Nanocellulose-Based Polymer Composites Functionalized with New Gemini Ionic Liquids.

The manuscript discusses the application of dimeric imidazolium ionic liquids with an aliphatic linker of different lengths, constituting a new class of compounds called gemini, for the modification of renewable materials. This innovative functionalization with the use of ionic liquids made it possible to obtain polymer composite nanomaterials with renewable fillers, which will reduce the consumption of petroleum-based raw materials and also be directly related to the reduction of energy intensity. Renewable filler in the form of nanocellulose modified with ionic liquids, as well as polymer composites with such filler obtained by extrusion and injection molding techniques, were subjected to detailed characterization using techniques like: X-ray diffraction (XRD), Fourier transform spectroscopy (FTIR), dispersion studies (DLS), morphological analysis (SEM), differential scanning calorimetry (DSC), hot-stage polarized light microscopy and characterization of mechanical properties. The use of innovative dimeric ionic liquids proved to be an effective method to carry out efficient functionalization of cellulose. This provided a stable space structure between polysaccharide particles, limiting aggregate formation. It was shown that chemical modification with ionic liquids has a significant effect on the nucleation activity of cellulose fillers and the formation of the supermolecular structure of the polymer matrix, which consequently allowed to obtain polymer composites with excellent strength characteristics and increased flexibility, which will allow to increase their application potential. Innovative ionic liquids have contributed to obtaining green nanomaterials with excellent functional properties, which have not been described in the literature so far.

Antimicrobial and Cytotoxic Activity of Novel Imidazolium-Based Ionic Liquids.

In this study, a series of 10 novel 1-methyl-3-octyloxymethylimidazolium derivatives carrying various anionic moieties (4-hydroxybenzenesulfonate, benzenesulfonate, carvacroloxyacetate, chloride, formate, propionate, thymoloxyacetate, vanillinoxyacetate, eugenoloxyacetate and trimethylacetate) were synthesized. Compounds were tested for their antimicrobial activity against six microbe strains (Staph-ylococcus aureus, Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Enterococcus faecalis, and Candida albicans), cytotoxic activity against the mouse melanoma cell line (B16 F10), and surface active properties. All synthesized compounds exhibited antimicrobial activity (expressed as minimum inhibitory concentration; in range of 0.10-27.82 mM/L), especially against Gram-positive bacteria and fungi. In addition, all compounds demonstrated cytotoxicity on B16 F10 cells (IC50 values 0.0101-0.0197 mM/L). Surface properties defined as CMC values, ranged from 0.72 to 32.35 mmol L-1. The obtained results provide an insight into the promising activity of a novel group of quaternary imidazolium derivatives having ionic liquid properties. The most potent compounds, containing a thymoloxyacetate and eugenoloxyacetate moiety, could be candidates for new antimicrobial agents or surfactants.

The Process of Binding and Releasing of Genetic Material from Lipoplexes Based on Trimeric Surfactants and Phospholipids.

Nonviral vectors for gene therapy such as lipoplexes are characterized by low toxicity, high biocompatibility, and good transfection efficiency. Specifically, lipoplexes based on polymeric surfactants and phospholipids have great potential as gene carriers due to the increased ability to bind genetic material (multiplied positive electric charge) while lowering undesirable effects (the presence of lipids makes the system more like natural membranes). This study aimed to test the ability to bind and release genetic material by lipoplexes based on trimeric surfactants and lipid formulations of different compositions and to characterize formed complexes by circular dichroism (CD) spectroscopy and atomic force microscopy (AFM). The cytotoxicity of studied lipoplexes was tested on HeLa cells by the MTT cell viability assay and the dye exclusion test (trypan blue). The presence of lipids in the system lowered the surfactant concentration required for complexation (higher efficiency) and reduced the cytotoxicity of lipoplexes. Surfactant/lipids/DNA complexes were more stable than surfactant/DNA complexes. Surfactant molecules induced the genetic material condensation, but the presence of lipids significantly intensified this process. Systems based on trimeric surfactants and lipid formulations, particularly TRI_N and TRI_IMI systems, could be used as delivery carrier, and have proven to be highly effective, nontoxic, and universal for DNA of various lengths.

