Session 2
1Department of Environmental Chemistry and Bioanalytics, Faculty of Chemistry, Nicolaus Copernicu University in Toruń, Gagarina7 str. Pl-87 100 Toruń (Poland)
2Interdyscyplinary Center of Modern Techniology, Nicolaus Copernicu University in Toruń, Gagarina7 str. Pl-87 100 Toruń (Poland)
3Departament of Materiale Engineering and Production, Faculty of Mechanical Engineering, Białystok University of Technology, Wiejska 45c, Pl-15 351 Białystok (Poland)
4Center of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza str. 112, Pl-90 001 Łódź (Poland)
This email address is being protected from spambots. You need JavaScript enabled to view it.
Silica has always been the object of interest of specialists and used for many purposes. Particularly for over 100 years, it has been used in chromatography and other separation techniques as an adsorbent or a carrier for stationary phases. Due to the high demands placed on chromatographic stationary phases, synthetic silica is used to provide high column efficiencies and avoid many adverse interactions. Recently, bio-silica obtained as a result of biogenic processes carried out by the selected strains of algae turned out to be an alternative to the synthetic silica [1]. This material, in contrast to the synthetic one, is characterized by a micro- or nano-hierarchical structure. Biosilica is an inorganic polymer formed by organisms such as diatoms or siliceous sponges of orthosilicate units in which two silanol groups are joined together to one bond or siloxane. Its low manufacturing cost as well as high quality in terms of chemical composition, mechanical stability and resistance are guaranteed by a good biosynthesis reproducibility. In this paper, the conditions of bio-silica biosynthesis, used as an adsorbent and carrier of stationary phases for liquid chromatography and related techniques, will be presented. The characteristics of bare and modified materials using porosimetric techniques, microscopic imaging, surface architecture characteristics via spectral and spectroscopic methods as well as chromatographic assessment will be discussed. Potential application possibilities (first proposals in the literature) in chromatographic separation and sample preparation will also be presented.
Acknowledgements
This work was financially supported by the Foundation for Polish Science co-financed by the European Union under the European Regional Development Found, project Advanced bio-composites for tomorrow’s economy BIOG-NET, FNP POIR.04.04.00-00-1792/18-00. The project is carried out within the TEAM-NET program.
Reference
[1] M. Sprynskyy, P. Pomastowski, M. Horonowska, A. Król, K. Rafińska, B. Buszewski, Mater. Des., 132 (2017) 22-29.
8:40-9:05 Tony Edge: ACHIEVING RAPID LC-MS ANALYSES USING SHORT 10 mm COLUMNS
1VWR, part of Avantor, VWR International Ltd., Hichrom, 1-3 The Markham Centre, Station Road, Theale, Reading, UK
2Analytical Services International, St. George’s University of London, UK
3Environmental Research Group, School of Public Health, Imperial College London, UK
This email address is being protected from spambots. You need JavaScript enabled to view it.
Achieving fast LC analyses is essential in high sample throughput laboratories, such as clinical, drug discovery and environmental labs. Over the last two decades, UHPLC has enabled many labs to dramatically increase sample throughput, through use of shorter columns packed with sub-2 micron particles. However, at the same time, the performance of modern mass spectrometers has continued to evolve. Improved sensitivity and ultra-fast data acquisition capabilities, provide opportunities to further reduce analytical run times, using specially designed, high throughput columns.
This presentation will look at the use of 10 mm columns for the analysis of complex samples, either derived from biological or environmental sources. The presentation will initially outline the theoretical considerations of short columns, starting with van Deemter theory, before moving to a more detailed kinetic plot interpretation of their application. From here, practical considerations of the use of such short columns will be discussed, specifically looking at dwell volumes, tubing and data acquisition rates.
The analysis of complex samples requires a degree of sample preparation prior to application of high throughput LC-MSMS, due to matrix issues. The presentation will investigate the impact that the level of sample preparation has on the data integrity when applied to high throughput scenarios. Finally, the presentation will conclude with a series of applications detailing the benefits that the use of 10 mm length columns can have for high throughput analysis, without the loss of data integrity. The applications will include a series of therapeutic drugs, environmental pollutants and some samples from a hospital laboratory.
1School of Chemistry and the Analytical & Biological Chemistry Research Facility (ABCRF), University College Cork, College Road, Cork T12 YN60, Ireland
2Department of Chemistry, College of Science, King Faisal University, P.O. Box 380, Al-Ahsa, 31982, Saudi Arabia
3School of Microbiology, University College Cork, College Road, Cork T12 YN60, Ireland
This email address is being protected from spambots. You need JavaScript enabled to view it.
