Carbohydrates

Chapter 25

25-1

Carbohydrates
x

x

Carbohydrate: A polyhydroxyaldehyde, a polyhydroxyketone, or a compound that gives either of these compounds after hydrolysis. Monosaccharide: A carbohydrate that cannot be hydrolyzed to a simpler carbohydrate.
• They have the general formula CnH2nOn, where n varies from 3 to 8. • Aldose: a monosaccharide containing an aldehyde group. • Ketose: a monosaccharide containing a ketone group.

25-2

Importance of Carbohydrates to us….

polymerize CO2 + H2 O photosynthesis glucose chlorophyll light polymerize

cellulose giving structure to plants

clothing fiber wood

starch, plant seeds eaten by animals

CO2 + H2 O + energy

glucose

glycogen (liver)

25-3

Monosaccharides
x

Monosaccharides are classified by their number of carbon atoms:
Name Triose Tetrose Pentose Hexose Heptose Octose Formula C2H2 2 O C2H2 2 O C2H2 O2 2 C2H2 O2 2 C2H2 O2 2 C2H2 O2 2

25-4

and so forth tellling the number of carbon atoms present.Monosaccharides x There are only two trioses: CHO CHOH CH2OH Glyceraldehyde  (an aldotriose) CH2OH C=O CH2OH Dihydroxyacetone    (a ketotriose) Chiral Center R and S stereoisomers x These compounds are referred to simply as trioses. 25-5 . tetroses.

Review Fischer Projections x Fischer projection: A two dimensional representation for showing the configuration of carbohydrates. OH CH2OH (R)­Glyceraldehyde (three­dimensional representation) CH2OH (R)­Glyceraldehyde (Fischer projection) 25-6 . CHO H C OH convert to a Fischer projection CHO H . • Vertical lines represent bonds projecting to the rear. • The more highly oxidized carbon is shown at the top. • Horizontal lines represent bonds projecting forward.

D.and L.2 D D 25-7 .to the enantiomers of glyceraldehyde.2 [α]2   = ­22 .L Monosaccharides x In 1891. Emil Fischer made the arbitrary assignments of D. CHO H OH CH2OH CHO HO H CH2OH D­Glyceraldehyde L­Glyceraldehyde (R)­Glyceraldehyde (S)­Glyceraldehyde 2 2 [α]2   = + 22 .

its -OH is on the right when written as a Fischer projection. • L-monosaccharide: A monosaccharide that has the same configuration at its penultimate carbon as Lglyceraldehyde. 25-8 . that is.D. that is.L Monosaccharides x According to the conventions proposed by Fischer: • D-monosaccharide: A monosaccharide that has the same configuration at its penultimate (next to bottom) carbon as D-glyceraldehyde. its -OH is on the left when written as a Fischer projection.

. Four D. Two D and two L. four 25-9 L. D-aldopentoses Expect total of 8 (=23) steroisomers.D.L Monosaccharides x D-aldotetroses and the two most abundant Daldopentoses in the biological world: CHO CHO H OH H OH D­Erythrose CH2OH CHO HO H H OH D­Threose CH2OH H H H OH OH OH CH2OH D­Ribose H H H CHO H OH OH CH2OH 2 ­Deoxy­D­ ribose D-aldotetroses Expect four stereoisomer 22 for aldotetroses.

Four D and four L. ketohexose Expect 8 stereoisomers 24 for ketohexoses. Eight D and eight L.L Monosaccharides x The most abundant hexoses: CHO H OH HO H H OH H OH CH2OH D-Glucose CHO H OH HO H HO H H OH CH2 OH D-Galactose CH2OH C O HO H H OH H OH CH2OH D-Fructose aldohexoses Expect 16 stereoisomers 24 for aldohexoses.D. 25-10 .

D Aldohexoses binary display DAllose CHO DAltrose CHO OH OH OH OH HO H H H H OH OH OH CH2 OH H HO H H DGlucose CHO OH H OH OH CH2 OH HO HO H H DMannose CHO H H OH All altruists gladly make gum in gallon tanks.Fieser H H HO H CHO OH OH H OH 2 HO H HO H 2 H OH H OH H HO HO H 2 OH H H OH HO HO HO H There is CH OH 3=011 also the L series. the DTalose mirror CHO image H structures H 2 OH H OH 2 4=100CH OH CH OH 5=101 CH 6=110 OH CH 7=111 OH 25-11 . H H H H 0= 000 DGulose CH2 OH 1=001 DIdose CHO 2=010 DGalactose CHO L.

