Chap2_Carbohydrates_第1頁(yè)
Chap2_Carbohydrates_第2頁(yè)
Chap2_Carbohydrates_第3頁(yè)
Chap2_Carbohydrates_第4頁(yè)
Chap2_Carbohydrates_第5頁(yè)
已閱讀5頁(yè),還剩71頁(yè)未讀 繼續(xù)免費(fèi)閱讀

下載本文檔

版權(quán)說(shuō)明:本文檔由用戶提供并上傳,收益歸屬內(nèi)容提供方,若內(nèi)容存在侵權(quán),請(qǐng)進(jìn)行舉報(bào)或認(rèn)領(lǐng)

文檔簡(jiǎn)介

1、1Chapter 2. CarbohydratesP.235第三代新生物技術(shù)-糖生物工程來(lái)源:中國(guó)科學(xué)報(bào) 日期: 2012年07月27日2繼基因工程、蛋白質(zhì)工程之后,糖生物工程已成為最引人注目的生物技術(shù)新領(lǐng)域,被國(guó)際科技界稱為第三代新生物技術(shù)。糖是生物界儲(chǔ)量豐富的生物資源,是蘊(yùn)藏大量生命信息的生命大分子,參與調(diào)控包括生殖、生長(zhǎng)、發(fā)育、免疫等幾乎全部生命過(guò)程。糖制劑還具有調(diào)節(jié)腸道生態(tài)平衡、促進(jìn)營(yíng)養(yǎng)物質(zhì)消化吸收、調(diào)節(jié)免疫的特點(diǎn)。正在被應(yīng)用于飼料添加劑、生物肥料、生物農(nóng)藥。具有安全無(wú)毒、高效及不易產(chǎn)生抗藥性等特點(diǎn)。3I. Introduction41. ExistenceI. Introductio

2、nP.152. FunctionI. IntroductionP.163. Definition葡萄糖果糖甘油醛二羥基丙酮Carbohydrates are polyhydroxy aldehydes or ketones (多羥基醛/多羥基酮) or substances that yield such compounds on hydrolysis.7Three major classes of carbohydratesI. Introduction85. Characteristic chemical features (化學(xué)通性)I. IntroductionP.29II. Mono

3、saccharides101. Two families: Aldoses & ketosesAldoses(醛糖)Ketoses(酮糖)II. Monosaccharides甘油醛二羥丙酮丙糖己糖112. StereochemistryII. Monosaccharides12(1) Plane-polarized light (平面偏振光 )Plane-polarized light (平面偏振光) a light with its electric vector vibrating on a specific plane called the plane of polarizat

4、ion (偏振面)Polarimeter (偏振器偏振器) an instrument used to measure optical activity.Polarimeter(偏光計(jì))Light source(non-polarized light)非偏振光Polarizer(偏光器)Plane-polarized light(平面偏振光 )Sample tube棱鏡Plane of polarization rotated(偏振面發(fā)生了旋轉(zhuǎn))棱鏡13(2) Optical activity (旋光性)A material which can rotate the plane of the

5、plane-polarized light is called to have optical activity, and this material is an optically active substance. (能使平面偏振光的偏振面發(fā)生旋轉(zhuǎn)的物質(zhì)被稱為具有旋光性)t = t c lRotation(旋光度)Specific rotation (比旋)Concentration (濃度, g/ml)Length (dm)Wavelength (波長(zhǎng), nm)TemperatureRotation 14(3) Chirality (手性)Optically active molecul

6、e Chiral molecule(旋光性分子 手性分子)Optical activity (旋光性) Chirality (手性)Chiral centers(手性中心)?15True or false:vChiral molecules are always optically active.( )vOptically active molecules always have chiral centers.( )vChiral molecules have always chiral centers.( )vMolecules with chiral centers are always

