List of 50 best-cited publications from the Faculty of Chemistry, Adam Mickiewicz University, according to the Web of Science

Recent Faculty Publications

1. Although water is a very simple compound from a chemist's point of view, its importance in nature cannot be overestimated. Suffice it to say that it constitutes as much as 60% of the human body weight, and its scarcity is one of the greatest problems affecting humanity. Despite the fact that water is one of the best-studied substances, its properties never cease to surprise.

Currently one of the intensively explored areas of research concerns substances capable of controlled and reversible absorption, storage and release of water. Such properties are particularly desirable in, for example, pharmaceutical formulations and desiccants. Most of the known materials of this type release water at higher temperatures, often well above the normal boiling point of water, making the dehydration process expensive and energy-intensive. To make water harvesting from the atmosphere cost-effective, materials are sought that can release water at temperatures only slightly above room temperature.

On April 12, 2023, the journal Nature published a paper entitled "Dehydration of a crystal hydrate at subglacial temperatures," in which scientists from the Adam Mickiewicz and Stellenbosch Universities demonstarted that crystals of a chiral macrocyclic compound, conventionally called trianglimine, have the ability to spontaneously absorb water and release it at sub-zero temperatures. More specifically, the lowest temperature at which this cyclic process can be observed is -70 °C. Below this temperature, the water exists in glass-like state in the hydrate crystals, which is equivalent to losing its ability to flow.

The  crystal structure of trianglimine resembles  a so-called hollow brick, in which the channel diameter is 1 nm, and the walls are made of macrocycles. The process of water absorption and desorption is visualized as a change in the colour of the crystal from yellow to red and vice versa, which is a consequene of a change in the electron configuration within the macrocycle, associated with reversible proton transfer. Water uptake and realase do not change the crystal structure; the process prooceeds very fast and can be repeated many times without any signs of physical damage to the sample.

The presented research is an important step toward the rational design of materials capable of reversible water capture from the atmosphere, even at low humidity. This is particularly important in so-called arid regions of the world, such as steppes and deserts. Another area of application is humidity indicators for the food and pharmaceutical industries, including the transport and storage of frozen food and vaccines.

Open access to the article is available through the ID-UB program

Eaby A.C. Myburgh D.C., Kosimov A., Kwit M., Esterhuysen C., Janiak A.M., Barbour L.J. Dehydration of a crystal hydrate at subglacial temperatures. Nature, 2023, 616, 288-292. Doi: 10.1038/s41586-023-05749-7



2. We kindly inform about publication of our paper in Advanced Functional Materials (IF = 19.924), entitled: „Giant Pressure‐Induced Spectral Shift in Cyan‐Emitting Eu²⁺‐Activated Sr₈Si₄O₁₂Cl₈ Microspheres for Ultrasensitive Visual Manometry”. The paper is a result of fruitful collaboration of three research groups from Poland, China and Spain, i.e.: I) Department of Rare Earths, Faculty of Chemistry, Adam Mickiewicz University in Poznań (Poland); II) Department of Microelectronic Science and Engineering, School of Physical Science and Technology, Ningbo University (China); III) Group of Optical Spectroscopy and High-Pressure, Departamento de Física - Universidad de La Laguna (Spain). This publication deals with development of new, ultra-sensitive optical (luminescent) pressure sensor, exhibiting the highest pressure sensitivity (dλ/dP = 9.7 nm/GPa) among all currently reported optical manometers.
   Zheng, T.; Runowski, M.; Xue, J.; Luo, L.; Rodríguez‐Mendoza, U. R.; Lavín, V.; Martín, I. R.; Rodríguez‐Hernández, P.; Muñoz, A.; Du, P. Giant Pressure‐Induced Spectral Shift in Cyan‐Emitting Eu²⁺‐Activated Sr₈Si₄O₁₂Cl₈ Microspheres for Ultrasensitive Visual Manometry. Advanced Functional Materials, 2023, 2214663. DOI: 10.1002/adfm.202214663.
   
3. The prestigious journal ACS Applied Materials & Interfaces (IF = 10,383, 200 pts. MEiN) published a paper entitled. "Noncentrosymmetric Lanthanide-Based MOF Materials Exhibiting Strong SHG Activity and NIR Luminescence of Er3+: Application in Nonlinear Optical Thermometry." The paper is the result of a fruitful collaboration between three research groups i.e., the Department of Rare Earths, Faculty of Chemistry, UAM; the Department of Functional Nanostructure Synthesis, Faculty of Chemistry, UAM; and the Optical and High Pressure Spectroscopy Group, Faculty of Physics, University of La Laguna, Spain. Taking advantage of the different sensor responses under changed thermal conditions, a nonlinear optical thermometer based on non-centrosymmetric Ln-MOF (Lanthanide Metal-Organic Frameworks) - doped MOF-Yb³⁺/Er³⁺ material was developed. In the presented system, the intensity of the SHG (Second Harmonic Generation) signal decreases with increasing temperature, while the emission band of Er³⁺ ions in the NIR broadens slightly, enabling ratiometric temperature monitoring by measuring the change in the intensity ratio of Er³⁺/SHG emission bands (1550 nm/488 nm). Moreover, the presented non-centrosymmetric system can be synthesized from achiral substrates, in a high-throughput hydrothermal synthesis process using only a metal salt and an organic solvent, which significantly simplifies access to this group of compounds. Our research provides a basis for the rational design of easily accessible and self-monitoring NLO-active Ln-MOFs with desirable optical and electronic properties.
   Runowski M., Marcinkowski D., Soler-Carracedo K., Gorczyński A., Ewert E., Woźny P., Martín, I. R. Noncentrosymmetric Lanthanide-Based MOF Materials Exhibiting Strong SHG Activity and NIR Luminescence of Er³⁺: Application in Nonlinear Optical Thermometry. ACS Appl. Mater. Interfaces 2023, 15, 2, 3244–3252. DOI: 10.1021/acsami.2c22571


