17th Nordic Mass Spectrometry Conference in Espoo

In the last week of August, the 17th Nordic Mass Spectrometry conference was held in Espoo, Finland. With around 150 participants from Nordic countries, the conference covered various different topics within the field of mass spectrometry.

Anneli making her presentation at the 17th NordicMS

From our group, Anneli Kruve presented some of the most recent results in the field of quantitative suspect screening for pesticides and mycotoxins. Riin Rebane presented a poster about analyzing metanephrine (MN) and normetanephrine (NMN) and also about unusual matrix interferences related to the analysis (results have been published here). Artur Gornischeff presented some very exciting results on the ionization studies of derivatized amino acids which have also been published here.

  • Riin with her poster
  • Artur with his poster

NordicMS is a mass spectrometry conference taking place every three years and hosted in turns by nordic countries. This time it was Finland’s turn. The three-day conference had roughly 150 attendees; as expected, primarily from Finland and other Nordic countries. The conference covered all major areas of application of mass spectrometry: food characterization, metabolomics, drug discovery, proteomics, doping discovery and forensics. Topics covered analysis from the sea bottom (Hanna Niemikoski’s presentation about the identification of novel chemical warfare agents) up to the sky (Kari Hartonen’s presentation about sampling from air with drones).

The conference showed that even in the small circle of Nordic countries the research in the field of mass spectrometry is diverse and every mass spectrometry enthusiast will find his or her spot in the field.

Our acid-base research at 19th European Symposium on Fluorine Chemistry 2019

On 26.08.19 at 19th European Symposium on Fluorine Chemistry 2019 Ivo Leito gave a talk Acidities of molecules and media: the united pKa-pHabs scale in 1,2-dichloroethane.

For the first time in a low-polarity solvent, the scale has a dual nature, being both a pKa scale of the involved acids (i.e. describing acidity of molecules) and at the same time a pH scale, describing the acidity of the solutions (media).

The scale spans 28 orders of magnitude (pH or pKa units) and is composed of 87 acids of diverse nature. The scale is linked to the unified acidity (pHabs) scale and expressed in values, which makes the acidities of the solutions directly comparable to the conventional aqueous pH scale. This in turn makes the scale a useful tool in future studies of acid-driven processes (reaction mechanisms, catalysis, strong oxidants, etc) in low-polarity media.

This work has been published in: Chem. Sci., 2017, 8, 6964-6973. A unified view to Brønsted acidity scales: do we need solvated protons?.

It is part of a larger endeavor – to promote a wider usage the unified pH scale by the research and technology communities, which is currently in progress via the UnipHied. The project is funded from the EMPIR programme (project 17FUN09) co-financed by the Participating States and from the European Union’s Horizon 2020 research and innovation programme.  

18th International Conference on Density-Functional Theory and its Applications

The conference was held with the participation of 190 scientists from 36 countries representing the 5 continents during 22-26 July 2019 in the University of Alicante, Alicante, Spain. One of our group members, Dr. Ali Ghiami-Shomami, presented a poster during this conference. The presented topic, “DFT and TD-DFT Studies of Some Aminoacridines as Matrices in MALDI-MS”, is an effort towards exploring the factors influencing matrix performance in MALDI-MS technique using computational chemistry and in collaborations with our experimentalists. Some visitors appreciated the work and found it interesting. They emphasized that the MALDI-MS technique is very tricky and therefore, finding some insights about it from computational chemistry is valuable. More information about the conference can be found here: www.dft2019.es

48th International Symposium on High-Performance Liquid Phase Separations and Related Techniques

Between the 16th to 20th of June our group presented itself in HPLC 2019 in Milan. It was a 5-daylong and intense learning opportunity with more than 300 speakers and around 500 posters.

Topics ranged from fundamentals of HPLC, miniaturization to different omics, pharmaceutical analysis and innovative technologies (can HPLC have a FID as a detector?). For the first time, a whole section was dedicated to 3D printing technologies – a technique that is used to build 3 dimensional separation modules: for example, fascinating talks on using 3D printing to do liquid chromatography in 3 dimensions.

