基于低共熔溶剂法提取夏枯草中总黄酮:一种新型绿色合成溶剂的应用
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摘要
黄酮类化合物由于其较好的抗炎、抗氧化、抗肿瘤等作用,其研究一直备受关注。目前,黄酮类化合物的提取主要以有机溶剂提取为主,而使用绿色安全的溶剂作为溶媒的研究相当有限。因此,该研究通过绿色合成不同类型的低共熔溶剂(deep eutectic solvents,DESs),考察其对夏枯草中黄酮类化合物提取的影响并优化其工艺,同时,考察DESs溶剂回收利用效率和总黄酮的回收方法。该研究以总黄酮提取率作为评价指标,以中心组合设计(central composite design,CCD)响应面法来优化DESs提取条件。结果表明,总黄酮的最佳提取最优条件为水与DESs(氯化胆碱-甘油1∶4)的体积比为27%,液固比为15m L·g~(-1),提取温度83℃,提取时间42 min。在此条件下,提取率的平均值(Y=75.05)与预测值相(Y=77.86)符合。而且,DESs法所得结果较先前报道的传统提取方法具有更高效、经济和环保等优势,此外,运用AB-8大孔树脂可对夏枯草总黄酮达到97.88%吸附率;采用5倍树脂量的100%乙醇可达到88.12%解吸附剂,收集上述处理后的DESs溶液按照同样方法提取样品,可达到95.23%重复提取率,说明大孔树脂的方法可进行高效简单的回收以及重利用,该项研究表明,DESs可作为一种可持续和高效的天然产物提取介质用于夏枯草等中药中黄酮类组分的提取。
Flavonoids have attracted much attention due to their good anti-inflammatory,anti-oxidation and anti-tumor effects. At present,the extraction of flavonoids is mainly based on organic solvent,while the researches on the use of green and safe solvents are quite limited. Therefore,in the present study,different types of deep eutectic solvents( DESs) were applied to investigate their effect on extraction of flavonoids and optimize the process,also investigate the recovery efficiency of DESs and evaluate the recovery method for total flavonoids. The extraction yield of the total flavonoids acted as the comprehensive evaluation indexes,and a central composite design( CCD) of response surface methodology( RSM) was employed to further optimize the alcohol-based DES extraction conditions.The results showed that the optimized extraction conditions were as follows: water-DES ratio of 27%,solid-liquid ratio of 15 m L·g~(-1),extraction temperature of 83 ℃ and extraction time of 42 min in Ch Cl-glycerol at 1∶ 4 ratio. Under these conditions,the mean experimental value of the extraction yield( 75. 05 mg·g~(-1)) corresponded well with the predicted value( 77. 86 mg·g~(-1)). Moreover,these experimental results showed more advantages such as in higher efficiency,economy and environmental protection as compared with previously reported conventional extraction methods. In addition,the recovery yield of the total flavonoids from the DESs extraction solution achieved 97. 88% by using AB-8 macroporous resin,and 88. 12% desorption ratio can be achieved by 100% ethanol with 5 times resin content. After the above treated DESs were collected,the extraction yield with the same method reached 95. 23%,indicating that the method of macroporous resin can be used for efficient and simple recovery and reuse. This study suggests that DESs can be used as a kind of sustainable and efficient natural extraction solvents for extraction of flavonoids from Prunella vulgaris.
Flavonoids have attracted much attention due to their good anti-inflammatory,anti-oxidation and anti-tumor effects. At present,the extraction of flavonoids is mainly based on organic solvent,while the researches on the use of green and safe solvents are quite limited. Therefore,in the present study,different types of deep eutectic solvents( DESs) were applied to investigate their effect on extraction of flavonoids and optimize the process,also investigate the recovery efficiency of DESs and evaluate the recovery method for total flavonoids. The extraction yield of the total flavonoids acted as the comprehensive evaluation indexes,and a central composite design( CCD) of response surface methodology( RSM) was employed to further optimize the alcohol-based DES extraction conditions.The results showed that the optimized extraction conditions were as follows: water-DES ratio of 27%,solid-liquid ratio of 15 m L·g~(-1),extraction temperature of 83 ℃ and extraction time of 42 min in Ch Cl-glycerol at 1∶ 4 ratio. Under these conditions,the mean experimental value of the extraction yield( 75. 05 mg·g~(-1)) corresponded well with the predicted value( 77. 86 mg·g~(-1)). Moreover,these experimental results showed more advantages such as in higher efficiency,economy and environmental protection as compared with previously reported conventional extraction methods. In addition,the recovery yield of the total flavonoids from the DESs extraction solution achieved 97. 88% by using AB-8 macroporous resin,and 88. 12% desorption ratio can be achieved by 100% ethanol with 5 times resin content. After the above treated DESs were collected,the extraction yield with the same method reached 95. 23%,indicating that the method of macroporous resin can be used for efficient and simple recovery and reuse. This study suggests that DESs can be used as a kind of sustainable and efficient natural extraction solvents for extraction of flavonoids from Prunella vulgaris.
