Biochemistry

9. Carbohydrates

CONCEPT: CARBOHYDRATES

hydroxyl
●Carbohydrates: structurally & functionally diverse, carbon-based-molecules rich in _______________ groups (-OH).
□ Also referred to as ___________________,
saccharides the Greek word meaning “sugars”.
●When “_____________________”
carbonydrates was originally coined, it referred to compounds with the formula Cn(H2O)n, where n ≥ 3.
□ ___________
Simple carbohydrates: fit Cn(H2O)n formula exactly.
□ ___________ P
carbohydrates: can slightly differ from Cn(H2O)n & can also have ____, N or S atoms too.
complex

simple complet

6 12 6 P6 119

PRACTICE: Which of the following chemical formulas represents that of a simple carbohydrate?
a) C2H2O2. b) C6H12O6. c) C5H4O3. d) C3H6O9.

3 Size Classes of Carbohydrates

1) _________saccharide:
mono a single carbohydrate unit (or ______________).
monomer

2) _________saccharide:
Oligo 2 to ~_______
20 covalently linked monosaccharides.
3) _________saccharide: >
_____ 20 covalently linked monosaccharides.
Poly

di

Tri

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CONCEPT: CARBOHYDRATES
Proteins vs. Carbohydrates

PRACTICE: Which of the following is a monosaccharide?

Intro to Carbohydrate Functions

●Recall: Carbohydrates have incredibly diverse biological functions including acting-as/participating-in:
□ Short-term ___________ Sources: carbohydrate oxidation is the central energy-yielding pathway in most cells.
□ ____________ & Protective Components: carbs make up part of nucleotide structures & plant/bacterial cell walls.
□ Cell ___________________: carbohydrates participate in cell recognition/adhesion/coordination.
□ Designate Intracellular __________________: carbohydrate modifications can determine area & metabolic fates.

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CONCEPT: MONOSACCHARIDES
●Recall: monosaccharides are individual carbohydrate _____________ & the simplest form of sugar.
□ Names generally end with the suffix “-_______” (ex. glucose).
□ Monosaccharides can be _______________ in several different ways.

Aldoses or Ketoses
●Monosaccharides can be classified into ______ groups based on the nature of their carbonyl group:
1) _____________: a sugar whose carbonyl group is an ________________ (-CHO).
2) _____________: a sugar whose carbonyl group is a _____________.
EXAMPLE: Aldoses vs. Ketoses.

Monosaccharides Grouped By # of Carbons

●Monosaccharides are also grouped based on the number of their ____________ atoms.
□ Monosaccharides with 3, 4, 5, & 6 carbons are respectively _____oses, ______oses, ______oses & _____oses.
□ These prefixes can be preceded by “________-” or “________-” to respectively indicate an aldose or ketose.
EXAMPLE: Classify the following monosaccharides based on their number of carbon atoms & carbonyl groups.

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CONCEPT: MONOSACCHARIDES
PRACTICE: Select the appropriate label for each of the three following monosaccharides:
A) Arabinose: B) Threose: C) Erythrulose:
a) Aldopentose. a) Ketohexose. a) Aldotetrose.
b) Ketopentose. b) Aldopentose. b) Ketopentose.
c) Aldotetrose. c) Aldotetrose. c) Aldopentose.
d) Ketotetrose. d) Ketotetrose. d) Ketotetrose.

Assigning Numbers to the Carbons of Linear Monosaccharides

●Carbon atoms in linear monosaccharides are numbered based on positioning of the __________ group (aldehyde or ketone).
□ Carbonyl carbon atom part of the aldehyde or ketone should be assigned the ______________ possible number.
□ Numbered carbons are designated as C-1, C-2, C-3, etc.
EXAMPLE: Appropriately number the carbon atoms in the following linear monosaccharides.

PRACTICE: Number the carbon atoms in the following linear form of fructose below:

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CONCEPT: STEREOCHEMISTRY OF MONOSACCHARIDES

●Recall: WAY back in previous videos, we did Organic Chemistry review. Be sure to check those out before moving on!
●To represent 3D structures on paper, linear monosaccharides are commonly displayed using _____________ Projections.

