BIOCHEMISTRY – LECTURE (MIDTERMS) HOW TO CLASSIFY CARBOHYDRATES

1. NUMBER OF CARBONS
CARBOHYDRATE METABOLISM PART I - Suffix ‘ose’ – carbohydrates

CARBOHYDRATES GENERIC NAMES EXAMPLES

- “Hydrates of carbon” 3 Carbons: Triose Glyceraldehyde
- General formula: Cn(H2O)n 4 carbons: Tetroses Erythrose
- Polyhydroxy aldehydes/ketones 5 carbons: Pentoses Ribose (present in nucleic acids)
- Water-soluble (polar compounds) 6 carbons: Hexoses - Glucose
- Sweet taste - Fructose
- Most abundant organic molecule - Galactose
- Most common example: Glucose - Mannose
7 carbons: Heptoses Sedoheptulose
ROLES OF CARBOHYDRATES 9 carbons: Nonose Neuraminic acid (present in nervous
system)
Energy Source Carbohydrates give energy
Storage Molecule Monosaccharides – building block 2. TYPE OF CARBONYL GROUP PRESENT
Polymer – polysaccharides  NAMING:
- Aldose – glucose (aldehyde containing)
Main storage Starch – plants - Ketone – ‘ul’ (ketose)
molecules for Glycogen – animals  Examples:
energy: o Xylose = xylulose
Cellular Present as glycoprotein o Ribose = ribulose
Communication - Can help in signaling certain
communication within the cells. MONOSACCHARIDES: STRUCTURE
- Can also be present as glycolipids 1. FISCHER PROJECTION
- In glycolipids, sugars are bound to - 2D diagram of 3D chirality
non-sugar components. - Numbering starts from carbonyl carbon
- Only for amino acids and monosaccharides
2 COMPONENTS OF GLYCOPROTEIN:  Amino acids:
- Carbohydrates o Humans: L sugar
- Protein  Monosaccharides:
Structural Polymer Examples: o Humans: D sugar
- Cellulose – important structural 2. ISOMER
polymer; plants - Molecules having the same formula, different structure
- Peptidoglycan – bacteria - Monosaccharides often occur as isomers
- Chitin – present in 1 fungi, insects and o Epimers
crustaceans  Isomers that differ at only 1 carbon
 Monnose – Carbon 2 Epimer of
Glucose
 Galactose – Carbon 4 Epimer of
Glucose

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 - Ability of sugar to undergo oxidation becomes the basis of
o Enantiomer another way of classifying them whether they are reducing
 Non super-imposable mirror image sugars or not
 Sugars exists as a ring not linear structure in - Oxidation = reducing sugar
solution - All monosaccharides are reducing sugar but not all
 1 hydroxyl (OH) group will react with the disaccharides
carbonyl carbon forming a ring - Basis for some color reactions
- For oxidation to happen, hydroxyl group must be free for
3. CYCLIZATION ring to revert to open-chain form
- One hydroxyl group reacts with carbonyl carbon - Oxidation of terminal OH
o Anomeric carbon o Aldose = alduronic acid (suffix ‘uronic acid’)
 Anomers  Glucoronic acid: Important for the body bc
 Sugars/monosaccharides that differs only in it is used/added to substances marked to
the hydroxyl group orientation at the be excreted
carbonyl carbon  Vitamic C: humans cannot produce vitamin
 Isomers but not epimer c
 Only occur when monosaccharide forms a - Both terminal and aldehyde hydroxyl group
ring o Aldose = aldaric acid (suffix ‘aric acid’)
 Pyran/pyranose – 6 membered ring (most 4. Reduction
stable and dominant for glucose) - Reduction of aldehyde group
 Furan/furanose – 5 membered ring o Sugars can also get reduced producing alditol
o Haworth projection o Aldehyde = alcohol (suffix ‘itol’)
o Cyclic form of sugar  Non-sucrose sweeteners
o Fischer projection o Glucitol/sorbitol (glucose that is reduced)
o Linear o Xylitol (xylose)
5. Amine Formation
MONOSACCHARIDES: REACTION - One of the hydroxyl groups gets replaced by amino groups
1. Mutarotation o Glucose = glucosamine (suffix ‘amine’)
- Interconversion between two cyclic groups - May be further transformed by addition of acetyl group
- In solution, equilibrium is present (both -beta and -alpha o Glucosamine
glucopyranose) o N-acetylglucosamine (component of cell wall;
- Beta D glucopyranose is much stable present in chitin)
2. Phosphorylation - Present of these amine sugar helps form some structural
- Simple addition of phosphate group carbohydrates
- Helps traps sugars inside the cell 6. Polymerization
- Lipid bilayer: non-polar - Monomer = polymer through the formation of glycosidic
- Activate sugar for further reaction bonds
- Condensation between phosphoric acid and hydroxyl group - Dehydration reaction
3. Oxidation o Loss of water
- Oxidation of aldehyde groups o Position of anomeric hydroxyl group of first sugar
o Aldose = aldonic acid (suffix ‘onic acid’) o Locants of C group
- Undergoes oxidation, LEORA - Can also form between non-carbohydrate components
o Glycoprotein = carbohydrate & protein

