Pemanfaatan Hidrofobik Deep Eutectic Solvents dalam Penyisihan Dimetoat, Klorpirifos, dan Profenofos pada Buah Tomat dan Sayur Brokoli

Organophosphate insecticide is a type of pesticide that is commonly used, where this pesticide can be toxic to environmental organisms even to humans. Hydrophobic Deep Eutectic Solvent (DES) is a new generation nonpolar solvent of ionic liquids because it has better physical properties and chemical properties so that it can be used in the extraction process. DES was synthesized at 50 oC for 15 minutes with a stirring speed of 300 rpm and a molar ratio of Dl-menthol: lauric acid varied from 1: 1, 2: 1, and 3: 1. Pesticide removal is done by mixing 5 ml of DES with 200 ml of aquadest and then Tomatoes and Broccoli vegetables are washed with the solution. DES characteristics are done by analyzing the shape and measuring the freezing point, density and viscosity of DES. The concentration of pesticide residues was analyzed using Gas Chromatography-Mass Spectrometer (GC-MS). The highest elimination of pesticides obtained with DES hydrophobic which has a molar ratio of dl-menthol: lauric acid is 3: 1 where the highest elimination of pesticides in Tomatoe is 44.82% for Dimethoate pesticide, 84.1% for Chlorpyrifos pesticide, and 83.72% for Profenofos pesticide and Broccoli 35.19% for Dimetoat pesticide, 64.64% for Chlorpyrifos pesticide, and 55.28% for Profenofos pesticides.

Download Full-text

Silica Gel Impregnated by Deep Eutectic Solvents for Adsorptive Removal of BTEX from Gas Streams

Materials ◽

10.3390/ma13081894 ◽

2020 ◽

Vol 13 (8) ◽

pp. 1894 ◽

Cited By ~ 2

Author(s):

Patrycja Makoś ◽

Edyta Słupek ◽

Aleksandra Małachowska

Keyword(s):

Lactic Acid ◽

Silica Gel ◽

Choline Chloride ◽

Specific Interaction ◽

Chemical Properties ◽

Deep Eutectic Solvents ◽

Molar Ratio ◽

Gas Streams ◽

Tetrapropylammonium Bromide ◽

Sorbent Materials

The paper presents the preparation of new adsorbents based on silica gel (SiO2) impregnated with deep eutectic solvents (DESs) to increase benzene, toluene, ethylbenzene, and p-xylene (BTEX) adsorption efficiency from gas streams. The DESs were synthesized by means of choline chloride, tetrapropylammonium bromide, levulinic acid, lactic acid, and phenol. The physico-chemical properties of new sorbent materials, including surface morphology and structures, as well as porosity, were studied by means of thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and Brunauer–Emmett–Teller analysis. The effect of DESs type, flow rate, and initial concentration of BTEX were also investigated followed by regeneration and reusability of adsorbents. The results indicate that SiO2 impregnated with tetrapropylammonium bromide and lactic acid in a 1:2 molar ratio have great potential for the removal of BTEX from gas streams. Its adsorption capacity was higher than the pure SiO2 and other developed SiO2-DES adsorbents. This result can be explained by the specific interaction between DESs and BTEX, i.e., hydrogen bonds interaction.

Download Full-text

Saffron Processing Wastes as a Bioresource of High-Value Added Compounds: Development of a Green Extraction Process for Polyphenol Recovery Using a Natural Deep Eutectic Solvent

Antioxidants ◽

10.3390/antiox8120586 ◽

2019 ◽

Vol 8 (12) ◽

pp. 586 ◽

Cited By ~ 15

Author(s):

Achillia Lakka ◽

Spyros Grigorakis ◽

Ioanna Karageorgou ◽

Georgia Batra ◽

Olga Kaltsa ◽

...