4. The prestigious scientific journal Chemical Engineering Journal (IF = 16.744) has published a work entitled "Temperature invariant ratiometric luminescence manometer based on Cr³⁺ ions emission". The work was published as a result of fruitful cooperation between three research groups, i.e., the Department of Rare Earths, Faculty of Chemistry, Adam Mickiewicz University in Poznań; Institute of Low Temperature and Structure Research, Polish Academy of Sciences in Wrocław; Optical and High Pressure Spectroscopy Group, Faculty of Physics, University of La Laguna, Spain. The research paper concerns the development of an optical high pressure sensor based on the Li₂Mg₃TiO₆ matrix doped with optically active Cr³⁺ ions. The basis for the development of the contactless, luminescenct manometer was the emission band of the radiative transition ⁴T₂→⁴A₂ with a high value of the spectral shift (Δλ ≈ 70 nm) under the high-pressure conditions up to 7.75 GPa. The changes in the luminescence intensity ratio (LIR) for emission band in the two spectral ranges (i.e. 825 - 935 nm and 1005 - 1095 nm) made it possible to determine the linear change of the LIR parameters and to correlate it with the pressure value in the system. Additionally, the LIR analysis under the changed temperature conditions (123 - 543 K) showed a slight (approx. 5%) change in the value of the LIR parameter, which enables pressure measurement regardless of temperature fluctuations in the system.

Szymczak, M., Woźny, P., Runowski, M., Pieprz, M., Lavín, V., Marciniak, Ł., Temperature invariant ratiometric luminescence manometer based on Cr³⁺ ions emission. Chemical Engineering Journal (Chem. Eng. J.) 2022,453,139632.doi: 10.1016/j.cej.2022.139632



5. The paper „Structural diversity and biological relevance of benzenoid and atypical ansamycins and their congeners” by Natalia Skrzypczak and Prof. Piotr Przybylski has been published in Natural Product Reports (Royal Society of Chemistry, IF = 15.111, 200pkt. MEiN). The article was highlighted as the front cover of the current issue. The publication presents the classification and structural features of benzenoid ansamycins and describes their biosynthetic pathways led by bacteria. The enormous diversity of natural benzenoid ansamycins is the result of not only the biosynthesis of these compounds by bacteria, but also various muta- and semi-synthetic approaches that enable the assembly of various types of ansamycin bridges with structurally diverse cores. The study also discusses the attractive anticancer activity of this type of ansamycins in relation to their molecular targets (heat shock proteins, tubulins) and problems related to cytotoxicity to healthy cells. Review article, also based on the achievements of the Team of prof. Przybylski, shows some opportunities in optimizing the anticancer activity of this type of natural products with reduced toxicity created by new hybrid synthetic strategies, chemical (semisynthesis) and biological (mutasynthesis).

The research was financed by the National Science Center under grant no.: UMO-2017/25/B/ST5/00291 Opus 13.

Skrzypczak N., Przybylski P. Structural diversity and biological relevance of benzenoid and atypical ansamycins and their congeners. Nat. Prod. Rep., 2022, 39, 1678-1704, https://doi.org


6. The paper „Modifications, biological origin and antibacterial activity of naphthalenoid ansamycins” by Natalia Skrzypczak and Prof. Piotr Przybylski has been published in Natural Product Reports (Royal Society of Chemistry, IF = 15.111, 200 pkt. MEiN). The structures of ansamycin antibiotics discussed in the review also became a front cover of the current issue of the journal. The publication presents the structural division of natural naphthalenoid ansamycins according to the type of core and length of the ansamycin chain, as well as ansamycins biosynthetic pathways. The enormous diversity of the naphthalenoid ansamycin biosynthetic pathways translates into the structural diversity of the ansamycin bridges or the naphthalenoid cores. The paper discusses and compares the biological activity of natural and semisynthetic naphthalenoid ansamycins in relation to their molecular targets (binding sites in bacterial cells). The high antibacterial activity of naphthalenoid ansamycins seems to be depended on the length and conformational lability of the ansa chain - the higher the flexibility of the ansa bridge, the higher the antibacterial potency, while intramolecular equilibria such as the zwitterionization of the ansamycin scaffolds, are also important, as evidenced i.a. by studies performed in the Team of prof. Przybylski.

The research was financed by the National Science Center under grant no.: UMO-2017/25/B/ST5/00291 Opus 13.

Skrzypczak N., Przybylski P. Modifications, biological origin and antibacterial activity of naphthalenoid ansamycins, Nat. Prod. Rep., 2022, 39, 1653-1677. https://doi.org/10.103


7. In August the book "Perfluoroalkyl Substances: Synthesis, Applications, Challenges and Recipes" has been published by the Royal Society of Chemistry Publishing. The author of one of the chapters is Prof. UAM dr. hab. Justyna Walkowiak-Kulikowska. This chapter presents essential information on per- and polyfluoroalkyl substances (PFASs) and a brief historical overview and ways of classification and discusses their chemical structures and also their physicochemical, mechanical, thermal and surface properties. Furthermore, it elaborates on general synthetic methods used for preparing PFASs and provides examples of their wide applications in numerous advanced industrial and common consumer products.

The theme of the book are perfluoroalkyl substances (PFAS) - a diverse group of human-made chemicals that are used in a wide range of consumer and industrial products. They are under intense scrutiny due to environmental concerns and there is a call to ban new PFASs entering the market. That said, this book is not intended to wave the banner against PFASs per se; rather it provides a balanced overview of the field, from basic synthesis through to applications, why some current PFASs are and may remain the right substance for the job, as well as addressing the challenges and alternatives.
Covering organofluorine chemistry to fluoropolymers and their applications in various sectors from biomedical to agrochemical, energy and electrical industries, this book is a solid introduction to the topic and demonstrates why fluorinated products are still useful in many domains. With risk assessment and alternatives to PFASs included, it provides a considered account of both the positive applications of PFASs and the pressing environmental concerns.
Suitable for academics and industrial practitioners working in the fields of organic and macromolecular chemistries, it will also appeal to end-users who want to learn about the technology, applications and elimination or recycling of such fluorinated products.

