Ecotoxicity studies reveal that organic cations in dicamba-derived ionic liquids can pose a greater environmental risk than the herbicide itself.

The following research provides novel and relevant insights into potential environmental consequences of combination of various organic cations with commercial systemic herbicide (dicamba), in accordance with a 'herbicidal ionic liquids' (HILs) strategy. Toxicity assays of five dicamba-based HILs comprising different hydrophobic and hydrophilic cations, namely choline [CHOL][DIC], ethyl betainate [BETC2][DIC], decyl betainate [BETC10][DIC], hexadecyl betainate [BETC16][DIC] and didecyldimethylammonium [DDA][DIC]), have been tested towards bacteria (Pseudomonas putida, Escherichia coli, Bacillus subtilis), algae (Chlorella vulgaris), fresh and marine water crustaceans (Daphnia magna, Artemia franciscana). The structure of respective substituents in the cation emerged as a decisive determinant of toxicity in the case of tested species. In consequence, small ions of natural origin ([CHOL] and [BETC2]) demonstrated toxicity numerous orders of magnitude lower compared to fully synthetic [DDA]. These results emphasize the role of cations' hydrophobicity, as well as origin, in the observed acute toxic effect. Time-dependent toxicity assays also indicated that betaine-type cations comprising an ester bond can rapidly transform into less harmful substances, which can generally result in a reduction in toxicity by even several orders of magnitude. Nonetheless, these findings challenge the concept of ionic liquids with herbicidal activity and give apparent parallels to adjuvant-dependent toxicity issues recently noted in typical herbicidal formulations.

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

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.

Sorption of ionic liquids in soil enriched with polystyrene microplastic reveals independent behavior of cations and anions.

Recently, much attention has been focused on the application of the Ionic Liquids (ILs) with herbicidal activity in agriculture. It has been suggested that through the appropriate selection of cations and anions, one can adjust the properties of ILs, particularly the hydrophobicity, solubility, bioavailability, toxicity. In practical agricultural conditions, it will be beneficial to reduce the mobility of herbicidal anions, such as the commonly applied 2,4-dichlorophenoxyacetic acid [2,4-D] in the soil. Furthermore, microplastics are becoming increasingly prevalent in the soil, potentially stimulating herbicidal sorption. Therefore, we investigated whether cations in ILs influence the mobility of anions in OECD soil supplemented with polystyrene microplastic (PS). For this purpose, we used the 2,4-D based ILs consisting of: a hydrophilic choline cation [Chol][2,4-D] and a hydrophobic choline cation with a C12chain [C12Chol][2,4-D]. Characterization of selected micropolystyrene was carried out using the BET sorption-desorption isotherm, particle size distribution and changes in soil sorption parameters such as soil sorption capacity and cation exchange capacity. Based on the batch sorption experiment, the effect of microplastic on the sorption of individual cations and anions in soil contaminated with micropolystyrene was evaluated. The results obtained indicate that the introduction of a 1-10% (w/w) PS resulted in an 18-23% increase of the soil sorption capacity. However, the sorption of both ILs' cations increased only by 3-5%. No sorption of the [2,4-D] anion was noted. This suggests that cations and anions forming ILs, behave independently of each other in the environment. The results indicate the fact that ILs upon introduction into the environment are not a new type of emerging contaminant, but rather a typical mixture of ions. It is worth noting that when analyzing the behavior of ILs in the environment, it is necessary to follow the fate of both cations and anions.

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

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.

A comprehensive study demonstrating the influence of the solvent composition on the phytotoxicity of compounds, as exemplified by 2,4-D-based ILs with a choline-type cation.

