Grants in progress

Projekt SONATA 172021/43/D/ST5/00853 finansowany przez Narodowe Centrum Nauki pod tytułem „Wykorzystanie cieczy jonowych i rozpuszczalników głęboko eutektycznych w syntezie materiałów inspirowanych procesami biomineralizacji”

Przemysław Bartczak, Marcin Wysokowski, Kacper Szylińczuk, Majka Odalanowska, Teofil Jesionowski, Sławomir Borysiak

Green synthesis of chitin/lignin based-polyurethane composites

Abstract: Polyurethanes (PU) are still among the most promising high-performance materials in industrial applications. Nevertheless, the development of sustainable and efficient materials is an ongoing challenge for the plastics industry. In recent years there has been growing interest in utilizing natural materials such as chitin and lignin as additives in polyurethane foam production. This study focuses on the utilization of sustainable chitin–lignin filler for polyurethanes with the aim of producing sustainable, cost-effective, and efficient foam materials. A chitin–lignin filler was prepared using a mechanochemical approach, and flexible polyurethane foams (FPUFs) were synthesized with varying amounts of chitin–lignin additive. The resulting foams were characterized using various analytical techniques, including scanning electron microscopy, compression testing, tensile strength analysis, and measurements of surface free energy and contact angle. Possible interactions between the filler and PU were analyzed by means of FTIR spectroscopy. The results show that the addition of chitin–lignin filler improved the mechanical properties (in comparison to pristine chitin and lignin as filler), with a significant reduction in the compression set of the polyurethane foams, a crucial property in the production of seat foams. Synergy was observed between chitin–lignin filler in PU foam. Overall, the study demonstrates the potential of chitin–lignin as a sustainable and efficient natural filler that can be effectively applied on the industrial scale. The combination of these two biopolymers led to a polyurethane composite with better mechanical properties. Additionally, the use of biopolymers (chitin and lignin) as a filler for FPUFs is one of the options for the management of waste materials, which is in line with the idea of sustainable production.

Klaudia Wysokowska, Zuzanna Cupiał, Maciej Staszak, Agnieszka Zgoła‑Grześkowiak,
Jan Koziolek, Łukasz Ławniczak, Marcin Wysokowski, Bogdan Wyrwas

Photocatalytic degradation of non-ionic, anionic, and cationic surfactants: from batch experiments through equilibrium/kinetic study to ecotoxicology analysis

Abstract: Surface-active compounds constitute a group of important and widespread environmental pollutants. Among different methods used for their treatment, photocatalytic degradation is a promising and efficient solution. Nevertheless, the exact outcome of photodegradation of surfactants may be difficult to predict in case of concentrations used at the industrial scale and considering that the associated mechanism involves radicals which may potentially result in the formation of toxic by-products. In consequence, the aim of this study was to analyze the catalytic photodegradation of three groups of surfactants (three structurally diverse representatives of cationic, anionic, and non-ionic surfactants). Nanoparticles of zinc oxide were synthesized and used as a photocatalyst. The efficiency of photodegradation ranged from 93 to 100% at 10 mg/L, from 38 to 94% at 100 mg/L, and from 15 to 66% when the surfactants were supplied at 1000 mg/L, and the results depended on the structure of the compound subjected to treatment. Subsequent investigation of kinetics revealed that Freundlich, Langmuir or Dubinin-Radushkevich isotherms may be used to describe the adsorption of surfactants (1–65%) and allowed to establish the following order of reactivity: cationic > non-ionic > anionic. Subsequent LC–MS/MS studies of the residues were the basis for identification of photodegradation products for each respective compound. Ultimately, due to the fact that treated graywater is often used as potable water, the phytotoxicity of the degradation products was tested toward sorghum. It was established that in the majority of cases the treatment was efficient (in some cases stimulation of plant growth compared to control samples was observed), whereas an increase in toxicity was observed in case of two cationic surfactants (CTAB and benzalkonium chloride). Overall, the results presented in this study support the application of photocatalytic degradation as an efficient solution for treatment of surfactant-rich effluents.