Sugar

Shadow

Fischer
Projection

Calculating # of Stereoisomers
●# of Stereoisomers a molecule has = ______ (where ____ = # of chiral carbons).
□ Recall: Chiral Carbon: a carbon atom covalently bound to ______ distinct chemical groups.
EXAMPLE: Circle all of the chiral centers and determine how many stereoisomers each of the following molecules have.
A) B)

# of Stereoisomers: ____________ # of Stereoisomers: ____________

CONCEPT: STEREOCHEMISTRY OF MONOSACCHARIDES

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PRACTICE: Which sugar is an enantiomer of sugar A? How many stereoisomers does sugar A have? ____________
a) None of them.
b) Sugar B only.
c) Sugar C only.
d) Sugar D only.
e) Both Sugars B and D.

Monosaccharide Epimers
●____________:
epimers diastereomers that differ ONLY in configuration of any one-single chiral carbon.

epimers

HO H

PRACTICE: Use the Fischer projections of the four monosaccharides below to answer the next two problems (A & B).
A) The term that best describes the relationship of all four sugars to each other is:
a) Diastereomers. b) Enantiomers. c) Epimers.
1 2 4
3

B) Sugars 2 and 4 are:

a) C1-epimers. d) C4-epimers.
b) C2-epimers. e) C5-epimers.
c) C3-epimers.

CONCEPT: STEREOCHEMISTRY OF MONOSACCHARIDES

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●Review of the different types of monosaccharide isomers.

same

dasteromecs
noT

D L

epimer

PRACTICE: Two sugars which differ from one another only in configuration of one of many chiral carbon atoms are termed:
a) Epimers. c) Optical isomers. e) Conformers.
b) Enantiomers. d) Stereoisomers. f) None of these are correct.

CONCEPT: STEREOCHEMISTRY OF MONOSACCHARIDES

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PRACTICE: Amongst the aldopentoses shown below, identify the pairs that are enantiomers.
____ and ____

e
____ and ____
____ and ____
____ and ____

PRACTICE: Which term best describes the relationship between D-Mannose & L-Mannose?
a) Enantiomers. b) Anomers. c) Epimers. d) Diastereomers. e) Same molecules

PRACTICE: According to the Fischer projections of the following monosaccharides, circle the C-5 epimer of L-Talose?

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CONCEPT: MONOSACCHARIDE CONFIGURATIONS

●Recall: configurations of monosaccharide chiral carbons can be designated using _______ different systems:
1) Cahn-Ingold-Prelog (____/____). 2) Fischer’s Convention (____/____).

1) R/S Configuration
●Cahn-Ingold-Prelog system designates absolute ____/____ configurations.
□ Assign priorities 1 4 (based on atomic _____________) to each chemical group attached to the chiral carbon.
□ Determine if priorities 1 2 3 (ignoring 4) are in a clockwise (____) or counter-clockwise (___) configuration.
□ Only if priority ____ is on a wedge (popping out of the page), assign the opposite configuration that it “looks like.”
EXAMPLE: Determine the Cahn-Ingold-Prelog (R/S) configurations for glyceraldehyde’s chiral center:

2) D/L Configuration
●Fischer’s Convention designates ____/____ configurations relative to ____________________ enantiomers.
□ ____ configuration = -OH group __________; usually D = ____ configuration.
□ ____ configuration = -OH group __________; usually L = ____ configuration.
●Monosaccharides have the same configuration as the _______________ numbered chiral carbon.
□ In other words, a monosaccharide’s configuration is that of the chiral carbon __________ from its carbonyl group.
EXAMPLE: Determine the Fischer Convention (D/L) configurations of the following glucose monosaccharides?

Standard Fischer Projection:

- Carbonyl group is on _______.

- ______________ carbon-chain is vertical.

●Unlike biological amino acids (which are usually ___ configuration), biological carbohydrates are usually ___ configuration.
□ The reason why life prefers L-amino-acids but ____-carbohydrates is unknown.

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CONCEPT: MONOSACCHARIDE CONFIGURATIONS

PRACTICE: Identify the D/L and R/S configuration of all of the following monosaccharides:
a) ______ b) ______ c) ______ d) ______

PRACTICE: How many D-stereoisomers are possible for a D-ketopentose?

a) 4. b) 8. c) 24. d) 2. e) 16.

