On June 10, 2019 the master thesis defence of the third cohort of the EACH programme took place at Uppsala University! Angelique Sanchez Dafun, Diana Visanu, Allen Jun Penez Anies, Mohan Ghorasaini, Shidong Chen, Fadillah Putri Patria and Daniel Papp successfully defended their master’s theses.

Congratulations to all of you!

The topics of the theses embraced a wide area of modern biomed- and environmental analytical problems – LC-MS analysis marine biotoxins in mussels, determining of triacylglyceride regioisomers in rat liver; isotope exchange and supercharging techniques in MS etc. All of them featured the use of highly sophisticated analytical instrumentation, such as UPLC, UPC2, different designs of mass spectrometers, etc. This choice of topics is largely directed by the world-famous biomedical analysis research direction at Uppsala University led by prof. Jonas Bergquist.

The average quality level of the theses was found to be very high by the defence committee members.

(On photo from left: Allen, Daniel, Angelique, Ivo, Fadillah, Diana, Shidong, Mohan, Jonas)

 

During May 20-21, 2019 the Eurachem 2019 Scientific workshop Validation of targeted and non-targeted methods of analysis took place in Dorpat Conference Centre in Tartu. 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).

 

Measurement_Uncertainty_MOOC_Successfully_FinishedOn May 14, 2019 the on-line course (MOOC) Estimation of measurement uncertainty in chemical analysis offered by University of Tartu finished successfully.
Eventually altogether 590 people registered (270 in 2014, 489 in 2015, 757 in 2016, 363 in 2017, 521 in 2018) from 86 countries (a number of participants joined after the start of the course). 381 participants actually started the course (i.e. tried at least one graded test at least once) and out of them 238 successfully completed the course (141 in 2014, 169 in 2015, 308 in 2016, 148 in 2017, 358 in 2018). The overall completion rate was 40% (52% in 2014, 34% in 2015, 40% in 2016, 41% in 2017, 42% in 2018). The completion rate of participants who started the studies was 62% (67% in 2014, 60% in 2015, 67% in 2016, 68% in 2017, 61% in 2018). The completion rates are consistent over the last years and can be considered very good for a MOOC, especially one that has quite difficult calculation exercises, which need to be done correctly for completing the course.

The participants were very active and asked lots of questions. The questions were often very much to the point and addressed things that are really important to analysts in their everyday work. The course has several forums (general and by topic) and the overall number of posts to them during the course period exceeded 400 (!) (overall number of posts, both from participants and from teachers) and the forums are still active and posts are still coming in.

This active participation made teaching of this MOOC a great experience also for us, the teachers. The discussion threads gave a lot of added value to the course and some of them triggered making important modifications to the course materials, even during the course.

We want to thank all participants for helping to make this course a success!

We plan to repeat this course again in Spring 2020.

 

During Apr 22 to May 4 we had the pleasure to host visiting scholar, prof. Todd Pagano from the Rochester Institute of Technology (RIT), USA. He conducted, for the second time, a two week-intensive course Principles and applications of fluorescence spectroscopy.

In this course, students reviewed the principles of fluorescence spectroscopy, were introduced to the impact of photophysical phenomena on fluorescence data, and discussed new directions of fluorescence in analytical chemistry. Techniques in multidimensional fluorescence spectroscopy with chemometric analysis were highlighted, especially in the context of novel applications in environmental and related fields. The course consisted of lectures, seminars, tutorial sessions and two lab practicals. The latter were specifically set up for this course by prof. Pagano and were very much appreciated by students.

The first practical was about discovering the fundamental concepts of fluorescence (excitation and emission spectra, Stokes shift, Vavilov’s rule, fluorescence lifetime, etc). The second practical was about analysis of caffeine in beverages using salicylic acid as a fluorescent chemosensor. This analysis utilizes the ability of caffeine to quench the fluorescence of salicylic acid and introduces students to the fluorescence quenching, Stern-Volmer equation and inner filter effects.

Altogether 30 students (out of them 14 EACH students) participated in the course and their feedback was overwhelmingly positive.

 

Prof. Pagano is a passionate educator. He was the initiator of the Laboratory Science Technology program at Rochester Institute of Technology’s National Technical Institute for the Deaf, which is a unique science programme, specifically designed for deaf students. He was named “2012 U.S. Professor of the Year” by the Council for Advancement and Support of Education and the Carnegie Foundation for the Advancement of Teaching.