7、chiral.( )II. MonosaccharidesP.3CHOC*OHHC*HHOC*OHHC*OHHCH2OHn = 4 24 = 16 isomers16(4) Fischer projections (Fischer投影式)投影式甘油醛(+)()RSDL透視式II. MonosaccharidesP.417CHOOHHHHOOHHOHHCH2OHCHOHHOOHHHHOHHOCH2OHD-(+)-GlucoseL-(-)-GlucoseD or L refers to the configuration of the C* farthest from the carbonyl C

8、.4 C* 24 = 16 isomers8 D-forms8 L-forms18Aldoses (醛糖)19Ketoses (酮糖)II. Monosaccharides20Two systems of specifying the absolute configurations(絕對(duì)構(gòu)型的兩種表達(dá)體系)Group 4 with the lowest priorityD/L referring to the configuration of the molecule (對(duì)整個(gè)分子而言)R/S referring to the configuration of a specific C* (對(duì)

9、單個(gè)C*原子而言)D-glucose2R,3S,4R,5R-aldohexose (己醛糖) R/S convention priority rulesCHOCOHHCHHOCOHHCOHHCH2OH123456+/ referring to the optical activity of the chiral molecule(指分子的旋光性,與分子或原子的構(gòu)型無(wú)直接關(guān)系)21qD-forms of monosaccharides predominate in nature.qL-Monosaccharides also exist in nature.qD-glucose is the e

10、nantiomer of L-glucose. But D-aldohexoses (己醛糖) are not necessarily enantiomers of all of their L-isomers.II. MonosaccharidesThe above four are stereoisomers.CHOCOHHCHHOCOHHCOHHCH2OH123456CHOCHHOCOHHCHHOCHHOCH2OH123456CHOCHHOCHHOCOHHCOHHCH2OH123456D-GlucoseL-GlucoseD-MannoseCHOCOHHCOHHCHHOCHHOCH2OH1

11、23456L-MannoseEnantiomerEnantiomerDiastereomerDiastereomer223. StructureII. Monosaccharides23Epimers two diasteroisomers that differ only in the configuration around one carbon atom.Epimers are usually diastereomers. (差向異構(gòu)體多是非對(duì)映異構(gòu)體)差向異構(gòu)體是僅有一個(gè)手性碳原子的構(gòu)型不同的Anomers Two monosaccharides that differ only in

12、 their configuration about the hemiacetal or hemiketal carbon atom.Anomers are epimers. (異頭物是差向異構(gòu)體)差向異構(gòu)體.差向異構(gòu)體異頭物24Hemiacetals (半縮醛) and hemiketals (半縮酮)醛酮半縮醛半縮酮縮醛縮酮Addition(加成反應(yīng))Substitution(取代反應(yīng))25Cyclic structure (1): FormationII. MonosaccharidesP.9異頭物-Anomer-Anomer-D-吡喃葡糖-D-吡喃葡糖Anomeric C (異頭碳)2

13、6Cyclic structure (2): Haworth projections (Haworth透射式)When lining up clockwisely:-CH2OH above the ring - D-configuration-CH2OH below the ring -L-configuration-OH at the anomeric C and -CH2OH:On the opposite side On the same side D or L? or ?CHOCOHHCHHOCOHHCOHHCH2OHOHOHHOHHOHHOHCH2OHHOHOHOHHHOHHOHCH

14、2OHH123456123456123456Fischer projection formulasHaworth projection formulasP.10TopBottom27-D-glucoseD-glucose(Linear)-D-glucose36%0.024%64%20D = +112.2o20D = +18.7oCyclic structure (3): , anomersMutarotation (變旋變旋):在水溶液中糖的-和-異頭物之間互相轉(zhuǎn)化導(dǎo)致其旋光度發(fā)生變化的現(xiàn)象146oC m.p.148-155oC m.p.II. Monosaccharides+52.6oP.8