Keyword(s):

Hydrogen Bond ◽

Maximum Yield ◽

Deep Eutectic Solvent ◽

Value Added ◽

Extraction Process ◽

Mass Spectrometry Analysis ◽

Molar Ratio ◽

Optimal Conditions ◽

Hydrogen Bond Acceptor ◽

Natural Deep Eutectic Solvent

The current investigation was undertaken to examine saffron processing waste (SPW) as a bioresource, which could be valorized to produce extracts rich in antioxidant polyphenols, using a green, natural deep eutectic solvent (DES). Initially, there was an appraisal of the molar ratio of hydrogen bond donor/hydrogen bond acceptor in order to come up with the most efficient DES composed of L-lactic acid/glycine (5:1). The following step was the optimization of the extraction process using response surface methodology. The optimal conditions thus determined were a DES concentration of 55% (w/v), a liquid-to-solid ratio of 60 mL g−1, and a stirring speed of 800 rounds per minute. Under these conditions, the extraction yield in total polyphenols achieved was 132.43 ± 10.63 mg gallic acid equivalents per g of dry mass. The temperature assay performed within a range of 23 to 80 °C, suggested that extracts displayed maximum yield and antioxidant activity at 50–60 °C. Liquid chromatography-mass spectrometry analysis of the SPW extract obtained under optimal conditions showed that the predominant flavonol was kaempferol 3-O-sophoroside and the major anthocyanin delphinidin 3,5-di-O-glucoside. The results indicated that SPW extraction with the DES used is a green and efficient methodology and may afford extracts rich flavonols and anthocyanins, which are considered to be powerful antioxidants.

Download Full-text

Design Optimization of Deep Eutectic Solvent Composition and Separation Performance of Cyclohexane and Benzene Mixtures with Extractive Distillation

Processes ◽

10.3390/pr9101706 ◽

2021 ◽

Vol 9 (10) ◽

pp. 1706

Author(s):

Fang Bai ◽

Chao Hua ◽

Yongzhi Bai ◽

Mengying Ma

Keyword(s):

Tetrabutylammonium Bromide ◽

Deep Eutectic Solvent ◽

Ternary Systems ◽

Deep Eutectic Solvents ◽

Extractive Distillation ◽

Molar Concentration ◽

Molar Ratio ◽

Coefficient Of Determination ◽

Separation Performance ◽

Equilibrium Data

Deep eutectic solvents (DESs) have properties that make them suitable candidates to be used as entrainers for extractive distillation. In the previous work, it was proven that DES(1:2) (tetrabutylammonium bromide: levulinic acid, 1:2, molar ratio) can break the cyclohexane-benzene azeotrope. In the present work, the HBA and HBD ratio and molar concentration of DES were optimized to obtain a better constitute and condition of DES to be utilized in cyclohexane and benzene extractive distillation. The physical properties and structure of the prepared DESs were characterized. Vapor–liquid equilibrium data of the ternary system (benzene + cyclohexane + DESs) were also measured at atmospheric pressure. All experimental equilibrium data were correlated with Wilson, nonrandom two-liquid (NRTL), and universal quasichemical (UNIQUAC) activity coefficient models, from which the coefficient of determination (R2) of the three pseudo-ternary systems fitting was calculated. From the obtained results, the best HBA and HBD ratio in the DESs is elucidated as 1:2, the best molar concentration of DES is 0.1, and the NRTL model predicts the experimental data more accurately than the Wilson and UNIQUAC models. From the derived mechanism, the formation of stronger hydrogen bond and π–π bond interactions between DES and benzene is obtained when HBA and HBD ratio in DES is 1:2. In other conditions, the azeotrope cannot be broken, or the efficiency is low. The present work provides an environmentally friendly method to separate aromatic/aliphatic mixtures and act as a guide for further study of DESs in extractive distillation.

Download Full-text

Performance of p-Toluenesulfonic Acid–Based Deep Eutectic Solvent in Denitrogenation: Computational Screening and Experimental Validation

Molecules ◽

10.3390/molecules25215093 ◽

2020 ◽

Vol 25 (21) ◽

pp. 5093 ◽

Cited By ~ 1

Author(s):

Ainul F. Kamarudin ◽

Hanee F. Hizaddin ◽

Lahssen El-blidi ◽

Emad Ali ◽

Mohd A. Hashim ◽

...