New insight into the motivations of anglers and fish release practices in view of the invasiveness of angling.

The popularity of angling on a global scale reflects the individual needs of people from different social groups in many countries. The socio-economic background and intensity of needs are variable over time and can be modified. These arguments support the development and need to update research among anglers. A new insight into angling research is to link the hierarchy of needs with socio-economic factors concerning and the preferences of anglers in handling fish. These relationships were analyzed using ordinal probit regression and graphically interpreted in an ordination space. The endogenous need for communing with nature is constant in its intensity, regardless of any external factors. Other needs weaken with increasing income, education levels and years engaged in angling. The majority of anglers support releasing fish (66%) and say that the possibility of keeping the fish is not important (62%). It is crucial to identify those anglers for whom the possibility of keeping fish is important and who do not feel extremely negative about releasing fish. The study found that they represent about 25% of the angling population. These findings help to explain the variation in the invasive impact of the identified motivational-preferential profiles of anglers. Cooperation between the associated angling communities and water managers is crucial. By gathering anglers around their own fishing places, they can implement their own educational and organizational solutions.

Structural characterization of transfection nanosystems based on tricationic surfactants and short double stranded oligonucleotides.

For several years cationic surfactants have been the subjects of extensive studies as potential transgene carriers to be used in gene therapy. We report the formation of stable complexes between 21 base pairs oligonucleotides - siRNA, enhancing DMPK gene, and dsDNA and two tricationic surfactants (1,2,3-propanetri[oxymethyl-3-(1-dodecylimidazolium)]chloride and 1,2,3-propanetri[(oxymethyl)dimethyldodecylammonium]chloride. Structural studies by SAXS and TEM have shown that the dominant structure of the obtained lipoplexes is based on hexagonal, lamellar and cubic phases, packed in highly ordered aggregates. It has been established that tricationic surfactants can be used as siRNA carriers in gene therapy.

Ammonium Gemini Surfactants Form Complexes with Model Oligomers of siRNA and dsDNA.

Dimeric cationic surfactants (gemini-type) are a group of amphiphilic compounds with potential use in gene therapy as effective carriers for nucleic acid transfection (i.e., siRNA, DNA, and plasmid DNA). Our studies have shown the formation of lipoplexes composed of alkanediyl-α,ω-bis[(oxymethyl)dimethyldodecylammonium] chlorides and selected 21-base-pair nucleic acid (dsDNA and siRNA) oligomers. To examine the structure and physicochemical properties of these systems, optical microscopy, circular dichroism spectroscopy (CD), small-angle X-ray scattering of synchrotron radiation (SR-SAXS), and agarose gel electrophoresis (AGE) were used. The lengths of spacer groups of the studied surfactants had a significant influence on the surfactants' complexing properties. The lowest charge ratio (p/n) at which stable lipoplexes were observed was 1.5 and the most frequently occurring microstructure of these lipoplexes were cubic and micellar phases for dsDNA and siRNA, respectively. The cytotoxicity tests on HeLa cells indicated the non-toxic concentration of surfactants to be at approximately 10 µM. The dicationic gemini surfactants studied form complexes with siRNA and dsDNA oligomers; however, the complexation process is more effective towards siRNA. Therefore these systems could be applied as transfection systems for therapeutic nucleic acids.

Functional Hybrid Materials Based on Manganese Dioxide and Lignin Activated by Ionic Liquids and Their Application in the Production of Lithium Ion Batteries.

Kraft lignin (KL) was activated using selected ionic liquids (ILs). The activated form of the biopolymer, due to the presence of carbonyl groups, can be used in electrochemical tests. To increase the application potential of the system in electrochemistry, activated lignin forms were combined with manganese dioxide, and the most important physicochemical and morphological-microstructural properties of the novel, functional hybrid systems were determined using Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA), scanning electron microscopy (SEM), zeta potential analysis, thermal stability (TGA/DTG) and porous structure analysis. An investigation was also made of the practical application of the hybrid materials in the production of lithium ion batteries. The capacity of the anode (MnO2/activated lignin), working at a low current regime of 50 mA·g-1, was ca. 610 mAh·g-1, while a current of 1000 mA·g-1 resulted in a capacity of 570 mAh·g-1. Superior cyclic stability and rate capability indicate that this may be a promising electrode material for use in high-performance lithium ion batteries.