引文
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[18]Feng S,Luo Z,Zhang Y,et al.Phytochemical contents and antioxidant capacities of different parts of two sugarcane(Saccharum officinarum L.)cultivars[J].Food Chem,2014,151(5):452.
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[23]ahin S,Demir C,Malyer H.Determination of phenolic compounds in Prunella L.by liquid chromatography-diode array detection[J].J Pharm Biomed Anal,2011,55(5):1227.
[24]Wong F C,Chai T T,Hoo Y W.Antioxidation and cytotoxic activities of selected medicinal herbs used in Malaysia[J].J Med Plants Res,2012,6(16):3169.
[25]Rado2evic'K,Bubalo M C,Srcˇek V G,et al.Evaluation of toxicity and biodegradability of choline chloride based deep eutectic solvents[J].Ecotoxicol Environ Saf,2015,112:46.
[26]Nam M W,Zhao J,Lee M S,et al.Enhanced extraction of bioactive natural products using tailor-made deep eutectic solvents:application to flavonoid extraction from Flos Sophorae[J].Green Chemistry,2015,17(3):1718.
[27]Jeong K M,Lee M S,Nam M W,et al.Tailoring and recycling of deep eutectic solvents as sustainable and efficient extraction media[J].J Chromatogr A,2015,1424:10.
[28]Dai Y,Witkamp G J,Verpoorte R,et al.Natural deep eutectic solvents as a new extraction media for phenolic metabolites in Carthamus tinctorius L.[J].Anal Chem,2013,85(13):6272.
[29]Peng X,Duan M H,Yao X H,et al.Green extraction of five target phenolic acids from Lonicerae Japonicae Flos with deep eutectic solvent[J].Sep Purif Technol,2016,157:249.
[2]Cao Y,Zhang R,Cheng T,et al.Imidazolium-based ionic liquids for cellulose pretreatment:recent progresses and future perspectives[J].Appl Microbiol Biotechnol,2017,101(2):521.
[3]Earle M J,Esperan9a J M S S,Gilea M A,et al.The distillation and volatility of ionic liquids[J].Nature,2006,439(7078):831.
[4]Petkovic M,Seddon K R,Rebelo L P N,et al.Ionic liquids:a pathway to environmental acceptability[J].Chem Soc Rev,2011,40(3):1383.
[5]Abbott A P,Boothby D,Capper G,et al.Deep eutectic solvents formed between choline chloride and carboxylic acids:versatile alternatives to ionic liquids[J].J Am Chem Soc,2004,126(29):9142.
[6]Kalmode H P,Vadagaonkar K S,Murugan K,et al.Deep eutectic solvent:a simple,environmentally benign reaction media for regioselective synthesis of 2,3,4-trisubstituted 1 H-pyrroles[J].RSC Advances,2015,5(44):35166.
[7]Abbott A P,Capper G,Davies D L,et al.Novel solvent properties of choline chloride/urea mixtures[J].Chem Comm,2003,9(1):70.
[8]Zheng Y,Ye L,Yan L,et al.The electrochemical behavior and determination of quercetin in choline chloride/urea deep eutectic solvent electrolyte based on abrasively immobilized multi-wall carbon nanotubes modified electrode[J].Int J Electrochem Sci,2014,9(11):238.
[9]Wagle D V,Zhao H,Baker G A.Deep eutectic solvents:sustainable media for nanoscale and functional materials[J].Acc Chem Res,2014,47(8):2299.