Keyword(s):

Deep Eutectic Solvent ◽

Deep Eutectic Solvents ◽

Fuel Oil ◽

Proton Nuclear Magnetic Resonance ◽

Molar Ratio ◽

Nitrogen Compounds ◽

Green Solvents ◽

Computational Screening ◽

Toluenesulfonic Acid ◽

Fuel Oils

Deep eutectic solvents (DESs) are green solvents developed as an alternative to conventional organic solvents and ionic liquids to extract nitrogen compounds from fuel oil. DESs based on p-toluenesulfonic acid (PTSA) are a new solvent class still under investigation for extraction/separation. This study investigated a new DES formed from a combination of tetrabutylphosphonium bromide (TBPBr) and PTSA at a 1:1 molar ratio. Two sets of ternary liquid–liquid equilibrium experiments were performed with different feed concentrations of nitrogen compounds ranging up to 20 mol% in gasoline and diesel model fuel oils. More than 99% of quinoline was extracted from heptane and pentadecane using the DES, leaving the minutest amount of the contaminant. Selectivity was up to 11,000 for the heptane system and up to 24,000 for the pentadecane system at room temperature. The raffinate phase’s proton nuclear magnetic resonance (1H-NMR) spectroscopy and GC analysis identified a significantly small amount of quinoline. The selectivity toward quinoline was significantly high at low solute concentrations. The root-mean-square deviation between experimental data and the non-random two-liquid (NRTL) model was 1.12% and 0.31% with heptane and pentadecane, respectively. The results showed that the TBPBr/PTSADES is considerably efficient in eliminating nitrogen compounds from fuel oil.

Download Full-text

Effective Extraction of Limonene and Hibaene from Hinoki (Chamaecyparis obtusa) Using Ionic Liquid and Deep Eutectic Solvent

Molecules ◽

10.3390/molecules26144271 ◽

2021 ◽

Vol 26 (14) ◽

pp. 4271

Author(s):

Rina Yasutomi ◽

Riki Anzawa ◽

Masamitsu Urakawa ◽

Toyonobu Usuki

Keyword(s):

Ionic Liquid ◽

Organic Solvent ◽

Essential Oils ◽

Control Method ◽

Deep Eutectic Solvent ◽

Deep Eutectic Solvents ◽

Chamaecyparis Obtusa ◽

Molar Ratio ◽

Gas Chromatography Mass Spectrometry ◽

Selected Ion Monitoring

The essential oils of hinoki (Chamaecyparis obtusa) leaves have anti-bacterial, anti-fungal, and relaxation properties that are likely associated with the major components such as sabinene, α-terpinyl acetate, limonene, elemol, myrcene, and hibaene. The present study describes the use of a cellulose-dissolving ionic liquid (IL) [C2mim][(MeO)(H)PO2] and low-toxicity solvents called betaine-based deep eutectic solvents (DESs) for the efficient extraction of hinoki essential oils. As a control method, organic solvent extraction was performed using either hexane, ethyl acetate (EtOAc), or acetone at 30 °C for 1 h. Both the experimental and control methods were conducted under the same conditions, which relied on partial dissolution of the leaves using the IL and DESs before partitioning the hinoki oils into the organic solvent for analysis. Quantitative analysis was performed using gas chromatography–mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. The results indicated that extraction using the [C2mim][(MeO)(H)PO2]/acetone bilayer system improved the yields of limonene and hibaene, 1.5- and 1.9-fold, respectively, when compared with the control method. In addition, extraction using betaine/l-lactic acid (molar ratio 1:1) gave the greatest yields for both limonene and hibaene, 1.3-fold and 1.5-fold greater, respectively, than when using an organic solvent. These results demonstrate the effective extraction of essential oils from plant leaves under conditions milder than those needed for the conventional method. The less toxic and environmentally begin DESs for the extraction are also applicable to the food and cosmetic industries.