The conference gala dinner was held at the beautiful central courtyard of University of Milan under relieving cool evening sky opposing the hot temperatures of the day. HPLC 2019 also had two new additions that hopefully will become annual traditions: Separation Science Slam and HPLC Tube, offering an opportunity for scientists to express their love for their work in modern ways. The competitions were extremely creative and both the audience and participants were thoroughly enjoying the events. Participants from our analytical chemistry chair gave multiple contributions to the conference.

Ecstasy content in tablets is uneven

Max giving his talk

Max Hecht, MSc, presented an oral presentation on the evaluation of MDMA (also known as ecstasy and  ‘Molly’) content in 412 tablets and dissolution properties in 247 tablets, collected in the UK in the time period of 2001-2018. It was found that there are no physical tablet characteristics which correlate to dissolution rate classification, hence no way of users knowing a priori whether tablets were more likely to be fast or slow-releasing. Further, large within-batch variation in the dose and also dissolution rate was observed, giving the combined result of increasing significantly the danger of over-dosing.

Standard substance free quantification in LC/ESI/MS

Anneli giving her talk

Dr. Anneli Kruve presented the recent work of her group on standard substance free quantification of metabolites in green tea samples. In the metabolomics studies, the standard substances for all detected and identified metabolites are hardly ever available. The peak areas obtained from LC/HRMS analysis are also generally usable as different compounds ionize with vastly different ionization efficiencies; the differences may reach 100 million times. With the aid of ionization efficiency predictions, this shortcoming can be overcome and the absolute concentrations estimated. The current prediction accuracy for the green tea metabolites is 1.7 times, which allows comparison of different tea samples and also the identification of the samples with different origin. Importantly, the standard substance free quantitation allows transferring quantitative data from one lab to another. Anneli has also summarized the current status of standard substance free quantitation for the last issue of LCGC. You can find out more about it from kruvelab.com and quantem.co.

Novel eluent additives diversify analyst´s toolkit

Ruta giving her talk

Ruta Veigure, MSc, showed that fluoroalcohols, such as perfluoropinacol (PP) and 1,1,1,3,3,3-hexafluoro-2-methyl- 2-propanol (HFTB), are very useful alternatives to common eluent additives in RP HPLC-MS analysis, acting, among other effects, as weak ion-paring reagents. Novel eluent additives influenced elution of protonated bases by significantly improving analyte’s retention on C18 stationary phase as well as reduce the retention of acidic analytes, which are deprotonated. A comparison was performed to commonly used ammonium acetate and ammonium bicarbonate mobile phase additives. Her research will be rather influential for the analysis of pharmaceuticals, from whom the majority are basic.

Revolutionalizing pH measurements

Prof. Ivo Leito presented a poster introducing a conceptually new approach of measuring pH of mixed-solvent liquid chromatography (LC) mobile phases: the pHabs approach. The new approach is based on the recently introduced unified pH scale (pHabs scale), which enables direct comparison of acidities of solutions made in different solvents or solvents mixtures based on chemical potential of the proton in the solutions. The viewers praised the fact that real numerical values are now available showing how different the conventional pH values are from pHabs, as well as the educative aspect of the whole endeavour. Some visitors were eager to start immediately applying pHabs in their own work.

This work is part of a larger endeavor – to promote a wider usage the unified pH scale (pHabs) by the research and technology communities, which is currently in progress via the UnipHied. The UnipHied project is funded from the EMPIR programme (project 17FUN09) co-financed by the Participating States and from the European Union’s Horizon 2020 research and innovation programme.

  • Ivo presenting his poster
  • Asko presenting his poster

Automate what can be automated in method validation

Dr. Asko Laaniste introduced the progress on ValChrom, a software for the automation of chromatographic method validation. The development of ValChrom is ongoing and feedback is being gathered from potential users in different fields of chromatography in order to adapt to real needs (contact at valchrom@ut.ee). Feedback from viewers cemented the understanding of the problem that often validation is done in spreadsheets and textual software, that are prone to error. Viewers of the poster approved the endeavour for aiming to help small and medium-sized laboratories that do not have an affordable alternative. They were equally excited to promote the software further to their colleagues in the validation department.