15、-9-D-glucose and -D-glucose are not enantiomers to each other; they are epimers and anomers with different properties.(-D-glucose和-D-glucose不是互為對(duì)映異構(gòu)體,是差向異構(gòu)體和異頭物,具有不同的物理/化學(xué)性質(zhì)。)28Mutarotation (變旋)36%20D = +112.2o146oC m.p.64%20D = +18.7o148-155oC m.p.(0.024%)At equilibrium, 20D = +52.6o29OHOHOHHHOHHOH

16、CH2OHHOOHHHOHHHOHHOOHHHOHOHHOHHHCH2OHCH2OHOH-D-Glucose-L-GlucoseFlipping30Cyclic structure (4): Pyranoses & furanosesPyranoses(吡喃糖)Furanoses(呋喃糖)II. MonosaccharidesP.1031CHOCOHHCHHOCOHHCOHHCH2OHOHOHHOHHOHHOHCH2OHHOHOHOHHHOHHOHCH2OHH123456123456123456CH2OHCOCHHOCOHHCOHHCH2OH123456OOHOHOHCHOHCH2OH

17、OOHOHOHCHOHCH2OHOHOHCH2OHOHOHOHHHOHOHOHCH2OHOHOHHH123456123456OOHOHCH2OHOHCH2OHOOHOHOHCH2OHCH2OH123456123456123456123456-D-吡喃葡糖-D-吡喃葡糖-D-呋喃葡糖-D-呋喃葡糖-D-吡喃果糖-D-吡喃果糖-D-呋喃果糖-D-呋喃果糖D-glucoseD-fructose32Cyclic structure (5): ConformationFor D-glucose, -form is more stable than -form.For other aldohexoses,

18、 -form is more stable than -form.OHOHHHOHHHOHOH2CHOHOOHHOHHOHOHHHCH2OHHTwo possible chair conformations of -D-glucoseII. MonosaccharidesP.13334. PropertiesII. Monosaccharides34Chemical propertiesII. MonosaccharidesP.15CHOCOHHCHHOCOHHCOHHCH2OH1234563521%2.5%II. Monosaccharides63.5%CCOHHCHHOCOHHCOHHCH

19、2OHOHCCOHCHHOCOHHCOHHCH2OHOHHD-GlucoseD-Ba(OH)2CH2OHCCHHOCOHHCOHHCH2OHOD-FructoseD-CCHHOCHHOCOHHCOHHCH2OHOHD-MannoseD-P.15-1636Chemical Properties (2): OxidationCH=OCH2OHOHOHOHHOCOOHCH2OHOHOHOHHOCH=OCOOHOHOHOHHOCOOHCOOHOHOHOHHOCu2+OH-Dehydrogenase(脫氫酶)HNO3Aldonic acid醛糖酸Uronic acid糖醛酸Aldaric acid醛糖二

20、酸Sugar acids(糖酸)Br2/H2O37Oxidizing agents (氧化劑): H2O2, Ag+, Fe3+, Cu2+Fehling reagents: tartrate (酒石酸鉀鈉),NaOH, CuSO4Benedict reagents: citric acid (檸檬酸), Na2CO3, CuSO4Reducing sugar (還原糖):Capable of reducing oxidizing agents (可以還原以上的氧化劑)All aldoses and many ketoses are reducing sugars (所有醛糖和多數(shù)酮糖)Fru

21、ctose is a reducing sugar (果糖是還原糖)CHOOHHHHOOHHOHHCH2OH+ 2Cu2+ + 4OH-COOHOHHHHOOHHOHHCH2OH+ 2CuOH + H2OAldoseAldonic acidCu2OA qualitative test for reducing sugars (還原糖還原糖)P.16(Red precipitate)還原糖的定性檢測(cè)38Measurement ofBlood Glucose ConcentrationOHOHHOCH2OHOCH-OH + O2HHHHOHOHHOCH2OHOHHHH=O + H2O2Glucos