 

(Images: top left, group photo of prof. Pagano with course participants; right: prof. Pagano with students in lab)

 

Choosing the best possible ion source is a very important step in liquid chromatography mass spectrometry (LC/MS) method development. In a recent paper ESI outcompetes other ion sources in LC-MS trace analysis Anal. Bioanal. Chem. 2019 Asko Laaniste from the UT Analytical chemistry group carried out a large scale survey of differen LCMS ion sources (and their different working modes) as applied to pesticide analysis. He compared electrospray ionisation (ESI) source, thermally focused/heated electrospray (HESI), atmospheric pressure photoionisation (APPI) source with and without dopant, and multimode source in ESI mode, atmospheric pressure chemical ionisation (APCI) mode, and combined mode using both ESI and APCI, i.e. altogether seven different ionisation modes for the analysis of 40 pesticides (see list below).

The lowest limits of detection (LoDs) were obtained by ESI and HESI. The widest linear ranges were observed with the conventional ESI source without heated nebulizer gas. ESI source was significantly less affected by matrix effect than the HESI source. APPI ranked second (after ESI) by not being influenced by matrix effect; therefore, it would be a good alternative to ESI if low LoDs are not required.

It was somewhat unexpected that ESI outperformed HESI. This may be caused by the instability of the additional heated gas (sheath gas) in HESI that is used in addition to the nebulising gas.

In conclusion, as a broad generalisation, Asko’s results show that although several new ion sources have been introduced during the last decade, the conventional ESI performs at least equally to these new ion sources in the case of polar to medium polarity pesticides. ESI with thermal focusing (HESI) performed more or less equally with ESI in terms of LoD. At the same time, HESI had significantly poorer intermediate precision of matrix effect values for most compounds. Thus, for trace analysis, ESI is still the ion source of choice.

(Full list of pesticides: pymetrozine, thiamethoxam, methiocarb-sulfoxide, chloridazon, imidacloprid, acetamiprid, methiocarb-sulfone, thiacloprid, imazalil, thiophanate-methyl, metribuzin, pyrimethanil, fenpropimorph, spiroxamine, propoxur, triasulfuron, bupirimate, paclobutrazol, methiocarb, azoxystrobin, epoxiconazole, myclobutanil, fenhexamid, fluquinconazole, flusilazole, mepanipyrim, bitertanol, propiconazole, triazophos, methoxychlor, ditalimfos, tebufenozide, benalaxyl, pyrazophos, buprofezin, indoxocarb, trifloxustrobin, quinoxyfen, pirimiphos-ethyl, hexythiazox)

 

(Image top left: Asko Laaniste preparing solutions; Image right: Comparison of accuracy of LC-MS analysis using different ion sources)

 

I was that lucky person, who got accepted to EACH program in 2016. And by saying lucky – I mean it. EACH was not only a kick-off point in my career, but it was a life changing experience.

Our journey began in Tartu. There we had a very good life. We were well taken care of, living was easy and fun. All the professors were extremely nice and respectful towards each of us. This first year gave me very good basics of analytical chemistry, uncertainties, and chemometrics.  It helped me a lot along the way and up to now. Measurement uncertainty online course is an absolute must! Everything is explained in a very understandable way. For me, this course was my salvation to uncover the mystery of uncertainties.

 

And here comes Uppsala! Us, students, spoiled by the life in Tartu, Uppsala hit like a huge wave of hard and non-stopping marathon of work. We had only one course at the time. But we were going deeply into theory and then putting our knowledge into the practice in our daily lab work. Our routine mode back then was “lab work – writing report – repeat”. It was a lot of work, but on the other hand – a lot of experience. We had our hands on such instruments like ICP-AES, HPLC, GC, MS, MALDI, etc.  For analytical chemist, this place is called paradise. And it was also the perfect time to find yourself and your place in this area.

Group work was a big part of our studies here. Basically, each person’s workload was heavily dependent on other people. Therefore, good teamwork was the key to success. I was lucky to have the best group ever! During that time we supported and helped each other. Making a cup of coffee definitely counts!