67th ASMS Conference on Mass Spectrometry and Allied Topics

From 1st to 6th of June, two PhD fellows Piia Liigand and I presented our recent results at 67th ASMS annual conference in Atlanta, USA.

100% renewable energy utopia or reality?

The conference was kicked off with a plenary lecture by Prof. Mark Z. Jacobson on the topic of “Transitioning the World Energy for All Purposes to Stable Electricity Powered by 100% Wind, Water, and Sunlight”. He introduced how global, country wise, neighbourhood and individual energy production and preservation are feasible based on 100% renewable energy. I found fascinating the example of Prof. Jacobson himself as he has built his own house that uses and produces 100% renewable energy needed for maintaining the house and charging his electric car.

From simple ambient ionization techniques to “fishoil” from canola

The conference consisted of four days full of exciting talks which covered the fundamentals of mass spectrometry to application in diverse fields from cannabis analysis to proteomics. It was very encouraging to hear about the journey of Prof Dr Sarah Trimpin, this year Biemann medal awardee and her studies of very simple ionization techniques. I found exciting the results of a group from CSIRO, Australia. They applied mass spectrometry in food safety analysis, but even more fascinating was the genetically modified canola which can produce omega-3 fatty acids in large amounts to prevent overfishing to obtain omega-3-rich fish oil.

Quantem provides unification of ionization efficiencies from literature and standard substance free quantification in LC/ESI/MS

  • Piia presenting her poster
  • Jaanus presenting his poster

Piia presented her results on “Unifying ionization efficiencies: a quantitative comparison of diverse data sets and validation of prediction models” as a poster and there was a great interest in her topic and fruitful discussions about the findings retrievable from the unified datasets.

I presented the results on “Standard Substance Free Quantification of LC/ESI/MS on the Example of Pesticides in Cereal”. Although my poster was scheduled on the last day there was remarkable interest in our topic. Furthermore, future collaborations were arranged to test out our Quantem approach on datasets from different fields, metabolomics to the vaping industry.

The conference ended with the gala dinner in Georgia aquarium. The sea life, especially whale sharks and beluga whales, were astonishing. It was great to meet old friends and get to know new ones. We thank the ASMS team for a very nice conference in Atlanta and hope to meet next year in Houston at 68th ASMS annual conference. Additionally, we thank Graduate School of Functional materials and technologies and Kristjan Jaak scholarship for travel costs.

Eurachem 2019 workshop successfully finished!

Our group was the main organiser of the Eurachem 2019 Scientific workshop Validation of targeted and non-targeted methods of analysis, which took place in Dorpat Conference Centre in Tartu during May 20-21, 2019. This workshop also marks the 30th anniversary of Eurachem.

Approximately 160 people attended the workshop, which is the largest number of participants in the history of Eurachem workshops! The participants were from 42 countries of the member countries in Eurachem as well as Asia, North America, South America and Middle East. The farthest participants were from Fiji, the Philippines, Uruguay and Brazil.

The workshop was held with 13 oral presentations from established researchers, young scientists as well as industries. Together with 22 posters all presentations reflected the current and potential future developments related to methods validation. The workshop addressed the current status of analytical method validation in general and specifically validation of the non-targeted methods (i.e. ones where the analyte is not defined beforehand). With the speaker permissions, all presentations will shortly be available at the Eurachem website. In addition to presentations, each day a Working Group session was organised with 3 topics in parallel (Image on the left: Welcome by Dr Marina Patriarca, the Eurachem chair).

Non-targeted methods are an especially noteworthy part of the programme, because their validation involves specific issues and their validation is significantly less developed than validation of targeted methods (i.e. the “normal” analytical methods, where the analyte is known beforehand). At the same time non-targeted methods are becoming increasingly important in environmental protection, food safety, different omics areas, etc. (Image on the right: Prof. Jon Benskin from Stockholm University presenting an introduction to non-targeted analysis)

All sessions raised new issues and challenges, especially related to non-target method validation. The workshop clearly was also very inspirational for Eurachem from the point of view of preparing new guideline materials – especially the topics related to non-targeted analysis are still essentially not covered by official guidance documents.