22、e oxidaseD-GlucoseD-Glucono-lactone(葡萄糖氧化酶)39Chemical Properties (2): Oxidation (continued)CHOOHHHHOOHHOHHCH2OHCOOHOHHHHOOHHOHHCH2OHBr2/H2OpH 6.0CH=OCH2OHOHOHOHHOHHHHHCOOH4 HCOOHHCHO+IO4-This reaction is specific for aldoses.(此反應(yīng)只適用于醛糖)This reaction is useful in providing structural information (此反應(yīng)

23、可幫助分析糖的結(jié)構(gòu))II. Monosaccharides401,2-linkage1,4-linkage1,6-linkageOxidation by IO4-OOHOOCH2OHOHO=HCO=HCOOOCH2OHIO4-H2CH2COOOCH2OHHOHONaBH4H2CH2COOHOHCH2OHHOHOH2CH2CCH=OOHOHCH2OHHOHOCH2OHHCCH2OHOHCHOHCCH2OHOH+H+OOOOHOHCH2OHIO4-NaBH4CH2OHHOHCCHOHCHOCH2OH+H+CHOOHCOOOCH2OHCH2H2COOOCH2OHOHOHCH2H2COOHOHCH2O

24、HOHOHCH2H2CCHOOHOHCH2OHOHOHCH2OHOOHOOHOHCH2IO4-NaBH4CH2OHHCCHOCH2OH+CH2OHOOHCOHCOOCH2O+ HCOOHCH2H2COOCH2+ HCOOHOHHOOOCH2H2COOHCH2OH+ HCOOHOHHOCH2H2CCHOOHCH2OH+ HCOOHOHHOOH+ HCOOHH+P.7241Chemical Properties (3): ReductionCH=OCH2OHOHOHOHHOCH2OHCH2OHOHOHOHHOCH2OHCH2OHOHHOCH=OCH2OHOHHOHOHONaBH4NaBH4180o

25、RotationD-葡萄糖D-葡萄醇L-古洛糖L-古洛醇C=OCH2OHHOOHOHCH2OHC=OCH2OHHOOHCH2OHHOHOHOD-果糖L-山梨糖NaBH4NaBH4Sugar alcohols(糖醇)42Sugar alcohols (糖醇)CH2OHCH2OHOHOHOHHOD-Glucitol(D-葡萄醇)Sorbitol (山梨醇)CH2OHCH2OHOHOHHOD-Mannitol(D-甘露醇)HOCH2OHCH2OHOHOHHOD-Xylitol(D-木糖醇)CH2OHCH2OHOHGlycerol(甘油醇)HHHHHHHHHHHHII. Monosaccharides

26、43Chemical Properties (4): Formation of osazone(糖脎)CHOOHHHHOOHHOHHCH2OH3 C6H5-NH-NH2+CHN=NHC6H5HHOOHHOHHCH2OHN-NHC6H5+ C6H5-NH2 + NH3 + 2H2OHAcpH4-6苯肼苯脎 (黃色晶體)This reaction is useful in characterizing reducing sugars (此反應(yīng)用于鑒定還原糖).Yellow crystals withv Different crystal shapesv Different melting poin

27、tsII. Monosaccharides44Chemical Properties (5): Sugar Esters & Sugar Ethers(糖酯和糖醚)OHHOHHOHHOHHOHOHOHH3COCOHH3COCOHHOCOCH3HOCOCH3OCOCH3(CH3CO)2OPyridine, 0oCOHHOHHOHOHOHHHOHOHH3COHH3COHOCH3OCH3HHOCH31). CH3SOCH2Na2). CH3IAcetylation(乙酰化)Methylation(甲基化)Phosphorylation(磷酸化)OHHOHHOHOHOHHHOHOHHOHHOH

