Artykuły IChO PAN

Displaying 1 - 5 of 170 records

Automated Research Platform for Development of Triplet–Triplet Annihilation Photon Upconversion Systems
(American Chemical Society, 2025) Baronas, Paulius; Lekavičius, Justas; Majdecki, Maciej; Elholm, Jacob Lynge; Kazlauskas, Karolis; Gaweł, Przemysław; Moth-Poulsen, Kasper; Department of Chemical Engineering, Universitat Politècnica de Catalunya, Spain; Institute of Photonics and Nanotechnology, Vilnius University, Lithuania; The Institute of Materials Science of Barcelona, ICMAB-CSIC, Spain; Institute of Organic Chemistry, Polish Academy of Sciences; Catalan Institution for Research & Advanced Studies, ICREA, Spain; Department of Chemistry and Chemical Engineering, Chalmers University of Technology, Sweden
Triplet–triplet annihilation photon upconversion (TTA-UC) systems hold great promise for applications in energy, 3D printing, and photopharmacology. However, their optimization remains challenging due to the need for precise tuning of sensitizer and annihilator concentrations under oxygen-free conditions. This study presents an automated, high-throughput platform for the discovery and optimization of TTA-UC systems. Capable of performing 100 concentration scans in just two hours, the platform generates comprehensive concentration maps of critical parameters, including quantum yield, triplet energy transfer efficiency, and threshold intensity. Using this approach, we identify key loss mechanisms in both the established and novel TTA-UC systems. At high porphyrin-based sensitizer concentrations, upconversion quantum yield losses are attributed to sensitizer triplet self-quenching via aggregation and sensitizer triplet–triplet annihilation (sensitizer-TTA). Additionally, reverse triplet energy transfer (RTET) at elevated sensitizer levels increases the upconversion losses and excitation thresholds. Testing novel sensitizer–annihilator pairs confirms these loss mechanisms, highlighting opportunities for molecular design improvements. This automated platform offers a powerful tool for advancing TTA-UC research and other photochemical studies requiring low oxygen levels, intense laser excitation, and minimal material use.
α-Selective syn-Carbotrifluoromethylthiolation of Alkynes
(American Chemical Society, 2025) Shah, Prachi; Chaładaj, Wojciech; Institute of Organic Chemistry, Polish Academy of Sciences
Trifluoromethylthiolative difunctionalization of alkynes typically proceeds in an anti-fashion delivering the SCF3 group in the β-position (anti-Markovnikov). Herein, we disclose a vicinal syn-arylation-trifluoromethylthiolation of alkynes enabling α-selective introduction of the SCF3 group (Markovnikov). The unique selectivity was achieved via a merge of Ni-catalyzed carbomagnesiation with a subsequent Cu-mediated trifluoromethylthiolation of the resulting vinyl-magnesium species. The former component of the sequential process determines both the regio- and stereoselectivity of the overall transformation.
Relative rates of addition of carbanions to substituted nitroarenes: can quantum chemical calculations give meaningful predictions?
(Royal Society of Chemistry, 2025) Błaziak, Kacper; Świder, Paweł; Mąkosza, Mieczysław; Danikiewicz, Witold; Faculty of Chemistry, University of Warsaw; Biological and Chemical Research Center, University of Warsaw; Institute of Organic Chemistry, Polish Academy of Sciences
Computational description and kinetic properties based on density functional theory methods of the key step of the addition reaction between a model nucleophile and nitroaromatic ring in positions occupied by hydrogen are presented. A wide series of DFT functionals (PBE0, B3LYP, ωB97XD, M062X, PBE1PBE-D3, B3LYP-D3 and APFD) was used to track the influence of functional groups in nitroaromatic rings on reaction activation barriers. The comparison of experimentally determined relative rates of nucleophilic addition and their calculated thermodynamic counterparts at various positions in a series of ortho-, meta- and para-substituted nitroarenes are provided. It was shown that different DFT methods provide a good correlation between computed thermodynamic parameters and logarithms of experimental relative reaction rates. In addition, presented results show that DFT computations can be used for reliable prediction of relative reaction rates of vicarious nucleophilic substitution (VNS)-type of reactions. This work provides a valuable tool in the form of structure–thermodynamic property correlation data that can be used in the synthesis design process or QSAR type of analysis, where explicit trends are often required.
Synthesis, Antimicrobial Activity, and Tyrosinase Inhibition by Multifunctional 3,4-Dihydroxy-Phenyl Peptidomimetics
(MDPI, 2025) Wavhal, Deepak S.; Koszelewski, Dominik; Kowalczyk, Paweł; Brodzka, Anna; Ostaszewski, Ryszard; Fernández-García, Marta; Institute of Organic Chemistry, Polish Academy of Sciences; Department of Animal Nutrition, The Kielanowski Institute of Animal Physiology and Nutrition, Polish Academy of Sciences
