Maan Hayyan

Superoxide Ion: Generation and Chemical Implications

Superoxide ion (O2(•-)) is of great significance as a radical species implicated in diverse chemical and biological systems. However, the chemistry knowledge of O2(•-) is rather scarce. In addition, numerous studies on O2(•-) were conducted within the latter half of the 20th century. Therefore, the current advancement in technology and instrumentation will certainly provide better insights into mechanisms and products of O2(•-) reactions and thus will result in new findings. This review emphasizes the state-of-the-art research on O2(•-) so as to enable researchers to venture into future research. It comprises the main characteristics of O2(•-) followed by generation methods. The reaction types of O2(•-) are reviewed, and its potential applications including the destruction of hazardous chemicals, synthesis of organic compounds, and many other applications are highlighted. The O2(•-) environmental chemistry is also discussed. The detection methods of O2(•-) are categorized and elaborated. Special attention is given to the feasibility of using ionic liquids as media for O2(•-), addressing the latest progress of generation and applications. The effect of electrodes on the O2(•-) electrochemical generation is reviewed. Finally, some remarks and future perspectives are concluded.

Are deep eutectic solvents benign or toxic

In continuation of investigation for environmentally benign protocol for new solvents termed deep eutectic solvents (DESs), it is herein reported results concerning the toxicity and cytotoxicity of choline chloride (ChCl) based DESs with four hydrogen bond donors including glycerine, ethylene glycol, triethylene glycol and urea. The toxicity was investigated using two Gram positive bacteria Bacillus subtilis and Staphylococcus aureus, and two Gram negative bacteria Escherichia coli and Pseudomonas aeruginosa. The cytotoxicity effect was tested using the Artemia salina leach. It was found that there was no toxic effect for the tested DESs on all of the studied bacteria confirming their benign effects on these bacteria. Nevertheless, it was found that the cytotoxicity of DESs was much higher than their individual components (e.g. glycerine, ChCl) indicating that their toxicological behavior is different. For our best knowledge this is the first time that toxicity and cytotoxicity of DESs were studied. The toxicity and cytotoxicity of DESs varied depending on the structure of components. Careful usage of the terms non-toxicity and biodegradability must be considered. More investigation on this matter is required.

Assessment of cytotoxicity and toxicity for phosphonium-based deep eutectic solvents.

In this work, the cytotoxicity and toxicity of phosphonium-based deep eutectic solvents (DESs) with three hydrogen bond donors, namely glycerine, ethylene glycol, and triethylene glycol were investigated. The cytotoxicity effect was tested using brine shrimp (Artemia salina). The toxicity was investigated using the two Gram positive bacteria Bacillus subtilis and Staphylococcus aureus, and two Gram negative bacteria Escherichia coli and Pseudomonas aeruginosa. The cytotoxicity of tested DESs was much higher than that of their individual components, indicating their toxicological behavior was different. It was also found that there was toxic effect on the studied bacteria, indicating their potential application as anti-bacterial agents. To the best of our knowledge, this is the first time the cytotoxicity and toxicity of phosphonium-based DESs were studied.

Environmental application of nanotechnology: air, soil, and water.

Global deterioration of water, soil, and atmosphere by the release of toxic chemicals from the ongoing anthropogenic activities is becoming a serious problem throughout the world. This poses numerous issues relevant to ecosystem and human health that intensify the application challenges of conventional treatment technologies. Therefore, this review sheds the light on the recent progresses in nanotechnology and its vital role to encompass the imperative demand to monitor and treat the emerging hazardous wastes with lower cost, less energy, as well as higher efficiency. Essentially, the key aspects of this account are to briefly outline the advantages of nanotechnology over conventional treatment technologies and to relevantly highlight the treatment applications of some nanomaterials (e.g., carbon-based nanoparticles, antibacterial nanoparticles, and metal oxide nanoparticles) in the following environments: (1) air (treatment of greenhouse gases, volatile organic compounds, and bioaerosols via adsorption, photocatalytic degradation, thermal decomposition, and air filtration processes), (2) soil (application of nanomaterials as amendment agents for phytoremediation processes and utilization of stabilizers to enhance their performance), and (3) water (removal of organic pollutants, heavy metals, pathogens through adsorption, membrane processes, photocatalysis, and disinfection processes).

