Analysis of anticancer compound,indole-3-carbinol,in broccoli using a new ultrasound-assisted dispersive-filter extraction method based on poly(deep eutectic solvent)-graphene oxide nanocomposite

Indole-3-carbinol(I3C),an important anticancer compound found in broccoli,has attracted considerable attention.The rapid extraction and accurate analysis of I3C in the pharmaceutical industry in broccoli is challenging as I3C is unstable at low pH and high temperature.In this study,a rapid,accurate,and lowcost ultrasound-assisted dispersive-filter extraction(UADFE)technique based on poly(deep eutectic solvent)-graphene oxide(PDES-GO)adsorbent was developed for the isolation and analysis of I3C in broccoli for the first time.PDES-GO with multiple adsorption interactions and a fast mass transfer rate was synthesized to accelerate adsorption and desorption.UADFE was developed by combining dispersive solid-phase extraction(DSPE)and filter solid-phase extraction(FSPE)to realize rapid extraction and separation.Based on the above two strategies,the proposed PDES-GO-UADFE method coupled with high-performance liquid chromatography(HPLC)allowed the rapid(15-16 min),accurate(84.3%-96.4%),and low-cost(adsorbent:3.00 mg)analysis of I3C in broccoli and was superior to solid-phase extraction,DSPE,and FSPE methods.The proposed method showed remarkable linearity(r=0.9998;range:0.0840-48.0 mg/g),low limit of quantification(0.0840 mg/g),and high precision(relative standard deviation<5.6%).Therefore,the PDES-GO-UADFE-HPLC method shows significant potential in the field of pharmaceutical analysis for the separation and analysis of anti-cancer compounds in complex plant samples.

Experimental investigation on coal pore-fracture variation and fractal characteristics synergistically affected by solvents for improving clean gas extraction

Chemical solvents instead of pure water being as hydraulic fracturing fluid could effectively increase permeability and improve clean methane extraction efficiency.However,pore-fracture variation features of lean coal synergistically affected by solvents have not been fully understood.Ultrasonic testing,nuclear magnetic resonance analysis,liquid phase mass spectrometry was adopted to comprehensively analyze pore-fracture change characteristics of lean coal treated by combined solvent(NMP and CS_(2)).Meanwhile,quantitative characterization of above changing properties was conducted using geometric fractal theory.Relationship model between permeability,fractal dimension and porosity were established.Results indicate that the end face fractures of coal are well developed after CS2and combined solvent treatments,of which,end face box-counting fractal dimensions range from 1.1227 to 1.4767.Maximum decreases in ultrasonic longitudinal wave velocity of coal affected by NMP,CS_(2)and combined solvent are 2.700%,20.521%,22.454%,respectively.Solvent treatments could lead to increasing amount of both mesopores and macropores.Decrease ratio of fractal dimension Dsis 0.259%–2.159%,while permeability increases ratio of NMR ranges from 0.1904 to 6.4486.Meanwhile,combined solvent could dissolve coal polar and non-polar small molecules and expand flow space.Results could provide reference for solvent selection and parameter optimization of permeability-enhancement technology.

Insight into the experiment and extraction mechanism for separating carbazole from anthracene oil with quaternary ammonium-based deep eutectic solvents

Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in chemical engineering.Deep eutectic solvents (DESs) as a sustainable green separation solvent have been proposed for the separation of carbazole from model anthracene oil.In this research,three quaternary ammonium-based DESs were prepared using ethylene glycol (EG) as hydrogen bond donor and tetrabutylammonium chloride (TBAC),tetrabutylammonium bromide or choline chloride as hydrogen bond acceptors.To explore their extraction performance of carbazole,the conductor-like screening model for real solvents (COSMO-RS) model was used to predict the activity coefficient at infinite dilution (γ^(∞)) of carbazole in DESs,and the result indicated TBAC:EG (1:2) had the stronger extraction ability for carbazole due to the higher capacity at infinite dilution (C^(∞)) value.Then,the separation performance of these three DESs was evaluated by experiments,and the experimental results were in good agreement with the COSMO-RS prediction results.The TBAC:EG (1:2) was determined as the most promising solvent.Additionally,the extraction conditions of TBAC:EG (1:2) were optimized,and the extraction efficiency,distribution coefficient and selectivity of carbazole could reach up to 85.74%,30.18 and 66.10%,respectively.Moreover,the TBAC:EG (1:2) could be recycled by using environmentally friendly water as antisolvent.In addition,the separation performance of TBAC:EG (1:2) was also evaluated by real crude anthracene,the carbazole was obtained with purity and yield of 85.32%,60.27%,respectively.Lastly,the extraction mechanism was elucidated byσ-profiles and interaction energy analysis.Theoretical calculation results showed that the main driving force for the extraction process was the hydrogen bonding ((N–H...Cl) and van der Waals interactions (C–H...O and C–H...π),which corresponding to the blue and green isosurfaces in IGMH analysis.This work presented a novel method for separating carbazole from crude anthracene oil,and will provide an important reference for the separation of other high value-added products from coal tar.

Study on the green extraction of corncob xylan by deep eutectic solvent

Corn as one of the world's major food crops,its by-product corn cob is also rich in resources.However,the unreasonable utilization of corn cob often causes the environmental pollution,waste of resources and other problems.As one of the most abundant polymers in nature,xylan is widely used in food,medicine,materials and other fields.Corn cob is rich in xylan,which is an ideal raw material for extracting xylan.However,the intractable lignin is covalently linked to xylan,which increases the difficulty of xylan extraction.It has been reported that the deep eutectic solvent(DES)could preferentially dissolve lignin in biomass,thereby dissolving the xylan.Then,the xylan in the extract was separated by ethanol precipitation method.The xylan precipitate was obtained after centrifugation,while the supernatant was retained.The components of the supernatant after ethanol precipitation were separated by the rotary evaporator.The ethanol,water and DES were collected for the subsequent extraction of corn cob xylan.In this study,a novel way was provided for the green production of corn cob xylan.The DES was used to extract xylan from corn cob which was used as the raw material.The effects of solid-liquid ratio,reaction time,reaction temperature and water content of DES on the extraction rate of corn cob xylan were investigated by the single factor test.Furthermore,the orthogonal test was designed to optimize the xylan extraction process.The structure of corn cob xylan was analyzed and verified.The results showed that the optimum extraction conditions of corn cob xylan were as follows:the ratio of corn cob to DES was 1:15(g:mL),the extraction time was 3 h,the extraction temperature was 60℃,and the water content of DES was 70%.Under these conditions,the extraction rate of xylan was 16.46%.The extracted corn cob xylan was distinctive triple helix of polysaccharide,which was similar to the structure of commercially available xylan.Xylan was effectively and workably extracted from corn cob by the DES method.This study provided a new approach for high value conversion of corn cob and the clean production of xylan.

Research Progress of Deep Eutectic Solvents in Extraction of Plant Flavonoids

As a new type of green solvents,deep eutectic solvents(DESs)have the advantages of strong extraction ability,designability,simple preparation,low price,recoverability and biodegradation,and show great application potential in the field of plant flavonoid extraction.In this paper,the definition,classification and preparation methods of DESs were introduced.The effects of DES composition,molar ratio of DES components,water content of DES systems,liquid-material ratio,extraction temperature,extraction time and extraction auxiliary techniques on the extraction yield of plant flavonoids were expounded.The recycling methods of DESs were summarized.Existing problems of DESs in the field of plant flavonoids extraction were pointed out,and further research direction and trend were analyzed and prospected.