28、OHOHHHOPO3-+ ATP+ ADPP.1945OHOHHOCH2OHHHHOHHOOHOHHOCH2OHHHHO-CH3HOHemiacetal(半縮醛)Acetal(縮醛)Glycone (糖基)Aglycone(配基)Glycosidic bond(糖苷鍵)Chemical Properties (6): Glycoside (糖苷)Glycoside (糖苷)Monosaccharide (單糖)II. MonosaccharidesGlycosidic bond is unstable under acidic conditions.(糖苷鍵在酸性條件下不穩(wěn)定)P.19H+46

29、Difference between a monosaccharide and its glycoside:Glucose (單糖): Hemiacetal (半縮醛) reducing sugar (還原糖)Glycoside (糖苷):Acetal (縮醛) non-reducing sugar (非還原糖)Methyl- -D-glucosideMethyl- -D-glucosideD-GlucoseCHOOHHHHOOHHOHHCH2OHOHHOHHOHOCH3OHHHOHOHHOHHOHHOHHOCH3OHCH3OHHCl47Chemical Properties (7): Deh

30、ydration5-Hydroxymethyl furfural5-羥甲糠醛CHOCOHHCHHOCOHHCOHHCH2OHCHOCOHCHCOHHCOHHCH2OHCHOCOCHCOHHCOHHCH2OHCHCHOCOCCHCOHHCH2OHCHOOCHOHOH2CHOHCHOHOH2C-H2O-H2ODifferent furfurals react with polyphenols to generate different specific colors, therefore this reaction is useful in characterizing the monosacch

31、arides.(用于單糖的定性檢測(cè))II. MonosaccharidesP.2048OCHOHOH2COHOH-H2O(Seliwanoff test)糠醛-萘酚蒽酚紅紫色縮合物 (Molish test)糠醛藍(lán)綠色復(fù)合物 (蒽酚反應(yīng))5-羥甲糠醛-H2OOCHOOHOHHOCH3OHHO (Bial test)鑒定酮糖鑒定戊糖鑒定糖類測(cè)定總糖量糠醛49II. MonosaccharidesP.2250Important monosaccharides甘油醛二羥丙酮丙糖己糖戊糖What is honey?II. Monosaccharides51Some hexose derivatives

32、 important in biologyII. Monosaccharides52Sugar phosphate(糖的磷酸酯)Adenosine triphosphate (ATP)II. MonosaccharidesNNNNNH2OOHOHHHHHOPOO-OPOO-OP-OO-O53III. Oligosaccharides (寡糖)541.Glycosidic bonds (糖苷鍵)麥芽糖III. OligosaccharidesReducing end()Nonreducing end()55Maltose (麥芽糖)Glucose-1,4-glucoseCellobiose(纖維

33、二糖)glucose-1,4-glucoseIsomaltose(異麥芽糖)Glucose- -1,6-glucoseOOHOOHOHCH2OHCHOHOOHOHOHCH2OOHOHOHCH2OHCHOOHOHCH2OHOOHOOHOHOHCH2OHOOHOHCH2OHOCHOHO-D-glucopyranosyl-(14)-D-glucopyranoseO-D-吡喃葡糖基-(14)-D-吡喃葡糖Glc (14) Glc(14) (16) (14)562. Nomenclature (命名)-乳糖半乳糖-葡萄糖Gal (14) Glc蔗糖葡萄糖-果糖Glc (12) FruFru (21) G

34、lc海藻糖葡萄糖-葡萄糖Glc (1 1) GlcNonreducing sugarsReducing sugarsO-D-吡喃半乳糖基-(14)-D-吡喃葡糖P.24357583. Some oligosaccharide examplesIII. OligosaccharidesP.36-4059Cyclodextrins (環(huán)糊精)-OH at C-6-OH at C-2, C-3HydrophobicInside(內(nèi)部疏水)HydrophilicOutside(外部親水)60IV. Polysaccharides (多糖)611. ExistenceIV. Polysaccharide

