Amir Sada Khan

Synthesis, characterization and the effect of temperature on different physicochemical properties of protic ionic liquids

In this work, eleven protic ionic liquids (PILs) containing different cations and anions were prepared and their physicochemical properties were measured. The structures of all the PILs were confirmed using NMR, and elemental analysis (CHNS) was carried out. The physicochemical properties such as density, surface tension, viscosity and thermal degradation behaviour were measured, and the effect of the cations/anions was investigated. The density and viscosity were measured within the temperature range of 293.15–373.15 K at atmospheric pressure. The thermal expansion coefficient values were calculated from the density data. Surface tension was measured in the temperature range of 293.15 to 353.15 K and the values were used to estimate the surface entropy and enthalpy of the ionic liquids at 303.15 K. The boiling and critical temperature are also estimated according to the Eotvos and Rebelo methods. The refractive indices were measured within the temperature range of 293.15 to 323.15 K. The thermal gravimetric analysis was performed in the temperature range of 373.15–773.15 K.

Potential biosorbent derived from Calligonum polygonoides for removal of methylene blue dye from aqueous solution.

The ash of C. polygonoides (locally called balanza) was collected from Lakki Marwat, Khyber Pakhtunkhwa, Pakistan, and was utilized as biosorbent for methylene blue (MB) removal from aqueous solution. The ash was used as biosorbent without any physical or chemical treatment. The biosorbent was characterized by using various techniques such as Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The particle size and surface area were measured using particle size analyzer and Brunauer-Emmett-Teller equation (BET), respectively. The SEM and BET results expressed that the adsorbent has porous nature. Effects of various conditions such as initial concentration of methylene blue (MB), initial pH, contact time, dosage of biosorbent, and stirring rate were also investigated for the adsorption process. The rate of the adsorption of MB on biomass sample was fast, and equilibrium has been achieved within 1 hour. The kinetics of MB adsorption on biosorbent was studied by pseudo-first- and pseudo-second-order kinetic models and the pseudo-second-order has better mathematical fit with correlation coefficient value (R 2) of 0.999. The study revealed that C. polygonoides ash proved to be an effective, alternative, inexpensive, and environmentally benign biosorbent for MB removal from aqueous solution.

A new approach of probe sonication assisted ionic liquid conversion of glucose, cellulose and biomass into 5-hydroxymethylfurfural

5-Hydroxymethylfurfural (HMF) has been identified as a promising biomass-derived platform chemical. In this study, one pot production of HMF was studied in ionic liquid (IL) under probe sonication technique. Compared with the conventional heating technique, the use of probe ultrasonic irradiation reduced the reaction time from hours to minutes. Glucose, cellulose and local bamboo, treated with ultrasonic, produced HMF in the yields of 43%, 31% and 13% respectively, within less than 10min. The influence of various parameters such as acoustic power, reaction time, catalysts and glucose loading were studied. About 40% HMF yield at glucose conversion above 90% could be obtained with 2% of catalyst in 3min. Negligible amount of soluble by-product was detected, and humin formation could be controlled by adjusting the different process parameters. Upon extraction of HMF, the mixture of ionic liquid and catalyst could be reused and exhibited no significant reduction of HMF yield over five successive runs. The purity of regenerated [C4C1im]Cl and HMF was confirmed by NMR spectroscopy, indicating neither changes in the chemical structure nor presence of any major contaminants during the conversion under ultrasonic treatment. 13C NMR suggests that [C4C1im]Cl/CrCl3 catalyses mutarotation of α-glucopyranose to β-glucopyranose leading to isomerization and finally conversion to HMF. The experimental results demonstrate that the use of probe sonication technique for conversion to HMF provides a positive process benefit.

Efficient conversion of lignocellulosic biomass to levulinic acid using acidic ionic liquids

In the present research work, dicationic ionic liquids, containing 1,4-bis(3-methylimidazolium-1-yl) butane ([C4(Mim)2]) cation with counter anions [(2HSO4)(H2SO4)0], [(2HSO4)(H2SO4)2] and [(2HSO4)(H2SO4)4] were synthesised. ILs structures were confirmed using 1H NMR spectroscopy. Thermal stability, Hammett acidity, density and viscosity of ILs were determined. Various types of lignocellulosic biomass such as rubber wood, palm oil frond, bamboo and rice husk were converted into levulinic acid (LA). Among the synthesized ionic liquids, [C4(Mim)2][(2HSO4)(H2SO4)4] showed higher % yield of LA up to 47.52 from bamboo biomass at 110°C for 60min, which is the better yield at low temperature and short time compared to previous reports. Surface morphology, surface functional groups and thermal stability of bamboo before and after conversion into LA were studied using SEM, FTIR and TGA analysis, respectively. This one-pot production of LA from agro-waste will open new opportunity for the conversion of sustainable biomass resources into valuable chemicals.