Walkowiak-Kulikowska J.,  Poly/Perfluorinated Alkyl Substances (PFASs) – Synthetic Methods, Properties and Applications,  Perfluoroalkyl Substances: Synthesis, Applications, in: Challenges and Regulations, Royal Society of Chemistry Publishing, 2022, doi.org/10.1039/9781839167591-00022
book: https://pubs.rsc.org/en/content/ebook/978-1-83916-568-9

8. We kindly inform about publication of new paper in Chemical Engineering Journal(IF = 13.273), entitled: „ Highly-efficient double perovskite Mn⁴⁺-activated Gd₂ZnTiO₆ phosphors: A bifunctional optical sensing platform for luminescence thermometry and manometry”. The paper is a result of fruitful collaboration of three research groups from Poland, China and Spain, i.e.: I) Department of Rare Earths, Faculty of Chemistry, Adam Mickiewicz University in Poznań (Poland); II) Department of Microelectronic Science and Engineering, School of Physical Science and Technology, Ningbo University (China); III) Group of Optical Spectroscopy and High-Pressure, Departamento de Física - Universidad de La Laguna (Spain). This publication deals with development of first, bifunctional optical sensor of high pressure and temperature, based on the emitting properties of the d-block metal ions, i.e., perovskites containing optically active Mn⁴⁺ ions.

Zheng, T.; Luo, L.; Du, P.; Lis, S.; Rodríguez-Mendoza, U. R.; Lavín, V.; Runowski, M. Highly-Efficient Double Perovskite Mn⁴⁺-Activated Gd₂ZnTiO₆ Phosphors: A Bifunctional Optical Sensing Platform for Luminescence Thermometry and Manometry. Chem. Eng. J. 2022, 446, 136839. DOI: 10.1016/j.cej.2022.136839



9. The paper by Daniel Łowicki and Piotr Przybylski “Cascade synthetic strategies opening access to medicinal-relevant aliphatic 3- and 4-membered N-heterocyclic scaffolds” has been published in European Journal of Medicinal Chemistry (IF = 6.514). Cascade (domino) reactions are one of the modern trends in organic synthesis as they are inspired by the processes occurring in nature. The cascade synthesis allows to perform several following transformations in a ‘one pot’ by mixing all reagents at ones, and without isolation of the intermediates. In each precisely planned step a newly formed functional group is able to react with another molecule or functional group present within the molecule, just like domino blocks. In this review paper the application of the tandem reactions for the synthesis of small aliphatic three-membered as well as four-membered rings is summarized. Synthesis of saturated 3- and 4-membered rings is challenging due to the ring strain. Nevertheless, they are essential pharmacophores present in many approved drugs, as well as those in the clinical trials. The aim of this study is to compare the cascade synthesis of modified aziridines, azirines, azetidines and azetidinones (β-lactams) with the biological activity of the molecules that contain such cyclic scaffolds. This review represents an interdisciplinary approach combining biological and medical applications with modern cascade synthesis of small ring-containing molecules, and therefore it may be useful inspiration for these scientists who are looking for new potential drugs, as well as those working on simple and efficient methods of their synthesis.

Łowicki D., Przybylski P., Cascade synthetic strategies opening access to medicinal-relevant aliphatic 3- and 4-membered N-heterocyclic scaffolds. European Journal of Medicinal Chemistry, 2022, 238, 114438, DOI: 10.1016/j.ejmech.2022.114438.


10. We kindly inform about publication of our paper in Chemical Engineering Journal(IF = 13.273), entitled: „Pressure-Triggered Enormous Redshift and Enhanced Emission in Ca₂Gd₈Si₆O₂₆:Ce³⁺ Phosphors: Ultrasensitive, Thermally-Stable and Ultrafast Response Pressure Monitoring”. The paper is a result of fruitful collaboration of research groups from the Department of Rare Earths, Faculty of Chemistry, Adam Mickiewicz University in Poznań (Poland) and the Group of Optical Spectroscopy and High-Pressure, Departamento de Física - Universidad de La Laguna (Spain). This publication deals with development of new, ultra-sensitive optical pressure sensor, exhibiting the highest pressure sensitivity (dλ/dP = 3 nm/GPa) among all currently reported luminescent gauges.

Zheng, T.; Luo, L.; Du, P.; Lis, S.; Rodríguez-Mendoza, U. R.; Lavín, V.; Martín, I. R.; Runowski, M. Pressure-Triggered Enormous Redshift and Enhanced Emission in Ca₂Gd₈Si₆O₂₆:Ce³⁺ Phosphors: Ultrasensitive, Thermally-Stable and Ultrafast Response Pressure Monitoring. Chemical Engineering Journal 2022, 443, 136414. DOI: 10.1016/j.cej.2022.136414



11. The paper "Copper Supported on Ceria Mesocellular Foam Silica as an Effective Catalyst for Reductive Condensation of Acetone to Methyl Isobutyl Ketone" by the teams: K. Grzelak, M. Trejda from Department of Heterogeneous Catalysis at the Faculty of Chemistry, AMU and A. Riisager from Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark was published in ChemSusChem journal (IF = 8.928). The production of methyl isobutyl ketone (MIBK) from acetone in one single process using Cu/Ce-MCF catalyst was proposed. A very good performance of the new catalytic system was explained by the presence of basic sites coming from ceria, necessary for the condensation of acetone to diacetone alcohol (DAA), Lewis acidity of the Cu²⁺ species required for the dehydration of DAA to mesityl oxide (MO) and presence of Cu⁰ centers active for the hydrogenation of MO to MIBK. The Cu/Ce-MCF catalyst had better catalytic performance and similar durability during continuous operation for 24 h as a preferred Pd/Ce-MCF catalyst recently reported in literature, implying that Cu can efficiently replace the noble metal Pd as active catalyst inventory for selective acetone condensation to MIBK.
    