35、s622. ClassificationIV. Polysaccharides633. Homopolysaccharides (同多糖)Function(功能)PolymerStructure(結(jié)構(gòu))Glycosidic bond(糖苷鍵)Size(No. of units)Source(來(lái)源)EnergyStarch (淀粉)Plantsstorage-Amylose(直鏈淀粉)Linear(14)Glc50-5000貯存多糖Amylopectin(支鏈淀粉)Branched(14)Glc(16)GlcUp to 106Glycogen(糖原)Branched(14)Glc(16)GlcU

36、p to 50000AnimalsStructuralCellulose(纖維素)Linear(14)GlcUp to 15000Plants結(jié)構(gòu)多糖Chitin(殼多糖)Linear(14)GlcNAcVery largeAnimals64Starch: Amylose & amylopectin(直鏈淀粉 & 支鏈淀粉)P.41 14A short segment of amylose (直鏈淀粉)( 16)( 14)A segment of amylopectin (支鏈淀粉)65Amylose (直鏈淀粉)The most stable three-dimensiona

37、l structure for the (14)-linked chains of starch and glycogen is a tightly coiled helix, stabilized by interchain H bonds.66A cluster of amylose and amylopectin67Amylose & amylopectin (直鏈和支鏈淀粉)P.42Fig.1-2468Cellulose(纖維素)IV. PolysaccharidesP.4569CelluloseIV. PolysaccharidesP.46Fig.1-27Chitin (殼多

38、糖)A linear homopolysaccharide composed of N-acetylglucosamine residues in (14) linkage.Principal component of the hard exoskeletons of arthropodsThe 2nd most abundant polsaccharide in nature1 billion tons are produced each year in biosphereDifferent from cellulose in: C-2Similar to cellulose in: 14

39、glycosidic bond linkage Extended fibers Cannot be digested by vertebrates70714. Hetereopolysaccharides(雜多糖)IV. Polysaccharides72Agar (瓊脂)Agarose (瓊脂糖)Agaropectin (瓊脂膠)IV. PolysaccharidesP.49Agarose (瓊脂糖)Remarkable gel-forming property useful in biochem lab.Double helical structure to trap water in the central cavityUsed as support for electrophoresisUsed as support for gel-filtration chromatography Sepharose (瓊脂糖凝膠)Used to form a surface fo

溫馨提示

  • 1. 本站所有資源如無(wú)特殊說(shuō)明,都需要本地電腦安裝OFFICE2007和PDF閱讀器。圖紙軟件為CAD,CAXA,PROE,UG,SolidWorks等.壓縮文件請(qǐng)下載最新的WinRAR軟件解壓。
  • 2. 本站的文檔不包含任何第三方提供的附件圖紙等,如果需要附件,請(qǐng)聯(lián)系上傳者。文件的所有權(quán)益歸上傳用戶所有。
  • 3. 本站RAR壓縮包中若帶圖紙,網(wǎng)頁(yè)內(nèi)容里面會(huì)有圖紙預(yù)覽,若沒(méi)有圖紙預(yù)覽就沒(méi)有圖紙。
  • 4. 未經(jīng)權(quán)益所有人同意不得將文件中的內(nèi)容挪作商業(yè)或盈利用途。
  • 5. 人人文庫(kù)網(wǎng)僅提供信息存儲(chǔ)空間,僅對(duì)用戶上傳內(nèi)容的表現(xiàn)方式做保護(hù)處理,對(duì)用戶上傳分享的文檔內(nèi)容本身不做任何修改或編輯,并不能對(duì)任何下載內(nèi)容負(fù)責(zé)。
  • 6. 下載文件中如有侵權(quán)或不適當(dāng)內(nèi)容,請(qǐng)與我們聯(lián)系,我們立即糾正。
  • 7. 本站不保證下載資源的準(zhǔn)確性、安全性和完整性, 同時(shí)也不承擔(dān)用戶因使用這些下載資源對(duì)自己和他人造成任何形式的傷害或損失。

評(píng)論

0/150

提交評(píng)論