BACKGROUND: Growing concern for the protection of the environment and existing ecosystems has resulted in increasing consideration of phytotoxicity tests as valid ecotoxicological indicators of the potential hazards of the use of ionic liquids (ILs) or any other chemical. The objective of this study was to gain a detailed understanding of the influence of the solvent composition of spray solutions on the phytotoxic effect of foliar application of ionic pairs with weak (choline 2,4-dichlorophenoxyacetate, [Chol][2,4-D]), medium (N-hexylcholine 2,4-dichlorophenoxyacetate, [C6 Chol][2,4-D]) and good (N-dodecylcholine 2,4-dichlorophenoxyacetate, [C12 Chol][2,4-D]) surface-active properties. RESULTS: Experimental results unambiguously demonstrated that the biological activity of the test salt solutions, particularly [Chol][2,4-D] and [C6 Chol][2,4-D], can be strongly affected by the addition of an organic solvent, such as methanol, ethanol, dimethylformamide (DMF) or dimethylsulfoxide (DMSO) compared to solutions in pure water. However, the observed tendency is less pronounced for the compound exhibiting good surface activity, [C12 Chol][2,4-D]. CONCLUSIONS: The collected findings show that caution is warranted in the exploitation or modification of methodologies for assessing phytotoxicity to ensure the reliable interpretation of obtained results for environmental risk assessment or building quantitative structure-activity relationship (QSAR) models. © 2023 Society of Chemical Industry.

2,4-D versus 2,4-D based ionic liquids: Effect of cation on herbicide biodegradation, tfdA genes abundance and microbiome changes during soil bioaugmentation.

The commercial formulations of herbicides rely on surfactants which increase the efficiency of active substance. Herbicidal ionic liquids (ILs), in which cationic surfactants are combined with herbicidal anions, allow for additives' reduction and ensure very good herbicide performance with lower doses. We aimed to test the impact of synthetic and natural cations on biological degradation of 2,4-dichlorophenoxyacetic acid (2,4-D). Although primary biodegradation was high, the mineralization in agricultural soil indicated incomplete conversion of ILs to CO2. Even the introduction of naturally-derived cations resulted in an increase in the herbicide's half-lives - from 32 days for [Na][2,4-D] to 120 days for [Chol][2,4-D] and 300 days for the synthetic tetramethylammonium derivative [TMA][2,4-D]. Bioaugmentation with 2,4-D-degrading strains improves the herbicides' degradation, which was reflected by higher abundance of tfdA genes. Microbial community analysis confirmed that hydrophobic cationic surfactants, even those based on natural compounds, played a negative role on microbial biodiversity. Our study provides a valuable indication for further research related to the production of a new generation of environmentally friendly compounds. Moreover, the results shed a new light on the ionic liquids as independent mixtures of ions in the environment, as opposed to treating them as new type of environmental pollutants.

Comprehensive Ecotoxicity Studies on Quaternary Ammonium Salts Synthesized from Vitamin B3 Supported by QSAR Calculations.

Lately, ionic forms (namely, quaternary ammonium salts, QASs) of nicotinamide, widely known as vitamin B3, are gaining popularity in the sectors developing novel pharmaceuticals and agrochemicals. However, the direct influence of these unique QASs on the development of various terrestrial plants, as well as other organisms, remains unknown. Therefore, three compounds comprising short, medium, and long alkyl chains in N-alkylnicotinamide were selected for phytotoxicity analyses, which were conducted on representative dicotyledonous (white mustard) and monocotyledonous (sorghum) plants. The study allowed the determination of the impact of compounds on the germination capacity as well as on the development of roots and stems of the tested plants. Interestingly, independently of the length of the alkyl chain or plant species, all QASs were established as non-phytotoxic. In addition, QSAR simulations, performed using the EPI Suite™ program pack, allowed the determination of the products' potential toxicity toward fish, green algae, and daphnids along with the susceptibility to biodegradation. The obtained nicotinamide derivative with the shortest chain (butyl) can be considered practically non-toxic according to GHS criteria, whereas salts with medium (decyl) and longest (hexadecyl) substituent were included in the 'acute II' toxicity class. These findings were supported by the results of the toxicity tests performed on the model aquatic plant Lemna minor. It should be stressed that all synthesized salts exhibit not only a lack of potential for bioaccumulation but also lower toxicity than their fully synthetic analogs.

Adjustment of the Structure of the Simplest Amino Acid Present in Nature-Glycine, toward More Environmentally Friendly Ionic Forms of Phenoxypropionate-Based Herbicides.