H HO H H CHO NH2 H OH OH CH2OH CHO H2N 2 H HO H H OH H OH CH2OH CHO H NH2 HO H HO 2 H H OH CH2OH H HO H H CHO O NHCCH2 H OH OH CH2OH D­Glucosamine  D­Mannosamine  D­Galactosamine N­Acetyl­D­ glucosamine 25-12 .Amino Sugars x Amino sugar: A sugar that contains an -NH2 group in place of an -OH group. • Only three amino sugars are common in nature • N-Acetyl-D-glucosamine is a derivative of Dglucosamine.

• sweetness relative to sucrose: Sweetness Relative to  Carbohydrate Sucrose Fructose 22 . but only slightly soluble in ethanol.2 Maltose 22 .2 Galactose 22 .2 Glucose 22 .2 Sweetness Relative to  Artificial  Sweetener Sucrose Saccharin 22 2 Acesulfame­K 22 2 Aspartame 22 2 25-13 .2  Honey 22 . very soluble in water.Physical Properties x Monosaccharides are colorless crystalline solids.2 Invert sugar 22 .2 Sucrose (table sugar) 2 2 .2  Lactose (milk sugar) 2 2 .

Cyclic Structure x Monosaccharides have hydroxyl and carbonyl groups in the same molecule and those with five or more carbons exist almost entirely as five. • Anomers: Carbohydrates that differ in configuration at their anomeric carbons named α and β.and six-membered cyclic hemiacetals. 25-14 . • Anomeric carbon: The new stereocenter created as a result of cyclic hemiacetal formation.

• They are commonly written with the anomeric carbon on the right and the hemiacetal oxygen to the back right.Haworth Projections x Haworth projections • Five. 25-15 . • The designation β.means that it is trans to the terminal -CH2OH.means that the -OH on the anomeric carbon is cis to the terminal -CH2OH.and six-membered hemiacetals are represented as planar pentagons or hexagons viewed through the edge. α.

cis.Haworth Projections CHO H OH HO H H OH CH2 OH 2 redraw to show the ­OH  on carbon­2  close to the aldehyde on carbon­2 top H 2 OH D­Glucose Lay molecule on side. β CH2 OH H2 OH O H OH H C 2H HO H anomeric    carbon OH trans. α CH2 OH O OH(β) H H OH H HO H H OH β­D­Glucopyranose     (β­D­Glucose) CH2 OH O H H H + OH H HO OH(α) H OH α­D­Glucopyranose ( α­D­Glucose) anomeric carbon 25-16 .

furan O O Furan Pyran 25-17 . pyran • Five-membered hemiacetal rings are shown by the infix -furan-.Haworth Projections • Six-membered hemiacetal rings are shown by the infix -pyran-.

HOCH2 H H O H H HOCH2 H O OH (β) H OH (α) H H OH OH OH H β­2 ­Deoxy­D­ribofuranose α­D­Ribofuranose (β­2 ­Deoxy­D­ribose) (α­D­Ribose) 25-18 .Conformational Formulas • Five-membered rings are so close to being planar that Haworth projections are adequate to represent furanoses.

2 2 HOCH2 2 2 CH2 OH HOCH2 2 O H HO H CH2 OH 2 H HO OH(α) α -D­Fructofuranose (α -D­Fructose) C=O HO H 2 H OH 2 H OH 2 CH2 OH D­Fructose 2 O H HO H OH (β) 2 H HO CH2 OH 2 β -D­Fructofuranose (β-D­Fructose) 25-19 .Conformational Formulas • Other monosaccharides also form five-membered cyclic hemiacetals. a ketohexose. • Here are the five-membered cyclic hemiacetals of Dfructose.

Ascorbic Acid (Vitamin C) x L-Ascorbic acid (vitamin C) is synthesized both biochemically and industrially from D-glucose. H HO H H CHO biochemial OH and industrial H syntheses OH OH CH2OH CH2OH H OH O H HO O OH D­Glucose L­Ascorbic acid   (Vitamin C) 25-20 .

