Efficient and selective extraction of sinomenine by deep eutectic solvents

Sinomenine is the main bio-active ingredient of Sinomenii Caulis and usually produced by solventextraction techniques. However, the extraction of sinomenine suffers from the lack of highly efficient and environmentally-benign solvents. In this work, deep eutectic solvents(DESs) based on fragrances were synthesized, hydrogen-bond donors(HBDs) and hydrogen-bond acceptors(HBAs) components of DESs were identified and their extraction ability for sinomenine was evaluated and the extraction conditions were optimized by single-factor and orthogonal design experiments. It was found that the hydrogen-bonding interaction between sinomenine and DESs was the main extraction driving force and there was no explicit relationship between the extraction ability and the hydrophobicity of the DESs. The DESs could be recycled and sinomenine could be recovered quantitatively via backextraction. High-purity sinomenine((95.0 ± 2.3)%) could be produced. These findings suggest that DESs are highly-effective solvents for the isolation of sinomenine and exhibit great potential for the extraction of other bio-active compounds.

Dissolution of highly molecular weight cellulose isolated from wheat straw in deep eutectic solvent of Choline/L-Lysine hydrochloride

Green solvents for cellulose dissolution is a key topic for green chemistry,especially natural cellulose with high molecular weight,and there are scarce solvents reported.Deep eutectic solvent(DES)is a typical kind of green solvent that has been attracted much attention recently.Here,high molecular weight natural cellulose(DP>3000)was first isolated from wheat straw and then be directly dissolved in the choline/L-lysine(Ch/Lys)DES.The solution owns excellent stability,and the solubility reaches^5%.Rheological studies revealed that the natural cellulose can be well dispersed in the DES solution and showed gelation at high concentrations.The dissolved cellulose can be regenerated when the dilute acid aqueous solution was added into the solution.It provides an energy conversation and an environmentally friendly route to prepare a cellulose solution,which makes it possible to convert cellulose to valuable chemicals and materials in its homogeneous solution.

Okara Cellulose Nanofibrils Produced by Pretreatment with Sustainable Deep Eutectic Solvent Coupled with Various Mechanical Treatments

In this study,a green,environmentally friendly method for rapid cellulose nanofribril(CNF)preparation with a significant cost advantage was developed.Pretreatment with a deep eutectic solvent(DES)synthesized from oxalic acid dihydrate and choline chloride(ChCl-O)was combined with various mechanical treatment methods to produce okara CNFs from agricultural waste,with different diameter distributions.The results showed that high-speed stirring produced CNFs with an average diameter of 27 nm.This method was advantageous because it consumed about 94%less energy than traditional high-pressure homogenization method.The DES recovery rate was more than 90%,and DES served as a highly effective treatment,indicating that DES pretreatment is an economical,convenient,and effective strategy for okara CNF preparation.

Degradation of Alkaline Lignin in the Lactic Acid-Choline Chloride System under Mild Conditions

Lignin is a natural polymer,second only to cellulose in natural reserves.Degradation is one of the ways to achieve the high-value transformation of lignin.Deep eutectic solvent(DES)thermal degradation of lignin can be used as an excellent green degradation method.This paper introduces the degradation mechanism and effect of the lactic acid-choline chloride DES system in dissolving and degrading alkaline lignin,and the final solvent recovery.It can also be found from the scanning electron microscope(SEM)images that the surface of the degraded solid product is transformed from smooth to disordered.Fourier transform infrared(FTIR)spectroscopy and 1H-NMR spectroscopy were used to characterize the changes in lignin functional groups during DES treatment.The results showed that the content of phenolic hydroxyl groups increased after degradation,indicating that theβ-O-4 ether bond was broken.The molecular weight of the degraded lignin was observed by gel permeation chromatography(GPC),and the lignin residue with low molecular weight and narrow polydispersity index was obtained.The lowest average molecular weight(Mw)reached 2512 g/mol.The ratio of oxygen to carbon atoms in lignin increased substantially during degradation as measured by X-ray photoelectron spectroscopy(XPS),probably because DES treatment was accompanied by many oxidation reactions,which led to significant structural changes in lignin and a large number of ether bond breakage reactions during the reaction.The main final degradation products are aromatic monomers,vanillin,butyrovanillone,etc.