Dicationic Surfactants with Glycine Counter Ions for Oligonucleotide Transportation.

Gemini surfactants are good candidates to bind, protect, and deliver nucleic acids. Herein, the concept of amino acids (namely glycine) as counter ions of gemini surfactants for gene therapy application was explored. This study was conducted on DNA and RNA oligomers and two quaternary bis-imidazolium salts, having 2,5-dioxahexane and 2,8-dioxanonane spacer groups. The toxicity level of surfactants was assessed by an MTT assay, and their ability to bind nucleic acids was tested through electrophoresis. The nucleic acid conformation was established based on circular dichroism and infrared spectroscopic analyses. The structures of the formed complexes were characterized by small-angle scattering of synchrotron radiation. Both studied surfactants appear to be suitable for gene therapy; however, although they vary by only three methylene groups in the spacer, they differ in binding ability and toxicity. The tested oligonucleotides maintained their native conformations upon surfactant addition and the studied lipoplexes formed a variety of structures. In systems based on a 2,5-dioxahexane spacer, a hexagonal phase was observed for DNA-surfactant complexes and a micellar phase was dominant with RNA. For the surfactant with a 2,8-dioxanonane spacer group, the primitive cubic phase prevailed.

Histological Aspects of the Early Development of the Digestive System of Burbot Lota lota L. (Lotidae, Gadiformes).

The ontogeny of the digestive tract was studied histologically in burbot, Lota lota L., from hatching to 42 days post-hatch (dph). At hatching, the digestive tract consisted of a straight tube with discernible digestive accessory glands (the liver and the pancreas) dorsally attached to the yolk sac. Most of the yolk sac reserves were consumed during the first 12 days and were completely depleted by 17 dph. The first PAS-positive goblet cells appeared at 6 dph, dispersed within the epithelium of the oesophagus and increasing substantially in number and distribution as development progressed. At 12 dph, the first vacuoles (neutral lipids) appeared in the intestine, indicating the functional absorption of nutrients from food. Differentiation of gastric glands was first noticed at 17 dph and was extensive by 27 dph. L. lota larvae have a morphologically complete digestive tract by 32 dph. These findings on the development of the digestive system in L. lota may contribute to a better understanding of its ontogeny and can be useful for improvement of the larval rearing techniques of this promising species for freshwater aquaculture diversification.

Enhanced cycle life of starter lighting ignition (SLI) type lead-acid batteries with electrolyte modified by ionic liquid.

The aim of the presented work was to improve the lifetime of lead-acid SLI (starting, lighting and ignition) batteries through electrolyte modification with ionic liquids. The conducted research included the synthesis and determination of the influence of di(hexadecyldimethylammonium) and di(octadecyldimethylammonium) sulphates on the basic parameters (capacity, cranking performance) of the starter battery as well as parameters affecting its lifetime (dynamic charge acceptance, corrosion, water consumption). It has been shown that the addition of these compounds increases corrosion resistance and reduces water consumption, resulting in an increase in cyclic durability by up to 36%. The improvement is associated with the absorption of ionic liquid molecules into the mass of lead(ii) sulphate, which was confirmed by physicochemical and electrochemical studies.

The Significance of Angling in Stress Reduction during the COVID-19 Pandemic-Environmental and Socio-Economic Implications.