• Both are physiologically active and are found in most body fluids.Ascorbic Acid (Vitamin C) • L-Ascorbic acid is very easily oxidized to Ldehydroascorbic acid. CH2OH H OH O H HO OH O oxidation reduction H H CH2OH OH O O O O L­Ascorbic acid   (Vitamin C) L­Dehydroascorbic acid 25-21 .

H OH HO HO H HO H OH H OH HO HO H H H OH H OH OH H O Open chain form β­D­Glucopyranose (β­D­Glucose) H OH HO HO H H rotate about C-2 C-2 to bond H OH H OH OH O H HO HO HO OH OH H H H α­D­Glucopyranose (α­D­Glucose) 25-22 .Conformational Formulas. the six-membered ring is more accurately represented as a chair conformation. β to α conversion • For pyranoses.

Conformational Formulas • The orientations of groups on carbons 1-5 in the Haworth and chair projections of β-D-glucopyranose are up-down-up-down-up. 2 CH2 OH 2 2 H 2 OH HO 2 H 2 O OH(β) H 2 2 HO HO CH2 OH 2 2 2 O OH 2 OH(β) H H OH β­D­Glucopyranose (Haworth projection) β-D­Glucopyranose (chair conformation) 25-23 .

2 2 +2. [α] after % Present at Monosaccharide [α] Mutarotation Equilibrium α­D­glucose 2 2 +2.2 2 HO HO 2 2 2 2 CH2OH O HO OH β­D­Glucopyranose [α]D22 +2.2 +2.2 2 +2.2 β­D­glucose +2.2 2 +2.2 2 2 2 α­D­galactose β­D­galactose HO HO CH2 OH O OH (β) +22 2.2 2 +22 2.2 2 OH (α) α­D­Glucopyranose 2 25-24 [α]D 2 +22 2 .Mutarotation x Mutarotation: The change in specific rotation that occurs when an α or β form of a carbohydrate is converted to an equilibrium mixture of the two.

Unstable in base) (Unstable in Acid.Hemiacetals and Acetals. (Unstable in Acid. carbonyls and alcohols Addition reaction. Stable in base) Substitution reaction 25-25 .

• methyl β-D-glucopyranoside (methyl β-D-glucoside) glycosidic bond CH2 OH CH2 OH CH2 OH O OH OH O OCH2 H H + H H H H H + CH2OH + OH H OH H OH H -H2O HO H HO OCH2 H HO H OH H OH H OH β­D­Glucopyranose Methyl β­D­gluco­ Methyl α­D­gluco­ (β-D­Glucose) pyranoside pyranoside (Methyl β­D­glucoside) (Methyl α­D­glucoside) 25-26 .Glycosides. x Glycoside: A carbohydrate in which the -OH of the anomeric carbon is replaced by -OR. acetal formation. anomeric OH becomes OR.

acetals x x Glycosidic bond: The bond from the anomeric carbon of the glycoside to an -OR group. Glycosides are named by listing the name of the alkyl or aryl group bonded to oxygen followed by the name of the carbohydrate with the ending -e replaced by -ide.Glycosides. -ide • methyl β-D-glucopyranoside • methyl α-D-ribofuranoside 25-27 .

N-Glycosides x The anomeric carbon of a cyclic hemiacetal also undergoes reaction with the N-H group of an amine to form an N-glycoside. • N-glycosides of the following purine and pyrimidine bases are structural units of nucleic acids. O HN O N H Uracil O N N H Cytosine NH2 HN O O CH2 N N NH2 N HN H2N N O N N H N H Thymine N H Adenine Guanine 25-28 .

N-Glycosides • The β-N-glycoside formed between D-ribofuranose and cytosine. NH2 N HOCH2 H H HO O O H N a β-N­glycosidic bond H anomeric carbon OH 25-29 .

Reactions 25-30 .

Reduction to Alditols. including NaBH4 and H2/M. HO HO CH2 OH O OH CHO H OH HO H H OH H OH CH2OH D­Glucose CH2OH H OH HO H H OH H OH CH2OH  D­Glucitol (D­Sorbitol) NaBH2 OH β­D­Glucopyranose An alditol 25-31 . aldehyde  alcohol x The carbonyl group of a monosaccharide can be reduced to an hydroxyl group by a variety of reducing agents.