Optimization of Ultrasound-assisted Extraction Conditions for Polysaccharides from Pinus tabulaeformis Seed Shells

[Objective] This study aimed to investigate the optimal technological condi- tions for ultrasouqd-assisted extraction of polysaccharides from Pinus tabulaeformis seed shells. [Melhod] Polysaccharides were extracted from P. tabulaeformis seed shells by ultrasound-assisted hot water extraction method and detected by phenol- concentrated sulfuric acid method. The effect of extraction temperature, extraction duration, solid-liquid ratio and extraction frequency on the extraction of polysaccha- rides was investigated using single-factor gradient experiment and the extraction conditions for polysaccharides from P. tabulaeformis seed shells were optimized us- ing L9（34） orthogonal design. [Result] The content of polysaccharides extracted twice at 60 ℃ for 25 min with solid-liquid ratio of 1：3.5 reached the maximum. The re- covery rate （n=-5） ranged from 97.71% to 100.67% and RSD was 1.56%, suggesting high stability. [Conclusion] A simple and efficient method for ultrasound-assisted ex- traction of polysaccharides from P. tabulaeformis seed shells was established in this study, which laid solid foundation for the development and utilization of abandoned pine nut shell resources.

Optimization of ultrasound-assisted extraction of camptothecin from Camptotheca acuminata seeds

Naturally occurring camptothecin（CPT） is an important source of chemotherapeutic agents.The extraction from Camptotheca acuminata is still the main approach to obtain CPT compared with total synthesis.In the present study,ultrasound-assisted extractions（UAE） of CPT from C.acuminata seeds with alkaline solutions were investigated and CPT yield were determined by High Performance Liquid Chromatography.The conditions of alkaline species and concentrations,extraction time,extraction temperature and ultrasonic power were optimized.Results show that both Na3PO4 and Na2CO3 solutions gain good extraction yields,whereas Na3PO4 solution has stronger basicity and need higher concentration than Na2CO3 solution does,thus aqueous Na2CO3 is more beneficial for the extraction.The optimal condition was ultrasonically extracted with 0.5% aqueous Na2CO3 at 50°C and ultrasonic power of 400 W for 60 min.Comparing with UAE with ethanol,the extraction with 0.5% Na2CO3 solution achieves higher yield.Moreover,aqueous Na2CO3 as a solvent has various advantages including non-toxicity,inflammable,non-corrosive and low cost,which ensure this UAE method is a superior method with high utilizing prospect.

Ultrasound-assisted Enzymatic Extraction of SDF on Passion Fruit Seeds

Ultrasound-assisted enzymatic extraction of soluble dietary fiber(SDF) from passion fruit seeds was carried out in order to shorten the extraction time and increase the yield of SDF. The effects of cellulase concentration, ultrasonic power, extraction temperature, solid-liquid ratio and water bath time on the SDF yield of passion fruit were studied by single factor analysis. And the orthogonal experiment was designed to optimize the extraction conditions. The results showed that the optimum conditions for the extraction of SDF from passion fruit by ultrasoundassisted enzymatic method were cellulase concentration 1.5%, ultrasonic power 120 W, solid-liquid ratio(g/mL) 1 ∶ 15, extraction temperature 55 ℃, and water bath time 160 min. The SDF extraction rate was determined to be 5.12%.

Pectinmethylesterase extraction from orange solid wastes: Optimization and comparison between conventional and ultrasound-assisted treatments

During orange juice production, a half of fresh oranges weight is considered as production waste (peels, pulp, seeds, orange leaves and damaged orange fruits). An alternative for the management of these wastes is their treatment by addition of lime and a latter pressing, obtaining a press cake and a press liquor rich in sugars (10&#176;Brix) and citric acid, protein, pectin and ethanol. For non-thermal concentration of press liquor to obtain citruss molasses (65&#176;-70&#176;Brix), the removal of pectin is necessary. Traditionally, depectinization of juices has been done by using pectinmethylesterase (PME) enzymes from external sources. In this work it performed the extraction of PME enzymes from orange peels to obtain the optimum extraction conditions. Two different methods of solventextraction were compared (conventional andultrasound-assisted methods). For the conventional extraction experiments, a central composite design with three variables ([NaCl], pH and time) and five replicates of the center point was used. For ultrasound-assisted extraction, experiments were done at pH = 5.5 and [NaCl] = 1.25M), varying extraction time (1-30 min). Response variables were PME activity, protein content and a ratio between them, named PME effectiveness (ηPME). At the same experimental conditions (pH =5.5, [NaCl] = 1.25 M, t = 15 min) it was found that conventional extractions led to slightly better results in terms of ηPME than ultrasound-assisted extraction method.