Some example topics of the workshop: Validation of targeted methods: where are we? Validation of non-targeted methods – differences from targeted methods. Detection of a multitude of (unknown) components in complex samples: criteria for identification. Managing the huge amounts of complex data from non-targeted methods. Recent instrumental developments. Software tools for validation. (Image on the left: Dr. Koit Herodes presenting the ValChrom validation software)

The workshop certaily had a significant educational value and we are pleased by the large number of student participants: altogether close to 50! The international master’s programmes Excellence in Analytical Chemistry and Applied Measurement Science were both heavily represented: the majority of students of those programmes participated in the workshop (Image on the left: EACH and AMS students at the workshop).

The workshop was jointly organized by Eurachem and ECAC (University of Tartu, Tallinn University of Technology and the Estonian Environmental Research Centre).

 

TechnArt 2019 conference: Analytical techniques in cultural heritage

Anu, Signe, Pilleriin and Eliise

From 7th to 10th of May 2019 four members of our UT Analytical Chemistry group – Dr Signe Vahur, Dr Anu Teearu-Ojakäär, PhD students Pilleriin Peets and Eliise Tammekivi – attended the 7th international TechnArt conference in Bruges, Belgium.

The biggest conference of analytical techniques of cultural heritage

TechnArt is a place to present and discuss the newest results of the usage of analytical techniques in the field of cultural heritage. It is the biggest conference among its kind as it was also seen in TechnArt 2019, where the number of participants was about 400! The conference included three parallel oral presentation sessions, two poster sessions with 270 posters, a visit and dinner at the Halve Maan Brewery and an excursion with a boat trip in the historical city centre of Bruges, that has been listed as a UNESCO world heritage.

From Girl with a Pearl Earring to warship Mary Rose

Some of the most interesting talks included the presentation by Dr Abbie Vandivere from The Hague about the analysis of the painting Girl with a Pearl Earring (Johannes Vermeer, approx. 1665) and the difficult conservation of the remains of the warship Mary Rose (warship of the English navy under the command of King Henry VIII, sank in 1545) by Dr Eleanor Schofield from the Mary Rose Trust/Imperial College. Another interesting topic was addressed by Dr Lucia Toniolo who gave a talk on the conservation and monitoring issues of historical architecture, also addressing the hazard of climate change. However, with four days and three parallel oral sessions filled with presentations by the top scientists and conservators of the world, it is almost impossible to highlight all of the interesting and inspiring talks.

The highlights of our recent results

  • Anu presenting her poster
  • Eliise presenting her poster
  • Pilleriin presenting her poster

Also, TechnArt 2019 was the conference, where the attendance by our Cultural Heritage group members was the highest! Anu presented her poster „Analysis of resinous materials“, where ATR-FT-IR, SEM-EDS, GC-MS and ESI-FT-ICR-MS methods were combined for the analysis of the embalming materials obtained from two human mummies originating from Egypt and now exhibited at the University of Tartu Art Museum. Pilleriin presented her poster „Attenuated total reflectance and reflectance approaches for analysis of textile fibres with FT-IR spectroscopy“. This study showed, that both mentioned approaches are suitable and very useful methods for the identification of natural and synthetic fibres. Eliise presented her poster „Comparison of derivatization methods for the quantitative gas chromatographic analysis of oils“ where four widely used derivatization methods for the analysis of heritage samples were compared on the basis of absolute quantification.

Overall, TechnArt 2019 gave the members of our Cultural Heritage group the possibility to introduce their scientific work results, hear the inspiring lectures and have fruitful discussions in the magical historic city of Bruges.

How to make maximum use of the available pKa data in non-aqueous solvents?

On 11.04.2019 Ivo Leito gives a presentation titled “How to make maximum use of the available pKa data in non-aqueous solvents?” at 26th Croatian Meeting of Chemists and Chemical Engineers (26HSKIKI), in Šibenik (Croatia). The presentation discusses the principles of acid-base behaviour in solvents and on how to estimate the pKa values of compounds in solvents where direct experimental data are not available.