Recreational fishing and other outdoor recreational activities have been proven to have positive effects on mental health, including neutralizing pandemic stress. This study aims to identify the perceptions and behavior of recreational anglers during the COVID-19 pandemic along with identifying the factors that determine attitudes. This study is essential for understanding the complex economic, social, and environmental implications associated with a pandemic. Perceptions of pandemic stress reduction were confirmed by 63.8% of anglers, and nearly 98% felt there was no risk of infection from fishing. These feelings were most strongly positively associated and explained by a preference for fishing with friends and family and the frequency of fishing. Over 26% of respondents fished more frequently during the pandemic. Additional free time and the need to escape the pandemic media hype were the main factors for the increase in angler activity. The balance of benefits from changes in angler pandemic behavior was ambiguous. This was determined by considering the potential increase in pressure on the environmental resources that anglers use. Given the positive effects of angling on stress reduction, it is not advisable for policymakers to restrict recreational fishing access. Instead, best management practices should reduce sanitary bottlenecks to increase safety on fishing grounds.

Impact of Personal Experience of COVID-19 Disease on Recreational Anglers' Attitudes and Behaviors.

BACKGROUND: Anglers are a large social group with access to a "relatively safe" form of recreation, that allows the opportunity to relieve stress. An important question, however, is how they did so, and to what extent their perceived COVID-19 transition status influenced decisions both in life and at the fishing site. AIM: Our study aimed to determine the dynamics of anglers' attitudes and behaviors during the COVID-19 pandemic as a result of the different statuses of their exposure to the SARS-CoV-2 virus. We assumed that the behavior of anglers who have not experienced the disease (were not ill and not sure if ill) will be similar and, on the other hand, different from the behavior of those who have experienced COVID-19. METHODS: The web-assisted interviews survey was used among 586 anglers with different COVID-19 disease experience statuses. Their pandemic behavior and activities by four age groups were studied using non-metric multidimensional scaling. Redundancy analysis has been used to identify the relationship between anglers' life attitudes and socioeconomic and demographic factors, taking into account their preferences and involvement in fishing. RESULTS: We have demonstrated that the behavior of anglers who have not experienced COVID-19 disease and do not present a reckless attitude toward pandemic threats, do not show significant differences from the life attitudes of the group experienced by the SARS-CoV-2 virus. These two groups comprise more than 70% of anglers. However, the rest show a lack of interest in an aware diagnosis of their health and a low level of acceptance of self-restraint in the area of direct social contact. CONCLUSIONS: Unawareness, combined with ignorance, could be a potential factor in the transmission of the virus while fishing. The behaviors of almost 30% of anglers are particularly risky when combined with a strong need to fish in the company of friends and familiar people. Anglers' social identity should be tapped by fishery managers. Targeted educational campaigns should be aimed at groups around specific fishing spots. The need for self-limitation under the pandemic should be promoted for the benefit of the general public and to maintain the reputation of angling as a safe recreational activity.

Potential Factors Conditioning the Compliance to Mandatory Face Covering in the Public Space Due to SARS-CoV-2 Pandemic.

BACKGROUND: During the SARS-CoV-2 pandemic, we could observe different attitudes towards restrictive bans and orders. AIM: The research aimed to examine the potential psychological factors, such as generalized anxiety, fear of COVID-19 or social approval, related to the approach to mandatory face covering in public spaces. METHODS: The web-assisted interviews survey was used among 202 participants, which included socio-demographical data, approach to face covering, the Generalized Anxiety Disorder Scale, the COVID-19 Anxiety Scale, and The Questionnaire of Social Approval. RESULT: The data showed a statistically significant correlation between compliance to the rule of face and nose covering vs. anxiety and compliance to the rule of face and nose covering vs. generalized anxiety. The results indicate differences between vaccinated and non-vaccinated people in the anxiety of COVID-19, generalized anxiety, and compliance with the rule of face and nose covering. CONCLUSIONS: People vaccinated has a higher level of anxiety and more often compliance with the rule of face covering. It is worth noting that an overly pronounced fear of COVID-19 could be a risk factor for mental health. More research about coping with anxiety in the group of vaccinated people is recommended.

The Influence of COVID-19 on University Students' Well-Being, Physical Activity, Body Composition, and Strength Endurance.