Marcin Wysokowski, Rachel K. Luu, Sofia Arevalo, Eesha Khare, Witold Stachowiak,
Michał Niemczak, Teofil Jesionowski, Markus J. Buehler

Untapped Potential of Deep Eutectic Solvents for the Synthesis of Bioinspired Inorganic–Organic Materials

Abstract: Since the discovery of deep eutectic solvents (DESs) in 2003, significant progress has been made in the field, specifically advancing aspects of their preparation and physicochemical characterization. Their low-cost and unique tailored properties are reasons for their growing importance as a sustainable medium for the resource-efficient processing and synthesis of advanced materials. In this paper, the significance of these designer solvents and their beneficial features, in particular with respect to biomimetic materials chemistry, is discussed. Finally, this article explores the unrealized potential and advantageous aspects of DESs, focusing on the development of biomineralization-inspired hybrid materials. It is anticipated that this article can stimulate new concepts and advances providing a reference for breaking down the multidisciplinary borders in the field of bioinspired materials chemistry, especially at the nexus of computation and experiment, and to develop a rigorous materials-by-design paradigm.

Rachel K. Luu, Marcin Wysokowski, Markus J. Buehler

Generative discovery of de novo chemical designs using diffusion modeling and transformer deep neural networks with application to deep eutectic solvents

Abstract: We report a series of deep learning models to solve complex forward and inverse design problems in molecular modeling and design. Using both diffusion models inspired by nonequilibrium thermodynamics and attention-based transformer architectures, we demonstrate a flexible framework to capture complex chemical structures. First trained on the Quantum Machines 9 (QM9) dataset and a series of quantum mechanical properties (e.g., homo, lumo, free energy, and heat capacity), we then generalize the model to study and design key properties of deep eutectic solvents (DESs). In addition to separate forward and inverse models, we also report an integrated fully prompt-based multi-task generative pretrained transformer model that solves multiple forward, inverse design, and prediction tasks, flexibly and within one model. We show that the multi-task generative model has the overall best performance and allows for flexible integration of multiple objectives, within one model, and for distinct chemistries, suggesting that synergies emerge during training of this large language model. Trained jointly in tasks related to the QM9 dataset and DESs, the model can predict various quantum mechanical properties and critical properties to achieve deep eutectic solvent behavior. Several combinations of DESs are proposed based on this framework.

Marcin Wysokowski, Tomasz Machałowski, Joanna Idaszek, Adrian Chlanda, Jakub Jaroszewicz, Marcin Heljak, Michał Niemczak, Adam Piasecki, Marta Gajewska, Hermann Ehrlich, Wojciech Święszkowski, Teofil Jesionowski

Deep eutectic solvent-assisted fabrication of bioinspired 3D carbon–calcium phosphate scaffolds for bone tissue engineering

Abstract: Tissue engineering is a burgeoning field focused on repairing damaged tissues through the combination of bodily cells with highly porous scaffold biomaterials, which serve as templates for tissue regeneration, thus facilitating the growth of new tissue. Carbon materials, constituting an emerging class of superior materials, are currently experiencing remarkable scientific and technological advancements. Consequently, the development of novel 3D carbon-based composite materials has become significant for biomedicine. There is an urgent need for the development of hybrids that will combine the unique bioactivity of ceramics with the performance of carbonaceous materials. Considering these requirements, herein, we propose a straightforward method of producing a 3D carbon-based scaffold that resembles the structural features of spongin, even on the nanometric level of their hierarchical organization. The modification of spongin with calcium phosphate was achieved in a deep eutectic solvent (choline chloride : urea, 1 : 2). The holistic characterization of the scaffolds confirms their remarkable structural features (i.e., porosity, connectivity), along with the biocompatibility of α-tricalcium phosphate (α-TCP), rendering them a promising candidate for stem cell-based tissue-engineering. Culturing human bone marrow mesenchymal stem cells (hMSC) on the surface of the biomimetic scaffold further verifies its growth-facilitating properties, promoting the differentiation of these cells in the osteogenesis direction. ALP activity was significantly higher in osteogenic medium compared to proliferation, indicating the differentiation of hMSC towards osteoblasts. However, no significant difference between C and C–αTCP in the same medium type was observed.