Download Full-text

Enhanced Furfural Production in Deep Eutectic Solvents Comprising Alkali Metal Halides as Additives

Molecules ◽

10.3390/molecules26237374 ◽

2021 ◽

Vol 26 (23) ◽

pp. 7374

Author(s):

Eduarda S. Morais ◽

Mara G. Freire ◽

Carmen S. R. Freire ◽

Armando J. D. Silvestre

Keyword(s):

Alkali Metal ◽

Lithium Bromide ◽

Deep Eutectic Solvent ◽

Deep Eutectic Solvents ◽

Operating Conditions ◽

Molar Ratio ◽

Metal Halides ◽

Promising Alternative ◽

Operational Conditions ◽

Alkali Metal Halides

The addition of alkali metal halide salts to acidic deep eutectic solvents is here reported as an effective way of boosting xylan conversion into furfural. These salts promote an increase in xylose dehydration due to the cation and anion interactions with the solvent being a promising alternative to the use of harsh operational conditions. Several alkali metal halides were used as additives in the DES composed of cholinium chloride and malic acid ([Ch]Cl:Mal) in a molar ratio of 1:3, with 5 wt.% of water. These mixtures were then used as both solvent and catalyst to produce furfural directly from xylan through microwave-assisted reactions. Preliminary assays were carried out at 150 and 130 °C to gauge the effect of the different salts in furfural yields. A Response Surface Methodology was then applied to optimize the operational conditions. After an optimization of the different operating conditions, a maximum furfural yield of 89.46 ± 0.33% was achieved using 8.19% of lithium bromide in [Ch]Cl:Mal, 1:3; 5 wt.% water, at 157.3 °C and 1.74 min of reaction time. The used deep eutectic solvent and salt were recovered and reused three times, with 79.7% yield in the third cycle, and the furfural and solvent integrity confirmed.

Download Full-text

Structural and Transport Properties of Binary Mixtures of Deep Eutectic Solvent (Ethaline) with Primary Alcohols: A Molecular Dynamics Study

10.26434/chemrxiv.14381996.v1 ◽

2021 ◽

Author(s):

kishant kumar ◽

Anand Bharti ◽

Aditya Sinha

Keyword(s):

Molecular Dynamics ◽

Transport Properties ◽

Binary Mixtures ◽

Choline Chloride ◽

Deep Eutectic Solvent ◽

Deep Eutectic Solvents ◽

Md Simulations ◽

Molar Ratio ◽

Green Solvents ◽

Primary Alcohols

<table><tr><td>Deep eutectic solvents (DESs) are classified as the green solvents which are considered as an alternative to volatile organic solvents. In this work, the thermophysical, structural and transport properties of binary mixtures of DES ethaline (choline chloride (ChCl) + ethylene glycol (etgly) at a molar ratio of 1:2) with primary alcohols (methanol/ethanol) are studied using molecular dynamics (MD) simulations</td></tr></table> <br>

Download Full-text

A green extraction design for enhancing flavonoid compounds from Ixora javanica flowers using a deep eutectic solvent

Royal Society Open Science ◽

10.1098/rsos.201116 ◽

2020 ◽

Vol 7 (10) ◽

pp. 201116

Author(s):

Nina Dewi Oktaviyanti ◽

Kartini Kartini ◽

Mochammad Arbi Hadiyat ◽

Ellen Rachmawati ◽

Andre Chandra Wijaya ◽

...

Keyword(s):

Extraction Method ◽

Choline Chloride ◽

Deep Eutectic Solvent ◽

Extraction Process ◽

Raw Material ◽

Molar Ratio ◽

Flavonoid Compound ◽

Total Flavonoids ◽

Green Extraction ◽

Optimum Extraction

In this study, an environmentally friendly extraction method for flavonoid compound from Ixora javanica , as a new raw material candidate for herbal medicine and cosmetics, was developed. The objectives of the present work were to provide recommendations for the optimal extraction conditions and to investigate the effects of any extraction parameters on flavonoid yields from the I. javanica flower. The extraction process was performed using deep eutectic solvent (DES) (choline chloride and propylene glycol at molar ratio of 1 : 1) and the ultrasound-assisted extraction method. Both single-factor and response surface analyses using three-level and three-factor Box Behnken designs were conducted to obtain the optimum flavonoid concentrations. The results showed that the optimum extraction conditions for total flavonoids featured an extraction time of 40 min, 25% water content in DES and a solid-to-liquid ratio of 1 : 25 g ml −1 . An extract obtained under optimum extraction conditions showed higher total flavonoid yields than an ethanolic extract which was used for comparison. Scanning electron microscope images demonstrated that both of the solvents also showed different effects on the outer surface of the I. javanica flower during the extraction process. In summary, our work succeeded in determining the optimum conditions for total flavonoids in the I. javanica flower using a green extraction method.