Grzelak K, Trejda M, Riisager A.  Copper Supported on Ceria Mesocellular Foam Silica as an Effective Catalyst for Reductive Condensation of Acetone to Methyl Isobutyl Ketone, ChemSusChem, 2022, DOI:10.1002/cssc.202102012


12. Tandem reactions (cascade or domino) are an important alternative for traditional organic synthesis. The advantage of these reactions is the absence for the need of isolation and purification of intermediates after each subsequent step, as the well as often higher yield and lower cost in comparison to multistep total synthesis. Due to the features, tandem reactions meet the role of ‘green chemistry’. In this review published in w European Journal of Medicinal Chemistry (IF = 6.514), the application of tandem reaction for the synthesis of pyrrolidine rings has been demonstrated. The pyrrolidine ring is an important pharmacophore present in nearly 100 approved drugs and many new biologically active compounds discovered in recent years. The application of cascade reactions for the synthesis of biologically active pyrrolidine derivatives is very limited. In contrast to already published reviews on 5-membered N-heterocyclic rings, which are focused mainly on synthetic reactions or biological activities, this work combines both of these threads and shows the utility of the tandem strategy for the construction of potentially active molecules containing pirrolidine pharmacophores as a central motif.

Łowicki D., Przybylski P., Tandem construction of biological relevant aliphatic 5-membered N-heterocycles European Journal of Medicinal Chemistry, 2022, DOI: 10.1016/j.ejm



13. The paper " An approach to modify 14-membered lactone macrolide antibiotic scaffolds" by the team A. Janas, K. Pyta, and  P. Przybylski from Department of Chemistry of Natural Products and Professor M. Gdaniec at the Faculty of Chemistry was published in Journal of Organic Chemistry (IF= 4.354). The publication shows the synthesis of a ketolide derivative with the inverted configuration (12R) via a novel ketene acetal in acidic conditions. The structure of this atypical β-ketene acetal intermediate within the macrocyclic system has been determined by NMR and X-ray methods. The use of basic conditions at an elevated temperature yielded new, doubly α,β-unsaturated ketone macrolide derivatives with (4E) -configuration as two conformational isomers of folded-in or folded-out conformations. This work was supported by the Polish National Science Centre (NCN) under Grant Opus 10 no. 2015/19/B/ST5/00231.
    Janas A, Pyta K., Gdaniec M., Przybylski P, An approach to modify 14-membered lactone macrolide antibiotic scaffolds Journal of Organic Chemistry 2022,87 (5), 3758-3761; DOI: 10.1021/acs.joc.1c02799
    
14. The paper " Regioselective approach to colchiceine tropolone ring functionalization at C(9) and C(10) yielding new anticancer hybrid derivatives containing heterocyclic structural motifs " by the team K. Pyta, N. Skrzypczak and P. Przybylski from Department of Chemistry of Natural Products at the Faculty of Chemistry was published in Journal of Enzyme Inhibition and Medicinal Chemistry (IF= 5.051). The publication shows the influence of base type, temperature, and solvent on regioselective C(9)/C(10) modifications within the tropolone ring of colchiceine. New ether derivatives of colchiceine, bearing alkyne, azide, vinyl, or halide aryl groups enable assembly of the alkaloid portion with heterocycles or important biomolecules such as saccharides, geldanamycin or AZT into hybrid scaffolds by dipolar cycloaddition (CuAAC) or Heck reaction. Biological studies reveal that the bulkiness of the substituents and the substitution pattern of the tropolone proved to be essential for simply ether derivatives and that expanding the ether arms by terminal basic heterocycles as quinoline or pyridine, decreases the toxicity in HDF cells at high anticancer potency. This work was supported by the Polish National Science Centre (NCN) under Grant Opus 13 no. UMO-2017/25/B/ST5/00291.
    
    Pyta K., Skrzypczak N.,Ruszkowski P, Bartl F., Przybylski P, Regioselective approach to colchiceine tropolone ring functionalization at C(9) and C(10) yielding new anticancer hybrid derivatives containing heterocyclic structural motifs. Journal of Enzyme Inhibition and Medicinal Chemistry 2022,37 (1), 597-605; DOI: 10.1080/14756366.2022.2028782
    
    
15. The paper "Molecularly Imprinted Polymers with Enhanced Selectivity Based on 4 (Aminomethyl) pyridine-Functionalized Poly (2-oxazoline)s for Detecting Hazardous Herbicide Contaminants" by the teams: M. Cegłowski, G. Schroeder from Department of Supramolecular Chemistry at the Faculty of Chemistry, AMU and Y.W. Marien, S. Smeets, L. De Smet, D.R. D'hooge, R. Hoogenboom from Supramolecular Chemistry Group, Department of Organic and Macromolecular Chemistry, Ghent University was published in Chemistry of Materials journal (IF = 9.811). The publication presents an innovative method for the determination of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in water with the use of molecularly imprinted poly(2-oxazoline) polymers (MIP) combined with mass spectrometry performing sample ionization under ambient conditions using FAPA (Flowing Atmospheric - Pressure Afterglow) technique. The synthesis method and complete characteristics of the molecularly imprinted polymers functionalized with pyridine derivative (4-AMP) and the mechanism of interaction of the analyte with the receptors present in the structure of polymers are presented.  The use of MIP adsorbents as materials concentrating the analyte in the determination of 2,4,5-T in water and the FAPA-MS method allows the determination of this herbicide at the nanomolar level.