BACKGROUND: Very few scientific studies have simultaneously evaluated changes in well-being (WB), physical activity (PA), and strength endurance (SE) based on results from before and during the COVID-19 pandemic. AIM: The aim of the study was to assess WB, PA, and SE levels, as well as body composition parameters in university students before and during the pandemic. METHODS: The study included 30 males and 30 females (mean age: 21.7 ± 2.51 and 21.6 ± 2.34 years, respectively). Well-being using the Self-Perception Questionnaire (POMS), PA from the Polish regular version of the International Physical Activity Questionnaire (IPAQ), body composition parameters using the InBody 270 analyzer, and SE based on the results of a 12 min test involving a Concept 2PM-5 rowing ergometer were assessed before and during the pandemic. RESULTS: An assessment of university students' WB revealed a significant increase in variables such as tension, depression, anger, confusion, and a significant decline in vigor (p < 0.05). In both sexes, PA and SE decreased significantly-from 2115.4 to 1822.8 METs-min/week and from 2184.5 to 2035 m, respectively, in males, and from 1793.5 to 1699.8 METs-min/week and from 2021.5 to 1943.8 m, respectively, in females. At the same time, body mass and BMI values increased significantly (p < 0.001) in both females and males. CONCLUSIONS: The COVID-19 pandemic caused a significant decrease in WB, PA and SE levels in young females and males, and led to a significant increase in their body mass and BMI.

A new charophyte habitat with a stabilized good ecological potential of mine water.

Each newly-created pond which is supplied with mine water gives the opportunity to study a unique ecosystem in context of possible conditions for biotic live. Therefore, this research aimed to assess a phytoplankton-based ecological potential against the trophic conditions and the risk of contamination with trace elements, and demonstrate the possibility to stabilize at least good water quality of a clarification pond. The gradual decrease in turbidity-related variables (including suspended solids and iron) and nutrients, on the one hand, and an increase in phytoplankton-related indicators, on the other hand, were the most evident. Besides, relative stability in trace elements (the best water quality class), trophic level (slightly eutrophic level) and ecological potential (maximum potential), and relative instability in sulfates and calcium were also recorded. The final stabilization of water habitat resulted in abundant growth of charophyte Nitella mucronata. This all suggested a new ecological opportunity for settlement of a rare species and important for biodiversity enhancement. Furthermore, the study revealed that a clarification pond did not pose any toxic risk from the elevated content of trace elements or the growth of toxic or potentially toxic cyanobacteria which is essential for proper functioning and management of water ecosystems.

Facilitated Transport of Copper(II) across Polymer Inclusion Membrane with Triazole Derivatives as Carrier.

This study investigates copper(II) ion transport through a polymer inclusion membrane (PIM) containing 1-alkyl-1,2,4-triazole (n = 8, 9, 10, 11, 12, 14), o-nitrophenyl octyl ether as the plasticizer and cellulose triacetate as the polymer matrix. The feeding phase was a solution of 0.1 mol/dm3CuCl2 and an equimolar (0.1 mol/dm3) mixture of copper, nickel, and cobalt chlorides with varying concentrations of chloride anions (from 0.5 to 5.0 mol/dm3) established with NaCl. The receiving phase was demineralized water. The flow rate of the source and receiving phases through the membrane module was within the range from 0.5 cm3/min to 4.5 cm3/min. The tests were carried out at temperatures of 20, 30, 40 and 50 °C. Transport of NaCl through the membrane was excluded for the duration of the test. It was noted that the flow rate through the membrane changes depending on the length of the carbon chain in the alkyl substituent from 16.1 µmol/(m2s) to 1.59 µmol/(m2s) in the following order: C8> C9> C10> C11> C12> C14. The activation energy was 71.3 ± 3.0 kJ/mol, indicating ion transport through the PIM controlled with a chemical reaction. Results for transport in case of the concurrent separation of copper(II), nickel(II), and cobalt(II) indicate a possibility to separate them in a selective manner.

Catalyst-free activation of kraft lignin in air using hydrogen sulfate ionic liquids.