The purpose of the present study was to evaluate the synergistic effect of two important pharmacophores, 3,4-dihydroxyphenyl and peptidomimetic moieties, as mushroom tyrosinase inhibitors and antimicrobial agents targeting specific strains of pathogenic bacteria. The 3,4-dihydroxybenzaldehyde (protocatechuic aldehyde) was found to be an effective inhibitor of tyrosinase activity, and due to the fact that it is a safe natural substance with such a scaffolded structure, it is likely that dihydroxyl-substituted phenolic derivatives can exhibit potent tyrosinase inhibitory activity. Series of peptidomimetics with an incorporated 3,4-dihydroxyphenyl scaffold was synthesized and characterized. The inhibitory effects of peptidomimetics on a mushroom tyrosinase were studied. The results showed that among the compounds, five of them showed higher inhibitory activity than the parent 3,4-dihydroxybenzyl aldehyde. In silico docking studies with mushroom tyrosinase (PDB ID 2Y9X) predicted possible binding modes in the enzymatic pocket for these compounds. Furthermore, the antimicrobial activities of peptidomimetics against selected Gram-positive and Gram-negative bacterial strains (E. coli, A. baumannii, P. aeruginosa, E. cloacae, and S. aureus) were investigated. The results showed that all tested peptidomimetics have antimicrobial activities (MIC values from 0.25 to 4.0 μM) comparable with those observed for the commonly used antibiotics (ciprofloxacin, bleomycin, and cloxacillin). Notably, all evaluated compounds demonstrated significant activity against E. coli and S. aureus strains, which are primary sources of infections resulting in numerous fatalities. Additionally, the cytotoxicity of sixteen derivatives was assessed using the MTT assay on BALB/c3T3 mouse fibroblast cell lines. Cytotoxicity analyses indicated that the tested substances have a similar or reduced impact on cell proliferation compared to commonly utilized antibiotics within the range of therapeutic doses. This study presents the potential of peptidomimetics with 3,4-dihydroxyphenyl scaffolds could be beneficial for developing novel tyrosinase inhibitors and new potent food preservatives or cosmetic additives.
Indoloindolizines: The Complete Story of a Polycyclic Aromatic Scaffold from Theoretical Design to Organic Field-Effect Transistor Applications
(American Chemical Society, 2025) Pareek, Abhishek; Mehboob, Muhammad Yasir; Cieplak, Maciej; Majdecki, Maciej; Szabat, Hubert; Noworyta, Krzysztof; Połczyński, Piotr; Morawiak, Maja; Sharma, Piyush Sindhu; Foroutan-Nejad, Cina; Gaweł, Przemysław; Institute of Organic Chemistry, Polish Academy of Sciences; Institute of Physical Chemistry, Polish Academy of Sciences; Department of Chemistry, Laboratory of Electroanalytical Chemistry, Biological and Chemical Research Centre, University of Warsaw
The development of stable and tunable polycyclic aromatic compounds (PACs) is crucial for the advancement of organic optoelectronics. Conventional PACs, such as acenes, often suffer from poor stability due to photooxidation and oligomerization, which are linked to their frontier molecular orbital energy levels. To address these limitations, we designed and synthesized a new class of π-expanded indoloindolizines by merging indole and indolizine moieties into a single polycyclic framework. We developed a scalable synthetic protocol to produce a wide range of π-expanded derivatives. The structural, electronic, and optical properties of these compounds were extensively characterized. We achieved precise modulation of the electronic structure by controlling the aromaticity of specific rings. Benzannulation at targeted positions allowed fine-tuning of the HOMO–LUMO gap, leading to distinct shifts in the optoelectronic properties. Single-crystal X-ray diffraction confirmed their molecular structures, while theoretical calculations provided insights into the observed experimental trends. These indoloindolizines exhibit vivid colors and fluorescence across the visible spectrum and enhanced stability against photooxidation. Reactivity studies demonstrated high regioselectivity in electrophilic substitutions, highlighting the indole-like behavior of these compounds and opening avenues for further functionalization. To showcase the practical utility of our design rules, we fabricated organic field-effect transistors (OFETs) using the newly developed indoloindolizines, which revealed remarkable performance with ambipolar charge transport properties. Overall, our work establishes indoloindolizines as a promising platform for the development of stable, tunable organic materials for optoelectronic applications. Through rational molecular design, we have provided a new pathway for molecular innovation in organic electronics.

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