Effects of Ethanol Condensation Reflux Extraction and Ultrasound-assisted Extraction on the Content of Total Flavonoids of Pueraria edulis

With Pueraria edulis from different habitats in Yunnan Province,Guangdong Province and Guangxi Zhuang autonomous region as materials,the medicinal materials of P.edulis were extracted by ethanol condensation reflux extraction and ultrasound-assisted extraction,and the effects of different extraction methods the contents of total flavonoids in P.edulis from different areas were compared.The results showed that the best extraction time for P.edulis in Yunnan Province was 20 min,and that for Guangdong and Guangxi Zhuang Autonomous Region was 30 min.The yield of total flavonoids from P.edulis extracted by the condensation reflux extraction method was relatively better.The content of total flavonoids in P.edulis in Yunnan was the highest with an average content of 0.2557%,while the average content of total flavonoids in P.edulis in Guangdong was the lowest with an average content of 0.2108%.

Effect of Ultrasound-Assisted Extraction of Phenolic Compounds on the Characteristics of Walnut Shells

Walnuts are one of nature’s more waste-heavy products. 67% of the nut is shell and husk, low value by-products that are rich in phenolic compounds. The phenolic compounds extracted from walnut shells are potentially good natural sources of antioxidants for the food and pharmaceutical industries. In this study, phenolic compounds were extracted using an ultrasonic bath, an ultrasonic probe and a standard shaking method. The extraction yield achieved with an ultrasonic probe was 51.2 mg GAE/g DW, two times higher than both the shaking method and the ultrasonic bath method which were 20.6 mg GAE/g DW and 25.8 mg GAE/g DW, respectively. Phenolic extraction was further improved by a size reduction of the walnut shells. The best extraction yield of 52.8 mg GAE/g DW was attained when the particle size was between 45 - 100 mesh. The ultrasonic probe treatment is the best method for extraction of phenolic compounds from walnut shells. Scanning electron microscopy (SEM) imaging indicated that the ultrasonic probe treatment could better rupture the hard structure of the cells, increasing the penetration of solvents and thus the extraction yield.

Study on Extraction of Tea Saponin from Camellia oleifera Cake Using Water as Extraction Solvent

This paper studied the effects of liquid-solid ratio, temperature, time and pH value on the extraction rate of tea saponin from the cake of Camellia oleifera seeds by using single factor experiment with the cake of Camellia oleifera seeds as the raw materials, and water as the extraction solvent, and orthogonal test was used to determine the optimal extraction process conditions. The results showed that the extraction ratio of tea saponin could reach up to 95.50% when the liquidsolid ratio was 11：1, extracting temperature of 80 ℃, extraction time of 6 h, and pH value of 9.

Removal of chromium(Ⅲ) from aqueous waste solution by predispersed solvent extraction