Cegłowski M., Marien Y.W., Smeets S., De Smet L., D’hooge D.R., Schroeder G., Hoogenboom R. Molecularly Imprinted Polymers with Enhanced Selectivity Based on 4-(Aminomethyl)pyridine-Functionalized Poly(2-oxazoline)s for Detecting Hazardous Herbicide Contaminants. Chemistry of Materials 2022,34 (1), 84-96; DOI: 10.1021/acs.chemmater.1c02813


16. The team from the Laboratory of Functional Nanostructures (M.Sc. Marcin Konopka and Prof. Artur R. Stefankiewicz) have just published a paper in Scientific Reports (IF = 4.379). An unorthodox approach to dynamic covalent chemistry has been described. A single building block was used to generate a library of numerous disulfide-based architectures in a one-pot single-step process. The initially-unexpected in-situ hydrolysis of a bis-imide was employed to control the composition of a library of structurally diverse macrocycles. The dual-stimuli method is based on simultaneous changes in pH and DMSO concentration to expand the structural diversity of the macrocyclic products. It is a facile strategy for the synthesis of water-soluble, multicomponent and highly functionalized dynamic macrocycles, thus giving a prospect of their application in guest-driven phase transfer.

Konopka M., Stefankiewicz A. R., Expanding structural diversity in a library of disulfide macrocycles through in-situ imide hydrolysis, Scientific Reports, 2022, 12, 38. doi:10.1038/s41598-021-03944-y


17. A research paper authored by dr Monika Rzonsowska, MSc Katarzyna Mituła, MSc Julia Duszczak, dr Małgorzata Kasperkowiak, dr Rafał Januszewski, dr Anita Grześkiewicz, prof. Maciej Kubicki, MSc Daria Głowacka and prof. AMU dr hab. Beata Dudziec has been published in Inorganic Chemistry Frontiers (IF = 6.569). The paper discloses an unexpected Si-O-Si cage reorganization that was observed during the standard hydrolytic condensation procedure of tetrasilanol double-decker silsesquioxane (DDSQ) with respective mono- and di-chlorosilanes. A deeper look into the process to find out its possible mechanism was performed – a series o analytical techniques was used, incl. NMR, MALDI and ESI MS analysis along with the thorough verification of crystallographic structures (11 examples) of obtained silsesquioxanes. The resulted compounds were also verified in terms of their thermal stability. Also, the unusual behaviour of vinyl-substituted DDSQs in the silylative coupling reaction was revealed. These results 5are a significant contribution to the development of research on specific organosilicon compounds, such as silsesquioxanes, and in particular on the still not fully recognized DDSQ systems.
    
    Rzonsowska M, Mituła K, Duszczak J, Kasperkowiak M, Januszewski R, Grześkiewicz A, Kubicki M, Głowacka D, Dudziec B. Unexpected and frustrating transformations of double-decker silsesquioxanes. Inorg. Chem. Front. 2021. doi:10.1039/d1qi01363g.
    
18. The cooperation between two research teams i.e. the Laboratory of Functional Nanostructures (dr Anna Walczak, M.Sc. Gracjan Kurpik and Prof. Artur R. Stefankiewicz) and the Laboratory of Organometallic Catalysis (dr Maciej Zaranek, Prof. Piotr Pawluć) has led to the publication in the Journal of Catalysis (IF = 7.920). This article presents the synthesis and thorough spectro-structural characterization of the isomeric C,N-cyclopalladated complexes, in which two molecules of a flexidentate pyridyl-β-diketonate ligand simultaneously coordinate to the metal centre in two different modes - κ²O,O' and κ¹C,κ¹N. Both these isomers proved to be efficient (pre)catalysts for Heck reaction under relatively mild conditions and with low catalyst loading. Remarkable chemo- and stereoselectivity in cross-coupling of functionalized olefins with a broad scope of commercially available aryl iodides has been reported.
    
    Walczak A, Kurpik G, Zaranek M, Pawluć P, Stefankiewicz A. R.; C(sp³),N palladacyclic complexes bearing flexidentate ligands as efficient (pre)catalysts for Heck olefination of aryl halides. J. Catal., 2022, 405, 84-90. doi: 10.1016/j.jcat.2021.11.033
    
19. A recent paper in Nature Communications reports the discovery of the structure of a new enzyme (ReAV) splitting the amino acid asparagine into aspartate and ammonia. Enzymes with this function, called asparaginases, are urgently needed in medicine since under certain conditions they make excellent drugs for treating acute childhood leukemia. ReAV does not meet the criteria of a perfect drug but its structure allows molecular engineering aimed at fulfilling these conditions. The structure of ReAV is completely new in the asparaginase field. Its discovery crowns a 20-year effort of a research team led by Prof. Mariusz Jaskólski.

Loch J.I, Imiolczyk B, Sliwiak J, Wantuch A, Bejger M, Gilski M, Jaskolski M. Crystal structures of the elusive Rhizobium etli L-asparaginase reveal a peculiar active site. Nature Commun. 2021, 12, 6717. doi: 10.1038/s41467-021-27105-x


20. The team from the Laboratory of Functional Nanostructures (M.Sc. P. Cecot, dr A. Walczak, dr G. Markiewicz and Prof. A. R. Stefankiewicz) published an article in Inorganic Chemistry Frontiers (IF = 6.569), about the synthesis of new metallosupramolecular systems (M4L6 tetrahedral cages, M2L2 macrocycles and MLn mononuclear complexes) bearing the photoactive azobenzene units. The article presents the reversible switching between three types of structures by changing the stoichiometry of the reaction mixture or by the addition of a competing amine. The presented research has shown, that the photoactivity of azobenzene moieties within the organic ligand can be effectively gated upon the addition of d-electron metal ions, by trapping the ligand within rigid metallosupramolecular architectures.
    
