The paper is crucial milestone for the group serving as an excellent example of collaborative analytical work combining all the multiple expertises of the Archemy. The results do not only challenge our previous understanding of Conversion period social dietary practices in Estonia, but will serve as a key-reference for future multi-proxy and multi-method dietary analysis. The main findings include:
*There was no major dietary difference between men, women and children in the 12th-13th century AD Pada community: all had equal access to food sources!
*Meat-based foods were preferred in burial ritual contexts, whilst plant-based foods formed majority in daily food consumption.
*No single proxy approach or method can reveal the full spectrum of ancient dietary practices.
Many thanks to all the amazing collaborators who contributed to this work!
We are delighted to share that our latest article titled “A quantitative approach to determine water and moisture content of different types of lignin using attenuated total reflectance Fourier transform infrared spectroscopy combined with partial least squares regression” has been published in the journal of Biofuels, Bioproducts and Biorefining (Volume 20, 2026). The article was authored by Shrikant Shivaji Pawade, together with Dr Martin Vilbaste, Andres Siiman, Dr Lauri Toom, Associate Professor Koit Herodes, and Professor Ivo Leito. The article is Open Access and available online; click here to access it.
The study presents a quantitative methodology for determining water and moisture content in diverse lignin types using ATR-FTIR spectroscopy combined with partial least squares regression, with vapourisation–coulometric Karl Fischer titration (vap-C-KFT) and gravimetric methods used as reference techniques. In addition, the work introduces a sigmoid curve approach to temperature optimisation for vap-C-KFT and evaluates sampling and modelling uncertainties, thereby providing practical insights for reliable lignin characterisation. The robustness of the method was assessed by validation against vap-C-KFT, oven drying (7 h and 48 h), and freeze-drying, utilising diverse lignin types (Kraft, Dealkaline, and Lignova Fibenol) and achieving RMSEP values ranging from 0.33 to 1%.
The results demonstrate that ATR-FTIR combined with chemometrics modelling can provide a rapid, simple, and cost-effective alternative to conventional methods, while maintaining good accuracy across diverse lignin types.
The Cultural Heritage research group, as part of this year-end PRG1198 research project, has published an open-access article titled “Laser ablation APCI-HRMS method for the analysis of cultural heritage materials” by Anu Teearu, Martin Leissoo, Rynno Lohmus, Alexey Treshchalov, Tõiv Haljasorg, Victor Augusto Xavier da Silveira, Hilkka Hiiop, and Signe Vahur in the Journal of the American Society for Mass Spectrometry. The article is available here.
Graphical Abstract for the publication
This research article highlights a novel 355 nm optical fibre-coupled laser ablation (LA)-APCI-FT-ICR-MS system, developed for direct, controllable, rapid, and accurate analysis of organic materials from the solid surface of an artefact under ambient conditions with minimal surface damage and without the need for sample removal or sample preparation for the analysis. In this study, the effectiveness and capabilities of the developed LA-APCI-HRMS system for analysing five aged mock-up materials (copper resinate, Prussian blue oil and egg tempera paints, lead white oil paint and matte dammar varnish) and the blackish-brown material from an ointment jar from a 16th-century shipwreck were investigated. The results can be read in the article.
The PRG1198 project team has done excellent work over the past five years, culminating in a working laser-based HRMS system. The same team will begin next year with a new project, and we will continue to keep you updated on all new developments.
In the photo, the main members of the PRG team: team leader Dr Signe Vahur (in the centre), from left Dr Aleksei Treshchalov, Prof. Hilkka Hiiop, Dr Anu Teearu-Ojakäär, Dr Rünno Lõhmus and specialist Martin Leissoo.
“This comprehensive review brings together technical depth and years of personal lab experience, shaped by long hours at the bench, countless peer discussions, and valuable lessons learned along the way. It offers a detailed, practice-oriented guide to how derivatization can dramatically improve analyte retention and ionization in LC-MS, especially for challenging amino compounds. The article dives into reagent selection, method optimization, and real-world troubleshooting – tools I wish I’d had starting out.”
This work was supported by the Estonian Research Council grant PUT1589, and by the Estonian Ministry of Education and Research (TK210). The research was conducted using the Estonian Center of Analytical Chemistry, funded by the Estonian Research Council (TT4).