PRACTICE: Which TWO of the following traits apply to Fischer’s Convention for naming stereoisomers?
a) Utilizes (+) and (-) designations. d) Requires drawing the compound with aldehyde/ketone at the top.
b) Utilizes (D) and (L) designations. e) Based on optical properties of the compound in solution.
c) Utilizes (R) and (S) designations. f) Reflects stereochemistry at multiple centers.

PRACTICE: How many possible epimers of D-glucose exist?

a) 1. b) 2. c) 4. d) 6. e) 8. f) 16.

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CONCEPT: CYCLIC MONOSACCHARIDES

●Monosaccharides can cyclize to form many different rings, but 5 & 6-membered rings are most __________.
□ Furanose: monosaccharide with a ______-membered ring.
□ Pyranose: monosaccharide with a ______-membered ring.

Haworth Projections
●Cyclic monosaccharide structures are commonly depicted with ______________ Projections.
□ Darker/thicker lines pop out of the page, ____________ to us.
□ Lighter/thinner lines go into the page, ______________ away from us.
●Haworth projections can be misleading since cyclic monosaccharides are NOT planar (due to tetrahedral carbon bonds).

Standard Haworth Projection:

- Anomeric carbon is on __________-side.

- Highest numbered carbon points _____.

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CONCEPT: CYCLIC MONOSACCHARIDES

Converting Fischer Projections to Haworth Projections
●Chemical groups pointing _________ of a Fischer Projection point ____________ in a Haworth Projection.
●Chemical groups pointing _________ of a Fischer Projection point ____________ in a Haworth Projection.
EXAMPLE: Convert the D-glucose Fischer Projection into the D-glucopyranose Haworth Projection.

Assigning Numbers to the Carbons of Cyclic Monosaccharides

●Carbon atoms in cyclic monosaccharides are numbered based on positioning of the _______________ carbon.
□ Anomeric carbon: only ring carbon covalently attached to ______ oxygen atoms.
□ Anomeric carbon should be assigned the ________________ possible number.
EXAMPLE: Appropriately number the carbon atoms in the following cyclic form of glucose below.

PRACTICE: Below is the structure for a cyclic D-monosaccharide. Which labeled carbon is the anomeric carbon?
a) A. b) B. c) C. d) D. e) E. f) F.

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CONCEPT: CYCLIC MONOSACCHARIDES

PRACTICE: Which image represents the proper convention for carbon numbering of cyclic sugars?
a) A.
b) B.
c) C.
d) D.

PRACTICE: Which of the following is the correct Haworth projection of D-Gulose?

a) A.
b) B.
c) C.
d) D.

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CONCEPT: HEMIACETAL VS. HEMIKETAL

Cyclization of Monosaccharides
●Sugars cyclize via a nucleophilic addition reaction between an _____________ & an aldehyde/ketone.
□ Alcohols = ______________________ . □ Aldehydes & ketones = electrophilic.
□ Monosaccharide cyclization forms an ______________ carbon.
EXAMPLE: Alcohols react with aldehydes & ketones during monosaccharide cyclization.

Cyclization Forms Hemiacetals & Hemiketals

●Upon monosaccharide cyclization, the anomeric carbon becomes part of a relatively __________ hemiacetal or hemiketal.
□ Hemiacetals: half of an __________ group resulting from -OH + aldehyde.
□ Hemiketals: half of a __________ group resulting from -OH + ketone.
EXAMPLE: Hemiacetals & Hemiketals:

PRACTICE: Which of the following is a hemiketal?

a) A.
b) B.
c) C.
d) D.

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CONCEPT: HEMIACETAL VS. HEMIKETAL

PRACTICE: For monosaccharides to cyclize, an alcohol group must attack a carbonyl group within the same sugar.
A) Which carbon of the linear ketohexose shown below has the reactive carbonyl?
a) C1. b) C2. c) C3. d) C4. e) C5.

B) Upon cyclization, would a hemiacetal or hemiketal form?

a) Hemiacetal. b) Hemiketal.

PRACTICE: Use the image of the following glucose molecule to answer the questions.
A) Upon cyclization, which of the red circled carbons becomes the anomeric carbon?
a) A. b) B. c) C. d) D. e) E.

B) Upon cyclization, would a hemiacetal or hemiketal form?

a) Hemiacetal. b) Hemiketal.

PRACTICE: In the reaction shown below the compound on the far right is a:
a) Acetal.
b) Alcohol.
c) Ether.
d) Ester.
e) Hemiacetal.