    Cecot P, Walczak A, Markiewicz G, Stefankiewicz A. R.; Gating the photoactivity of azobenzene-type ligands trapped within a dynamic system of an M₄L₆ tetrahedral cage, an M₂L₂ metallocycle and mononuclear ML_n complexes. Inorg. Chem. Front., 2021, doi.org/10.1039/D1QI01063H
    
21. The work of dr Marcin Kaźmierczak and dr Monika Bilska-Markowska from Department of Synthesis and Structure of Organic Compounds has been published in European Journal of Organic Chemistry. Minireview shows some of the transformations of molecules using diethylaminosulfur trifluoride (DAST). This publication reveals that DAST does not only act as a fluorinating reagent, which as a result of nucleophilic substitution replaces the hydroxyl group with a fluorine atom but is also a mediator of other processes. It participates in rearrangement and cyclization reactions, resulting in valuable heterocyclic compounds, both fluorinated and non-fluorinated. Thus, it leads to significant building blocks as well as biologically active molecules.

Kaźmierczak M, Bilska-Markowska M. Diethylaminosulfur Trifluoride (DAST) Mediated Transformations Leading to Valuable Building Blocks and Bioactive Compounds. Eur. J. Org. Chem. 41, 5585-5604. Doi: 10.1002/ejoc.202101027


22. Daria Brykczyńska, a second-year PhD student from the Department of Synthesis of Functional Nanostructures, is a co-author of a publication that appeared in the journal Angewandte Chemie International Edition "Desulfonative Suzuki–Miyaura Coupling of Sulfonyl Fluorides" (https://doi.org/10.1002/anie.202111977).  The published work concerns the Suzuki-Miyaury coupling, where it was reacted with aryl sulfonyl fluorides, which are usually inert to transition metal catalysis. Interestingly, the paper presents the results of research confirming the receipt of the expected product also without the addition of a base, and even in a strongly acidic environment, which further proves the uniqueness of the published results carried out in the research group of Prof. Joseph Moran at the Institut de Science et d'Ingénierie Supramoléculaires in Strasbourg in which the PhD student completed a scientific internship.

Chatelain P, Muller C, Sau A, Brykczyńska D, Bahadori M, Rowley C, Moran J. Desulfonative Suzuki–Miyaura Coupling of Sulfonyl Fluorides. Angewandte Chemie International Edition 2021 60, 1-7. Doi: 10.1002/anie.202111977

23. The team of scientists from Department of Rare Earths has published the paper in Advanced Optical Materials
    (IF = 9.926), concerning development of bifunctional, luminescent sensor of high-pressure and temperature, based on the emission features of thulium ion (Tm²⁺), at its unusual +2 oxidation state. Such sensor allows monitoring of high-pressure to at least 13 GPa, and temperature of the system in the range from 10 to 400 K, using various spectroscopic parameters, such as band intensity ratios, spectral shift, emission line width or luminescence lifetimes. The developed sensor is a result of fruitful collaboration of research groups from the Department of Rare Earths, Faculty of Chemistry, Adam Mickiewicz University in Poznań and Faculty of Chemistry, University of Wroclaw.
    
    Zheng T,Runowski M, Woźny P, Lis S, Zych E. Tm²⁺ Activated SrB₄O₇ Bifunctional Sensor of Temperature and Pressure—Highly Sensitive, Multi‐Parameter Luminescence Thermometry and Manometry. Adv. Opt. Mater. 2021, 2101507. DOI: 10.1002/adom.202101507
    
24. The work of Sergiusz Napierała, prof. Maciej Kubicki and prof. UAM Monika Wałęsa-Chorab entiteled "Toward Electrochromic Metallopolymers: Synthesis and Properties of Polyazomethines Based on Complexes of Transition-Metal Ions" and the cover of the journal issue illustrating the research described in article have been published in Inorganic Chemistry (ACS, IF = 5.165).

The article presents a new method of preparation of metallopolymers containing Fe(II) or Cu(II) ions and their electrochromic properties. The metal polymers were obtained in the form of insoluble thin films on the surface of the working electrode as a result of the polycondensation reaction of complexes of transition metal ions containing amino groups and appropriate dialdehydes. It was shown that the polyazomethine obtained by polycondensation of the Fe(II) complex and a dialdehyde containing a triphenylamine group showed a reversible orange to gray color change and good electrochromic stability during multiple oxidation/reduction cycles. The conducted research has shown the usefulness of an on-substrate polycondensation reaction for the preparation of thin films of electrochromic metallopolymers.

Napierała S, Kubicki M, Wałęsa-Chorab M.Toward Electrochromic Metallopolymers: Synthesis and Properties of Polyazomethines Based on Complexes of Transition-Metal Ions. Inorganic Chemistry 2021, 60, 18, 14011-14021. doi: 10.1021/acs.inorgchem.1c01



25. Team of scientists from Department of Rare Earths has published the paper in Nanoscale (IF =  7.790). This work shows development of inorganic, optical nanothermometer, working in a broad spectral range (vis-NIR), utilizing lanthanide thermally and non-thermally coupled levels for remote temperature detection. They demonstrated how the applied laser power influence on the absolute and relative sensitivities and temperature sensing resolution, which are crucial for luminescence thermometry applications. This effect can be observed in the case of luminescent thermometers exhibiting non-linear phenomena, and using band intensity ratios associated with transitions having different number of photons participating in the relevant radiative processes.