The extraction experiments of chromium（W） from aqueous waste solution by predispersed solvent extraction （PDSE） process with extractant （HEHPEHE） and its mixture, including acidic extractant （D2EHPA）, alkaline extractant （TOA） and neutral extractant （TBP） were carried out respectively. It is found that the extractant HEHPEHE exhibited high extraction selectivity to chromium（III） from aqueous waste solution. The colloidal liquid aphrons （CLAs） were successfully generated using kerosene as a solvent, HEHPEHE as an extractant, sodium dodecyl benzene sulphate （SDBS） as a surfactant in aqueous phase and polyoxyethylene sorbitol anhydride monolaurate （Tween-20） in oil phase. To study the extraction efficiency and advantages of the PDSE process in the removal of chromium（III）, the effects of major factors, such as initial chromium（III） concentration, volume of colloidal gas aphrons （CGAs）, HEHPEHE volume fraction, phase ratio （solvent phase to water phase）, mass fraction of dodecyl trimethylammonium bromide （HTAB）, mass fraction of SDBS, mass fraction of Tween-20 and initial pH of aqueous waste solution were also investigated and the appropriate process conditions were obtained. Under the appropriate conditions, the extraction efficiency of chromium（III） above 99.9 % can be achieved and the treated aqueous waste solution can be discharged directly without polluting the environment.

Extracting vanadium from stone-coal by oxygen pressure acid leaching and solvent extraction

Vanadium extraction from stone-coal was investigated by oxygen pressure acid leaching and solvent extraction.The mineralogy of the stone-coal from Tongren City of Guizhou Province,China,was investigated by various determination methods. The effects of leaching time,leaching temperature,leaching agent concentration,leaching L/S ratio,granularity of material,additive consumption were investigated based on the mineralogy.The results show that under the conditions of leaching time of 3-4 h, temperature of 150℃,sulfuric acid consumption of 25%?30%,ratio of liquid to solid of 1.2:1,the granularity less than 0.074 mm, additive consumption of 3%-5%,and oxygen pressure of 1.2 MPa,and the vanadium leaching rate can be more than 92%by the method of two-step pressurized acid leaching.The powdery V2O5 product with 99.52%in V2O5 content is obtained by the flowsheet of acid recovery,removing iron by reduction process,solvent extraction,precipitating vanadium with ammonium water,and pyrolysis from the stone-coal oxygen pressure acid-leaching solution.The total recovery efficiency of vanadium is above 85%,which is more than 20%higher than that obtained in the conventional process.Furthermore,the new process does not cause air pollution since no HCl or Cl2 is released by calcination of the raw material.

Solvent extraction of vanadium from sulfuric acid solution

The behaviour of vanadium（V） extracted from sulfuric acid solution was investigated using Cyanex 923 as an extractant. The effects of the concentration of Cyanex 923 and the pH of the solution were studied. The extraction of vanadium（V） increases with the increase of Cyanex 923 concentration and shaking time. Cyanex 923 can extract vanadium（V） from sulfuric acid solution at low pH conditions, and the best pH conditions for extraction of vanadium（V） are at pH 1.0-2.0. The species extracted into the organic phase is VO2HSO4 with one molecule of Cyanex 923. Equilibrium studies were used to assess the extraction efficiency of vanadium（V） recovery from the sulfuric acid solution.

Selective separation of Cu(Ⅱ),Zn(Ⅱ),and Cd(Ⅱ)by solvent extraction

An experimental investigation was presented on the separation of Cu（Ⅱ）, Zn（Ⅱ）, and Cd（Ⅱ） from a rich sulfate leachate of zinc slag by solvent extraction. The results of orthogonal experiments indicate that LIX 984N is highly selective and very efficient in the extraction of Cu（Ⅱ）, and the analysis of variance indicates that the sequence of parameters according to their influence on the separation efficiency is phase ratio 〉 LIX 984N concentration 〉 pH value 〉 extraction time. The optimal condition for copper extraction is obtained as 25% of LIX 984N concentration, 7 rain of extraction time, 3：2 of phase ratio O/A, and pH = 1.7. The separation of Zn（Ⅱ） and Cd（Ⅱ） was performed after the copper extraction from the raffinate. Comparative analysis of the separation with di-2-ethylhexyl phosphoric acid （D2EHPA）, D2EHPA-tributyl- phosophate （TBP） synergistic extracting system, and 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester （HEHEHP） was made at pH = 2.0. It is demonstrated that the extraction efficiency with D2EHPA is improved after being saponified by sodium hydroxide, and D2EHPA-TBP synergistic extracting, as well as HEHEHP, has a superior selectivity to Zn（Ⅱ） over Cd（Ⅱ）.