Other alditols • Other alditols common in the biological world are: CH2OH H OH H OH CH2OH Erythritol CH2OH HO H HO H H OH H OH CH2OH D­Mannitol CH2OH H OH HO H H OH CH2OH Xylitol 25-32 .

Nitric Acid oxidizes aldoses to dicarboxylic acids (Aldaric acids). Later for that. Not synthetically useful due to side reactions. Enzyme catalyzed oxidation of terminal OH to carboxylic acid (Uronic Acid) Periodic Acid oxidizes and breaks C C bonds. Tollens reagent (Ag+(NH3)2 or Benedict’s solution (Cu2+ tartrate complex).Oxidations Oxidation can be done in several ways. 25-33 . Bromine water oxidizes aldoses (not ketoses) to monocarboxylic acids (Aldonic Acids).

The group can be oxidized and is detected with Tollens or Benedicts solution. Ketone groups converted to aldehyde via tautomeric shifts (later).Reducing Sugars x Sugars with aldehyde (or ketone group) in solution. 25-34 .

CH2OH (2 ) C=O (CHOH) n CH2OH A 2 ­ketose CHOH C-OH (2 ) (CHOH) n CH2OH An enediol CHO CHOH (2 ) (CHOH) n CH2OH An aldose COOH CHOH (CHOH) n CH2OH An aldonic acid Ketose to aldose conversion via keto enol tautomerism Oxidation Reducing sugar 25-35 .Problem with Tollens x 2-Ketoses are also oxidized to aldonic acids in basic solution (Tollens).

Oxidation to Aldonic Acids: aldehyde  carboxylic x The -CHO group can be oxidized to -COOH. O HO HO CH2 OH O OH OH H HO H H OH oxidizing H OH agent H HO H OH basic H OH OH solution H OH CH2OH CH2OH D­Glucose  D­Gluconate C H O C O- β-D­Glucopyranose (β -D­Glucose) 25-36 .

Oxidation to carboxylic acids CO2 H H HO H OH H OH OH CH2 OH H OH H OH OH CH2 OH Br2water CHO H HO H H Aldonic Acid HNO2 CO2 H H HO H H CO2 H OH Aldaric Acid H OH OH 25-37 .

CHO H OH enzyme­catalyzed oxidation HO H H OH H OH CH2OH D­Glucose H HO H H CHO OH COOH O H HO OH HO OH OH COOH D­Glucuronic acid (a uronic acid) OH 25-38 .Oxidation to Uronic Acids x Enzyme-catalyzed oxidation of the terminal -OH group gives a -COOH group.

Oxidation to Uronic Acids • In humans. HO HO COO - O OH O HO Propofol A urine­soluble glucuronide 25-39 . D-gluconic acid is an important component of the acidic polysaccharides of connective tissue. such as phenols and alcohols. one example is the intravenous anesthetic propofol. • It is also used by the body to detoxify foreign hydroxyl-containing compounds.

Oxidation by periodic acid. HIO4 or H5IO6 x Periodic acid cleaves the C-C bond of a glycol. OH C OH O -2 2O H + I OH C OH HO OH HO A  2 ­diol .2 Periodic acid OH O I OH C O OH C O A cyclic periodic          ester C O C O + H2IO2 Iodic acid 25-40 .

Oxidation by HIO4 • It also cleaves α-hydroxyketones H H C OH C O R H H H2IO2 H C O HO C O R + H2O H C OH HO C OH α-Hydroxyketone Hydrated intermediate R • and α-hydroxyaldehydes. H C H C OH R α-Hydroxyaldehyde + H2O O OH H C OH H C OH R H2IO2 OH H C O H C O R 25-41    Hydrated intermediate .

Examples. A + 2 HIO2 yielded 2 HCO2 + HCHO + OHC-CO2 H H B + 2 HIO2 yielded 2 HCO2 + 2 H HCHO C + 2 HIO2 yielded 2 HCO2 + 2 H OHC-CO2 H Analysis of A: 4 moles of periodic acid used. Identify each of the glucose derivatives. 4 bonds broken.or CHO-. Products: Formic acid from –CHOH. Formaldehyde from CH2OHOHC-CO2H from –CHOH-CO2H H HO H H CO2 H OH H OH OH CH2 25-42 OH .