Stopikowska N, Runowski M, Skwierczyńska M, Lis S. Improving performance of luminescent nanothermometers based on non-thermally and thermally coupled levels of lanthanides by modulating laser power. Nanoscale 2021, doi: 10.1039/D1NR01395E



26. Inversion  tunneling in a symmetric double minimum potential is a challenging large amplitude motion problem which causes all rotational energy levels to split into a symmetric and an antisymmetric level. Not like other types of large amplitude motion such as internal rotation, inversion tunneling appears less often, but the fundamental knowledge gained from this motion is essential to understand the complex structures in coordination chemistry. This review summarizes four most classic examples of molecules featuring inversion tunneling motion and their coordination complexes. The first molecule presented in the paper is a textbook example, ammonia, with its umbrella motion. In the second classic example, methylamine, CH₃NH₂, the inversion motion of the amino group –NH₂ is coupled with a methyl internal rotation –CH₃. The third subject is focused on hydrazine with complex internal dynamics governed by three large amplitude motions: two –NH₂ tunneling motions and an internal rotation (torsion) of the two amino groups around the N-N bond. Finally, secondary amines feature inversion tunneling of the hydrogen atom attached to the nitrogen, which is accompanied by two methyl internal rotations but not strongly coupled with them so that they can be treated separately.

Nguyen H. V. L., Gulaczyk I., Kręglewski M., Kleiner I., Large amplitude inversion tunneling motion in ammonia, methylamine, hydrazine, and secondary amines: From structure determination to coordination chemistry, Coordination Chemistry Reviews 2021, Vol. 436, 213797. doi.org/10.1016/j.ccr.2021.213797


27. An international team of scientists from our faculty (Department of Rare Earths) has published the paper in Advanced Optical Materials (IF =  8.286). Using micron-sized perovskite crystals, a novel strategy in optical thermometry is presented for the first time. The temperature sensing concept is based on the nonlinear processes of second harmonic generation (SHG) and upconversion luminescence (UCL) phenomena. This highly sensitive method exploits a new and effective pathway for contactless temperature sensing – the nonlinear optical thermometry, which is a promising alternative method to conventional luminescence thermometry. The developed sensor is a result of fruitful collaboration of research groups from the Department of Rare Earths, Faculty of Chemistry, Adam Mickiewicz University in Poznań; Universidad de La Laguna, Departamento de Física (Spain); Departament de Química Inorgànica and Institut de Recerca de Química Teòrica i Computacional, Universitat de Barcelona (Spain); Departamento de Química, Universidad Católica del Norte (Chile).

Zheng T, Runowski M, Martín I.R., Lis S, Vega M, Llanos J. Nonlinear Optical Thermometry—A Novel Temperature Sensing Strategy via Second Harmonic Generation (SHG) and Upconversion Luminescence in BaTiO₃ :Ho³⁺,Yb³⁺ Perovskite. Adv. Opt. Mater. 2021, 2100386. doi: 10.1002/adom.202100386



28. Phosphorus, occurring mainly in the form of phosphate, is an essential element for the proper functioningof living systems. Phosphate and polyphosphate groups occur as inorganic phosphate (free phosphateanion in solution) and are present in biomolecules such as phosphorylated amino acids, nucleotides,and phytic acid. In solution, phosphates can exist in four different forms depending on pH, and theyare involved in non-covalent interactions with positively charged species. This review summarizes theparticipation of phosphates of nucleotides, phosphorylated amino acids, and phytic acid in weak interac-tions with biogenic amines and in complexes with biometal ions not only in solution but also in solidstate. The study of these processes can enable to understand many of the most important aspects of acell’s life, thus explaining why, for example, abnormal phosphorylation leads to the development of dis-eases, and highlighting the role of phosphates in chemical interactions. In addition, the formation of one-,two-, and three-dimensional polynuclear metal-phosphonate assemblies by phosph(on)ate ligands hasbeen described.

Jastrzab R, Nowak M, Zabiszak M, Odani A, Kaczmarek M.T. Significance and properties of the complex formation of phosphate and polyphosphate groups in particles present in living cells,Coordin. Chem. Rev. 2021, 435, 213810, doi.org/10.1016/j.ccr.2021.213810.

29. The work of M.Sc. Maciej Skrodzki, Prof. Violetta Patroniak, Prof. Piotr Pawluć has been published in Organic Letters (ACS, IF = 6.091). Interdepartmental collaboration of Organometallic and Functional Nanostructure Synthesis groups resulted in development of new, highly selective catalytic system for hydrosilylation of alkynes. In contradiction to known hydrosilylation catalysts consisting of noble metals and molecular-heavy and complex ligands, new catalyst is founded on widely abundant metal – cobalt, and simple and rational Schiff Base type ligands. Mild condition, low catalyst loading (5000 - 500ppm), functional group tolerance and compatibility with primary, secondary and tertiary silanes proves uniqueness and yet universality of new catalytic system.

Skrodzki M, Patroniak V, Pawluć P. Schiff Base Cobalt(II) Complex-Catalyzed Highly Markovnikov-Selective Hydrosilylation of Alkynes. Org. Lett. 2021, 23, 663-667. doi: 10.1021/acs.orglett.0c03721

30. The article presents the synthesis of core/shell nanoparticles doped with Er3+, Tm3+ or Yb3+ ions and their spectroscopic properties. The obtained nanoparticles show photon up-conversion phenomenon - the property of converting infrared radiation with a wavelength of 808, 975, 1208 or 1532 nm, to radiation with energy higher than the absorbed. What distinguishes this publication from different in the field of up-conversion is the emission of nanoparticles under irradiation with a wavelength other than 975 nm - used the most frequently in other studies. Due to the properties of the lanthanide ions used, emission bands were obtained in a wide spectral range from 475 to 1625 nm, which is important for their use in bioimaging, as well as in anti-counterfeit applications. The selection of ions allowed for the manipulation of energy transfer processes between them, thus obtaining unique spectroscopic properties. Another important feature of the obtained nanoparticles is their intense luminescence, with variable characteristics depending on the wavelength of the excitation radiation.