Our group’s journey into catalytic studies began years ago. In the first period our main activity was measuring the pKa values of Brønsted acids catalysts and relating them with catalytic activity. However, it was always problematic that the catalytic activity was quantified by different authors in very different ways: different reactions, different substrates of the same reaction, different ways to express activity (rate constant, yield), different solvents, different concentrations, different temperatures… All this diversity makes comparing catalytic activity difficult to impossible.
So, we set forth to find a model reaction, define conditions and a unified quantitative parameter for expressing acatlytic activityof various Brønsted acid catalysts.
This endeavour has now reached its first result: PhD student gleb Maksimov from our group discovered that the transfer hydrogenation reaction with substituted quinoline has the suitable characteristics for this work and utilizing the Kimball-Collins theory modelling approach applied to rate constante (measured by NMR), a catalytic activity parameter was defined that enables unified and comparable quantification of the catalytic activity of Brønsted acids! The proof of principle is now published: Molecular Catalysis2025, 573, 114846. Towards quantifying catalytic activity of homogeneous Brønsted acid catalysts.
Congratulatuons, Gleb!
However, this work is far from complete. Gleb together with new students will continue to improving te methodolog and widening the applicability of the approach so that many more results and with higher quantitative accuracy would be possible in the future. We are excited about the potential advancements and look forward to sharing more updates as the research progresses.
(This research was supported by grant PRG690 from the Estonian Research Council)
Within the framework of the PRG1198 research project Dr Signe Vahur with her team (Dr Anu Teearu, Dr Rünno Lõhmus, Martin Leissoo, Dr Alexey Treshchalov, Dr Janis Lungevics, Dr Georg Arju, Dr Hilkka Hiiop) has published a new article titled “Characterisation of laser-ablated craters of different painting materials and evaluation with modified LA-APCI-MS system” in the Journal of Talanta. The article is available here: https://doi.org/10.1016/j.talanta.2025.127856
The article presents preliminary results obtained by investigating the pulsed 355 nm Nd:YAG laser’s impact on specific painting materials (oil and acrylic paints and varnish) surfaces by characterising the area and volume of laser-ablated craters (measured with an optical microscope and 3D profilometer) obtained with different laser energies and the number of pulses at 90°, 70°, and 45° incidence angles and evaluating intensity of corresponding MS signals obtained with APCI-MS.
For the first time, potentiometric pH measurement traceable to the conventional aqueous pH scale has been successfully demonstrated in a low-polarity solvent, 1,2-dichloroethane (1,2-DCE)!
Paulo and Jaan from our group achieved this remarkable result, which has now been published: “Experimental Unified pH Scale in 1,2-Dichloroethane” (Phys. Chem. Chem. Phys., 2025, 27, 3810–3816).
The measurement approach is rooted in the unified pH scale (pHabs scale) concept and is based on pairwise differential potentiometric comparisons of solutions yielding their pHabs differences (ΔpHabs values). 85 such pair-wise measurement comparisons were carried out between solutions prepared in 1,2-DCE, some solutions in mixed solvents and aqueous standard pH buffer solutions. The resulting pHabs “ladder” is pictured in Figure 1.
Figure 1. pHabs scale of solutions in 1,2-DCE, linked to the standard aqueous buffer solutions and comparison against reported pHabs values in the literature.
Applying a least squares minimization approach to the ΔpHabs values and taking into account the reference values of the aqueous standard buffers allowed us to assign pHabs values to 19 equimolar buffer solutions in 1,2-DCE, yielding a pHabs range of −2.9 to 11.0. The consistency standard deviation of 0.17 pH units—higher than similar measurements in polar solvents—reflects the experimental challenges of working in low-polarity media.
Multiple salt bridge configurations (shown in Figure 2) were tested to improve measurement stability. Out of the four tested configurations, a separate salt bridge configuration (SB4) with PEEK capillary tubes yielded the most stable and reliable results, extending measurements for up to five hours without significant drift.
Figure 2. Different salt bridge setup configurations used in the work.