The use of chemicals for various purposes in agriculture has numerous consequences, such as the contamination of ecosystems. Thus, nowadays it is perceived that their development should adhere to the principles of green chemistry elaborated by Paul Anastas. Consequently, to create more environment-friendly herbicides, we elaborated a 'green' synthesis method of a series of ionic liquids (ILs) containing cations derived from glycine. The appropriately modified cations were combined with an anion from the group of phenoxy acids, commonly known as 2,4-DP. The products were obtained with high yields, and subsequently, their properties, such as density, viscosity and solubility, were thoroughly examined to elucidate existing structure-property relationships. All ILs were liquids at room temperature, which enabled the elimination of some serious issues associated with solid active forms, such as the polymorphism or precipitation of an active ingredient from spray solution. Additionally, the synthesized compounds were tested under greenhouse conditions, which allowed an assessment of their effectiveness in regulating the growth of oilseed rape, selected as a model dicotyledonous plant. The product comprising a dodecyl chain exhibited the greatest reduction in the fresh weight of plants, significantly surpassing not only a commercially used reference herbicide but also the potassium salt of 2,4-DP.

Glyphosate versus glyphosate based ionic liquids: Effect of cation on glyphosate biodegradation, soxA and phnJ genes abundance and microbial populations changes during soil bioaugmentation.

The applicability of herbicidal ionic liquids (HILs) as an alternative form of herbicides is currently evaluated. Yet, the available research is lacking information on the behaviour of herbicidal ionic liquids upon addition to the environment, i.e., if cations and anions act as separate moieties or remain an ionic salt. Hence, we tested degradation of five HILs with the glyphosate anion, their bioavailability in soil, toxicity towards microorganisms, impact on the biodiversity and the abundance of phnJ and soxA genes. The cations were proven to be slightly or moderately toxic. The properties of cations determined the properties of the whole formulation, which might suggest that cations and anion act as the independent mixture of ions. The mineralisation efficiencies were in the range of 15-53%; however, in the case of cations (except non-toxic choline), only 13-20% were bioavailable for degradation. The hydrophobic cations were proven to be highly sorbed, while the anion was readily available for microbial degradation regardless of its counterion. The approach to enrich test samples with isolated microorganisms specialised in glyphosate degradation resulted in higher degradation efficiencies, yet not high enough to mitigate the negative impact of cations. In addition, increased activity of enzymes participating in glyphosate degradation was observed. In the view of obtained results, the use of cationic surfactants in HILs structure is not recommended, as sorption was shown to be determining factor in HILs degradation efficiency. Moreover, obtained results indicate that corresponding ions in HILs might act as separate moieties in the environment.

Toward revealing the role of the cation in the phytotoxicity of the betaine-based esterquats comprising dicamba herbicide.

In this study, two homologous series of esterquats comprising alkyl (from ethyl to octadecyl) betainate cations and bromide as well as dicamba anions were successfully synthesized, starting from a renewable raw material - glycine betaine. Due to the favorable octanol-water partition coefficient and utilization of biodegradable cations of natural origin, synthesized esterquats can be considered promising alternatives to currently applied dicamba-based formulations. In addition, the obtained results allowed us to verify whether the organic cations in quaternary ammonium salts containing herbicidally active anions (such as dicamba) play the role of biologically inactive adjuvants that only enhance the efficiency of the active ingredient or if they simultaneously exhibit a significant degree of phytotoxicity. Analysis of the influence of alkyl betainate esterquats containing nonherbicidal (bromide) anions on seedlings of white mustard revealed that alkyl betainate cations promote the germination of white mustard seeds; however, the subsequent growth of the seedlings was significantly inhibited. Further studies performed on white mustard and cornflower plants in a stage of 4-6 leaves allowed us to conclude that in the case of sensitive plants, the high phytotoxicity can be attributed to the presence of the dicamba anion, whereas for more resistant plants the additional influence of the cation on the phytotoxic effect is visible. Esterquats comprising a dodecyl substituent or longer had high surface active properties. Nonetheless, their contact angle values were not correlated with phytotoxicity data, indicating an additional influence of the cation on this stage of plant development. Interestingly, subsequent dose-response experiments conducted for two selected dicamba-based products confirmed that the greatest phytotoxicity was expressed by compounds containing a decyl substituent.

Sustainable Design of New Ionic Forms of Vitamin B3 and Their Utilization as Plant Protection Agents.

This study demonstrates the utilization of naturally occurring nicotinamide (vitamin B3) in the sustainable synthesis of organic salts with application potential as environmentally friendly agrochemicals. The designed ionic pairs, obtained with high yields, consisted of N-alkylnicotinamide cation and commercially available herbicidal anions: 2,4-dichlorophenoxyacetate (2,4-D) and 4-chloro-2-methylphenoxyacetate (MCPA). The study confirmed the strong influence of the length of alkyl chain in products on the physicochemical properties as well as the development of cornflower and oil-seed rape. The majority of tested salts showed significantly better herbicidal activity (by approx. 30-50%) compared to the reference herbicide. Furthermore, N-hexadecylnicotinamide 4-chloro-2-methylphenoxyacetate was significantly more effective than the commercial formulation in the dose-response test. Their negligible vaporization, multiple times lower than that of commonly used dimethylammonium salts, eliminates one of the greatest threats of currently applied plant protection agents. Additionally, the risk of product migration or bioaccumulation in the environment was assessed as extremely low.

Ionic liquid-assisted synthesis of chitin-ethylene glycol hydrogels as electrolyte membranes for sustainable electrochemical capacitors.

A novel chitin-ethylene glycol hybrid gel was prepared as a hydrogel electrolyte for electrical double-layer capacitors (EDLCs) using 1-butyl-3-methylimidazolium acetate [Bmim][Ac] as a chitin solvent. Examination of the morphology and topography of the chitin-EG membrane showed a homogeneous and smooth surface, while the thickness of the membrane obtained was 27 µm. The electrochemical performance of the chitin-EG hydrogel electrolyte was investigated by cyclic voltammetry and galvanostatic charge/discharge measurements. The specific capacitance value of the EDLC with chitin-EG hydrogel electrolyte was found to be 109 F g-1 in a potential range from 0 to 0.8 V. The tested hydrogel material was electrochemically stable and did not decompose even after 10,000 GCD cycles. Additionally, the EDLC test cell with chitin-EG hydrogel as electrolyte exhibited superior capacitance retention after 10,000 charge/discharge cycles compared with a commercial glass fiber membrane.

Dicationic Herbicidal Ionic Liquids Comprising Two Active Ingredients Exhibiting Different Modes of Action.

In the framework of this study, dicationic herbicidal ionic liquids (HILs) containing tetramethylene-1,4-bis(decyldimethylammonium) and dodecylmethylene-1,12-bis(decyldimethylammonium), including two different herbicidal anions exhibiting different modes of action, were synthesized and characterized. One herbicide incorporated into the HILs was a tribenuron-methyl belonging to ALS inhibitors, while the second herbicidal anion was a synthetic auxin that acts as a growth regulator, namely 2,4-dichlorophenoxyacetate (2,4-D), 2-(2,4-dichlorophenoxy)propionate, (2,4-DP), 2,4,5-trichlorophenoxyacetate (2,4,5-T), 4-chloro-2-methylphenoxyacetiate (MCPA), 2-(4-chloro-2-methylphenoxy)propionate (MCPP), and 4-chlorophenoxyacetate (4-CPA). The obtained products were found to be unstable and decomposed, which can be attributed to the presence of an additional methyl group within the sulfonylurea bridge of the tribenuron-methyl. The synthesized HILs exhibited good affinity with polar and semipolar solvents, with ethyl acetate and hexane as the only solvents that did not dissolve the HILs. Greenhouse tests demonstrated that most of the obtained HILs were more effective than the reference herbicide containing tribenuron-methyl. The length of the alkyl chain in the cation also influenced the effectiveness of the HILs. Better effects were observed for dodecylmethylene-1,12-bis(decyldimethylammonium) cations compared to tetramethylene-1,4-bis(decyldimethylammonium). Therefore, the novel dicatonic HILs showed to integrate the advent of the combination of the different herbicides into a single molecule, enhance herbicidal efficacy, and reduce the risk of weed resistance due to the various modes of action of the applied treatment.

Transformation of Iodosulfuron-Methyl into Ionic Liquids Enables Elimination of Additional Surfactants in Commercial Formulations of Sulfonylureas.

Efficient use of herbicides for plant protection requires the application of auxiliary substances such as surfactants, stabilizers, wetting or anti-foaming agents, and absorption enhancers, which can be more problematic for environment than the herbicides themselves. We hypothesized that the combination of sulfonylurea (iodosulfuron-methyl) anion with inexpensive, commercially available quaternary tetraalkylammonium cations could lead to biologically active ionic liquids (ILs) that could become a convenient and environment-friendly alternative to adjuvants. A simple one-step synthesis allowed for synthesizing iodosulfuron-methyl based ILs with high yields ranging from 88 to 96% as confirmed by UV, FTIR, and NMR. The obtained ILs were found to possess several favorable properties compared to the currently used sodium salt iodosulfuron-methyl, such as adjustable hydrophobicity (octanol-water partition coefficient) and enhanced stability in aqueous solutions, which was supported by molecular calculations showing cation-anion interaction energies. In addition, soil mobility and volatility of ILs were more beneficial compared to the parental herbicide. Herbicidal activity tests toward oil-seed rape and cornflower revealed that ILs comprising at least one alkyl chain in the decyl to octadecyl range had similar or better efficacy compared to the commercial preparation without addition of any adjuvant. Furthermore, results of antimicrobial activity indicated that they were practically harmless or slightly toxic toward model soil microorganisms such as Pseudomonas putida and Bacillus cereus.

Voltammetric sensor based on long alkyl chain tetraalkylammonium ionic liquids comprising ascorbate anion for determination of nitrite.

An electrochemical sensor was fabricated utilizing ionic liquids possessing cations with long alkyl chains such as trimethyl octadecylammonium and behenyl trimethylammonium and ascorbate anion. The ionic liquids were drop-coated onto the electrode. Thin modifying layers were prepared. Cyclic voltammetric investigations revealed electrostatic interactions between the electrochemical probes and the modified surface, proving that a positive charge was established at the film surface. Hence, negatively charged species such as nitrite can be pre-concentrated on the surface of presented modified electrodes. The fabricated electrodes have been used as a voltammetric sensor for nitrite. Due to the electrostatic accumulation properties of long alkyl cation, the assay exhibits a remarkable improvement in the voltammetric response toward nitrite oxidation. The influence of pH on the electrode response was thoroughly investigated, and the mechanism of the electrode was established. The developed sensor showed a linear electrochemical response in the range 1.0-50 µM with a detection limit of 0.1 µM. The electrode revealed good storage stability, reproducibility, and anti-interference ability. The determination of nitrite performed in curing salts brought satisfactory results.

Iodosulfuron-Methyl-Based Herbicidal Ionic Liquids Comprising Alkyl Betainate Cation as Novel Active Ingredients with Reduced Environmental Impact and Excellent Efficacy.

A new family of bio-based herbicidal ionic liquids (HILs) has been synthesized starting from the renewable resource glycine betaine (a derivative of natural amino acids). After esterification, the obtained alkyl betainate bromides containing straight alkyl chains varying from ethyl to octadecyl were combined with a herbicidal anion from the sulfonylurea group (iodosulfuron-methyl). The melting points of the iodosulfuron-methyl-based salts were in a range from 51 to 99 °C, which allows their classification as ionic liquids (ILs). In addition, the new HILs exhibited good affinity for polar and semipolar organic solvents, such as DMSO, methanol, acetonitrile, acetone, and chloroform, while the presence of bulky organic cations reduced their solubility in water. The synthesized products turned out to be stable during storage at 25 °C for over 6 months; however, at 75 °C they underwent fast, progressive degradation and released volatile byproducts. The values of the logarithm of the octanol-water partition coefficient of ILs with alkyls longer than hexyl occurred in the "safe zone" (between 0 and 3); hence, the risk of their migration into groundwater after application or the possibility of their bioaccumulation in the environment is lower in comparison with the currently available commercial form (iodosulfuron-methyl sodium salt). Greenhouse studies confirmed a very high herbicidal efficacy for the obtained salts toward tested plants of oilseed rape, indicating that they may become an attractive replacement for the currently available sulfonylurea-based formulations.

Herbicidal Ionic Liquids: A Promising Future for Old Herbicides? Review on Synthesis, Toxicity, Biodegradation, and Efficacy Studies.

The transformation of agrochemicals into herbicidal ionic liquids (HILs) has been suggested as a solution to problems associated with commercial forms of herbicides. The aim of this review was to summarize the latest progress in the field of HILs, including their synthesis as well as physicochemical and biological properties, and to address the areas that require further research in order to ensure their safe commercialization (e.g., data regarding biodegradability, toxicity, and environmental fate). The first part of the review provides an in-depth summary of the current state of knowledge regarding HILs, particularly the anions and cations used for their synthesis. The second part highlights the employed synthesis methods and elucidates their respective advantages and limitations. The third section is focused on the characterization of HILs with emphasis on the methods and factors that are significant in terms of their practical application. Subsequently, the issues associated with the biodegradation and toxic effects of HILs are discussed based on the relevant literature reports. All sections include comprehensively tabulated data in order to enable rapid comparison of utilized approaches. Finally, all the findings are critically analyzed in terms of crucial disadvantages (especially the lack of standardization), which allowed us to establish future recommendations and basic guidelines that are presented in the last section.