Study of the antimicrobial activity of cyclic cation-based ionic liquids via experimental and group contribution QSAR model

Over the past decades, Ionic liquids (ILs) have gained considerable attention from the scientific community in reason of their versatility and performance in many fields. However, they nowadays remain mainly for laboratory scale use. The main barrier hampering their use in a larger scale is their questionable ecological toxicity. This study investigated the effect of hydrophobic and hydrophilic cyclic cation-based ILs against four pathogenic bacteria that infect humans. For that, cations, either of aromatic character (imidazolium or pyridinium) or of non-aromatic nature, (pyrrolidinium or piperidinium), were selected with different alkyl chain lengths and combined with both hydrophilic and hydrophobic anionic moieties. The results clearly demonstrated that introducing of hydrophobic anion namely bis((trifluoromethyl)sulfonyl)amide, [NTF2] and the elongation of the cations substitutions dramatically affect ILs toxicity behaviour. The established toxicity data [50% effective concentration (EC50)] along with similar endpoint collected from previous work against Aeromonas hydrophila were combined to developed quantitative structure-activity relationship (QSAR) model for toxicity prediction. The model was developed and validated in the light of Organization for Economic Co-operation and Development (OECD) guidelines strategy, producing good correlation coefficient R2 of 0.904 and small mean square error (MSE) of 0.095. The reliability of the QSAR model was further determined using k-fold cross validation.

Swelling mechanism of urea cross-linked starch–lignin films in water

ABSTRACT Coating fertilizer particles with thin films is a possibility to control fertilizer release rates. It is observed that novel urea cross-linked starch–lignin composite thin films, prepared by solution casting, swell on coming into contact with water due to the increase in volume by water uptake by diffusion. The effect of lignin content, varied from 0% to 20% in steps of 5% at three different temperatures (25°C, 35°C and 45°C), on swelling of the film was investigated. By gravimetric analysis, the equilibrium water uptake and diffusion coefficient decrease with lignin content, indicating that the addition of lignin increases the hydrophobicity of the films. When temperature increases, the diffusion coefficient and the amount of water absorbed tend to increase. Assuming that swelling of the thin film is by water uptake by diffusion, the diffusion coefficient is estimated. The estimated diffusion coefficient decreases from 4.3 to 2.1 × 10−7 cm2/s at 25°C, from 5.3 to 2.9 × 10−7 cm2/s at 35°C and from 6.2 to 3.8 × 10−7 cm2/s at 45°C depending on the lignin content. Activation energy for the increase in diffusion coefficient with temperature is observed to be 16.55 kJ/mol. An empirical model of water uptake as a function of percentage of lignin and temperature was also developed based on Fick’s law.

Development of collagen/PVA composites patches for osteochondral defects using a green processing of ionic liquid

Abstract Osteochondral defects are still a big challenge for the surgeons because of good biocompatibility and higher mechanical strength requiring issues of the implants. In this study, different concentrations of collagen (dissolved in ionic liquid) up to 60% were blended with polyvinyl alcohol to prepare hydrogels of good mechanical strength, with the best biocompatibility and excellent fluid uptake ability. Ionic liquid was used as a green solvent for dissolution of collagen at a higher concentration as compared to other normal solvents. The prepared hydrogels were characterized with Fourier transform infrared spectroscopy (FTIR) which showed the characteristic peaks assigned to collagen and PVA. The surface morphology was investigated using scanning electron microscopy (SEM) which revealed homogeneity of the composite patches. Thermal gravimetric analysis (TGA) performed for samples show good thermal stabilities. Fluid uptake ability showed the massive uptake of fluid by the hydrogels. Biocompatibility was tested using hemolysis and MTT assay. Electrodynamic fatigue testing system was used for evaluating the mechanical properties and measured the tensile strength in the range of 2.4 to 8.5 MPa. The prepared osteochondral patches show good biocompatibility and mechanical properties. Graphical Abstract

Effect of Ball Milling on the Catalytic Conversion of Cellulose to Levulinic Acid

The yield of levulinic acid from cellulose is very low because of a strong network of intera-and intermolecular hydrogen bonding. Ball milling cause significant decrease in the cellulose crystalinity and thus increase the production of levulinic acid (LA) by using Aluminum Chloride (AlCl3) as a catalyst. By means of AlCl3 depolymerization, cellulose can produce 5-Hydroxymethylfurfural (5-HMF) and subsequently LA. The effect of reaction temperature and time were investigated. The maximum yield of LA (36.5 mol %) was achieved using 180 oC and 240 min. Keyword: Ball milling, Levulinic Acid, Cellulose, Aluminium (III) Chloride, 5-Hydroxymethylfurfural