Grzyb T, Kamiński P, Przybylska D, Tymiński A, Sanz-Rodríguez F, Haro Gonzalez P. Manipulation of up-conversion emission in NaYF4 core@shell nanoparticles doped by Er³⁺, Tm³⁺, or Yb³⁺ ions by excitation wavelength—three ions—plenty of possibilities. Nanoscale, 2021. doi:10.1039/D0NR07136F

31. The following study presents an analysis of fragrance ingredients used in cosmetics using flowing atmospheric- pressure afterglow mass spectrometry (FAPA-MS). The performance of the method was shown during the determination of fragrance components: patchoulol, farnesol, safrole, geraniol, eucalyptol, and R-carvone. The proposed method offers rapid and reliable analysis, avoiding the pre-separation step and can be an alternative to electronic nose (e-nose) for on-site analysis of cosmetics components. The developed method was used for determination of the fragrance ingredients found in commercial cosmetics and it allowed for fast determination whether a particular fragrance is of high-quality or is it a low-cost alternative product imitating the original.

Guć M, Cegłowski M, Pawlaczyk M, Kurczewska J, Reszke E, Schroeder G. Application of FAPA mass spectrometry for analysis of fragrance ingredients used in cosmetics. Measurement, 2021, 168, 108326. doi: 10.1016/j.measurement.2020.108326

32. The environmental impact of molecularly imprinted polymers (MIPs) was investigated. The molecularly imprinted polymers (MIPs)  were synthesized, as  templates: herbicides (2,4-dichlorophenoxy acetic acid (2,4-D) or 4-chloro-2-methylphenoxy acetic acid (MCPA)) and  flavonoids (rutin (Ru) or quercetin (Q)) were used. Analysis of binding in the molecularly imprinted and non-imprinted polymer (NIP) has proved that MIP shows a higher affinity towards the analytes, compared to NIP. MIPs were used to determine analytes in water using the Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (FAPA-MS) technique. In this approach, the method limit of detection (MLOD) of 2,4-D, MCPA, Ru, and Q in MIP was 4, 3, 10, and 5μg in 1 g MIP, respectively.
    The release kinetics of the analytes from MIP and their stability in water was studied. The cultures of Tetradesmus obliquus (Turpin) M.J. Wynne and Daphnia magna Straus were used for in vivo toxicity studies revealing that only Ru-MIP and Q-MIP had negative effect on the living organisms used in the bioassays.

Guć M, Messyasz B, Schroeder G. Environmental impact of molecularly imprinted polymers used as analyte sorbents in mass spectrometry. Sci. Total Environ., 2021, 772, 145074. doi:10.1016/j.scitotenv.2021.145074

33. The most recently identified coronavirus, SARS-CoV-2, possesses a threat to human health and life. Although the world has been struggling with the epidemic of the disease it causes, COVID-19, for over a year, there is still no effective drug dedicated to its treatment.

    The article discusses, among the others, the life cycle of SARS-CoV-2, potential therapeutic targets (structural proteins and enzymes essential for the viral life cycle), as well as known pharmaceutical agents currently finding new use in COVID-19 treatment trials. The possibility of using therapeutic strategies based on nucleic acid technology or the involvement of human deaminases (APOBEC deaminanses) in the fight against SARS-CoV-2 was also presented. It was indicated that some biologically active natural products may support this fight.

    Pluskota-Karwatka D, Hoffmann M, Barciszewski J. Reducing SARS-CoV-2 Pathological Protein Activity with Small Molecules. Journal of Pharmaceutical Analysis, 2021, doi: 10.1016/j.jpha.2021.03.012

34. An international team of scientists from our faculty has published the paper in Journal of Materials Chemistry C (IF = 7.059). For the first time, they have developed the broad-range optical (luminescent) manometer, operating within the unprecedentedly broad pressure range (from 10^-4 to 10⁵ bar). The developed sensor allows non-invasively (contactless) monitor pressure of the system, alike in the vacuum and under high-pressure conditions in a diamond anvil cell. The developed sensor is a result of fruitful collaboration of research groups from the Department of Rare Earths, Faculty of Chemistry, Adam Mickiewicz University in Poznań and Faculty of Physics, University of La Laguna in Spain.

    Runowski M, Woźny P, Martín I.R. Optical pressure sensing in vacuum and high-pressure ranges using lanthanide-based luminescent thermometer–manometer. J. Mater. Chem. C, 2021, 9, 4643-4651. doi:10.1039/D1TC00709B.

    

35. An international team of structural biologists mobilized by Prof. Mariusz Jaskolski (Department of Crystallography) has published a series of high-impact papers on the validation of structural models of SARS-CoV-2 proteins that are potential targets for rational design of COVID-19 drugs. The most recent papers appeared in the crystallographic flagship journal IUCrJ, and are concerned with the structure of 3CLpro, a key enzyme of the SARS-CoV-2 coronavirus (DOI: 10.1107/S2052252521001159), and with the strategy that structural biologists should work out to be prepared for future global health emergencies (DOI: 10.1107/S2052252521003018).
    
    Jaskolski M, Dauter Z, Shabalin IG, Gilski M, Brzezinski D, Kowiel M, Rupp B, Wlodawer A. Crystallographic models of SARS-CoV-2 3CLpro: in-depth assessment of structure quality and validation. IUCrJ, 2021, 8, 238-256. doi: 10.1107/S2052252521001159
    Grabowski M, Macnar JM, Cymborowski M, Cooper DR, Shabalin IG, Gilski M, Brzezinski D, Kowiel M, Dauter Z, Rupp B, Wlodawer A, Jaskolski M, Minor W. Rapid Response to Emerging Biomedical Challenges and Threats. IUCrJ 2021, 8. doi: 10.1107/S2052252521003018.

.