In this research we use ionic liquids in combination with mild process conditions to provide a selective increase in the content of carbonyl groups in the kraft lignin structure. Such modification can improve the properties of the pristine biopolymer. In this study, aromatic substituted ionic liquids were synthesized using [C4C1Im][HSO4] as a template structure. The substituents were intended to increase the affinity of the ionic liquid to the aromatic structure of kraft lignin, and to increase access to the oxidizing agent, which was atmospheric oxygen. [Benzyl(C2OC1)Im][HSO4] and [benzylC4Im][HSO4] activate the surface of the biopolymer more effectively than [C4C1Im][HSO4]. This was confirmed based on X-ray photoelectron spectroscopy, which showed the content of CO groups to be almost doubled compared with unmodified lignin. The analysis also revealed targeting of the hydroxyl groups of lignin to the carboxyl groups during activation in [C4C1Im][HSO4].

Development of Acidic Imidazolium Ionic Liquids for Activation of Kraft Lignin by Controlled Oxidation: Comprehensive Evaluation and Practical Utility.

A novel, eco-friendly method for the activation of lignin by controlled oxidation was studied. The results obtained for six acidic imidazolium ionic liquids containing the hydrogen sulfate anion were compared. The key goal of this research was to increase the content of carbonyl groups in the lignin structure because these may play the main role in the transport of protons and electrons in active materials for electrochemical applications. By means of a variety of analytical techniques (FTIR, 13 C CP/MAS NMR, and X-ray photoelectron spectroscopy; selected reactions to determine the presence of carbonyl groups; SEM; zeta-potential analysis; thermogravimetric analysis/differential thermogravimetric analysis; and porous structure analysis), it was determined that the product obtained after treatment with 3-cyclohexyloxymethy-1-methylimidazolium hydrogen sulfate had favorable properties, in terms of the target application. Electrochemical tests proved that the obtained materials could be used as anodes in lithium batteries. The results show that the activation of lignin with ionic liquids can increase its capacity and maintain stability.

Clear distinction between CAC and CMC revealed by high-resolution NMR diffusometry for a series of bis-imidazolium gemini surfactants in aqueous solutions.

The aggregation behavior in the transition region was studied for a series of dicationic surfactants 3,3'-[α,ω-(dioxaalkane)]bis(1-dodecylimidazolium)dichlorides with varied spacer length from two to twelve carbon atoms. We employed Nuclear Magnetic Resonance diffusometry and Bayesian DOSY analysis to obtain the aggregate size distribution in the transition region. The critical concentrations CC were independently obtained from surface tension, electric conductivity, UV-Vis and NMR methods. The micelle aggregation numbers were estimated from the self-diffusion coefficients and were independently confirmed using steady-state fluorescence quenching. The morphology of the aggregates was characterized by small-angle scattering of synchrotron radiation and molecular dynamics simulations. The obtained CC values are identified as critical aggregation concentrations CAC. A broad transition region was observed, and stable micelles were obtained at much higher concentrations than CAC. The accurate CMC values could not be identified for the systems in the study. We indicated that the distribution of aggregate size becomes small and the system becomes homogeneous at much larger concentrations than CAC (typically 15-20 mM). The existence of a slow exchange between two environments, an aggregate and aqueous environment, was confirmed by 1H NMR and 2D HSQC NMR spectroscopy.

Prediction of antifungal activity of gemini imidazolium compounds.

The progress of antimicrobial therapy contributes to the development of strains of fungi resistant to antimicrobial drugs. Since cationic surfactants have been described as good antifungals, we present a SAR study of a novel homologous series of 140 bis-quaternary imidazolium chlorides and analyze them with respect to their biological activity against Candida albicans as one of the major opportunistic pathogens causing a wide spectrum of diseases in human beings. We characterize a set of features of these compounds, concerning their structure, molecular descriptors, and surface active properties. SAR study was conducted with the help of the Dominance-Based Rough Set Approach (DRSA), which involves identification of relevant features and relevant combinations of features being in strong relationship with a high antifungal activity of the compounds. The SAR study shows, moreover, that the antifungal activity is dependent on the type of substituents and their position at the chloride moiety, as well as on the surface active properties of the compounds. We also show that molecular descriptors MlogP, HOMO-LUMO gap, total structure connectivity index, and Wiener index may be useful in prediction of antifungal activity of new chemical compounds.