 

UT Analytical chemistry at Suprachem 2019: From receptor synthesis to ion-selective electrode

During 24-26.02.2019 the Suprachem 2019 conference took place at University of Würzburg (Germany). The UT Analytical chemistry chair was represented by two posters: Optimization of the reaction pathway for the synthesis of substituted 1,3-bis(carbazolyl)urea anion receptors by Alo Rüütel and Mihkel Ilisson and From receptor-anion binding ladder to ion-selective electrode by Kerli Martin, Sandip A. Kadam, Ulriika Mattinen, Johan Bobacka and Ivo Leito.

Synthesis of 1,3-bis(carbazolyl)urea based anion receptors

The presentation from Alo and Mihkel focused on optimization of the synthesis route of anion receptors (ionophores) based on the 1,3-bis(carbazolyl)urea building block, augmented with additional amide functionalities (see the poster). The developed synthesis route is very valuable for the synthesis of a wide variety of analogous receptors (ionophores) that have previously been demonstrated to bind carboxylates with high affinity (see K. Martin et al, Eur. J. Org. chem. 2017, 5231-5237).

First solid contact acetate electrodes using receptor molecules

Kerli Martin et al present the first practical application of such receptors: a solid-contact acetate-selective electrodes. For acetate anion the electrodes show linearity over the activity range of 10-4.50 – 10-1.10 with a sub-Nernstian slope of -51.3 mV per decade and a detection limit of 10-5.00. The anion-selectivity pattern of these electrodes deviates markedly from the pattern found in DMSO solution and from the Hofmeister pattern. The selectivity coefficients of SCN–, I–, NO3– and Br– decrease by 3-5 orders of magnitude when adding the studied ionophore to the membrane. The selectivity coefficients of hydrophilic anions such as Cl–, F–, HPO42–, and SO42– are significantly lower than in case of the ionophore-free control membrane. All in all, it is clear that a lot of work is still needed for improving the selectivity of the electrode.
This work has been accepted for publication: K. Martin et al Electroanalysis 2019 (the link will work soon).

The combined contributions from our group stood out from the majority (the conference altogether had 27 oral and 111 poster presentations) by a clear line of development from fundamental research (receptor design) to highly practical application (ion-selective electrode).

(Photos: above left: Mihkel Ilisson explaining his work to Dr Diane Smith from Wiley; right: Poster by Kerli Martin et al)

 

Eurachem 2019 workshop: Validation of targeted and non-targeted methods of analysis

Our group is proud to be the leading organiser of the 2019 Eurachem General Assembly and the accompanying scientific workshop “Validation of targeted and non-targeted methods of analysis”!

The Workshop will take place in Tartu (Dorpat conference centre) on May 20th and 21st. The programme of the workshop, as well as registration and abstract submission are available at the event website:
https://eurachem2019.akki.ut.ee/

The workshop addresses the current status of analytical method validation in general and specifically validation of the non-targeted methods (i.e. ones where the analyte is not defined beforehand). Non-targeted methods are an especially noteworthy part of the workshop programme, because their validation involves specific issues (since analyte is not known it is not possible to make validation experiments with it) and is significantly less developed than validation of targeted methods (i.e. the “normal” analytical methods, where the analyte is known beforehand). At the same time non-targeted methods are becoming increasingly important in environmental protection, food safety, different omics areas, etc.

Some example topics of the workshop are: Validation of targeted methods: where are we? Validation of non-targeted methods – differences from targeted methods. Detection of a multitude of (unknown) components in complex samples: criteria for identification. Managing the huge amounts of complex data from non-targeted methods. Software solutions for validation.

Compact overview of the workshop can be found in the 2nd circular.

These events mark the 30th anniversary of Eurachem and are jointly organized by Eurachem and ECAC (University of Tartu, Tallinn University of Technology and the Estonian Environmental Research Centre).

We are hoping to see many of you in Tartu in May!