Ionic liquids as potentially new antifungal agents against Alternaria species

The fungal genus Alternaria Nees 1816 includes the most prevalent pathogenic species that can cause crop diseases such as blight, black spot, and dark leaf spot. In accordance with the aim of developing modern sustainable approaches in agriculture for the replacement of synthetic and toxic substances with environmentally friendly alternatives, the objective of this study was to examine thein vitro antifungal activities of 18 newly synthesized ionic liquids (ILs) against three Alternaria strains: A. padwickii, A. dauci and A. linicola. The antifungal activities of the ILs were estimated via a microdilution method to establish minimal inhibitory concentration (MIC) and minimal fungicidal concentration (MFC) values. The results confirmed that 17 of the 18 ILs showed strain specificity, including good antifungal activity toward Alternaria strains, with MIC and MFC values in the range of 0.04 to 0.43 mol dm(-3). The strongest antifungal effects toward all analyzed Alternaria strains were displayed by the compounds with long alkyl chains: [omim][Cl] (MIC/MFC: 0.042 mol dm(-3)), [dmim][Cl] (MIC/MFC: 0.043 mol dm(-3)), [ddmim][Cl] (MIC/MFC: 0.053 mol dm(-3)), [ddTSC][Br] (MIC/MFC: 0.053 mol dm(-3)), and [Allyl-mim][Cl] (MIC/MFC: 0.054 mol dm(-3)). The introduction of oxygen as a hydroxyl group resulted in less-pronounced toxicity towards Alternaria compared to the introduction of an ether group, while the contribution of the hydroxyl group was shown to be a more determining factor than the prolongation of the side-chain, resulting in overall fungicidal activity decrease. Our results indicate the possibility that the most effective ILs ([Allyl-mim][Cl], [omim][Cl], [dmim][Cl], [ddmim][Cl], [bTSC][Br], [hTSC][Br], [oTSC][Br], [dTSC][Br], and [ddTSC][Br]) could be applied to the control of plant diseases caused by Alternaria species, based on their potential as an environmentally friendly crop protection approach. Since salts based on TSC cations are significantly cheaper to synthesize, stable under mild conditions, and environmentally friendly after degradation, thiosemicarbazidium-based ILs can be a suitable replacement for commercially available imidazolium ILs

Aqueous biphasic systems comprising copolymers and cholinium-based salts or ionic liquids: insights on the mechanisms responsible for their creation

Aqueous biphasic systems (ABS) formed by copolymers and ionic liquids (ILs) have demonstrated to be effective separation platforms, but there is still a gap on the complete understanding of the molecular-level mechanisms ruling the two-phase formation for this type of systems. This work addresses the determination of the liquid-liquid equilibrium of ABS composed of cholinium-based salts or cholinium-based ILs and the triblock copolymer Pluronic PE6200 (PL6200). It is demonstrated that PL6200 can form ABS with all investigated cholinium-based salts or ILs, contrarily to most poly(ethylene)glycol polymers, which is due to the presence of hydrophobic propylene oxide (PO) blocks. From the phase diagrams behavior and IL/salt anions properties, it is shown that the formation of ABS with cholinium-based salts is ruled by the anions polar surface and ability to be hydrated, whereas in systems comprising ILs van der Waals interactions between the copolymer and the IL cannot be discarded. The partition of a series of alkaloids in these systems, namely caffeine, nicotine, theophylline, and theobromine, was additionally appraised. It is shown that caffeine, theophylline, and theobromine preferentially migrate to the more hydrophobic PL6200-rich phase, and that their partition depends on the water content in the respective phase, being ruled by the phases’ hydrophobicity. On the other hand, nicotine, with the most prominent hydrophobic character amongst the studied alkaloids, preferentially migrates to the salt- or IL-rich phase, in which interactions occurring between this alkaloid and the IL/salt cannot be discarded. The ABS formed by cholinium dihydrogenphosphate is the most selective system identified to separate nicotine from the remaining alkaloids, giving some insights into their investigation as separation platforms for alkaloids from natural extracts.publishe

Antifungal activity of surfactant ionic liquids on mycotoxigenic molds

Traditionally, mold control usually involves usage of highly toxic compounds, and this practice must be replaced with more environmentally friendly solutions (green chemistry). In this paper, antifungal activity of five newly synthesized ionic liquids (IL) was tested, in vitro. All ionic liquids are based on N-decyl- N, N, N-trimethylammonium chloride which differs only by a single substituent on a quaternary N- atom. The antifungal activity of IL was tested on Fusarium, Aspergillus, Alternaria, Trichoderma and Penicillium strains using the microdilution method by determining the minimal inhibitory and minimal fungicidal concentrations. Selected genera are major problem in food industry since they are the primary pathogens of agronomically important plants, as well as mycotoxin producers. All five IL used in this study showed antifungal effect in the range of 0.002 mol/dm3 to 0.036 mol/dm3. The greatest antifungal activity was observed when strains were treated with (C2OH)C10DMACI and (C2OOEt)C10DMACI IL. Results obtained in this study showed that all examined ILs have the potential to be used as effective antifungal agents