Combining the nanomolar detectability at solid electrodes with high efficiency chromatographic media can provide selective multianalyte trace determination of key electroactive compounds. In this work, the coupling of electrochemical detection at a boron-doped diamond electrode (BDD) with core-shell chromatography (LC-BDD) is applied for the rapid nanomolar detection of targeted solutes including phenolics, neurotransmitters and microbial metabolites.
Among the applications examined is the rapid detection of key catecholamine biomarkers elevated in traumatic brain injury (dopamine, epinephrine and norepinephrine) using hydrophilic interaction liquid chromatography (HILIC) on superficially porous (core-shell) and porous Z-HILIC columns [1]. Key microbial metabolites are also rapidly detectable by Halo C18 LC-BDD exemplified by signalling molecules or bacterial pheromones for cell-to-cell communication (quorum sensing (QS)) from Pseudomonas aeruginosa, an antibiotic-resistant human pathogen associated with chronic lung infections.
Application is extended to the detection of guaiacol (2-methoxyphenol), a food and beverage spoilage metabolite indicative of contamination by the Gram-positive thermophilic Alicyclobacillus spp. bacterium [2]. Additionally, studies into the profiling of essential phenolic flavouring compounds in whiskey samples [3] and to selected pharmaceutical compounds are described [4].
Acknowledgements
The authors wish to acknowledge the following funding bodies for project grants and individual scholarships: Irish Research Council, Enterprise Ireland, the Ministry of Education (Saudi Arabia) and the Cultural Bureau (Dublin) and previously Science Foundation Ireland.
References
[1] M. Alsaeedi, H. Alghamdi, P. E. Hayes, A. M. Hogan and J. D. Glennon, Separations 8 (2021) 124.
[2] P. E. Hayes, A. Buzid, J. H. T. Luong and J. D. Glennon, Electroanalysis 33 (2021) 766-773.
[3] P. E. Hayes, J. H.T. Luong, E. S. Gilchrist, A. Buzid, J. D. Glennon, J. Chromatogr. A 1612 (2020) 460649.
[4] H. Alghamdi, M. Alsaeedi, A. Buzid, J. D. Glennon, J.H.T. Luong, Electroanalysis 33 (2021) 1137-1142.
1Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, KSA
2Advanced Membranes and Porous Materials Centre (AMPMC), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, KSA
This email address is being protected from spambots. You need JavaScript enabled to view it.
Using Metal-Organic Frameworks (MOFs) in chromatography as a stationary phase with superior properties has already given very promising results [1]. However, the use of MOF-polymer composite stationary phase is still very limited, and even more scarce in Gas Chromatography. MOF-polymer capillary monolithic columns combine MOFs properties in terms of the very high surface area, controlled structure, and limitless diversity, with the high permeability and flexible structure of the polymeric monoliths.
The present work discusses the fabrication of a composite material of sodilite topology Zeolite-like Metal Organic Framework (sod-ZMOF) nanocrystals incorporated into Divinylbenzene (DVB) monolithic polymer (ZMOF@DVB) in a capillary column (18cm × 250μm i.d.) to enhance the separation efficiency of the DVB monolith using a conventional low-pressure gas chromatograph.
5mg of sod-ZMOF nanocrystals were prepared and dispersed into DVB polymerization mixture, then polymerized to form ZMOF 5mg @DVB composite monolith in situ. Two batches of columns were prepared to investigate the effect of ZMOF incorporation in comparison to DVB blank monolithic columns. Chromatographic performance, as well as separation efficiency of various Volatile Organic Compounds (VOCs), isomers, and gases, were investigated.
To better understand the role of incorporating sod-ZMOF into the polymer matrix in its monolithic form, a thermodynamic characterization was carried out using Inverse Gas Chromatography (IGC) at infinite dilution under 0.5 Mpa column pressure and various column temperatures [2]. The free energy of adsorption (ΔGA), enthalpy of adsorption (ΔHA), and entropy of adsorption (ΔSA) were determined. Dorris-Gray and Schultz et al. methods estimated the dispersive component of surface energy. The acidic, KA, and basic, KD, parameters for both materials were estimated using a group of polar probes.
Acknowledgments:
This work was funded by the Researchers Supporting Project Number (RSP2022R429) King Saud University, Riyadh, Saudi Arabia.
References
[1] K. Yusuf, A. Aqel, Z. ALOthman, J. Chromatogr. A 1348 (2014) 1–16.
[2] K. Yusuf, O. Shekhah, Z. ALOthman, M. Eddaoudi, Appl. Sci. 1 (2021) 10243.
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, KSA
This email address is being protected from spambots. You need JavaScript enabled to view it.
