稀有糖L-半乳糖及其衍生物的合成研究
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摘要
目的制备L-半乳糖及其中间体D-半乳糖醛酸、L-半乳糖酸-1,4-内酯,并优化工艺。方法采用酶法水解果胶,制备D-半乳糖醛酸,并用正交试验设计法确立最佳酶水解工艺;D-半乳糖醛酸经还原、脱水转化为L-半乳糖酸-1,4-内酯,进一步还原合成L-半乳糖。结果酶水解最佳条件为50℃反应2 h,酶-果胶比为1.5∶10。合成产物结构经~1H-NMR、~(13)C-NMR表征。合成产率为31.4%。结论方法操作简便,步骤短,反应收率高,具有工业化生产前景。
OBJECTIVE L-galactose and its intermediate D-galacturonic acid and L-galactonic acid-1,4-lactones were prepared and optimized. METHODS D-galacturonic acid was prepared by enzymatic hydrolysis of pectin, and the best enzymatic hydrolysis technology was established by orthogonal experimental design. L-galactonic acid-1,4-lactones was synthesized from D-galacturonic acid via reduction and dehydration, L-galactose was synthesized from L-galactonic acid-1,4-lactones via reduction. RESULTS The optimum conditions for enzymatic hydrolysis were as follow: hydrolysis temperature was 50 ℃, The reaction time was 2 h, the enzyme-pectin ratio was 1.5∶10. The structure of products were characterized by ~1H-NMR and ~(13)C-NMR. The yield was 31.4%. CONCLUSION The method is simple and convenient, with short steps and high yield. It can be applied to industrial production.
OBJECTIVE L-galactose and its intermediate D-galacturonic acid and L-galactonic acid-1,4-lactones were prepared and optimized. METHODS D-galacturonic acid was prepared by enzymatic hydrolysis of pectin, and the best enzymatic hydrolysis technology was established by orthogonal experimental design. L-galactonic acid-1,4-lactones was synthesized from D-galacturonic acid via reduction and dehydration, L-galactose was synthesized from L-galactonic acid-1,4-lactones via reduction. RESULTS The optimum conditions for enzymatic hydrolysis were as follow: hydrolysis temperature was 50 ℃, The reaction time was 2 h, the enzyme-pectin ratio was 1.5∶10. The structure of products were characterized by ~1H-NMR and ~(13)C-NMR. The yield was 31.4%. CONCLUSION The method is simple and convenient, with short steps and high yield. It can be applied to industrial production.
引文
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[2]ZHOU C,YU X,ZHANG Y,et al.Ultrasonic degradation,purification and analysis of structure and antioxidant activity of polysaccharide from Porphyra yezoensis Udea[J].Carbohyd Polym,2012,87(3):2046-2051.
[3]BRETTING H,BUCK F,JACOBS G,et al.Tandem exploitation of Helix pomatia glycosyltransferases:facile syntheses of H-antigen-bearing oligosaccharides[J].Chemistry,2007,13(25):7144-7152.
[4]YAN J,SHI S S,WANG S C,et al.Sulfated galactan from grateloupia filicina:isolation,purification,structure characterization and its antiangiogenic activity[J].Chem JChin Univ(高等学校化学学报),2008,29(9):1755-1759.
[5]MAZUMDER S,GHOSAL P K,PUJOL C A,et al.Isolation,chemical investigation and antiviral activity of polysaccharides from Gracilaria corticata(Gracilariaceae,Rhodophyta)[J].Int J Biol Macromol,2002,31(1):87-95.
[6]RODRIGUEZ M C,MERINO E R,PUJOL C A,et al.Galactans from cystocarpic plants of the red seaweed Callophyllis variegata,(Kallymeniaceae,Gigartinales)[J].Carbohyd Res,2005,340(18):2742-2751.
[7]YUN E J,LEE S,KIM J H,et al.Enzymatic production of 3,6-anhydro-L-galactose from agarose and its purification and in vitro skin whitening and anti-inflammatory activities[J].Appl Microbiol Biotechnol,2013,97(7):2961-2970.
[8]JI H K,YUN E J,YU S,et al.Different levels of skin whitening activity among 3,6-anhydro-l-galactose,agarooligosaccharides and neoagarooligosaccharides[J].Mar Drugs,2017,15(10):E321.Doi:10.3390/md15100321..
[9]SANTOYO G F,BAER H H.Synthesis of L-gulose,L-galactose,and their acetylated aldehydo forms from6-S-phenyl-6-thio-D-hexoses[J].Carbohyd Res,1990,202(2):33-47.
[10]XIA T Y,LI Y B,YIN Z J,et al.Synthesis of L-glucose and L-galactose derivatives from d-sugars[J].Chin Chem Lett,2014,25(9):1220-1224.
[11]ORII R,IZUMI M,KAJIHARA Y,et al.Efficient Synthesis of L-galactose from D-galactose[J].J Carbohyd Chem,2015,34(9):560-566.
[12]邹礼平,陈锦华.植物抗坏血酸的合成和代谢以及相关酶基因的调控[J].植物生理学通信,2009,45(9):925-930.
[13]孙丽娜,石波,梁平.酶法制备寡聚半乳糖醛酸的研究[J].食品工业科技,2007(4):194-197.
[14]LIU Z R,HAO L.Optimization of pectinase enzymolysis mannitol extraction from Laminaria japonica areseh by response surface methodology[J].The Food Ind(食品工业),2018,39(2):177-181.
[15]SCHROVEN A,DEKANY G,ROHRIG C,et al.Method for producing L-fucos,US,20130245250 A1[P].2013.
[16]GONZáLEZ F S,BAER H H.Synthesis of L-gulose,L-galactose,and their acetylated aldehyde forms from6-s-phenyl-6-thio-d-hexoses[J].Carbohydr Res,1990,202(2):33-47.
[17]NOVOSEL I L,VOROPAEVA N L,SEMENOVA L N,et al.Trends in the science and applications of pectins[J].Chem Nat Compd,2000,36(1):1-10.
[18]PEREZ S,MAZEAU K,PENHOAT C H D.The three-dimensional structures of the pectic polysaccharides[J].Plant Physiol Bioch,2000,38(1):37-55.
[19]WILLATS W G,KNOX J P,MIKKELSEN J D,et al.Pectin:new insights into an old polymer are starting to gel[J].Trends Food Sci Tech,2006,17(3):97-104.