Biosynthesis and antibacterial activity of ZnO nanoparticles usingBuchanania obovatafruit extract and the eutectic-based ionic liquid.

The fruit extract ofBuchanania obovataand the eutectic-based ionic liquid were utilized, in an eco-friendly, inexpensive, simple method, for synthesizing zinc oxide nanoparticles (ZnO NPs). The influence of the reducing, capping and stabilizing agents, in both mediums, on the structure, optical, and morphological properties of ZnO NPs was extensively investigated. The surface plasmon resonance peaks were observed at 340 nm and 320 nm for the fruit-based and the eutectic-based ionic liquid mediums, respectively, indicating the formation of ZnO NPs. XRD results confirmed the wurtzite structure of the ZnO NPs, exhibiting hexagonal phases in the diffraction patterns. The SEM and TEM images display that the biosynthesized ZnO NPs exhibit crystalline and hexagonal shape, with an average size of 40 nm for the fruit-based and 25 nm for the eutectic-based ionic liquid. The Brunauer-Emmett-Teller (BET) surface area analysis, revealed a value ∼13 m2g-1for ZnO NPs synthesized using the fruit extract and ∼29 m2g-1for those synthesized using the eutectic-based ionic liquid. The antibacterial activity of the biosynthesized ZnO NPs was assessed against clinically isolated Gram-negative (E. coli) and Gram-positive (S. aureus) bacterial strains using the inhibition zone method. The ZnO NPs produced from the eutectic-based ionic liquids confirmed superior antibacterial activity against bothS. aureusandE. colicompared to those mediated by the utilized fruit extract. At a concentration of 1000, the eutectic-based ionic liquid mediated ZnO NPs displayed a maximum inhibition zone of 16 mm againstS. aureus, while againstE. coli, a maximum inhibition zone of 15 mm was observed using the fruit extract mediated ZnO NPs. The results of this study showed that the biosynthesized ZnO NPs can be utilized as an efficient substitute to the frequently used chemical drugs and covering drug resistance matters resulted from continual usage of chemical drugs by users.

Surface active dicationic ionic liquids as green oil spill dispersants.

The utilization of chemical dispersants as a way of mitigating of oil spills in marine eco-system has been extensively documented worldwide. Hence, in this research we have successfully synthesized two amphiphilic asymmetric Dicaionic Ionic Liquids (DILs). The efficacy of these synthesized DILs as dispersants was assessed using the baffled flask test (BFT). The results indicated a dispersant effectiveness ranging from 47.98 % to 79.76 % for the dispersion of heavy crude oil across various temperature ranges (10-30 °C). These dispersant-to-oil ratios (DOR) were maintained at 3: 100 (V%), showcasing promising dispersant capabilities for mitigating heavy crude oil spills. Additionally, acute toxicity tests conducted on Nile tilapia and Oreochromis niloticus have demonstrated the relatively low toxicity of the IL-dispersants, with Lethal Concentration 50 (LC50) values exceeding 100 ppm after 96 h. This suggests a practically slight toxic effect on the tested fish. In summary, the newly developed IL-dispersants are considered to be conducive to environmentally benign oil spill remediation.

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.

Introducing a protic ionic liquid from aminoethyl piperazine and triflic acid immobilized on pectin as a reusable nanocatalyst for the selective Schmidt synthesis of nitriles.

Preparation of reusable protic ionic liquid, triflic acid-immobilized aminoethyl piperazine-modified pectin (Pec-AEP-TfOH), with excellent activity and selectivity in modified Schmidt synthesis of nitriles from aldehydes and Si(CH3)3N3 has been described. The structure of the catalyst was characterized using FT-IR, XRD, FE-SEM, EDX-mapping, and TGA-DTA. The reaction demonstrated a broad substrate scope for a variety of benzaldehyde derivatives with electron withdrawing/donating substituents and heterocyclic aldehydes with yields between 85 and 96 % at room temperature. Also, the Pec-AEP-TfOH showed an excellent selectivity for the nitriles in which no formanilide was obtained. Furthermore, the Pec-AEP-TfOH revealed a remarkable chemoselectivity for aldehydes in the presence of acids or ketones. It is worth noting that TfOH as a precious superacid was immobilized for the first time in the selective Schmidt synthesis of nitriles to improve the eco-friendliness and economic efficiency of the process. Furthermore, the catalyst was cost-effective, metal-free, safe, scalable, and reusable (5 times) and its heterogeneity was confirmed by hot-filtration test.

