Nur Hasyareeda Hassan

Development of a New Binary Solvent System Using Ionic Liquids as Additives to Improve Rotenone Extraction Yield from Malaysia Derris sp.

Rotenone is one of the prominent insecticidal isoflavonoid compounds which can be isolated from the extract of Derris sp. plant. Despite being an effective compound in exterminating pests in a minute concentration, procuring a significant amount of rotenone in the extracts for commercialized biopesticides purposes is a challenge to be attained. Therefore, the objective of this study was to determine the best ionic liquid (IL) which gives the highest yield of rotenone. The normal soaking extraction (NSE) method was carried out for 24u2009hrs using five different types of binary solvent systems comprising a combination of acetone and five respective ionic liquids (ILs) of (1) [BMIM] Cl; (2) [BMIM] OAc; (3) [BMIM] NTf2; (4) [BMIM] OTf; and (5) [BMPy] Cl. Next, the yield of rotenone, % (w/w), and its concentration (mg/mL) in dried roots were quantitatively determined by means of RP-HPLC and TLC. The results showed that a binary solvent system of [BMIM] OTf + acetone was the best solvent system combination as compared to other solvent systems ( ). It contributed to the highest rotenone content of 2.69 ± 0.21% (w/w) (4.04 ± 0.34 mg/mL) at 14u2009hrs of exhaustive extraction time. In conclusion, a combination of the ILs with a selective organic solvent has been proven to increase a significant amount of bioactive constituents in the phytochemical extraction process.

Alcohol based-deep eutectic solvent (DES) as an alternative green additive to increase rotenone yield

Deep eutectic solvents (DESs) are basically molten salts that interact by forming hydrogen bonds between two added components at a ratio where eutectic point reaches a melting point lower than that of each individual component. Their remarkable physicochemical properties (similar to ionic liquids) with remarkable green properties, low cost and easy handling make them a growing interest in many fields of research. Therefore, the objective of pursuing this study is to analyze the potential of alcohol-based DES as an extraction medium for rotenone extraction from Derris elliptica roots. DES was prepared by a combination of choline chloride, ChCl and 1, 4-butanediol at a ratio of 1/5. The structure of elucidation of DES was analyzed using FTIR, 1H-NMR and 13C-NMR. Normal soaking extraction (NSE) method was carried out for 14 hours using seven different types of solvent systems of (1) acetone; (2) methanol; (3) acetonitrile; (4) DES; (5) DES + methanol; (6) DES + acetonitrile; and (7) [BMIM] OTf + acetone. Next, the yield of rotenone, % (w/w), and its concentration (mg/ml) in dried roots were quantitatively determined by means of RP-HPLC. The results showed that a binary solvent system of [BMIM] OTf + acetone and DES + acetonitrile was the best solvent system combination as compared to other solvent systems. It contributed to the highest rotenone content of 0.84 ± 0.05% (w/w) (1.09 ± 0.06 mg/ml) and 0.84 ± 0.02% (w/w) (1.03 ± 0.01 mg/ml) after 14 hours of exhaustive extraction time. In conclusion, a combination of the DES with a selective organic solvent has been proven to have a similar potential and efficiency as of ILs in extracting bioactive constituents in the phytochemical extraction process.

Deconstruction of Malaysian agro-wastes with inexpensive and bifunctional triethylammonium hydrogen sulfate ionic liquid

Ionic liquids (ILs) are known to be very effective at deconstructing biomass, but, they are typically 5-20 times more expensive than molecular solvents; this is a major impediment to the utilisation of ILs in biorefinery applications. In view of this, this paper is the first to report a preliminary study on the use of inexpensive and bifunctional triethylammonium hydrogen sulfate ionic liquid, [N2220][HSO4] IL, in deconstructing two Malaysian agro-wastes, oil palm empty fruit bunches (OPEFB) and coconut husk. The [N2220][HSO4] IL was synthesised via simple acid-base neutralisation route between two inexpensive precursors: sulfuric acid, H2SO4, and triethylamine, N222. The results of deconstruction of OPEFB and coconut husk under the applied conditions, IL/H2O (80/20 wt/wt) at 120 °C for 2 h, proved that the IL provided bifunctional action as: a Bronsted acid catalyst that hydrolysed chemical bonds linking carbohydrate-rich-material (cellulose and hemicellulose) and lignin fractions, and; a delignification agent that dissolved lignin, separating the biopolymer from the carbohydrate-rich-material. The outcomes of this study indicate that the deconstruction of Malaysian agro-wastes for isolating valuable biopolymers can be performed in a more economical and effective way using the [N2220][HSO4] IL.