Capillary liquid chromatography has become one of the most important developments in separation technology. Capillary chromatography performed using columns with an internal diameter ≤ 500 μm. This technique carried out using fused silica capillaries and prepared with a variety of different stationary phases. However, the successful development of this technique is closely related to the technical challenges associated with the columns manufacturing. Monolithic media have rapidly become popular and attracted increasing interest as separation phases. They consist of a single rigid piece of porous material that possesses a unique pore structure distribution with micrometer sized macropores and nanometer sized mesopores. Unfortunately, naked monolith is lake of small pores, which does not provide sufficient interaction sites for separation of small molecules especially with isocratic modes. Several approaches have been proposed to enhance the efficiency of the monolithic columns. In this work, small amounts of micro/nanoparticles such as carbon nanotubes and metal organic frameworks have been added into the porous polymer monoliths under specific conditions to enhance the separation efficiency of small molecules. Hydrodynamic and morphological properties of the prepared materials and columns were thoroughly characterized. The columns were evaluated by separation mixtures of different compounds such as hydrocarbons, phenols, and ketones. The combination of monoliths and capillary chromatography offer several advantages that include fast and sensitive analysis, in addition to the consumption of much smaller amounts of solvents, samples, and stationary phases, which will reflect positively on the environment and cost.
Acknowledgements
This project was funded by the national plan for science, technology & innovation (MAARIFAH), King Abdulaziz City for Science & Technology, KSA, Award No. 2-17-01-001-0053.
References
[1] A. Aqel, S. Alzahrani, A. Al-Rifai, M. Alturkey, K. Yusuf, Z. ALOthman, A. Badjah, Curr. Anal. Chem. 16 (2020) 223-233.
[2] A. Al-Rifai, A. Aqel, L. Al Wahibi, Z. ALOthman, A. Badjah, J. Chromatogr. A 1535 (2018) 17-26.
1Department of Analytical Chemistry, Faculty of Pharmacy, Charles University, Hradec Králové, Heyrovského 1203, 50005, Hradec Králové, Czech Republic
2The Technical University of Liberec, Faculty of Textile Engineering, Department of Nonwovens and Nanofibrous Materials, Studentská 1402/2, 46001 Liberec 1, Czech Republic
This email address is being protected from spambots. You need JavaScript enabled to view it.
Miniaturization of sample preparation and extraction techniques is currently a hot topic and nanofiber extraction techniques belongs to highly challenging and fundamental research goals. Sample preparation is an integral and usually the most complicated part of the analytical procedure that includes removal of problematic parts of the sample (interfering matrix components, proteins, lipids), as well as the pre-concentration of target analytes. Nanofibrous polymers feature a good loading capacity and enhanced kinetics of the adsorption resulting from the high surface to volume ratio [1,2].
In our contribution, we will present the advanced approaches in application of direct current spinning and alternating current spinning for electrospun polymers for extraction of contaminants (mycotoxins, endocrine disruptors, pesticides, pharmaceutical residues) from various samples – food, soft drinks, wine, beer, milk, human serum and plasma, and river waters. Pros and cons of extraction techniques based on nanofibers coupled to column switching liquid chromatography systems will be discussed and presented. Preparation of new composite materials consisting of polymer fibers comprising different chemistries specifically developed for extraction, coating, and functionalization of nanofibers with graphen will be introduced. Nanofibers with restricted access material functionality for direct extraction of pharmaceuticals from proteinaceous matrix – human serum and bovine milk will be presented too.
Acknowledgements
This work was supported by the grant project no. 20-19297S from Grant Agency of the Czech Republic and by the EFSA-CDN project (no. CZ.02.1.01/0.0/0.0/16_019/0000841) co-funded by the ERDF.
References
[1] M. Hakova, L. Chocholousova Havlíkova, P. Solich, F. Svec, D. Satinsky, Trac. Trends Anal. Chem. 110 (2019) 81–96.
[2] M. Hakova, L. Chocholousova Havlikova, F. Svec, P. Solich, D. Satinsky, Anal. Chim. Acta 1121 (2020) 83–96.
1Merck KGaA, Frankfurter Strasse 250, 64293 Darmstadt, Germany
2MilliporeSigma, 595 N. Harrison Road, Bellefonte, PA, 16823, USA
This email address is being protected from spambots. You need JavaScript enabled to view it.
Monolithic HPLC columns have been employed in chromatography for several years. This chromatographic modality has advantages over particle packed columns in that they can be run at higher flow rates with minimal backpressure drop and that they are resistant to matrix effects from samples. These columns have been used for rapid separations of small molecules, and more recently, in separating larger, biomacromolecules. In addition to expanding the utility of these columns into large molecule separations, advances in the overall architecture of the monolithic silica skeleton and geometry of the monolithic column have led to increases in the efficiency of this type of column. This presentation will discuss these advances in monolith design from both a fundamental level and from an application standpoint. Utilizing these modified monolithic HPLC columns, application examples for rapid, sensitive, and highly efficient separation for both small and large molecules will be showcased, demonstrating the utility of these columns to separate a broad range of compounds.
- Venue:
- Faculty of Chemistry and Chemical Technology