Dicamba-Based Herbicides: Herbicidal Ionic Liquids versus Commercial Forms.

Dicamba is a widely applied herbicide for crop protection and has potential for volatility. New formulations containing dicamba with greatly reduced volatility, introduced to the market in 2017, still caused foliar injury to crops and other plants in Arkansas and neighboring states in the United States. In response, we proposed the transformation of dicamba into protic as well as aprotic dicamba-based organic salts called herbicidal ionic liquids (HILs). All of the HILs were characterized by high stability, whereas the biological activity of the most effective products, evaluated during greenhouse studies, was found to be greater than that of currently used commercial analogues. Furthermore, the possibility of introducing an alkyl chain of a specific length allows one to obtain plant protection products with the desired physicochemical properties while maintaining herbicidal effectiveness. These studies are expected to aid in the design and development of new herbicidal formulations, which, depending on the weed species, could increase the efficacy of the applied active ingredient. Simultaneously, the volatility of the synthesized compounds, particularly those containing quaternary ammonium cations, was multiple times lower than that of the free acid of dicamba. This strategy minimizes the risk of off-site movement via volatilization, which may cause significant damage to neighboring broadleaf crops and pose a threat to existing ecosystems.

Synthesis and Structure-Property Relationships in Herbicidal Ionic Liquids and their Double Salts.

In this study, two homologous series of novel herbicidal ionic liquids (HILs) were synthesized in a simple metathesis reaction between alkyl[2-(2-hydroxyethoxy)ethyl]dimethylammonium bromides and alkali metal salts of 4-chloro-2-methylphenoxyacetic acid (MCPA) or 3,6-dichloro-2-methoxybenzoic acid (dicamba), known as popular herbicides from the class of growth regulators. These HILs were subsequently mixed to prepare double-salt herbicidal ionic liquids (DSHILs). The DSHILs were characterized by substantially altered parameters of viscosity, refractive index, glass transition temperatures and surface activity compared to the average values expected for ideal mixtures of their individual components (HILs). Interestingly, DSHILs possessed superior physicochemical properties such as relatively low viscosity or facilitated formation of micelles, which emphasizes the complex nature of multi-ion interactions in the microstructures of ionic liquid mixtures. The biological tests showed improved efficiency of DSHILs against tested weeds compared to the reference herbicides and parent HILs.

Pharmacokinetic Profile of 1-Methylnicotinamide Nitrate in Rats.

Treatment with 1-methylnicotinamide (MNA), a major metabolite of nicotinamide, exerts antithrombotic, anti-inflammatory, and vasoprotective effects. Yet, pharmacokinetic (PK) profile of MNA has not been fully characterized. In the present work, we analyze the PK profile of the MNA given as a nitrate (MNANO3) in comparison to nitrite (MNANO2) or chloride (MNACl) in rats. The bioavailability of MNA administered as MNANO3 equaled 22.4% as compared to MNANO2 or MNACl (9.2% and 9.1%, respectively). Moreover, in single-pass intestinal perfusion experiments, effective permeability of MNA given as MNANO3 was higher as compared to MNA administered as MNANO2 or MNACl. In turn, tmax was the shortest and Cmax the highest (0.22 h and 56.65µM) for intragastrically administered MNANO2 comparing to MNANO3 (1.92 h, 21.74µM) or MNACl (0.63 h, 16.13µM). Transfer constant between central and peripheral compartments (kcp) and volume of distribution (Vss) for MNANO3 (0.33 h-1 and 1.96 L/kg) were higher as compared to MNANO2 or MNACl (0.11 h-1, 0.08 h-1 for kcp and 1.05 L/kg, 0.76 L/kg for Vss, respectively). In conclusion, we characterized PK profile of MNA and demonstrated that nitrate ion augmented bioavailability and favorably modified PK profile of MNA. Furthermore, given vasoprotective properties of MNA as well as nitrate, MNANO3 represents a bifunctional compound.