Response Surface Optimization of Rotenone Using Natural Alcohol-Based Deep Eutectic Solvent as Additive in the Extraction Medium Cocktail

Rotenone is a biopesticide with an amazing effect on aquatic life and insect pests. In Asia, it can be isolated from Derris species roots (Derris elliptica and Derris malaccensis). The previous study revealed the comparable efficiency of alcohol-based deep eutectic solvent (DES) in extracting a high yield of rotenone (isoflavonoid) to binary ionic liquid solvent system ([BMIM]OTf) and organic solvent (acetone). Therefore, this study intends to analyze the optimum parameters (solvent ratio, extraction time, and agitation rate) in extracting the highest yield of rotenone extract at a much lower cost and in a more environmental friendly method by using response surface methodology (RSM) based on central composite rotatable design (CCRD). By using RSM, linear polynomial equations were obtained for predicting the concentration and yield of rotenone extracted. The verification experiment confirmed the validity of both of the predicted models. The results revealed that the optimum conditions for solvent ratio, extraction time, and agitation rate were 2u2009:u20098 (DESu2009:u2009acetonitrile), 19.34 hours, and 199.32u2009rpm, respectively. At the optimum condition of the rotenone extraction process using DES binary solvent system, this resulted in a 3.5-fold increase in a rotenone concentration of 0.49 ± 0.07u2009mg/ml and yield of 0.35 ± 0.06 (%, w/w) as compared to the control extract (acetonitrile only). In fact, the rotenone concentration and yield were significantly influenced by binary solvent ratio and extraction time ( ) but not by means of agitation rate. For that reason, the optimal extraction condition using alcohol-based deep eutectic solvent (DES) as a green additive in the extraction medium cocktail has increased the potential of enhancing the rotenone concentration and yield extracted.

Synthesis and characterization β-ketoamine ligands

β-ketoamine ligands are important members of heterodonor ligand because of their ease of preparation and modification of both steric and/or electronic effects. Complexes with β-ketoamine has received much less attention and there has been no study about this complex with β-ketoamine in ionic liquid reported. Two type of β-ketoamine ligands which are 4-amino-3-pentene-2-onato (A) and 3-amino-2-butenoic acid methyl ester (B) have been synthesized in this work. The resulting compound formed was characterized using standard spectroscopic and structural techniques which includes 1H and 13C, NMR spectroscopy and FTIR spectroscopy. The 1H and 13C NMR spectrum displayed all the expected signals with correct integration and multiplicity. And it is proved that there are some differences between two ligands as observed in NMR and FTIR spectrum.

Imidazolium-Based Ionic Liquid Binary Solvent System as an Extraction Medium in Enhancing the Rotenone Yield Extracted from Derris elliptica Roots

Rotenone, is a biopesticide which can be isolated from Derris species roots. However, procuring significant amount of rotenone using green alternative solvent rather than harmful organic solvents for commercialization is a challenge to be faced. Therefore, an approach using imidazolium-based ionic liquids (ILs) as an extraction medium was employed in this study. Five different types of binary solvent systems comprising a combination of acetone and five respective ionic liquids (ILs) of (1) [BMIM] Cl; (2) [BMIM] OAc; (3) [BMIM] NTf2; (4) [BMIM] OTf; and (5) [BMPy] Cl were used in the normal soaking extraction (NSE) of rotenone for a 24-hour extraction. The yield of the rotenone, % (w/w), and its concentration (mg/mL) in the dried roots was quantitatively determined by means of the reversed-phase high-performance liquid chromatography (RP-HPLC) and thin-layer chromatography (TLC). The results showed that a binary solvent system of [BMIM] OTf:acetone was the best solvent system combination compared to other solvent systems (p < 0.05). It contributed to the highest rotenone content of 2.69 ± 0.21% (w/w) (4.04 ± 0.34 mg/ml) at the 14th hour of the exhaustive extraction time. In conclusion, a combination of certain ILs with a selective organic solvent has been proven to be able to increase a significant amount of bioactive constituents in the phytochemical extraction process.