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 o Certain proteins are made up of non-protein o Oligosaccharide
components - 3-10 polymerization
- Simple Proteins
o Without non-protein component (pure protein)
o Ribosomes o Polysaccharide
- Conjugated Proteins - Carbohydates that have more than 10 up to 100
o With non-protein component (glycoprotein, sugar or monosaccharides bound together
lipid) - Rings do not open
o Golgi apparatus: responsible for the production of - Non-reducing & not sweet
conjugated proteins - Limited water solubility
- Need to be broken down into their monosaccharide before
o Disaccharide they can absorb and metabolize
- Formation of 2 polymerization - Destroyed by enzymes like amylase – you will get a lot of
 Examples: disaccharides when amylase destroyed polysaccharides.
o Sucrose These disaccharides need to be broken down by
- Glucose + Fructose in α(1,2) glycosidic disaccharidases. After breaking these down,
bond monosaccharides will now be absorbed by glucose
- Example of non-reducing sugar because it transporter.
no longer has a free anomeric hydroxyl
group (hindi na pwede magkaron ng o Homopolymer
aldehyde and oxidation and limited water - 1 repeating monosaccharide to form polysaccharide
solubility) o Heteropolymer
o Lactose - More than monosaccharide makes up
- Galactose + Glucose in β(1,4) polysaccharide
o Maltose - Examples:
- Glucose + Glucose (differs only in the  Starch
orientation of glycosidic bond)  Repeating glucose (-alpha 1,4)
- Alpha glycosidic bond  Starch is composed of amylose and mainly
o Cellubioles (cellulose) of amylopectin which has a more branched
- Component of cellulose structure (alpha 1,6 introduces branching)
- Glucose + Glucose (differs only in the  Amylose (20%)
orientation of glycosidic bond) o Less branched
- Beta glycosidic o Alpha (1,4)
- CANNOT BE ABSORBED but can help in  Amylopectin (80%)
digestion o More branched
- Alphaglucosidase: enzyme in the human o α(1,4) and α(1,6)
body responsible for the breakdown of - Glycogen
alphaglycosidic bond  More branched
- Betaglucosidase: only in bacterium  Molecule that is present only in the liver and
muscles
- Cellulose
 Most abundant organic substance on earth
 β(1,4)