Wajeeha Fatima, Junaid Munawar, Maryam Mazhar, Shahid Nawaz, Ehsan Ullah Rashid, Sana Hafeez, Muhammad Shahzeb Khan, Marcin Wysokowski, Teofil Jesionowski

Chitosan-based composites for oil-contaminated water treatment

Abstract: Water quality is constantly at risk due to heavy contamination by petroleum and oil pollutants in water bodies. As a result, scientists worldwide have been working on developing natural and environmentally friendly nanocomposites to reduce water contamination in wastewater and recover petroleum products. Techniques that make use of natural products are more convenient as they are nondepleting, nontoxic for the environment, and cost-effective. One of the best methods for oil-water separation is using chitosan and its composites, as they are cost-effective, safe for the environment, and are capable of removing contaminants. This chapter aims to address the concerns caused by oil and municipal contaminants in wastewater, their impact on nature, and all the efforts made toward using chitosan and its derivatives in the chemical industries, treatment of oil spillages, and wastewater treatment in the hydrocarbon industry. The chapter also discusses various methods for producing CS-nanocomposites, such as ceramic alumina, zirconium, lanthanum, iron, silver, MnO2-CS, TiO2-CS, ZnO-CS, Ti-Al, and polyaromatic-based chitosan composites. According to the publications reviewed, chitosan-based nanocomposites are evolving as potential sorbents and are considered the best candidates for treating wastewater.

Patrycja Frąckowiak, Eryk Jędrzejczak, Filip Kaspryszyn, Teofil Jesionowski, Marcin Wysokowski

Revolutionizing electrospinning: Sustainable solutions through deep eutectic solvents in biopolymer processing

Abstract: Electrospinning is currently one of the most used techniques for obtaining various types of nanofibers. In the era of sustainable development, it is essential to utilize environmentally friendly raw materials and solvents. This review summarizes the current state of the art in biopolymer electrospinning using deep eutectic solvents. To date, there have not been too many studies on the simultaneous application of these mixtures and biopolymers in the electrospinning process. Nevertheless, the use of natural origin raw materials and the replacement of conventional organic solvents with deep eutectic solvents appear promising in this technique due to many attractive properties of both the mixtures and biopolymers. This article aims to inspire scientists to further research in this direction, related to the development of electrospinning techniques aimed at reducing the negative environmental impact.

Marcin Wysokowski, Patrycja Frąckowiak, Tomasz Rzemieniecki, Aleksandra Sikora, Łukasz Ławniczak, Filip Kaspryszyn, Szymon Woziwodzki, Eryk Jędrzejczak, Krzysztof Nowacki, Adam Gorczyński, Michał Niemczak, Teofil Jesionowski

Urea-lactic acid as efficient lignin solvent and its practical utility in sustainable electrospinning

Abstract: The development of lignin-based materials presents a promising avenue for advancing green chemistry and mitigating environmental impact. However, the key challenge lies in the processability of lignin, which significantly affects its practical applications. Addressing the issues related to lignin’s complex structure, variability, and reactivity is crucial for optimizing its incorporation into high-performance materials. Therefore, in this study we explore the efficacy of a urea-lactic acid-based deep eutectic solvent (ULA) for the dissolution of kraft lignin, aiming to enhance its practical utility in sustainable electrospinning processes, for the first time. Results of elemental analysis, IR and 2D NMR spectroscopy, provide crucial insights into the structural properties of the regenerated material post-DES treatment. The findings confirm a high lignin recovery rate, reaching up to 96.6 % for samples dissolved at 100°C. Additionally, 2D NMR analysis indicates that the process leads to partial esterification of lignin with lactate ions. The ability of the studied DES to effectively solubilize lignin underscores its potential as an efficient lignin solvent and facilitates the fabrication of lignin-based nanofibers via electrospinning.
The incorporation of this DES in electrospinning processes promises significant advancements in the development of sustainable, lignin-derived materials and offers a green alternative for production of high-performance nanofibers. Preliminary results of electrochemical impedance spectroscopy and galvanostatic charge/discharge measurements confirm that the EDLC with prepared hydrogel electrolyte demonstrates attractive electrochemical properties (specific capacitance, CSP = 95 F g–1; series resistance RS = 2.2 Ω; charge transfer resistance, RCT = 1.6 Ω), which are comparable with the reference cell based on a commercial glass fibre separator. Hence, the DES-assisted-electrospinned lignin membrane can be viewed as a potential gel electrolyte matrix for practical use in construction of sustainable energy storage devices.

Marcin Wysokowski, Zuzanna Chmielewska, Mariusz Sandomierski, Jakub Zdarta, Teofil Jesionowski

Chitin membrane for efficient laccase immobilization and synergistic removal of 17α-ethynylestradiol from water-based solutions

Abstract: A unique chitin–laccase membrane was fabricated as an environmentally friendly biocatalytic platform, utilizing 1-butyl-3-methylimidazolium acetate as the solvent for chitin. Observations using scanning electron microscopy showed that the chitin-laccase membrane possessed a uniform and densely packed structure. Based on the presence of FT-IR signals at 1020 cm−1 and changes in the intensity of signals at 1540 cm−1 and 1645 cm−1, the effectiveness of laccase immobilization was confirmed. FT-IR mapping revealed that the enzyme is evenly distributed on the surface of the membrane. The catalytic activity of the native enzyme and laccase immobilized using the membrane was determined based on a model reaction, and the retention of high activity was confirmed using real solutions. Laccase immobilized using the chitinous membrane retained over 60 % of its initial activity after 30 days of storage at 4 °C. By contrast, the free enzyme retained <40 % of its initial activity. Moreover, the activity of chitin-laccase system remained at 85 % after 5 cycles. This novel chitin–laccase combination was tested in the 17α-ethynylestradiol (EE2) removal from water-based solutions. It was found that EE2 underwent synergistic degradation through concurrent adsorption and biocatalytic transformation, with enzymatic conversion as the dominant mechanism.

Adriana Olejniczak, Witold Stachowiak, Daniel Ziental, Jolanta Długaszewska, Tomasz Rzemieniecki, Marcin Wysokowski, Teofil Jesionowski, Michał Niemczak

Unraveling the Potential of Vitamin B₃-Derived Salts with a Salicylate Anion as Dermal Active Agents for Acne Treatment

Abstract: This study is focused on the utilization of naturally occurring salicylic acid and nicotinamide (vitamin B3) in the development of novel sustainable Active Pharmaceutical Ingredients (APIs) with significant potential for treating acne vulgaris. The study highlights how the chemical structure of the cation significantly influences surface activity, lipophilicity, and solubility in aqueous media. Furthermore, the new ionic forms of APIs, the synthesis of which was assessed with Green Chemistry metrics, exhibited very good antibacterial properties against common pathogens that contribute to the development of acne, resulting in remarkable enhancement of biological activity ranging from 200 to as much as 2000 times when compared to salicylic acid alone. The molecular docking studies also revealed the excellent anti-inflammatory activity of N-alkylnicotinamide salicylates comparable to commonly used drugs (indomethacin, ibuprofen, and acetylsalicylic acid) and were even characterized by better IC50 values than common anti-inflammatory drugs in some cases. The derivative, featuring a decyl substituent in the pyridinium ring of nicotinamide, exhibited efficacy against Cutibacterium acnes while displaying favorable water solubility and improved wettability on hydrophobic surfaces, marking it as particularly promising. To investigate the impact of the APIs on the biosphere, the EC50 parameter was determined against a model representative of crustaceans─Artemia franciscana. The majority of compounds (with the exception of the salt containing the dodecyl substituent) could be classified as “Relatively Harmless” or “Practically Nontoxic”, indicating their potential low environmental impact, which is essential in the context of modern drug development.

Abstract: Porous deep eutectic solvents (PDES) are capturing the imagination of scientists, promising a revolutionary leap in material science. These innovative materials, blending the versatility of deep eutectic solvents (DES) with the intricate architectures of porous structures, offer an exciting array of applications—from green chemistry and catalysis to energy storage and environmental remediation. However, the journey from laboratory curiosity to industrial application is fraught with challenges. This perspective article analyzes the realm of PDES, scrutinizing the cutting-edge advancements and the challenges that lie ahead. By exploring their synthesis, unique properties, and diverse application potential, the critical question is asked: are PDES an unfulfilled dream or the next big breakthrough in scientific innovation? A comprehensive analysis reveals a “landscape” ripe with opportunity, suggesting that with targeted research and development, PDES can indeed become a cornerstone technology, driving progress across multiple scientific domains.

Abstract: Lately, deep eutectic solvents (DESs) have been taken into detailed consideration as potential electrolytes for use in various electrochemical devices. This study reports a successful synthesis of three novel natural deep eutectic solvents (NADESs) based on betaine hydrochloride as the hydrogen bond acceptor and glycerol, glycolic acid, and ethylene glycol as hydrogen bond donors. Comprehensive research, including ATR-FTIR, surface tension, rheological properties, and ionic conductivity, revealed that the betaine hydrochloride–ethylene glycol (BETCl−:MEG) system exhibited superior physicochemical characteristics. This NADES was subsequently evaluated as an electrolyte in an electric double-layer capacitor (EDLC), demonstrating excellent electrochemical performance with a specific capacitance of 94 F g−1 (0.5 A g−1) and excellent electrochemical stability. Notably, this study represents the first successful application of a betaine hydrochloride-based NADES as a liquid electrolyte in an energy storage device, highlighting its potential as a sustainable alternative to other innovative electrolyte systems, such as deep eutectic solvents based on choline chloride. These findings suggest that betaine-based NADESs hold significant promise for future applications in energy storage technologies.

Abstract: This research explores the intricate chemistry of deep eutectic solvents (DESs), particularly those formed with carboxylic acids and choline chloride, highlighting their effectiveness in metal leaching and the potential for sustainable recovery of valuable materials from electronic waste. The utilization of DESs in this context demonstrates a promising avenue for advancing eco-friendly methods in the treatment of electronic waste, contributing to both resource recovery and environmental management. It has been found that especially natural eutectic solvents, with lactic acid as the hydrogen bond donor, could provide a green alternative to conventional methods of processing electronic waste and recovery of strategically important metals, which remain crucial in order to meet the demand of the exponentially increasing electronics production. Lactic acid-based DES (Lac-DES) showed higher selectivity in Cu leaching over Ag, compared to other DESs, while oxalic acid-based DES (Ox-DES), surprisingly, appeared to leach selectively only silver (up to 40%) in the presence of H2O2.

Abstract: Spongin is a fundamental biopolymer that has played a crucial role in the skeletogenesis of keratosan sponges for over 800 million years. This biomaterial had so far remained chemically unidentified and believed to be an enigmatic type of halogenated collagen-keratin-based bioelastomer. Here we show collagen I and III as the main structural components of spongin. Proteomics, 13C solid state NMR and Raman spectroscopy confirm the identity of collagenous domains in spongin with collagen from mammals. Using an HPLC-MS analysis, we found halogenated di- and tri-tyrosines as crosslinking agents in spongin. Using molecular dynamics modeling, we solvated the crystal structures of collagen mimetic peptides for type I and type III collagens in four different systems, including selected brominated crosslinks. The results underscore the complex interplay between the collagen structures and crosslinks, raising intriguing questions about the molecular mechanisms underlying collagen chemistry within spongin as an ancient biocomposite.