Download Full-text

Natural Deep Eutectic Solvent as Extraction Media for the Main Phenolic Compounds from Olive Oil Processing Wastes

Antioxidants ◽

10.3390/antiox9060513 ◽

2020 ◽

Vol 9 (6) ◽

pp. 513 ◽

Cited By ~ 7

Author(s):

Sonia Bonacci ◽

Maria Luisa Di Gioia ◽

Paola Costanzo ◽

Loredana Maiuolo ◽

Sofia Tallarico ◽

...

Keyword(s):

Phenolic Compounds ◽

Olive Oil ◽

Deep Eutectic Solvent ◽

Deep Eutectic Solvents ◽

Extraction Process ◽

Oil Processing ◽

Flight Mass Spectrometry ◽

Natural Deep Eutectic Solvents ◽

Processing Wastes ◽

Natural Deep Eutectic Solvent

In this new century, sustainable development challenges chemical sciences to develop new and clean technological processes. The agri-food industry produces significant quantities of waste, raising significant economic and environmental concerns. Food waste valorization using environmentally friendly procedures is of increasing importance. This study describes the use of several Natural Deep Eutectic Solvents (NADESs) for the microwave-assisted extraction (MAE) of valuable bioactive phenolic compounds from olive oil processing wastes. The extracted samples were characterized by liquid chromatography electrospray ionization quadrupole time-of-flight mass spectrometry (LC-ESI-QTOF/MS) analysis and the quantification of the phenolic compounds was performed by HPLC analysis. The obtained data were compared with those obtained using water as the solvent in the same extraction conditions. The extraction process is nontoxic, simple and selective and meets most of the criteria to be considered as a sustainable process, with the solvents arising directly from nature.

Download Full-text

Batch Stirred-Tank Green Extraction of Salvia fruticosa Mill. Polyphenols Using Newly Designed Citrate-Based Deep Eutectic Solvents and Ultrasonication Pretreatment

Applied Sciences ◽

10.3390/app10144774 ◽

2020 ◽

Vol 10 (14) ◽

pp. 4774

Author(s):

Spyros Grigorakis ◽

Abedalghani Halahlah ◽

Dimitris P. Makris

Keyword(s):

Hydrogen Bond ◽

Lactic Acid ◽

Deep Eutectic Solvents ◽

Extraction Process ◽

Dry Mass ◽

Stirred Tank ◽

Molar Ratio ◽

Salvia Fruticosa ◽

The One ◽

Optimal Settings

A series of citrate salts were tested as hydrogen bond acceptors to synthesize deep eutectic solvents (DES) based on lactic acid and glycerol, used as hydrogen bond donors. The DES produced were then screened to identify the highest performing system for the effective extraction of polyphenolic phytochemicals from the medicinal plant Salvia fruticosa Mill. (Greek sage). The most efficacious DES was the one composed of lactic acid and sodium citrate dibasic, at a molar ratio of 15:1 (LA-SCDB15). Furthermore, for the first time there has been evidence concerning DES pH and extraction efficiency. Using this solvent, a batch, stirred-tank extraction process was developed, by employing ultrasonication pretreatment and response surface methodology. The optimal settings determined were stirring speed 900 rpm, proportion of DES/water 77% (w/v), and ultrasonication pretreatment time 15 min. By adjusting these optimal settings, the predicted maximum total polyphenol yield was calculated to be 79.93 ± 1.92 mg gallic acid equivalents g−1 dry mass. The examination of temperature effects demonstrated that the batch, stirred-tank extraction stage was very energy-efficient, with a barrier of 7.64 kJ mol−1. Comparison of the extraction of Salvia fruticosa polyphenols with other green processes previously developed, illustrated the high extraction capacity of LA-SCDB15. The major polyphenols identified in the extracts produced under optimized settings were chlorogenic acid, luteolin 7-O-glucuronide and rosmarinic acid.

Download Full-text