In Vitro and In Vivo toxicity profiling of ammonium-based deep eutectic solvents.

The cytotoxic potential of ammonium-based deep eutectic solvents (DESs) with four hydrogen bond donors, namely glycerine (Gl), ethylene glycol (EG), triethylene glycol (TEG) and urea (U) were investigated. The toxicity of DESs was examined using In Vitro cell lines and In Vivo animal model. IC50 and selectivity index were determined for the DESs, their individual components and their combinations as aqueous solutions for comparison purposes. The cytotoxicity effect of DESs varied depending on cell lines. The IC50 for the GlDES, EGDES, UDES and TEGDES followed the sequence of TEGDES< GlDES< EGDES< UDES for OKF6, MCF-7, A375, HT29 and H413, respectively. GlDES was selective against MCF-7 and A375, EGDES was selective against MCF-7, PC3, HepG2 and HT29, UDES was selective against MCF-7, PC3, HepG2 and HT29, and TEGDES was selective against MCF-7 and A375. However, acute toxicity studies using ICR mice showed that these DESs were relatively toxic in comparison to their individual components. DES did not cause DNA damage, but it could enhance ROS production and induce apoptosis in treated cancer cells as evidenced by marked LDH release. Furthermore, the examined DESs showed less cytotoxicity compared with ionic liquids. To the best of our knowledge, this is the first time that combined In Vitro and In Vivo toxicity profiles of DESs were being demonstrated, raising the toxicity issue of these neoteric mixtures and their potential applicability to be used for therapeutic purposes.

Applications of deep eutectic solvents in biotechnology and bioengineering—Promises and challenges

Deep eutectic solvents (DESs) have been touted recently as potential alternatives to ionic liquids (ILs). Although they possess core characteristics that are similar to those of ILs (e.g., low volatility, non-flammability, low melting points, low vapor pressure, dipolar nature, chemical and thermal stability, high solubility, and tuneability), DESs are superior in terms of the availability of raw materials, the ease of storage and synthesis, and the low cost of their starting materials. As such, they have become the subject of intensive research in various sectors, notably the chemical, electrochemical, and biological sectors. To date, the applications of DESs have shown great promise, especially in the medical and biotechnological fields. In spite of these various achievements, the safety concern for these mixtures must be sufficiently addressed. Indeed, in order to exploit the vast array of opportunities that DESs offer to the biological industry, first, they must be established as safe mixtures. Hence, the biotechnological applications of DESs only can be implemented if they are proven to have negligible or low toxicity profiles. This review is the first of its kind, and it discusses two current aspects of DES-based research. First, it describes the properties of these mixtures with ample focus on their toxicity profiles. Second, it provides an overview of the breakthroughs that have occurred and the foreseeable prospects of the use of DESs in various biotechnological and biological applications.

Functionalization of graphene using deep eutectic solvents

Deep eutectic solvents (DESs) have received attention in various applications because of their distinctive properties. In this work, DESs were used as functionalizing agents for graphene due to their potential to introduce new functional groups and cause other surface modifications. Eighteen different types of ammonium- and phosphonium-salt-based DESs were prepared and characterized by FTIR. The graphene was characterized by FTIR, STA, Raman spectroscopy, XRD, SEM, and TEM. Additional experiments were performed to study the dispersion behavior of the functionalized graphene in different solvents. The DESs exhibited both reduction and functionalization effects on DES-treated graphene. Dispersion stability was investigated and then characterized by UV–vis spectroscopy and zeta potential. DES-modified graphene can be used in many applications, such as drug delivery, wastewater treatment, catalysts, composite materials, nanofluids, and biosensors. To the best of our knowledge, this is the first investigation on the use of DESs for graphene functionalization.