Construction of ternary PEG200-based DESs lubrication systems via tailoring tribo-chemistry

Designing novel lubricants with easily customized structures,devisable compositions,and simple and economic synthesis over traditional lubricants is critical to fulfilling complex applications,prolonging machine lifetime,and saving energy.Deep eutectic solvents(DESs),which show tunable composition,adjustable structure,easy fabrication,and environmental friendliness,are promising candidates for variable and complicated lubricants applications.To promote the use of DESs as lubricants,a series of PEG200-based DESs with active heteroatoms were fabricated to tailor the tribological performance via tribo-chemistry.Thereinto,PEG200/boric acid(BA)DES shows optimal lubrication performance by forming tribo-chemical reaction film composited of B2O3,iron oxides,and FeOOH,and PEG200/thiourea(TU)DES displays abrasive wear-reducing property by producing FeS tribo-chemical film.Given the excellent abrasive wear-resistance of PEG200/TU DES and friction reduction of PEG200/BA DES,ternary PEG200/BA/TU DESs,composited of PEG200/TU DES and PEG200/BA DES,are first exploited.The ternary DESs possess superior wettability and thermal stability,which render them potential lubricants.Tribological tests of the ternary DESs demonstrate that synergistic lubrication is achieved by forming a transfer film consisting of FexBy,BN,B2O3,and FeS.Wherein FexBy,BN,and B2O3 increase load bearing of the film,and FeS mitigates severe abrasive wear.The proposed design philosophy of novel DESs as lubricants opens up a unique realm that is unattainable by traditional DESs lubrication mechanisms and provides a platform to design next-generation DESs lubrication systems.

Oxidation of furfural to maleic acid and fumaric acid in deep eutectic solvent(DES)under vanadium pentoxide catalysis

Furfural is an alternative feedstock and has been used for the production of maleic acid(MA)and fumaric acid(FA)by an oxidation process.Deep eutectic solvents(DESs)were used as the green solvents while sodium chlorate was used as an oxidant and vanadium pentoxide was used as the catalyst at 70-90°C under atmospheric pressure.It was found that several acidic DESs are valid,such as acetic acid/choline chloride(AA/ChCl)and propionic acid/choline chloride(PA/ChCl),and AA/ChCl DES was selected as the solvent for the conversion.The optimal DES is AA/ChCl,and the effect of the amount of oxidant,time,and temperature on the yield of the MA and FA has been systematically studied,and the conversion of furfural can reach 100%while the yield of the MA and FA reached 66.5%under reaction temperature of 80℃ for 12 h,which provides a new green route to synthesis valuable monomers from furfural.

低共熔溶剂催化油酸制备生物柴油的工艺优化及其动力学分析

本文以油酸和甲醇为原料,对甲苯磺酸/甲基三苯基溴化鏻形成的低共熔溶剂为催化剂,考察醇酸摩尔比、催化剂用量、反应时间及反应温度等因素对油酸甲酯收率的影响,并通过响应面分析法优化生物柴油的制备工艺。结果表明,对苯甲磺酸与甲基三苯基溴化鏻摩尔比为2:1时所形成的低共熔溶剂(DES-2)具有最好的催化活性;以DES-2为催化剂时,生物柴油的最佳合成条件为:催化剂用量为油酸质量的1.08%,醇酸摩尔比5.8:1,反应时间2.8 h,温度373 K,此条件下,生物柴油的收率达97.3%,该结果与模型预测值基本相符。优化条件下,生物柴油合成反应的活化能为34.98 kJ/mol,动力学方程为:r=-(dC_A)/(dt)=1.44×10~3exp(34.98/t)C_A^(1.23)。

油酸甲酯的清洁合成

分别研究了对甲苯磺酸和氯化胆碱/对甲苯磺酸形成的低共熔溶剂(DES-1)对油酸与甲醇酯化反应的催化效果。结果表明,氯化胆碱与对甲苯磺酸物质的量比为1∶3时所形成的DES对油酸甲酯化的催化活性较高。在醇油物质的量比为3∶1,反应温度为75℃,催化剂用量为2%和反应时间为4 h的条件下,DES和对甲苯磺酸的催化活性接近。此外,考察了氯化胆碱与尿素物质的量比为1∶2形成的低共熔溶剂(DES-2)对酯化产品混合物中残存酸性催化剂的去除效果。同样的条件下,DES-2将DES-1催化的酯化产品混合物的酸值降得更低,对甲苯磺酸催化的酯化产品混合物的酸值下降较少,说明DES-1比对甲苯磺酸更容易被洗掉。洗涤后的低共熔溶剂可循环用于下一次洗涤。DES-1催化剂的制备工艺简单,酯化转化率较高,该催化剂重复使用多次仍具有较高的酯化活性。