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CONCEPT: ANOMER
Monosaccharide Cyclization Generates α and β Anomers
●________________: cyclic sugars that differ ONLY in configurations of their ______________ carbon.
□ Anomeric carbon: only ring carbon attached to ____ oxygens (used to be carbonyl carbon before cyclization).
●When a monosaccharide cyclizes, the anomeric carbon becomes a chirality center with ______ possible configurations:
1) ____ Anomer: anomeric carbon’s -OH is on the opposite side of its highest numbered carbon.
2) ____ Anomer: anomeric carbon’s -OH is on the _______ side of its highest numbered carbon.

EXAMPLE: Which of the following molecules are anomers?

a) Molecules 1 and 2.
b) Molecules 2 and 5.
c) Molecules 1 and 5.
d) Molecules 3 and 4.
e) Molecules 1 and 4.

PRACTICE: The ___/___ configuration of a monosaccharide is determined by the ________________ of the chiral carbon
furthest from the carbonyl group, while the ___/___ anomers are determined by _______________ of the anomeric carbon.
a) D ; L ; conformations ; R ; S ; configuration. d) D ; L ; configuration ; α ; β ; configuration.
b) R ; S ; conformation ; α ; β ; configuration. e) D ; L ; conformation ; α ; β ; conformation.
c) D ; L ; configuration ; α ; β ; conformation.

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CONCEPT: ANOMER
PRACTICE: Circle the  and β anomers for the following D-monosaccharide:

PRACTICE: Answer the following questions regarding the following cyclic monosaccharide shown below:
A) Clearly label the hemiacetal carbon.

B) The monosaccharide is a(n) _________ anomer.

a) Alpha ().
b) Beta (β).

C) Draw the opposite anomer.

D) Draw the  stereoisomer that differs in the arrangement of substituents at C2.

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CONCEPT: MUTAROTATION
Epimerization
●_______________________: process of interconverting epimers (changing one epimer into the other epimer).
□ Recall: epimers are diastereomers that differ ONLY in configuration of any one-__________ chiral carbon.
□ Requires a _____________ to break & reform the stable covalent bonds & change the ____________________.

Mutarotation
●_________________: a specific type of epimerization that interconverts _____________ (ex. converting α to β anomers).
□ Only _________ anomeric carbons forming a hemiacetal or hemiketal mutarotate.
●Mutarotation breaks/reforms bonds; HOWEVER, since hemiacetals/hemiketals are unstable, ______ catalyst is needed.
□ One ring anomer briefly opens up to the linear chain, then closes again to produce opposite ring anomer.

PRACTICE: The transformation of a monosaccharide to its ______________ occurs easily and does not require a catalyst.
a) Epimer. b) Anomer. c) Diastereomer. d) Enantiomer.

PRACTICE: Which of the following sugars undergoes mutarotation in neutral aqueous solution?
a) I and III.
b) III and IV.
c) II, III and IV.
d) I and IV.
e) I, II and IV.

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CONCEPT: PYRANOSE CONFORMATIONS

●Cyclic monosaccharides can exist in a variety of __________________ (potentially flexible 3D arrangements).
□ Recall: unlike configurations, conformations CAN change _____________ breaking/reforming bonds.

Pyranose Conformations
●Pyranose conformations include __________ & _________ conformations (just like cyclohexane).
□ Substituents can either occupy a more crowded __________ or a less crowded ________________ position.
□ Chair is _________ stable and thus predominates over the boat.

Boat

Chair Chair

Chair Flip
●Recall: pyranose rings can assume ______ chair conformations.
●Chair _________: process of converting one chair conformation to another.
□ Substituents change their _______/_____________ positions, but up/downwards positions are ______________.
□ Equatorial Preference: most stable conformation has bulky groups in less crowded ________________ positions.

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CONCEPT: PYRANOSE CONFORMATIONS

PRACTICE: Circle the TWO chair conformations that could apply upon cyclization of the following linear monosaccharide:

β-Anomer of Glucose Predominates

●Glucose exists predominantly in its cyclic _____-D-glucopyranose anomer.
□ Glucose composition: ~64% ____ anomer, ~35% ____ anomer, & >1% linear chain.
□ Glucose β anomer is most stable due to _________________ preference.
□ NOTE: chair-flip ≠ mutarotation.

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