Another example x Oxidation of methyl β-D-glucoside consumes two moles of HIO4 and produces one mole of formic acid. which indicates three adjacent C-OH groups. periodic acid cleavage at these two bonds H HO HO CH2OH O OH 2 HIO4 2HIO 2 O O C CH2OH O C H OCH2 OCH2 OH O C H Methyl β­D­glucopyranoside 25-43 .

Osazones. Epimers CHO CHOH 2 PhNHNH2 CH=NNHPh C=NNHPh O PhCHO O aldose osazone osone 25-44 .

Hence. if we know the configuration of (+) glucose we immediately have that of (+) mannose. Stereoisomers that differ in configuration at only one stereogenic center are called epimers. D-glucose and Dmannose are epimers.Use of osazone in structure determination Fischer found that (+) glucose and (+) mannose yielded the same osazone indicating that they differed only at the C2 configuration. NNHPH CHO H HO H H OH H OH OH CH2 OH PhHNN HO H H H OH OH CH2 OH HC HO HO H H CHO H H OH OH CH2 OH D glucose D mannose 25-45 .

25-46 . urine.Glucose Assay: diabetes (background) x The analytical procedure most often performed in the clinical chemistry laboratory is the determination of glucose in blood. or other biological fluid.

25-47 .Glucose Assay x The glucose oxidase method is completely specific for D-glucose.

• In one procedure. 25-48 . and is proportional to the concentration of glucose in the sample. • Molecular oxygen.Glucose Assay • The enzyme glucose oxidase is specific for β-Dglucose. whose concentration is determined spectrophotometrically. used in this reaction is reduced to hydrogen peroxide H2O2. O2. the hydrogen peroxide oxidizes otoluidine to a colored product. • The concentration of H2O2 is determined experimentally.

Killani-Fischer lengthening of chain epimers CHO HO H H H OH OH CH2 OH CN H HO H H OH H OH OH CH2 OH HO HO H H CN H H OH OH CH2 OH H CO2 H OH H OH OH CH2 OH HO HO H H CO2 H H H OH OH CH2 OH HCN aq acid HO H H + + D Arabinose CHO H CHO OH H OH OH HO HO H H H H OH OH CH 2 OH As lactones Get both epimers. Na HO H H + CH 2 OH 25-49 .

Ruff Degradation shortening of chain CHO H HO H H OH H OH OH CH2 OH H HO H H CO2 H OH H OH OH CH2 OH H CO2 )2Ca+2 Br2 OH H OH OH CH2 OH CHO CaCO 2 H2 2 O HO H OH OH CH2 OH HO H H Fe+2 H H 25-50 .

What was available to him in 1888? •Theory of stereoisomerism •Ruff degradation •Oxidation to aldonic and aldaric acids •Killani-Fischer synthesis •Various aldohexoses and aldopentoses 25-51 .Fischer proof of structure of glucose Emil Fischer received the 1902 Nobel prize for determining the structure of glucose.

Fischer proof of structure of glucose
glucose known to be an aldohexose but of unknown structure
CHO

f our chiral centers. 2 stereoisomers, 2 2 pairs of enantionmers, 2 and 2 D L

OH
CH 2 OH

Fischer could not work with absolute conf igurations. He assumed that naturally occuring glucose was D. He had to work out the relationship of the other three OH.

25-52

Fischer started with the aldopentoses
One monosaccharide that was available was (-) arabinose, an aldopentose.
CHO

three chiral centers 2 stereoisomers = 2 pairs of enantiomers = 2 + 2 L D

OH
CH 2 OH

Again, Fischer could not work with absolute conf igurations. He assumed that naturally occuring (-) arabinose was D. He had to work out the relationship of the other two OH.

25-53

Experiments on (-) arabinose
Fact: Nitric acid oxidation of (-) arabinose yielded an optically active aldaric acid
CHO HO CO2 H

HNO2

OH CH 2 OH CO2 H

OH

Conclusion: (-) arabinose is either
CHO HO OH HO CHO

assumed partial structure of (-) arabinose

optically active

or

HO OH CH2 OH

Must be an OH here

OH CH2 OH

25-54

Use KF to get aldohexoses
Fact: Killani Fischer synthesis on (-) arabinose yielded (+) glucose and (+) mannose
CHO HO CHO OH HO OH CH2 OH OH CH2 OH OH CH2 OH HO CHO

K. F.

+ HO

partial structure of arabinose

mixture of + glucose and + mannose, both of unknown structure. Which is glucose is unknown.