Malaysia snakehead channa striatus and micropeltes: Physico-chemical properties of fillet fish oil and water-soluble extract

Channa species is a local fish species in Malaysia. Channa striatus (Haruan) has been traditionally used for wound healing and reducing pain. This study was carried out to determine the availability of essential fatty acid (arachidonic acid) and other physico-chemical properties in the aqueous extract which has been proven to induce wound healing mechanism. Two Channa species were used in this study, which were Channa striatus (Haruan) and Channa micropeltes (Toman). Each sample was trimmed well to obtain the maximum fish fillet and extracted by using two different extraction methods. They were: 1) aqueous extraction and 2) Soxhlet extraction to procure the fish oil. The aqueous extract was characterised for its physico-chemical properties such as pH, moisture content, rheological properties (n = 3), amino acid composition and fatty acid determination (arachidonic acid) (n = 2) whilst fish oil was examined in terms of its colour, density, specific gravity, acid value (AV), free fatty acid (FFA) value, peroxide value (PV) (n = 3) and fatty acid composition (n = 2). Based on this study, Toman essence was found to be more neutral and had higher moisture content than Haruan essence (p < 0.05). They were considered having the same viscosity (p > 0.05). Both water extract of C. striatus and C. Both Haruan and Toman fish oils showed a relatively similar fatty acid profile and the arachidonic acid in a very low concentration. The physico-chemical properties of two Malaysia Channa species extracts revealed its potent ingredients (especially arachidonic acid) to induced wound healing process despite of its low concentration in the extracts. micropeltes were found to contain the essential amino acid, glycine and fatty acid (arachidonic acid) which aid in the process of wound healing despite their low concentration (p > 0.05). On the other hand, the highest yield of extracted fish oil (%, w/w) was obtained from C. micropeltes species, 9.51 ± 1.20 % (p < 0.05). The physico-chemical results of the fish oil from C. striatus and C. micropeltes, were as follows: colour – dark reddish with yellow of all species (p < 0.05), density 0.99 ± 0.08 g/mL, 0.99 ± 0.00 g/mL (p > 0.05), specific gravity 0.93 ± 0.10, 0.91 ± 0.03 (p > 0.05), AV 21.78 ± 2.30 mg KOH/g, 5.55 ± 1.64 mg KOH/g (p < 0.05), FFA 10.95 ± 1.16 %, 2.79 ± 0.83 % (p < 0.05) and PV 18.00 ± 6.56 mEq/kg, 14.67 ± 3.79 mEq/kg (p > 0.05).

Synthesis and characterization of acetic acid and ethanoic acid (based)-maleimide

A new route to the synthesis of maleimide is described. 2-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)acetic acid maleimide (1) and 2-(4-(2,5-Dioxo-2,5-dihydro- 1H-pyrrol-1-yl)phenyl)ethanoic acid maleimide (2) have been synthesized by the reaction of maleic anhydride with glycine and 4-aminophenyl acetic aicd. Maleimide (1) was synthesized by conventional technique while maleimide (2) was synthesized by microwave method. The compounds were characterized using FT-Infrared (FT-IR), 1H and 13C Nuclear Magnetic Resonance (NMR) spectroscopies and Mass Spectrometry.

Sintesis sebatian isoxazolidina melalui tindakbalas 1,3-dwikutub pensiklotambahan N-4-tetra-benzilidina nitron dan maleimida dalam cecair ionik berasaskan imidazolium

The development of environmentally friendly methodologies for pericyclic reactions such as Diels Alder reaction is astonishing. Nevertheless, this is still scarce for the rest of pericyclic reactions. In this work, diastereosiomeric cycloadducts were formed via 1,3-dipolar cycloaddition between N-4-Tert-Benzylidene nitrone and maleimide in imidazolium-based ionic liquids (ILs) at 25 °C. Cycloaddition between nitrone 1 and maleimide 2 give diastereoisomeric adducts with 1:1 and 1:2 trans/cis ratio in two ionic liquids, [Bmim][PF6] and [Bmim][BF4], respectively. [Bmim][PF6] give the desired cycloadducts in 43% yield compared to only 18% yield in [Bmim][BF4]. In comparison, when the similar reaction was conducted in chloroform, the diasteroeisomeric mixture favoured trans isomer in 6:0.2 ratio. We reasoned that the repulsive van der Waals interactions favouring exo transition state was assisted by imidazolium ionic liquids. Thus, ILs have shown great potential as second reaction media in dipolar cycloaddition reactions.