Process development for the direct solvent extraction of nickel and cobalt from nitrate solution:aluminum,cobalt,and nickel separation using Cyanex 272

A direct solvent extraction（DSX） process for purifying nickel and cobalt from the nitric acid leach solution of nickel laterite ores was conceived and experimentally probed. The proposed process consists of two solvent extraction（SX） steps but with only one extractant - bis（2,4,4-trimethylpentyl）phosphinic acid（Cyanex？ 272） - used in both steps. The first extraction step involved the removal of aluminum and zinc, whereas the second extraction step involved the separation of cobalt along with manganese from nickel. The experimental results showed essentially quantitative removal of aluminum（〉97%） and zinc（〉99%） in a single extraction stage using 20vol% Cyanex 272 at pH 2.1. Some cobalt（32%） and manganese（55%） were co-extracted but were easily scrubbed out completely from the loaded organic phase using dilute sulfuric acid at pH ≤ 1.38. Cobalt and manganese in the first extraction raffinate were extracted completely in four extraction stages at staggered pH values of 4.0, 4.4, 4.5, and 4.0 in the first, second, third, and fourth stages, respectively, using also 20vol% Cyanex 272. A small amount of nickel（up to 6.6%） was co-extracted but was easily scrubbed out completely with dilute sulfuric acid at pH 2.0. A flow diagram showing the input and output conditions and the metals separated under the deduced optimum conditions is presented.

Recovery of Copper（II） and Nickel（II） from Plating Wastewater by Solvent Extraction

The solvent extraction technology, was applied to recover Cu^2＋ and Ni^2＋ from plating wastewater.Lix984N was chosen as the extractant due to-its gooff extraction performance. The influence parame-ters were examlned. The results show that the separation of Cu^2＋ and Ni＂ from sulphate medium can be realized by adjusting pH value with the help of Lix984N. For extracting Cu^2＋ and Ni^2＋, the optimal pH values are 4 and 10.5, and the maximal extraction percentages are 92.9% and 93.0%, respectively .With recovered Cu^2＋ and Ni^2＋ stripped in 170g.L^ -1 and 200 g.L^-1 H2SO4 medium, the stripping percentages of Cu^2＋ and Ni^2＋ are 92.9% and 93.0%, respectively. This method is simple and can be used to recover Cu^2＋ and Ni^2＋ from plating wastewater. And a flow sheet for separation of Cu^2＋ and Ni^2＋ is presented.

Separation of middle rare earths by solvent extraction using 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester as an extractant

The extraction of the trivalent middle rare earths from chloride media by kerosene solutions of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester as an extractant was studied. The separation factors between the elements using solution simulating wastes from NiMH spent batteries have been evaluated: the order of the extractive ability of extractant can be confirmed in Tb>Gd>Eu>Sm.

The use of environmentally sustainable bio-derived solvents in solvent extraction applications——A review

Replacement of volatile organic compounds （VOCs） by greener or more environmentally sustainable solvents is becoming increasingly important due to the increasing health and environmental concerns as well as economic pressures associated with VOCs. Solvents that are derived from biomass, namely bio-derived solvents, are a type of green solvent that have attracted intensive investigations in recent years because of their advantages over con- ventional VOCs, such as low toxicity, biodegradability and renewability. This review aims to summarize the use of bio-derived solvents in solvent extraction applications, with special emphasis given to utilization of biodiesels and terpenes. Compared with the conventional VOCs, the overall performance of these bio-derived solvents is comparable in terms of extraction yields and selectivity for natural product extraction and no difference was found for metal extraction. To date most researchers have focused on laboratory scale thermodynamics studies. Future work is required to develop and test new bio-derived solvents and understand the kinetic performance as well as solvent extraction nilnt nlant studies.