25-55

CHO OH HO OH OH CH 2 OH HO CHO CHO OH HO OH OH CH 2 OH HO OH CH 2 OH HO CHO + HO + HO HO OH CH 2 OH Each yields optically active aldaric acid.Aldaric acids from glucose and mannose Fact: nitric acid oxidation of either glucose or mannose yields optically active aldaric acids. yields optically inactive aldaric yields optically active aldric C4 OH on right C4 OH on left 25-56 . This locates the OH on C4 since both aldaric acids have to be active.

A B 25-57 . A or B.Which is glucose?? CHO OH HO OH OH CH2 OH HO CHO + HO OH OH CH2 OH Which one. is glucose is determined by preparing the aldaric acids (dicarboxylic acids).

(+) mannose 25-58 . (+)gulose. (+) gulose which turns out to be an L aldohexose Aldaric acid f rom B comes only f rom B.Final piece of data… Fact: the aldaric acid from (+)glucose is also produced by nitric acid oxidation of a different aldohexose. CHO HO HO OH OH CHO OH OH CH2 OH CHO H HO H H OH H OH OH CH2 OH CO2 H OH CH2 OH OH HNO2 HO OH OH CO2 H HNO2 HO A structure of glucose aldaric acid f rom A.

Where are we? x x We have determined the straight chain structure of (+) glucose. But certain data indicates the problem is not yet solved. Conclude: glucose is a cyclic hemiacetal. not hemiacetals. Schiff test. Glucose is converted into two acetals (the methyl D-glucosides). • Bisulfite addition products cannot be made x x Mutarotation changes specific rotation. Glucose does not give some reactions characteristic of aldehydes • A qualitative test. by reaction with one mole of methanol (acid). for aldehydes is negative. 25-59 .

Two kinds of OH •OH at anomeric carbon •OH on backbone One of the backbone OH groups may be bonded to the anomeric carbon to form a ring. converting them into OMe. 25-60 . We can methylate the various OH groups. First review characteristics of hemiacetals and acetals.Now to determine ring size. We seek to detect which one.

Hemiacetals and Acetals. Unstable in base) (Unstable in Acid. Stable in base) Substitution reaction 25-61 . (Unstable in Acid. carbonyls and alcohols Addition reaction.

NaOH OCH 2 H2 CO H2 CO H H O dry HCl OCH 2 OCH2 H Methyl D glucoside CHO H2 CO H H H O OH H H OCH2 H OCH2 H OCH2 OH OCH2 dil HCl H2 CO H2 CO H2 CO C2 C2 cleavage C2 C2 cleavage OCH2 H OCH2 H H CO2 H H OCH2 H CO 2 CO2 H H H2 CO CO2 H oxidation HNO2 + H H CO2 H C2 C2 cleavage C2 C2 cleavage The observed 4 carbon and 5 carbon dicarboxylic acids indicate free OH was on C5.Methylation to find ring size. 25-62 . H HO H H HO HO H H OH H H O HO H HO HO H OH H H CH2 OH OH H2 CO H O (CH2 2 2 O) SO .

Conformation of the pyranose ring. Ring flips can occur. Generally the conformation with large groups equatorial dominate. HOH 2 C HO HO HO O OH CH 2 OH OH O OH more stable OH OH less stable β-D glucopyranose Generally the CH2OH should be made equatorial 25-63 .

Extreme case: a-D-Idopyranose axial OH HOH 2 C H H H HO H HO HO H HO CH 2 OH OH O O OH OH more stable α -D-Idopyranose 25-64 .

milk sugar 25-65 . table sugar Maltose. from barley Lactose.disaccharides x x x Sucrose.

Sucrose. table sugar x Table sugar. α-1. β-2 bond 25-66 . obtained from the juice of sugar cane and sugar beet.

Lactose x The principle sugar present in milk. 25-67 . 5 – 10%.