Natural deep eutectic solvents: cytotoxic profile

AbstractThe purpose of this study was to investigate the cytotoxic profiles of different ternary natural deep eutectic solvents (NADESs) containing water. For this purpose, five different NADESs were prepared using choline chloride as a salt, alongside five hydrogen bond donors (HBD) namely glucose, fructose, sucrose, glycerol, and malonic acid. Water was added as a tertiary component during the eutectics preparation, except for the malonic acid-based mixture. Coincidentally, the latter was found to be more toxic than any of the water-based NADESs. A trend was observed between the cellular requirements of cancer cells, the viscosity of the NADESs, and their cytotoxicity. This study also highlights the first time application of the conductor-like screening model for real solvent (COSMO-RS) software for the analysis of the cytotoxic mechanism of NADESs. COSMO-RS simulation of the interactions between NADESs and cellular membranes’ phospholipids suggested that NADESs strongly interacted with cell surfaces and that their accumulation and aggregation possibly defined their cytotoxicity. This reinforced the idea that careful selection of NADESs components is necessary, as it becomes evident that organic acids as HBD highly contribute to the increasing toxicity of these neoteric mixtures. Nevertheless, NADESs in general seem to possess relatively less acute toxicity profiles than their DESs parents. This opens the door for future large scale utilization of these mixtures.

Evaluation of toxicity and biodegradability for cholinium-based deep eutectic solvents

This study presented the toxicological and biodegradable assessment of different cholinium-based deep eutectic solvents (DESs). They were formed from choline chloride (ChCl) and N,N-diethyl ethanol ammonium chloride (EAC) as salts and four hydrogen bond donors, namely ethylene glycol (EG), glycerol (Gly), urea (U), malonic acid (MA), in addition to a metal salt, i.e. zinc chloride (ZnCl2), and a hydrated metal salt, i.e. zinc nitrate hexahydrate (ZnN). The toxicity towards Aspergillus niger of pure and aqueous DESs was evaluated by observing the inhibition zone using an agar well diffusion assay, and the minimum inhibition concentration (MIC) using a broth dilution assay, respectively. The MIC values of the DESs varied from 1 to 650 mg mL−1, whereas the inhibition zones changed according to the DES dose amount. Another test for acute toxicity was performed by evaluating the lethal concentration at 50% (LC50) of the same DESs on Cyprinus carpio fish. The LC50 of DESs ranged from practically harmless (e.g. ChCl : EG-DESaq) to highly toxic (e.g. EAC : ZnCl2-DESaq). The toxicity profile of the DESs depended on their concentration, type of individual components, and interaction with living organisms. Moreover, the DESs recorded higher toxicity compared to their individual components on fungi. However, lower toxicity was found for the DESs tested on Cyprinus carpio. Types I (organic salts and metal salt) and II (organic salt and hydrate metal salt) eutectics exhibited significantly higher toxicity than type III (organic salts and HBD). This was due to the presence of the innate toxicity of the metal salts. The biodegradability was appraised by a closed bottle test in which all the DESs were found to be readily biodegradable. To the best of our knowledge, there are no previous studies reported regarding the toxicity of cholinium-based DESs on freshwater fish or fungi and the biodegradability of EAC-based DESs. Therefore, this investigation can be used as a benchmark for future development of DESs.

Ethanesulfonic acid-based esterification of industrial acidic crude palm oil for biodiesel production.

An industrial grade acidic crude palm oil (ACPO) pre-treatment process was carried out using ethanesulfonic acid (ESA) as a catalyst in the esterification reaction. ESA was used in different dosages to reduce free fatty acid (FFA) to a minimum level for the second stage of biodiesel production via alkaline transesterification reaction. Different process operating conditions were optimized such as ESA dosage (0.25-3.5% wt/wt), methanol to ACPO molar ratio (1:1-20:1), reaction temperature (40-70 °C), and reaction time (3-150 min). This study revealed the potential use of abundant quantities of ACPO from oil palm mills for biodiesel production. The lab scale results showed the effectiveness of the pre-treatment process using ESA catalyst. Three consecutive catalyst recycling runs were achieved without significant degradation in its performance. Second and third reuse runs needed more reaction time to achieve the target level of FFA content. Esterification and transesterification using ESA and KOH respectively is proposed for biodiesel industrial scale production. The produced biodiesel meets the international standards specifications for biodiesel fuel (EN 14214 and ASTM D6751).