But don’t get scared! This work pays off afterward with all the acquired knowledge. After this program, I can certainly say that I am confident in myself, as an analytical chemist, and in my skills.  Now I am working in Gothenburg, Sweden, at AstraZeneca as an Analytical Scientist. Due to my experience from these studies, I could easily join the ongoing work.

But Uppsala is not only about the studies! This city is known as the city of bikes and Student Nations. I had always thought that I would never ride a bike during rain/ snow/ cold. Well… This was the time to disprove this truth. In Uppsala, biking is the main way to navigate yourself in the city, no matter if it’s raining or your hands are totally freezing. We were living in the student area called Flogsta. In the beginning, you can think that Flogsta itself and the room you live in is very plain and not cozy at all. But it’s not about the room – it’s about the people and atmosphere you create in it. Just a little bit of imagination, heart and, of course, FRIENDS – and wuola – you have the best room in the world that will recover your soul from any negativity it may have compiled over the time.

Looking back right now, it’s even hard to explain how much EACH program has turned my life upside down. I met amazing people during this time and I had an experience I never thought I would have. But the most important – I love what I do, I love where I am and I am proud to be a part of EACH alumni.

On Tuesday, March 26, 2019 the web course Estimation of Measurement Uncertainty in Chemical Analysis was launched the sixth time as a MOOC (Massive Online Open Course)!

Currently 530 participants from more than 80 countries are registered! As was the case in the previous years, the majority of participants are from analytical laboratories. This once again demonstrates the continuing need for training in measurement uncertainty estimation for practicing analytical chemists.

The full course material is accessible from the web page https://sisu.ut.ee/measurement/uncertainty. The course materials include videos, schemes, calculation files and numerous self-tests (among them also full-fledged measurement uncertainty calculation exercises). In order to pass the course the registered participants have to pass six graded tests and get higher than 50% score from each of them. These tests are available to registered participants via the Moodle e-learning platform.

This course also forms a part of the measurements and chemical analysis related master programmes at UT: Applied Measurement Science and Excellence in Analytical Chemistry.

 

Starting from last week the Analytical chemistry group of University of Tartu has the pleasure to host Dr Monika Lindner and Hendrik van Thienen from the group of professor Benjamin List – a worldwide known guru in the field of strongly acidic catalysts working at the Max-Planck-Institut für Kohlenforschung (Mülheim, Germany).

The purpose of their stay is to learn our pKa measurement method and set it up in Mülheim. This is the logical continuation of our group’s collaboration with the List group – the pKa values of a number of their catalysts have been measured here at Tartu (see Nature Chemistry 2018, 10, 888-894 and Angew. Chem. Int. Ed. 2017, 56, 1411-1415) – and we are glad that our pKa measurement method thereby gains even wider acceptance than it has now. We wish Monika and Hendrik all the success in learning the measurements!

(On photo, from left: Märt Lõkov, Monika Lindner and Hendrik van Thienen)

 


 

This year’s General Assembly of the Erasmus Mundus Association took place in Vienna, Austria, from 23-25 February. Our programme was represented by Nikola Obradović, EACH Programme Represantative (PR) within EMA. As always, the General Assembly brought together students from all around the world – both the current students of Erasmus Mundus Joint Master and Doctorate programmes and the alumni. Currently, around 9000 students are part of EMA!

One of the main activities of this year’s GA was the establishment of EMA as a non-government organization, with its seat in Brussels. After putting many months of hard work into establishing the legal basis of EMA as an NGO, the Steering Committee of EMA, together with its active members has had the opportunity to vote on the matters regarding the organization’s Statute and Internal Regulations.

In addition, there were many invited speakers from different organizations, both European and worldwide, who gave talks on subjects of youth, education, sustainable development goals and many more.

Apart from the legalities and “lectures”, the GA was a great opportunity for networking and cultural exchange. Even though it seemed to have passed in a fleeting second, the time was well enough for new friendships to be formed and innovative ideas to be born. One could say the whole event was one continuous brainstorming experience, filled with lots of talks on mutual projects between different programmes, countries… Of course, nothing can complement social events better than cultural food tables and gala dinners followed by traditional dances.

Are you a student or an alumnus/alumna of an Erasmus Mundus programme? Don’t hesitate – become a part of the big EMA family!

(Text: Nikola Obradović; Photo: EMA)

 

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.

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).

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)