Antifungal activities of ionic liquids against phytopathogenic Alternaria spp. strains

A modern sustainable approach in agricultural practice would be a replacement of synthetic and toxic substances in the treatment of crop with benign and environmentally friendly compounds, by using principles of green chemistry. One of the possible directions could be using of ionic liquids (ILs), salts with melting points below 100 °C, which are well-known for manifesting antimicrobial activity. ILs can be used in the development of novel sources of antimicrobial agents such as antiseptics, biocides and antifungal agents. Furthermore, ILs have already been reported as alternative ‘green’ solvents for a wide range of reactions and technological processes. Considering the importance of research in the area of bioactivity of ILs for discovery of new green ILs for diff erent purposes, the aim of this study was to examine antifungal activity of nine newly synthesized ILs against phytopathogenic Alternaria strains isolated from from rice (A. padwickii), carrot (A. dauci) and linseed (A. linicola). Antifungal eff ect was estimated by micro-plate microdilution method for establishing minimum inhibitory (MIC) and minimum fungicidal concentration (MFC). All ionic liquids showed strain specifi c but good antifungal activity on Alternaria strains with MIC and MFC detected at the range from 9.23 mg/ml to 75.89 mg/ml. Only in case of the 1-(4-hydroxy-2-oxy)butyl -3-methylimidazolium chloride [OHC2OC2mIm][Cl], no antifungal eff ect on A. dauci were observed. Comparing to A. padwickii and A. dauci., A. linicola showed higher sensitivity to all tested ILs. Th e obtained results indicate the possibility of usage of ILs in biocontrol of plant diseases, representing their application in crop protection. However, further research is necessary in order to examine their toxicity and biodegradability in the environment

Valorization of expired energydrinks by designed and integrated ionic liquid-based aqueous biphasic systems

Expired energy drinks are rich in bioactive value-added compounds that can be recovered and reused in order to valorize food waste within a circular economy perspective. However, to accomplish such requirements, it is necessary to develop sustainable extraction and recovery processes, which must consist of decreasing the number of steps required or developing integrated strategies. In this work, novel aqueous biphasic systems (ABS) composed of ionic liquids (ILs) and a biocompatible polymer polypropylene glycol (400 g·mol-1, PPG 400) were studied for the simultaneous extraction and recovery of three value-added compounds, namely, caffeine, taurine, and niacin, from expired energy drinks. ILs were designed and synthesized in order to have similar anions to the target compounds, thus allowing enhanced selectivity and biological activity, while avoiding an extra step of separation of these high-value compounds from the IL-rich phase. To this end, cholinium-based ILs comprising the anions lactate, pyruvate, taurate, and nicotinate were synthesized, and their cytotoxicity and ecotoxicity credentials were evaluated. Overall, taurine and niacin are majorly enriched in the IL-rich phase, while caffeine preferentially migrates in the majority of the cases toward the PPG-rich phase. However, caffeine also partitions to the IL-rich phase in the ABS formed by cholinium pyruvate or cholinium nicotinate. The ABS formed by cholinium nicotinate and PPG 400 is the best system identified, allowing the almost complete recovery (recovery efficiencies > 82%) of all target compounds into the IL-rich phase in one step. Furthermore, cholinium nicotinate exhibits marginal cytotoxic potential and is harmless from an ecotoxicological point of view. This system is thus a promising platform to simultaneously extract, recover, and reuse value-added compounds from expired energy drinks without the need of removing the IL or recovering the target compounds from the IL-rich phase, thus contributing to a sustainable and circular food economypublishe

Thermo-Analytical and Compatibility Study with Mechanistic Explanation of Degradation Kinetics of Ambroxol Hydrochloride Tablets under Non-Isothermal Conditions

Ambroxol hydrochloride (AMB), used as a broncho secretolytic and an expectorant drug, is a semi-synthetic derivative of vasicine obtained from the Indian shrub Adhatoda vasica. It is a metabolic product of bromhexine. The paper provides comprehensive and detailed research on ambroxol hydrochloride, gives information on thermal stability, the mechanism of AMB degradation, and data of practical interest for optimization of formulation that contains AMB as an active compound. Investigation on pure AMB and in commercial formulation Flavamed® tablet (FT), which contains AMB as an active compound, was performed systematically using thermal and spectroscopic methods, along with a sophisticated and practical statistical approach. AMB proved to be a heat-stable and humidity-sensitive drug. For its successful formulation, special attention should be addressed to excipients since it was found that polyvinyl pyrrolidone and Mg stearate affect the thermal stability of AMB. At the same time, lactose monohydrate contributes to faster degradation of AMB and change in decomposition mechanism. It was found that the n-th order kinetic model mechanistically best describes the decomposition process of pure AMB and in Flavamed® tablets