Direct pH measurement of 1,2-DCE solutions against standard aqueous pH buffers is challenging because of the very different nature of the solvents and possible water contamination of 1,2-DCE can significantly affect the measurements. Therefore, bridging solutions (a 60:40 acetonitrile/pH 4 formate solution and buffered ethanol) were employed to facilitate measurements against standard aqueous pH buffers. This approach allows the pHabs values in 1,2-DCE to be directly comparable to the aqueous pH values.
The obtained results confirm that potentiometric pHabs measurements are possible in low-polarity solvents, paving the way for experimentally linking many low-polarity solvents into a unified pH scale. Employing pHabs to compare solution acidity across different media will improve our understanding of how pH impacts processes in catalysis, liquid chromatography, sustainable energy, and the interpretation of acid-base processes in various solvents.
(This research was supported by grant PRG690 from the Estonian Research Council)
We’re delighted to share that members of our Archemy and Analysis of Cultural Heritage Objects groups have published a new article titled, “Influence of Mineral Composition and Firing Temperature on the Micro- and Mesoporosity of Replicate Archaeological Ceramics” in the journal of Clays and Clay Minerals (Volume 72, 2024, e13). Read the Open Access article here.
This study examines how the mineral composition of clay and temper, along with firing temperatures, influences the formation of micro- and mesopores in pottery. The porosity of ceramics is considered a significant factor in the absorption and preservation of organic compounds, such as lipids, within archaeological pottery. Our research provides the first quantitative analysis of pore structures in ceramics designed to replicate archaeological samples, establishing valuable baseline information for future investigations into ceramic porosity and organic residue analysis.
We are excited to share our latest publication titled, “pKaH values and θH angles of phosphanes to predict their electronic and steric parameters” (Dalton Trans., 2024, 53, 14226-14236. https://dx.doi.org/10.1039/d4dt01430h).
In this study, we delve into the fascinating world of phosphanes – a versatile class of organic bases that play a crucial role in a wide array of chemical applications. Phosphanes are known for their incredibly diverse range of basicities, with pKaH values spanning over 30 orders of magnitude. One of the key insights from our research is that pKaH values can be a valuable alternative to Tolman electronic parameters (TEP values) for assessing the electronic properties of phosphanes. This finding opens up new possibilities for researchers to evaluate phosphanes without the need for the time-consuming preparation or calculation of metal-ligand complexes.
In addition to electronic properties, we also propose new geometric parameters to assess the steric properties of phosphanes – the θH angles, which have the advantage of being accessible by simple computations. Together, the pKa values and θH angles provide a straightforward approach to understand and predict the behavior of phosphanes in various chemical environments and processes.
Our study combines computational and experimental findings to offer a fresh perspective on how phosphanes can be analyzed and utilized, and we believe it will be a valuable resource for researchers working with these compounds. We invite you to read the full article to explore the detailed findings and implications of our work.
The analytical chemistry scientists (Dr Signe Vahur, Dr Anu Teearu-Ojakäär, Prof Ivo Leito) together with physicists (Dr Rünno Lõhmus, Dr Aleksei Treshchalov, Prof Jaak Kikas) from the Institute of Physics at the University of Tartu and conservation scientists at the Estonian Academy of Arts (Prof Hilkka Hiiop, MSc Käthi Niman), have published a new tutorial review article, “Laser-based analytical techniques in cultural heritage science – Tutorial review“ in the journal of Analytica Chimica Acta. The article is available here: https://doi.org/10.1016/j.aca.2023.342107.
Graphical abstract in the journal of Analytica Chimica Acta (https://doi.org/10.1016/j.aca.2023.342107)
This comprehensive collaboration article is significant for the cultural heritage investigation workgroup and the PRG1198 project team, which is currently developing a new laser-based MS system.
The main focus of this tutorial review is to give a simple and accessible overview of the physical background of different lasers, their parameters, and examples of applications in analytical techniques useful for the identification of components of various complex materials from a cultural heritage point of view. Besides conservators and cultural heritage scientists, this review may also interest researchers and students of other fields (e.g., material science, physics, chemistry, forensics, etc.) who wish to know more about lasers.
The paper is crucial milestone for the group serving as an excellent example of collaborative analytical work combining all the multiple expertises of the Archemy. The results do not only challenge our previous understanding of Conversion period social dietary practices in Estonia, but will serve as a key-reference for future multi-proxy and multi-method dietary analysis. The main findings include:
