Magnetic nanoparticles coated with bioinspired polydopamine were obtained via a co-precipitation ... more Magnetic nanoparticles coated with bioinspired polydopamine were obtained via a co-precipitation method and oxidative polymerization of dopamine. Obtained particle were used for carrying doxorubicin to HeLa cells.
Gold nanoparticles (AuNPs), as an agent enhancing radiosensitivity, play a key role in the potent... more Gold nanoparticles (AuNPs), as an agent enhancing radiosensitivity, play a key role in the potential treatment of breast cancer (BC). Assessing and understanding the kinetics of modern drug delivery systems is a crucial element that allows the implementation of AuNPs in clinical treatment. The main objective of the study was to assess the role of the properties of gold nanoparticles in the response of BC cells to ionizing radiation by comparing 2D and 3D models. In this research, four kinds of AuNPs, different in size and PEG length, were used to sensitize cells to ionizing radiation. The in vitro viability, uptake, and reactive oxygen species generation in cells were investigated in a time- and concentration-dependent manner using 2D and 3D models. Next, after the previous incubation with AuNPs, cells were irradiated with 2 Gy. The assessment of the radiation effect in combination with AuNPs was analyzed using the clonogenic assay and γH2AX level. The study highlights the role of t...
Measurement of the nitric oxide (NO) concentration in living cells in the physiological nanomolar... more Measurement of the nitric oxide (NO) concentration in living cells in the physiological nanomolar range is crucial in understanding NO biochemical functions, as well as in characterizing the efficiency and kinetics of NO delivery by NO-releasing drugs. Here, we show that fluorescence correlation spectroscopy (FCS) is perfectly suited for these purposes, due to its sensitivity, selectivity, and spatial resolution. Using the fluorescent indicators, diaminofluoresceins (DAFs), and FCS, we measured the NO concentrations in NO-producing living human primary endothelial cells, as well as NO delivery kinetics, by an external NO donor to the immortal human epithelial living cells. Due to the high spatial resolution of FCS, the NO concentration in different parts of the cells were also measured. The detection of nitric oxide by means of diaminofluoresceins is much more efficient and faster in living cells than in PBS solutions, even though the conversion to the fluorescent form is a multi-st...
19F Nuclear Magnetic Resonance spin-lattice relaxation experiments have been performed for a seri... more 19F Nuclear Magnetic Resonance spin-lattice relaxation experiments have been performed for a series of ionic liquids including the same anion, bis(trifluoromethanesulfonyl)imide, and cations with alkyl chains of different lengths: triethylhexylammonium, triethyloctylammonium, decyltriethylammonium, dodecyltriethylammonium, decyltriethylammonium, and hexadecyltriethylammonium. The experiments have been carried out in a frequency range of 10 kHz to 10 MHz versus temperature. A thorough analysis of the relaxation data has led to the determination of the cation–anion as a relative translation diffusion coefficient. The diffusion coefficients have been compared with the corresponding cation–cation and anion–anion diffusion coefficients, revealing a correlation in the relative translation movement of the anion and the triethylhexylammonium, triethyloctylammonium, decyltriethylammonium, and dodecyltriethylammonium cations, whereas the relative translation diffusion between the anion and th...
1H spin-lattice relaxation experiments have been performed for a series of ionic liquids includin... more 1H spin-lattice relaxation experiments have been performed for a series of ionic liquids including bis(trifluoromethanesulfonyl)imide anion and cations of a varying alkyl chain length: triethylhexylammonium, triethyloctylammonium, decyltriethylammonium, dodecyltriethylammonium, triethyltetradecylammonium, and hexadecyltriethylammonium. The relaxation studies were carried out in abroad frequency range covering three orders of magnitude, from 10 kHz to 10 MHz, versus temperature. On the basis of a thorough, quantitative analysis of this reach data set, parameters characterizing the relative, cation-cation, translation diffusion (relative diffusion coefficients and translational correlation times), and rotational motion of the cation (rotational correlation times) were determined. Relationships between these quantities and their dependence on the alkyl chain length were discussed in comparison to analogous properties of molecular liquids. It was shown, among other findings, that the ra...
1H and 19F spin-lattice relaxation experiments have been performed for a series of ionic liquids ... more 1H and 19F spin-lattice relaxation experiments have been performed for a series of ionic liquids sharing the same anion: bis(trifluoromethanesulfonyl)imide but including cations of different alkyl chain lengths: butyltriethylammonium, triethyloctylammonium, dodecyltriethylammo-nium and hexadecyltriethylammonium. The studies have been carried out in the temperature range from 383 to 108 K at the resonance frequency of 200 MHz (for 1H). A quantitative analysis of the relaxation data has revealed two dynamical processes for both kinds of ions. The dynamics have been successfully modeled in terms of the Arrhenius law. The timescales of the dynamical processes and their temperature evolution have been discussed in detail, depending on the structure of the cation.
Production of ethanol from lignocellulosic biomass is considered the most promising proposition f... more Production of ethanol from lignocellulosic biomass is considered the most promising proposition for developing a sustainable and carbon–neutral energy system. The use of renewable raw materials and variability of lignocellulosic feedstock generating hexose and pentose sugars also brings advantages of the most abundant, sustainable and non-food competitive biomass. Great attention is now paid to agricultural wastes and overgrowing plants as an alternative to fast-growing energetic crops. The presented study explores the use of stinging nettle stems, which have not been treated as a source of bioethanol. Apart from being considered a weed, stinging nettle is used in pharmacy or cosmetics, yet its stems are always a non-edible waste. Therefore, the aim was to evaluate the effectiveness of pretreatment using imidazolium- and ammonium-based ionic liquids, enzymatic hydrolysis, fermentation of stinging nettle stems, and comparison of such a process with giant miscanthus. Raw and ionic liq...
The study objective was to model and predict the bioethanol production process from lignocellulos... more The study objective was to model and predict the bioethanol production process from lignocellulosic biomass based on an example of empirical study results. Two types of algorithms were used in machine learning: artificial neural network (ANN) and random forest algorithm (RF). Data for the model included results of studying bioethanol production with the use of ionic liquids (ILs) and different enzymatic preparations from the following biomass types: buckwheat straw and biomass from four wastelands, including a mixture of various plants: stems of giant miscanthus, common nettle, goldenrod, common broom, fireweed, and hay (a mix of grasses). The input variables consisted of different ionic liquids (imidazolium and ammonium), enzymatic preparations, enzyme doses, time and temperature of pretreatment, and type of yeast for alcoholic fermentation. The output value was the bioethanol concentration. The multilayer perceptron (MLP) was used in the artificial neural networks. Two model types...
1H and 19F spin-lattice relaxation experiments have been performed for butyltriethylammonium bis(... more 1H and 19F spin-lattice relaxation experiments have been performed for butyltriethylammonium bis(trifluoromethanesulfonyl)imide in the temperature range from 258 to 298 K and the frequency range from 10 kHz to 10 MHz. The results have thoroughly been analysed in terms of a relaxation model taking into account relaxation pathways associated with 1H–1H, 19F–19F and 1H–19F dipole–dipole interactions, rendering relative translational diffusion coefficients for the pairs of ions: cation–cation, anion–anion and cation–anion, as well as the rotational correlation time of the cation. The relevance of the 1H–19F relaxation contribution to the 1H and 19F relaxation has been demonstrated. A comparison of the diffusion coefficients has revealed correlation effects in the relative cation–anion translational movement. It has also turned out that the translational movement of the anions is faster than of cations, especially at high temperatures. Moreover, the relative cation–cation diffusion coeff...
The application of ionic liquids (ILs) has grown enormously, from their use as simple solvents, c... more The application of ionic liquids (ILs) has grown enormously, from their use as simple solvents, catalysts, media in separation science, or electrolytes to that as task-specific, tunable molecular machines with appropriate properties. A thorough understanding of these properties and structure–property relationships is needed to fully exploit their potential, open new directions in IL-based research and, finally, properly implement the appropriate applications. In this work, we investigated the structure–properties relationships of a series of alkyltriethylammonium bis(trifluoromethanesulfonyl)imide [TEA-R][TFSI] ionic liquids in relation to their thermal behavior, structure organization, and self-diffusion coefficients in the bulk state using DSC, FT-IR, SAXS, and NMR diffusometry techniques. The phase transition temperatures were determined, indicating alkyl chain dependency. Fourier-transformed infrared spectroscopy studies revealed the structuration of the ionic liquids along with...
One of the main goals of industrial biotechnology is to develop an effective method for ethanol p... more One of the main goals of industrial biotechnology is to develop an effective method for ethanol production for fuel purposes using lignocellulosic biomass. Variability of lignocellulosic raw materials, selection of an effective method for the pretreatment of raw material, and selection of microorganisms with the ability to ferment not only hexoses but also pentoses and are moreover resistant to environmental stress generated by the products of lignocellulosic complex decomposition, are the challenges encountered in ethanol production. The use of agricultural wastelands and overgrowing plants that have little possibility of application in processes other than energy production seem to be an interesting alternative to conventional, but very often rather cultivation demanding energy crops. The aim of this study was to evaluate the possibility of using the stems of fireweed (Epilobium angustifolium L.), European goldenrod (Solidago virgaurea L.), and common broom (Cytisus scoparius L.) for ethanol production. The key elements studied were characteristics of the lignocellulosic complex structure, influence of the selected ionic liquids on the structural changes in biomass, and efficiency of enzymatic hydrolysis and ethanol fermentation processes. The results showed that under the assumed conditions the best effect was observed with the fireweed materials subjected to pretreatment with 1‐ethyl‐3‐methylimidazolium acetate and enzymatic hydrolysis with Viscozyme® preparation. The final concentration of ethanol obtained was 2.509 g L−1 with a yield of 92.3%. This was due to the highest share of cellulose (40.9%) in the whole lignocellulosic complex compared to other raw materials, which in combination with the selection of an appropriate ionic liquid and an enzymatic preparation, led to high bioprocess efficiency.
Polydopamine (PDA)-coated magnetic nanoparticles functionalized with mono-6-thio-β-cyclodextrin (... more Polydopamine (PDA)-coated magnetic nanoparticles functionalized with mono-6-thio-β-cyclodextrin (SH-βCD) were obtained and characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), Nuclear and Magnetic Resonance Imaging (NMR and MRI), and doxorubicin (DOXO)-loading experiments. The liver cancer cellular internalization of DOXO-loaded nanoparticles was investigated by confocal imaging microscopy. Synthesized nanomaterials bearing a chemotherapeutic drug and a layer of polydopamine capable of absorbing near-infrared light show high performance in the combined chemo- and photothermal therapy (CT-PTT) of liver cancer due to the synergistic effect of both modalities as demonstrated in vitro. Moreover, our material exhibits improved ₂ contrast properties, which have been verified using Carr-Purcell-Meiboom-Gill pulse sequence and MRI Spin-Echo imaging of the nanoparticles dispersed in the agarose gel p...
Six ionic liqs. were synthesized by conversion resp. quaternary ammonium bromides with MeOCH2COOH... more Six ionic liqs. were synthesized by conversion resp. quaternary ammonium bromides with MeOCH2COOH and used for electroless deposition of Cu from its aq. solns. on steel surfaces. Only 1-dodecylpyridinium 2-methoxyacetate was an effective bath component and yielded Cu coatings of better quality than those obtained from a std. bath.
Magnetic nanoparticles coated with bioinspired polydopamine were obtained via a co-precipitation ... more Magnetic nanoparticles coated with bioinspired polydopamine were obtained via a co-precipitation method and oxidative polymerization of dopamine. Obtained particle were used for carrying doxorubicin to HeLa cells.
Gold nanoparticles (AuNPs), as an agent enhancing radiosensitivity, play a key role in the potent... more Gold nanoparticles (AuNPs), as an agent enhancing radiosensitivity, play a key role in the potential treatment of breast cancer (BC). Assessing and understanding the kinetics of modern drug delivery systems is a crucial element that allows the implementation of AuNPs in clinical treatment. The main objective of the study was to assess the role of the properties of gold nanoparticles in the response of BC cells to ionizing radiation by comparing 2D and 3D models. In this research, four kinds of AuNPs, different in size and PEG length, were used to sensitize cells to ionizing radiation. The in vitro viability, uptake, and reactive oxygen species generation in cells were investigated in a time- and concentration-dependent manner using 2D and 3D models. Next, after the previous incubation with AuNPs, cells were irradiated with 2 Gy. The assessment of the radiation effect in combination with AuNPs was analyzed using the clonogenic assay and γH2AX level. The study highlights the role of t...
Measurement of the nitric oxide (NO) concentration in living cells in the physiological nanomolar... more Measurement of the nitric oxide (NO) concentration in living cells in the physiological nanomolar range is crucial in understanding NO biochemical functions, as well as in characterizing the efficiency and kinetics of NO delivery by NO-releasing drugs. Here, we show that fluorescence correlation spectroscopy (FCS) is perfectly suited for these purposes, due to its sensitivity, selectivity, and spatial resolution. Using the fluorescent indicators, diaminofluoresceins (DAFs), and FCS, we measured the NO concentrations in NO-producing living human primary endothelial cells, as well as NO delivery kinetics, by an external NO donor to the immortal human epithelial living cells. Due to the high spatial resolution of FCS, the NO concentration in different parts of the cells were also measured. The detection of nitric oxide by means of diaminofluoresceins is much more efficient and faster in living cells than in PBS solutions, even though the conversion to the fluorescent form is a multi-st...
19F Nuclear Magnetic Resonance spin-lattice relaxation experiments have been performed for a seri... more 19F Nuclear Magnetic Resonance spin-lattice relaxation experiments have been performed for a series of ionic liquids including the same anion, bis(trifluoromethanesulfonyl)imide, and cations with alkyl chains of different lengths: triethylhexylammonium, triethyloctylammonium, decyltriethylammonium, dodecyltriethylammonium, decyltriethylammonium, and hexadecyltriethylammonium. The experiments have been carried out in a frequency range of 10 kHz to 10 MHz versus temperature. A thorough analysis of the relaxation data has led to the determination of the cation–anion as a relative translation diffusion coefficient. The diffusion coefficients have been compared with the corresponding cation–cation and anion–anion diffusion coefficients, revealing a correlation in the relative translation movement of the anion and the triethylhexylammonium, triethyloctylammonium, decyltriethylammonium, and dodecyltriethylammonium cations, whereas the relative translation diffusion between the anion and th...
1H spin-lattice relaxation experiments have been performed for a series of ionic liquids includin... more 1H spin-lattice relaxation experiments have been performed for a series of ionic liquids including bis(trifluoromethanesulfonyl)imide anion and cations of a varying alkyl chain length: triethylhexylammonium, triethyloctylammonium, decyltriethylammonium, dodecyltriethylammonium, triethyltetradecylammonium, and hexadecyltriethylammonium. The relaxation studies were carried out in abroad frequency range covering three orders of magnitude, from 10 kHz to 10 MHz, versus temperature. On the basis of a thorough, quantitative analysis of this reach data set, parameters characterizing the relative, cation-cation, translation diffusion (relative diffusion coefficients and translational correlation times), and rotational motion of the cation (rotational correlation times) were determined. Relationships between these quantities and their dependence on the alkyl chain length were discussed in comparison to analogous properties of molecular liquids. It was shown, among other findings, that the ra...
1H and 19F spin-lattice relaxation experiments have been performed for a series of ionic liquids ... more 1H and 19F spin-lattice relaxation experiments have been performed for a series of ionic liquids sharing the same anion: bis(trifluoromethanesulfonyl)imide but including cations of different alkyl chain lengths: butyltriethylammonium, triethyloctylammonium, dodecyltriethylammo-nium and hexadecyltriethylammonium. The studies have been carried out in the temperature range from 383 to 108 K at the resonance frequency of 200 MHz (for 1H). A quantitative analysis of the relaxation data has revealed two dynamical processes for both kinds of ions. The dynamics have been successfully modeled in terms of the Arrhenius law. The timescales of the dynamical processes and their temperature evolution have been discussed in detail, depending on the structure of the cation.
Production of ethanol from lignocellulosic biomass is considered the most promising proposition f... more Production of ethanol from lignocellulosic biomass is considered the most promising proposition for developing a sustainable and carbon–neutral energy system. The use of renewable raw materials and variability of lignocellulosic feedstock generating hexose and pentose sugars also brings advantages of the most abundant, sustainable and non-food competitive biomass. Great attention is now paid to agricultural wastes and overgrowing plants as an alternative to fast-growing energetic crops. The presented study explores the use of stinging nettle stems, which have not been treated as a source of bioethanol. Apart from being considered a weed, stinging nettle is used in pharmacy or cosmetics, yet its stems are always a non-edible waste. Therefore, the aim was to evaluate the effectiveness of pretreatment using imidazolium- and ammonium-based ionic liquids, enzymatic hydrolysis, fermentation of stinging nettle stems, and comparison of such a process with giant miscanthus. Raw and ionic liq...
The study objective was to model and predict the bioethanol production process from lignocellulos... more The study objective was to model and predict the bioethanol production process from lignocellulosic biomass based on an example of empirical study results. Two types of algorithms were used in machine learning: artificial neural network (ANN) and random forest algorithm (RF). Data for the model included results of studying bioethanol production with the use of ionic liquids (ILs) and different enzymatic preparations from the following biomass types: buckwheat straw and biomass from four wastelands, including a mixture of various plants: stems of giant miscanthus, common nettle, goldenrod, common broom, fireweed, and hay (a mix of grasses). The input variables consisted of different ionic liquids (imidazolium and ammonium), enzymatic preparations, enzyme doses, time and temperature of pretreatment, and type of yeast for alcoholic fermentation. The output value was the bioethanol concentration. The multilayer perceptron (MLP) was used in the artificial neural networks. Two model types...
1H and 19F spin-lattice relaxation experiments have been performed for butyltriethylammonium bis(... more 1H and 19F spin-lattice relaxation experiments have been performed for butyltriethylammonium bis(trifluoromethanesulfonyl)imide in the temperature range from 258 to 298 K and the frequency range from 10 kHz to 10 MHz. The results have thoroughly been analysed in terms of a relaxation model taking into account relaxation pathways associated with 1H–1H, 19F–19F and 1H–19F dipole–dipole interactions, rendering relative translational diffusion coefficients for the pairs of ions: cation–cation, anion–anion and cation–anion, as well as the rotational correlation time of the cation. The relevance of the 1H–19F relaxation contribution to the 1H and 19F relaxation has been demonstrated. A comparison of the diffusion coefficients has revealed correlation effects in the relative cation–anion translational movement. It has also turned out that the translational movement of the anions is faster than of cations, especially at high temperatures. Moreover, the relative cation–cation diffusion coeff...
The application of ionic liquids (ILs) has grown enormously, from their use as simple solvents, c... more The application of ionic liquids (ILs) has grown enormously, from their use as simple solvents, catalysts, media in separation science, or electrolytes to that as task-specific, tunable molecular machines with appropriate properties. A thorough understanding of these properties and structure–property relationships is needed to fully exploit their potential, open new directions in IL-based research and, finally, properly implement the appropriate applications. In this work, we investigated the structure–properties relationships of a series of alkyltriethylammonium bis(trifluoromethanesulfonyl)imide [TEA-R][TFSI] ionic liquids in relation to their thermal behavior, structure organization, and self-diffusion coefficients in the bulk state using DSC, FT-IR, SAXS, and NMR diffusometry techniques. The phase transition temperatures were determined, indicating alkyl chain dependency. Fourier-transformed infrared spectroscopy studies revealed the structuration of the ionic liquids along with...
One of the main goals of industrial biotechnology is to develop an effective method for ethanol p... more One of the main goals of industrial biotechnology is to develop an effective method for ethanol production for fuel purposes using lignocellulosic biomass. Variability of lignocellulosic raw materials, selection of an effective method for the pretreatment of raw material, and selection of microorganisms with the ability to ferment not only hexoses but also pentoses and are moreover resistant to environmental stress generated by the products of lignocellulosic complex decomposition, are the challenges encountered in ethanol production. The use of agricultural wastelands and overgrowing plants that have little possibility of application in processes other than energy production seem to be an interesting alternative to conventional, but very often rather cultivation demanding energy crops. The aim of this study was to evaluate the possibility of using the stems of fireweed (Epilobium angustifolium L.), European goldenrod (Solidago virgaurea L.), and common broom (Cytisus scoparius L.) for ethanol production. The key elements studied were characteristics of the lignocellulosic complex structure, influence of the selected ionic liquids on the structural changes in biomass, and efficiency of enzymatic hydrolysis and ethanol fermentation processes. The results showed that under the assumed conditions the best effect was observed with the fireweed materials subjected to pretreatment with 1‐ethyl‐3‐methylimidazolium acetate and enzymatic hydrolysis with Viscozyme® preparation. The final concentration of ethanol obtained was 2.509 g L−1 with a yield of 92.3%. This was due to the highest share of cellulose (40.9%) in the whole lignocellulosic complex compared to other raw materials, which in combination with the selection of an appropriate ionic liquid and an enzymatic preparation, led to high bioprocess efficiency.
Polydopamine (PDA)-coated magnetic nanoparticles functionalized with mono-6-thio-β-cyclodextrin (... more Polydopamine (PDA)-coated magnetic nanoparticles functionalized with mono-6-thio-β-cyclodextrin (SH-βCD) were obtained and characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), Nuclear and Magnetic Resonance Imaging (NMR and MRI), and doxorubicin (DOXO)-loading experiments. The liver cancer cellular internalization of DOXO-loaded nanoparticles was investigated by confocal imaging microscopy. Synthesized nanomaterials bearing a chemotherapeutic drug and a layer of polydopamine capable of absorbing near-infrared light show high performance in the combined chemo- and photothermal therapy (CT-PTT) of liver cancer due to the synergistic effect of both modalities as demonstrated in vitro. Moreover, our material exhibits improved ₂ contrast properties, which have been verified using Carr-Purcell-Meiboom-Gill pulse sequence and MRI Spin-Echo imaging of the nanoparticles dispersed in the agarose gel p...
Six ionic liqs. were synthesized by conversion resp. quaternary ammonium bromides with MeOCH2COOH... more Six ionic liqs. were synthesized by conversion resp. quaternary ammonium bromides with MeOCH2COOH and used for electroless deposition of Cu from its aq. solns. on steel surfaces. Only 1-dodecylpyridinium 2-methoxyacetate was an effective bath component and yielded Cu coatings of better quality than those obtained from a std. bath.
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Papers by Roksana Markiewicz