Leveraging the use of ionic liquid capillary columns and GC×GC-MS for fatty acid profiling in human colostrum samples.

Lipids in human colostrum provide the majority of energy intake and essential fatty acids for developing infants. The fatty acid composition of human colostrum is highly variable and influenced by multiple factors. Human colostrum is a complex sample bringing challenges to fatty acid profiling. This work aimed to optimize the use of ionic liquid (IL) columns and flow-modulated comprehensive two-dimensional gas chromatography coupled to mass spectrometry (FM-GC×GC-MS) for fatty acid profiling in human colostrum. Derivatization strategies were optimized and the elution behavior of fatty acid methyl esters (FAME) on various 1D column phases (Solgel-WAX, SLB-IL60i, SLB-IL76i, and SLB-IL111i). Derivatization with sodium methoxide yielded a satisfactory recovery rate (90%) at milder conditions and reduced time. The use of IL60 as the 1D column provided superior separation, good peak shape, and better utilization of elution space. As a proof of concept, the developed method was applied to access the effects of the mode of neonatal delivery (vaginal vs. C-section) on the fatty acid profile of human colostrum samples. The integrated multidimensional gas chromatography strategy improved FAME detection and separation and can be a useful tool for accessing the effects of different factors on the fatty acid profiling of complex samples.

Preparation of novel polyvinyl alcohol-carbon nanotubes containing imidazolyl ionic liquid/chitosan hydrogel for highly efficient uranium extraction from seawater.

A novel polyvinyl alcohol-carbon nanotube containing an imidazolyl ionic liquid/chitosan composite hydrogel (termed CBCS) was prepared for highly selective uranium adsorption from seawater. The results show that CBCS has good adsorption properties for uranium within the pH range of 5.0-8.0. Kinetics and thermodynamics experiments show that the theoretical maximum adsorption capacity of CBCS to U(VI) is 496.049 mg/g (288 K, pH = 6.0), indicating a spontaneous exothermic reaction. Mechanism analysis shows that the hydroxyl group, amino group, and CN bond on the surface of CBCS directly participate in uranium adsorption and that the dense pores on the surface of CBCS play an important role in uranium adsorption. The competitive adsorption experiment shows that CBCS has excellent uranium adsorption selectivity. In addition, CBCS exhibits good reusability. After five adsorption-desorption cycles, the uranium adsorption rate of CBCS can still reach >98 %. Hence, CBCS has excellent potential for uranium extraction from seawater.

Bifunctional solid-state ionic liquid supported amidoxime chitosan adsorbents for Th(IV) and U(VI): Enhanced adsorption capacity from the synergistic effect.

Uranium and thorium of symbiotic relationship commonly appear in one kind of raw or spent ore. The simultaneous enrichment toward both metals in the first step is essential during many hydrometallurgy processing. Therefore bifunctional solid-state ionic liquid supported amidoxime chitosan (ACS) adsorbents were developed to simultaneously adsorb the two metal from the aqueous solution. The adsorption capacity of the bifunctional adsorbents toward uranium and thorium were significantly superior to the ionic liquid-free amidoxime chitosan, obviously proving the synergistic effect. For both uranium and thorium, the adsorption capacity in the consequence of ACS-[N4444][DEHP], ACS-[N4444][EHEHP], ACS-[N1888][DEHP] and ACS-[N1888][EHEHP] prove the steric effect and PO bonding played important roles in the adsorption. Study on isotherms and kinetics demonstrated the adsorption of ionic liquid-ACS adopted monolayer and chemical way. The ΔGo of very small negative values highlighted ionic liquid-ACS were prone to adsorb uranium and thorium. The study showed feasibility of bifunctional solid-state ionic liquid supported amidoxime chitosan adsorbents for Th(IV) and U(VI).

Aggregation, toxicity, and biodegradability study of an ionic liquid-based formulation for effective oil spill remediation.

