-performance liquid chromatographic (HPLC) method was developed and validated to determine S-( )- and R-(+)-propranolol in rat serum. Enantio-meric resolution was achieved on cellulose tris(3,5-dimethylphenylcarbamate) immobilized onto spherical porous silica chiral stationary phase (CSP) known as Chiralpak IB. A simple analytical method was validated using a mobile phase consisted of n-hexane-ethanol-triethylamine (95:5:0.4%, v/v/v) at a flow rate of 0.6 mL min-1 and fluorescence detection set at excitation/emission wavelengths 290/375 nm. The calibration curves were linear over the range of 10–400 ng mL-1 (R = 0.999) for each enantiomer with a detection limit of 3 ng mL-1. The proposed method was vali-dated in compliance with ICH guidelines in terms of linearity, accuracy, precision, limits of detection and quantitation, and other aspects of analytical validation. Actual quantification could be made for propranolol isomers in serum obtained from rats that had been intraperitoneally (i.p.) administered a single dose of the drug. The proposed method established in this study is simple and sensitive enough to be adopted in the fields of clinical and forensic toxicology. Molecular modeling studies in-cluding energy minimization and docking studies were first performed to illustrate the mechanism by which the active enantiomer binds to the β-adrenergic receptor and second to find a suitable interpre-tation of how both enantiomers are interacting with cellulose tris(3,5-dimethylphenylcarbamate) CSP during the process of resolution. The latter interaction was demonstrated by calculating the binding affinities and interaction distances between propranolol enantiomers and chiral selector.
Abbas Amini Manesh
Payame Noor University, Iran
1-Buthyl-3-methyl imidazolium hydrogen sulfate ionic liquid as an efficient and reusable catalyst for the synthesis of 5-substituted 1H-tetrazoles
Abbas Amini Manesh(Biography)
Dr. Abbas Amini Manesh is an Assistant professor of Organic Chemistry in Payame Noor University of Hamedan (IRAN). Research Interests: Synthesis of new brominating reagent- Synthesis of new sulfonamides- Diels Alder reactions- Synthesis of polymer supported drugs- Oxidation reactions- Chemical Methodology.
Abbas Amini Manesh(Abstract)
Tetrazoles which containing four contiguous nitrogen atoms are one of the most stable nitrogen heterocyclic compounds among other heterocyclic systems1, however they not generally found in nature 2. Recently, tetrazoles are receiving much interest due to their important role in many fields. Tetrazoles show a wide range of applications in materials science, medicinal chemistry 3, photography 4, agriculture, 5 and as components of explosives.6 Ionic liquids (ILs) are a type of organic salts which are liquid at or near room temperature. Most of the ionic liquids are generally composed of a large asymmetric organic cation and either an organic or inorganic anion.7 In continuation of our research in the development of new synthetic methodology,8 herein we wish to report a simple and efficient method for the synthesis of 5-substituted 1H-tetrazoles by reaction of organic nitriles and sodium azide using 1-buthyl - 3- methyl imidazolium hydrogen sulfate: [bmim]HSO4 ionic liquid as an efficient and reusable catalyst in DMF, (Scheme 1). Scheme 1 Method for separation of the catalyst from aqueous phase: After completion of the reaction (as monitored by TLC), the reaction mixture was cooled to room temperature, and was treated with ethyl acetate (30 mL) and 6 N HCl (20 mL), it was stirred for 10 minute. The organic layer was separated, and the aqueous layer was again extracted with EtOAc (20 mL). The combined organic layers were dried over anhydrous sodium sulfate and evaporated under reduced pressure to give the tetrazole. The water was removed under reduced pressure from aqueous phase, then acetonitrile (20 mL) was added and stirred at 60 οC for 10 minute, and was filtered. Evaporation of acetonitrile gave pure catalyst ([bmim]HSO4) which can be used as least for 2 further reaction. Table 1 shows the results of the reaction: Table 1 Yield (%) Time (h) Tetrazoles Nitriles Entry 96 6 1 86 5 3 87 5.5 4 95 4.5 5 65 7.5 8 72 6,5 9 References: 1. B. Patil, Umakant, R. Kumthekar, Kedar, and M. Nagarkar, Jayashree, Tetrahedron Lett. 2012, 53, 3706. 2. P. B. Mohite and V. H. Bhaskar, Int. J. Pharm. Tech Res., 2001, 3, 1557. 3. R.N. Butler, in Comprehensive Heterocyclic Chemistry II; Katritzky, A. R.; Rees, C.W.; Scriven, E. F. V. Eds., Pergamon Press: Oxford, 1996, Vol. 4, p. 621, 905. 4. A. R. Modarresi-Alam, F. Khamooshi, M. Rostamizadeh, H. Keykha, M. Nasrollahzadeh, H. R. Bijanzadeh and E. Kleinpeter, J. Mol. Struct., 2007, 841, 61. 5. V. A. Ostrovskii, R. E. Trifonov and E. A. Popova, Russ. Chem. Bull., 2012, 61, 768. 6. B. S. Jursic and B. W. Leblanc, J. Heterocycl. Chem., 1998, 35, 405 and references cited therein. 7. K. Binnemans, Chem. Rev., 2007, 107, 2592. 8. A. Amini Manesh and B. S. Shirmardi, J. Chem. Sci., 2015, 3, 493.