25-68 .Maltose x From malt. the juice of sprouted barley and other cereal grains.

x Exists in two forms which undergo mutarotation.Structure Determinatin of (+) Maltose x x x Experimental Facts C12H22O11 Positive for Tollens and Fehlings solution. 25-69 . reducing sugar Reacts with phenylhydrazine to yield osazone. C12H20O9(NNHC6H5)2 x x Oxidizes by bromine water to monocaboxylic acid. Consistent with two aldoses linked together with one hemiacetal group.

Maltase hydrolysis is characteristic of α glucosides. Conclude something like CH 2 OH CH 2 OH OH α O 25-70 .More data…. Two glucose units joined together: glucose – acetal linkage (glucoside) – glucose – hemiacetal.. acid or maltase to yield two D (+) glucose units. x x Maltose undergoes hydrolysis with aq.

CH 2 OH CH 2 OH Br2 H2 . O O OH CH 2 OH O O CH 2 OH O OH CO 2 H O OH HO Me2 2 SO base OMe unmethylated O OMe OMe CO2 H aq acid Next Slide f ree OH methylated O MeO f ree OH methylated OMe 25-71 . Label the rings and label the free OH groups.How to proceed…..

Point of attachment to the other glucose unit. the Structure on next reducing sugar.Hydrolysis products CHO H MeO H H OMe H OMe OH CH 2 OMe H MeO H H CO 2 H OH H OH OMe CH 2 OMe Used in hemiacetal link. Not the reducing aldohexose unit (not the carboxylic acid). 25-72 . slide. This glucose derivative was the “free” CHO unit.

Maltose H OH H HO HO H H OH O HO H H OH HO H H O H O H OH 25-73 .

unbranched chains of up to 4000 D-glucose units joined by α-1.4-glycosidic bonds. chains consist of 24-30 units of D-glucose joined by α1. 25-74 . Amylopectin • Amylopectin: A highly branched polymer of D-glucose. Amylose • Amylose: A polysaccharide composed of continuous. amylose and amylopectin. each on complete hydrolysis gives only D-glucose.Starch x Starch is used for energy storage in plants • It can be separated into two fractions.4-glycosidic bonds and branches created by α-1.6glycosidic bonds.

glycogen is a nonlinear polymer of D-glucose units joined by α-1.Glycogen x Glycogen is the reserve carbohydrate for animals.and α-1. • The total amount of glycogen in the body of a wellnourished adult is about 350 g (about 3/4 of a pound) divided almost equally between liver and muscle. • Like amylopectin.6-glycosidic bonds bonds. 25-75 .4.

4-glycosidic bonds. corresponding to approximately 2800 D-glucose units per molecule. • Both rayon and acetate rayon are made from chemically modified cellulose. • It has an average molecular weight of 400.Cellulose x Cellulose: A linear polymer of D-glucose units joined by β-1. 25-76 .000 g/mol.

Acidic Polysaccharides x Hyaluronic acid: An acidic polysaccharide present in connective tissue. 25-77 . such as synovial fluid and vitreous humor.

• Following is a pentasaccharide unit of heparin. 25-78 .Acidic Polysaccharides x Heparin • Its best understood function is as an anticoagulant.

.6 linkage . A synthetic polysaccharide is composed of three monosaccharides units in the following order: (D-glucpyranose) – (L-fructofuranose) – (D-altropyranose). The linkages between the units and the structures of the individual D units are given below where the wavy lines are used to avoid specifying configuration.An example…. You must show stereochemistry clearly. CH2 OH CH2 OH OH O OH OH OH OH O OH CH 2 OH OH OH OH CH2 OH O OH OH D-glucopyranose O D-f ructof uranose D-altropyranose O O α2.2 β2 linkage D-Altrose D-Glucose L-Fructose β anomer Add all substituents to the rings and show the linkages between the units. 25-79 .

2 β2 linkage D-Altrose D-Glucose L-Fructose β anomer Now L fructose the β 1.6 linkage OH .Solution CH2 OH CH2 OH OH O OH OH OH OH O OH CH 2 OH OH OH OH CH2 OH O OH OH D-glucopyranose CH 2 OH D-f ructof uranose CH 2 OH CH 2 D-altropyranose O OH OH OH O OH O OH CH2 OH O O CH 2 OH OH 2 CH OH OH H OH OH OH OH α2.4 link D-Altrose the β ano mer Now the α 2.6 Now First the D glucose… Now Now 25-80 .

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