[10]Hu H C,Liu Y H,Li B L,et al.Deep eutectic solvent based on choline chloride and malonic acid as an efficient and reusable catalytic system for one-pot synthesis of functionalized pyrroles[J].RSC Advances,2015,5(10):7720.
[11]Azizi N,Mariami M,Edrisi M.Greener construction of 4Hchromenes based dyes in deep eutectic solvent[J].Dyes Pigm,2014,100(1):215.
[12]Peng X,Duan M H,Yao X H,et al.Green extraction of five target phenolic acids from Lonicerae Japonicae Flos with deep eutectic solvent[J].Sep Purif Technol,2016,157(1):249.
[13]Tan T,Zhang M,Wan Y,et al.Utilization of deep eutectic solvents as novel mobile phase additives for improving the separation of bioactive quaternary alkaloids[J].Talanta,2016,149(3):85.
[14]Zhang L,Wang M.Optimization of deep eutectic solvent-based ultrasound-assisted extraction of polysaccharides from Dioscorea opposita Thunb[J].Int J Biol Macromol,2017,95(2):675.
[15]Bajkacz S,Adamek J.Evaluation of new natural deep eutectic solvents for the extraction of isoflavones from soy products[J].Talanta,2017,168(6):329.
[16]Abbott A P,Boothby D,Capper G,et al.Deep eutectic solvents formed between choline chloride and carboxylic acids:versatile alternatives to ionic liquids[J].J Am Chem Soc,2004,126(29):9142.
[17]Xia B,Yan D,Bai Y,et al.Determination of phenolic acids in Prunella vulgaris L.:a safe and green extraction method using alcohol-based deep eutectic solvents[J].Anal Methods,2015,7(21):9354.
[18]Feng S,Luo Z,Zhang Y,et al.Phytochemical contents and antioxidant capacities of different parts of two sugarcane(Saccharum officinarum L.)cultivars[J].Food Chem,2014,151(5):452.
[19]Lo'pez-Porfiri P,Brennecke J F,Gonzalez-Miquel M.Excess molar enthalpies of deep eutectic solvents(DESs)composed of quaternary ammonium salts and glycerol or ethylene glycol[J].J Chem Eng Data,2016,61(12):4245.
[20]Dai Y,Witkamp G J,Verpoorte R,et al.Tailoring properties of natural deep eutectic solvents with water to facilitate their applications[J].Food Chem,2015,187(11):14.
[21]Leron R B,Li M H.Solubility of carbon dioxide in a choline chloride-ethylene glycol based deep eutectic solvent[J].Thermochim Acta,2013,551(1):14.
[22]Zhang G,He L,Hu M.Optimized ultrasonic-assisted extraction of flavonoids from Prunella vulgaris L.and evaluation of antioxidant activities in vitro[J].Innovative Food Sci Emerging Technol,2011,12(1):18.
[23]ahin S,Demir C,Malyer H.Determination of phenolic compounds in Prunella L.by liquid chromatography-diode array detection[J].J Pharm Biomed Anal,2011,55(5):1227.
[24]Wong F C,Chai T T,Hoo Y W.Antioxidation and cytotoxic activities of selected medicinal herbs used in Malaysia[J].J Med Plants Res,2012,6(16):3169.
[25]Rado2evic'K,Bubalo M C,Srcˇek V G,et al.Evaluation of toxicity and biodegradability of choline chloride based deep eutectic solvents[J].Ecotoxicol Environ Saf,2015,112:46.
[26]Nam M W,Zhao J,Lee M S,et al.Enhanced extraction of bioactive natural products using tailor-made deep eutectic solvents:application to flavonoid extraction from Flos Sophorae[J].Green Chemistry,2015,17(3):1718.
[27]Jeong K M,Lee M S,Nam M W,et al.Tailoring and recycling of deep eutectic solvents as sustainable and efficient extraction media[J].J Chromatogr A,2015,1424:10.
[28]Dai Y,Witkamp G J,Verpoorte R,et al.Natural deep eutectic solvents as a new extraction media for phenolic metabolites in Carthamus tinctorius L.[J].Anal Chem,2013,85(13):6272.
[29]Peng X,Duan M H,Yao X H,et al.Green extraction of five target phenolic acids from Lonicerae Japonicae Flos with deep eutectic solvent[J].Sep Purif Technol,2016,157:249.