Chemical dispersants are extensively used for marine oil spill remediation. However, the increased toxicity and low biodegradability of these dispersants restrict their employment in the marine environment. Hence, in this work, we have developed an eco-friendly formulation composed of an ionic liquid,1-butyl-3-methylimidazolium lauroyl sarcosinate [BMIM][Lausar] and sorbitan monooleate (Span) 80. Micellar and interfacial parameters, dispersion effectiveness, as well as the toxicity and biodegradability of the developed formulation were investigated. Micellar properties confirmed a high degree of synergism among the surfactant molecules and the formation of stable micelle. The dispersion effectiveness, at dispersant-to-oil ratio (DOR) of 1:25 (v/v), against three crude oils (Arab, Ratawi, and Doba) was assessed. We achieved a dispersion effectiveness of 68.49%, 74.05%, and 83.43% for Ratawi, Doba, and Arab crude oil, respectively, using a 70:30 (w/w) ratio of Span 80 to [BMIM][Lausar]. Furthermore, the results obtained from optical microscopy and particle size analysis (PSA) indicated that the oil droplet size decreased with higher DOR. Additionally, acute toxicity experiments were conducted on zebrafish (Danio rerio) using the developed formulation, confirming its non-toxic behavior, with LC50 values of 800 mg/L after 96 h. The formulation also exhibited high biodegradability, with only 25.01% of the original quantity remaining after 28 days. Hence, these results suggest that the new formulation has the potential to be a highly effective and environmentally friendly dispersant for oil spill remediation.

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.

Green dispersants for oil spill response: A comprehensive review of recent advances.

Green dispersants are so-called "green" because they are renewable (from bio-based sources), non-volatile (from ionic liquids), or are from naturally available solvents (vegetable oils). In this review, the effectiveness of different types of green dispersants, namely, protein isolates and hydrolysates from fish and marine wastes, biosurfactants from bacterial and fungal strains, vegetable-based oils such as soybean lecithin and castor oils, as well as green solvents like ionic liquids are reviewed. The challenges and opportunities offered by these green dispersants are also elucidated. The effectiveness of these dispersants varies widely and depends on oil type, dispersant hydrophilicity/hydrophobicity, and seawater conditions. However, their advantages lie in their relatively low toxicity and desirable physico-chemical properties, which make them potentially ecofriendly and effective dispersants for future oil spill response.

Advances of ionic liquid-based nanohybrids for biomedical applications.

Ionic liquids (ILs) are composed of asymmetric cationic and anionic moieties and are used as green solvents. Their non-toxic nature, favorable biocompatibility and adjustable structure facilitate wide biomedical applications. ILs promote the generation of various nanohybrids that exhibit multiple functions and novel/improved properties with respect to their precursors. Generally, nanostructures have a large specific surface area and abundant functional groups which enable loading and incorporation of ILs through physical interactions or chemical bonding. According to their main skeleton structures, IL-based nanohybrids may be divided into five categories, i.e., poly(ionic liquid)s (PILs), IL-inorganic nanohybrids, IL-metal organic framework nanohybrids (IL-MOF nanohybrids), ILs/carbon materials and ionic materials. These IL-based nanohybrids exhibit various specific features, including thermal responsive behavior, metal chelating, photothermal conversion and antibacterial capabilities. Taking advantage of these characteristics, IL-based nanohybrids may overcome the shortcomings of conventional medicines/drugs and exhibit promising prospects in biomedicine to facilitate controlled drug release, bactericidal treatment and thermotherapy. The present review presents the state-of-the-art progress made in the studies of IL-based nanohybrids in terms of their classifications, structure characteristics, versatile functionalities and biomedical and pharmaceutical applications. The challenges and future perspectives in the developments and applications of IL-based nanohybrids in biomedicine are discussed.

Fractionation of depectinated sugar beet pulp into cellulose, hemicellulose, and lignin with NaOH/urea/H2O and ionic liquid.

This study proposes a novel and feasible dissolution and fractionation method of depectinated sugar beet pulp (SBP) in NaOH/Urea/H2O, ionic liquid (IL) and alkaline treatment processes. Interestingly, the complicated structure of SBP can be treated with 30 % H2SO4 to increase the dissolution rate. Scanning electron microscope (SEM) analysis confirmed that the appearance of cellulose and hemicellulose obtained by two methods were different. At the same time, two lignin fractions showed irregular high-density clusters, which were composed of a large number of submicron particles. The crystal structure of two cellulose fractions changed from cellulose I to cellulose II. The thermal stability of cellulose and lignin obtained by ionic liquid was slightly better than that obtained by NaOH/urea/H2O. Results of Fourier transform infrared (FTIR) and 13C NMR showed that the chemical structures of SBP cellulose, hemicellulose and lignin regenerated from NaOH/urea/H2O and ionic liquid were similar.

Biobased natural deep eutectic system as versatile solvents: Structure, interaction and advanced applications.

The increasing emphasis on the development of green replacements to traditional organic solvents and ionic liquids (ILs) can be attributed to the rising concerns over human health and detrimental impacts of conventional solvents towards the environment. A new generation of solvents inspired by nature and extracted from plant bioresources has evolved over the last few years, and are referred to as natural deep eutectic solvents (NADES). NADES are mixtures of natural constituents like sugars, polyalcohols, sugar-based alcohols, amino acids and organic acids. Interest in NADES has exponentially grown over the last eight years, which is evident from an upsurge in the number of research projects undertaken. NADES are highly biocompatible as they can be biosynthesized and metabolized by nearly all living organisms. These solvents pose several noteworthy advantages, such as easy synthesis, tuneable physico-chemical properties, low toxicity, high biodegradability, solute sustainability and stabilization and low melting point. Research on the applicability of NADES in diverse areas is gaining momentum, which includes as - media for chemical and enzymatic reactions; extraction media for essential oils; anti-inflammatory and antimicrobial agent; extraction of bioactive composites; as chromatographic media; preservatives for labile compounds and in drug synthesis. This review gives a complete overview of the properties, biodegradability and toxicity of NADES which we propose can assist in further knowledge generation on their significance in biological systems and usage in green and sustainable chemistry. Information on applications of NADES in biomedical, therapeutic and pharma-biotechnology fields is also highlighted in the current article along with the recent progress and future perspectives in novel applications of NADES.

[Application and problems analysis of traditional Chinese medicine volatile oil preparation technology based on ionic liquids].

Ionic liquids(ILs) are salts composed entirely of anions and cations in a liquid state at or near room temperature, which have a variety of good physicochemical properties such as low volatility and high stability. This paper mainly reviewed the research overview of ILs in the application of traditional Chinese medicine(TCM) volatile oil preparation technology. Firstly, it briefly introduced the application of TCM volatile oil preparation technology and composition classification and physicochemical properties of ILs, and then summarized the application of ILs in the extraction, separation, analysis, and preparation of TCM volatile oil. Finally, the problems and challenges of ILs in the application of TCM volatile oil were explained, and the application of ILs in TCM volatile oil in the future was prospected.

Application of imidazolium based ionic liquids grafted on microcrystalline cellulose as demulsifiers for water in crude oil (W/O) emulsions.

Separation of water and oil from water-in-oil (W/O) emulsion before transportation and refining is very important and critical. Ionic liquids (ILs) and their derivatives have recently attracted much attention as efficient chemical agents for breaking emulsions. So, here, a series of microcrystalline cellulose (MCC) grafted with imidazolium-based ionic liquids (IM-ILs) were synthesized, named as MCC@IM-ILs, and evaluated as eco-friendly surface-active agents for the separation of water from the crude oil. Structure of the synthesized compounds was confirmed by different characterization techniques. Dehydration efficiency percent (DE%) of the synthesized demulsifiers was measured and compared with each other. Synthesized MCC@IM-ILs showed an acceptable DE% to demulsify three kinds of W/O emulsions with different water content after 5 min. Concentration, alkyl chain length, and counter-anion of the synthesized MCC@IM-ILs play a key role in separating water from crude oil. Demulsifier with C10 alkyl chain length showed better DE% than the corresponding demulsifier with C6 alkyl chain length in the W/O (30:70 v/v) emulsion. Also, demulsifier with Br counter anion showed lower DE% than the corresponding BF4 ion-exchanged compound with higher hydrophilicity. Synthesized demulsifiers immobilized on ILs have significant advantages compared to unsupported ILs due to the use of green and economical cellulosic substrate.

Molecularly imprinted miniature electrochemical biosensor for SARS-CoV-2 spike protein based on Au nanoparticles and reduced graphene oxide modified acupuncture needle.

Accurate detection of SARS-CoV-2 spike (SARS-CoV-2-S) protein is of clinical significance for early diagnosis and timely treatment of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Herein, a surface molecularly imprinted miniature biosensor was fabricated. Au nanoparticles (AuNPs), reduced graphene oxide (rGO), poly(methylene blue)/poly(ionic liquids) and poly(ionic liquids) were successively electrodeposited onto the pinpoint of an acupuncture needle (AN). The molecularly imprinted miniature biosensor was obtained after the template of SARS-CoV-2-S protein was removed, which could be used for sensitive detection of SARS-CoV-2-S protein. The linear range and limit of detection (LOD) were 0.1 âˆ¼ 1000 ng mL-1 and 38 pg mL-1, respectively, which were superior to other molecularly imprinted biosensors previously reported. The developed miniature biosensor also exhibited high specificity and stability. The reliability of the biosensor was evaluated by the detection of SARS-CoV-2-S protein in clinical serum samples.

Triphase dynamic extraction system involved with ionic liquid and deep eutectic solvent for various bioactive constituents from Tartary buckwheat simultaneously.

Friendly and highly efficient acquisition of multiple active components from foods is always of great interest. For synchronous extraction and separation flavonoids together with oil from Tartary buckwheat, a new triphase dynamic system was developed with magnetic nanofluid based on deep eutectic solvent (N888-Cl/lauric acid, 1:2) (liquid phase 1), ionic liquid ([C4mim]Br) aqueous solution (liquid phase 2) and raw material powders (solid phase). It was the first time that two types of green solvents were simultaneously applied and assisted by magnetic separation. Through the investigation on key properties and operational conditions of this system, the extraction efficiency of oil and flavonoids in liquid phase 1 and 2 was achieved as 35.29 and 41.17 mg/g respectively, which were higher than that of conventional ways. Then kinetic and thermodynamics mechanisms were discovered comprehensively. After targeted recovery, the spectral characterization and antioxidant activity of two products proved the effectiveness of the developed method.

Molecular imprinting technology and poly (ionic liquid)s: Promising tools with industrial application for the removal of acrylamide and furanic compounds from coffee and other foods.

Coffee is one of the most consumed beverages in the world. Coffee provides to the consumer special sensorial characteristics, can help to prevent diseases, improves physical performance and increases focus. In contrast, coffee consumption supplies a significant source of substances with carcinogenic and genotoxic potential such as furan, hydroxymethylfurfural (HMF), furfural (F), and acrylamide (AA). The present review addresses the issues around the presence of such toxic substances formed in Maillard reaction (MR) during thermal treatments in food processing, from chemical and, toxicological perspectives, occurrences in coffee and other foods processed by heating. In addition, current strategies advantages and disadvantages are presented along with application of molecular imprinting technology (MIT) and poly (ionic liquid) s (PIL) as an alternative to reduce the furan, HMF, F and AA content in coffee and other foods.

Application of supramolecular solvent based on the surface-active ionic liquid in dispersive liquid-liquid microextraction of triazine herbicides in tea samples.

In this study, a novel supramolecular solvent based on surface-active ionic liquid was prepared and used as an extraction solvent for dispersive liquid-liquid microextraction of four triazine herbicides in tea samples. The formation mechanism, microstructure and physicochemical properties of supramolecular solvent were studied. Some parameters, including the molar ratio of surface-active ionic liquid to tetrahydrofuran, volume of supramolecular solvent, vortex time, pH of sample solution, type and amount of salt, were investigated and optimized. The good linearities (r > 0.9990) for the analytes were obtained. The limits of detection and quantification for triazine herbicides were in the range of 1.7-2.1 µg kg-1 and 5.6-7.1 µg kg-1, respectively. The spiked recoveries were 80.0-119.9 %. The supramolecular solvent prepared in this study has the advantages of simple preparation process, low viscosity and good dispersibility. It can be used for the extraction and enrichment of trace triazine herbicides in tea samples.

Preparation and physicochemical characterization of deep eutectic solvents and ionic liquids for the potential absorption and biodegradation of styrene vapors.

Styrene emissions can be treated by physicochemical, biological, or physicochemical/biological means. Due to its low solubility in water an alternative to eliminate styrene emissions from air is the use of two-phase partitioning bioreactors (TPPBs) which comprised a hydrophobic non-aqueous phase (NAP) which can improve mass transfer of styrene. This study was devoted to prepare and evaluate the main physicochemical characteristics of novel NAPs such as Ionic liquids (ILs), Deep Eutectic Solvents (DESs) and Natural Deep Eutectic Solvents (NADEs) as well as their toxicity and biodegradability to treat styrene vapors. Absorption experiments of styrene showed that the best NAPs were the DESs formed with Tetrabutylammonium bromide and decanoic acid and the ILs [C6mim][FAP], [C4mim] [NTf2] and [C4mim] [PF6], since they presented a styrene partition coefficient between 0.0015 and 0.0041. Finally, the IL [C6mim][FAP] was used as a NAP in a TPPB batch process given its high styrene affinity, low solubility in water and non-biodegradability; styrene mineralization was three times higher in the TPPB compared with the control. ILs are potential adjuvant phases in biological degradation systems, as well as other solvents like DESs and NADESs.