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DIETARY CARBOHYDRATES: DIGESTION
 Goal: Breakdown monosaccharides to polysaccharide
 Can only use 1 monosaccharide
 Primary site of digestion: mouth & small intestines
 Glycoside hydrolases/glycosidases/glucosidase: Enzyme
responsible for breaking them down
 Amylases
- Initial digestive enzyme
- Can only break alpha 1,4 glycosidic bonds
 Salivary α-amylase
 Pancreatic α-amylase
 Dextrins
- Short branched oligosaccharides
 Disaccharidases
- Final digestive enzyme
- Maltase for maltose
- Sucrase for sucrose
- Lactase (β-galactosidase) for lactose
DIETARY CARBOHYDRATES: ABSORPTION
1. GLUcose Transporter (GLUT)
- Exists in the membrane
- Uses facilitated diffusion (used in bringing glucose)
- Along the gradient of glucose
- Certain tissues will have different form of glucose
transporter
- Tissue specific pattern of expression
o Insulin increases GLUT in muscle and adipose
tissue
 Insulin
- Peptide hormone
- Higher fed state = lower blood glucose
- It increases glucose transporter in
muscle and adipose tissue
o GLUT in the testes primarily transports fructose
instead of glucose
2. Sodium-dependent GLucose co-Transporter (SGLT)
- Transports glucose against its gradient
- Active transport channel
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- Uses existing Na+ gradient (Sodium will flow along its
concentration gradient. However, since they travel
together, glucose will enter into the cell)
- In specific tissues e.g. renal tubules
o Removes all glucose in urine
 Glucosuria – presence of glucose in
the urine (renal damage)
 SGLT ARE NO LONGER
FUNCTIONING PERHAPS
RENAL CELLS ARE ALREADY
GETTING DESTROYED
o SGLT-2 inhibitors: -gliflozin
 Gliflozin – to lower blood glucose
 Adverse effect: severe urinary tract
infection
DIETARY CARBOHYDRATES: FIBER
Dietary Fiber
- Naiiwan na cellulose since most animals have alpha but not
beta glycosidase
o Present in some bacteria
- Undigested plant material
o Primarily cellulose helps our intestines (small and
large) in its motility
ABNORMAL DEGRADATION
- In absence of specific disaccharidase activity
o Increased diffusion of water into large intestine:
osmotic diarrhea
o Bacterial fermentation: abdominal cramps, flatulence
 Produces acids, CO2
- Example: Lactose intolerance
o Age-dependent loss of lactase (all carbohydrates are
left as disaccharides and these disaccharides are able
to take up water. GI lining is watery that’s why we
experience osmotic diarrhea. Bacteria can ferment the
remaining disaccharides and it will form acids and
gases)
o More common in adults of African or Asian descent
 ANABOLISM
CARBOHYDRATE METABOLISM PART II  Build up small molecules into
Metabolism big molecules
- Reactions rarely occur in isolation  Synthetic (it creates new
- Must meet the need of cells molecules)
 Metabolic Pathways  Divergent (common
- Reactions are organized into multi-step, purposeful metabolites and from these
sequences common metabolites, you’ll
- Product of one reaction becomes the substrate of the get varied polymers)
next reaction  Uses energy (ATP)
 Connected via metabolites  Reactions are reductive (gain
 Metabolites – common metabolic electrons)
intermediates (e.g. pyruvate)  Reducing agents
 Glycolysis = pyruvate (has certain (NADH & NADPH)
enzyme that acts on pyruvate to make  Good supply of
it Acetyl Coenzyme A) reducing agents is a
o Acetyl Coenzyme A – must to undergo
connected to Triacylglycerols anabolism
synthesis
o Pyruvate Nicotinamide Adenine Dinucleotide
- Reduced form: NADH
METABOLIC PATHWAY OF AMINO ACIDS - Oxidized form: NAD+
CATABOLISM
 Cut down big molecules into
small molecules
 Degradative (break down
polymers into monomers)
 Convergent (all various
biomolecules convert into a
small group of metabolites)
 Releases energy
 Reactions are oxidative
o Oxidative (uses
NAD+)
o A lot of oxidizing
agents is needed to
undergo catabolism
such as NAD+
 Must increase to supply the
energy need for anabolism

NADPH
- Has a phosphate in structure
(phosphorylated)

CATABOLISM:
 Stage 1: Hydrolysis of complex molecules to their component
building blocks
o Proteases – breaks down proteins and peptide bonds
of proteins
o Disaccharidases – breaks down glycosidic bonds of
sugar
o Lipases – break down ester bonds of triacylglycerols to
make their monomers
 Stage 2: Conversion of building blocks to Acetyl CoA (or other
simple intermediates)
 Stage 3: Oxidation of acetyl CoA; oxidative phosphorylation

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REGULATION OF METABOLISM STAGES:
- Metabolism meets cellular needs Energy-Investment Phase Energy-Payoff Phase
 Speed up  cell deposits ATP  oxidative conversion of
 Slow down - Must slow down to prevent destroying the  phosphorylation of glucose glyceraldehyde 3-
biomolecules and its conversion to phosphate to pyruvate and
glyceraldehyde 3- the occupied formation of
INTRACELLULAR INTERCELLULAR phosphate ATP and NADH
COMMUNICATION COMMUNICATION  Uses an ATP molecule to
 Within the cell  Between cells make glucose into
 Rapid regulation  Slower response glucose-6-phosphate
 Synaptic
Rate of reaction influenced by: signaling – uses ENERGY INVESTMENT
 Availability of substrates neurotransmitters 1. Hexokinase  Uses ATP
 Product inhibition  Endocrine  Irreversible phosphorylation
signaling – uses of glucose
hormones (e.g.  Kinases use Mg2+
peptide hormone  Enzyme that catalyzes
insulin) phosphorylation of glucose
 Direct contact to glucose-6-phosphate
 Important for the organism 2. Phosphohexose  Isomerase: simple
to integrate all metabolic Isomerase rearrangement of molecule
pathways occurring in a cell  Changes Glucose-6-
phosphate to Fructose-6-
SECONDARY MESSENGERS phosphate
 External Molecules 3. Phosphofructokinase -  Uses ATP
- Must bind to the receptors to have an effect in any given cell 1 (PFK-1)  Irreversible
- Cascades the message form externa messenger to the o Rate-limiting
ultimate intracellular effect o Committed step
 Neurotransmitters  Fructose-6-phosphate into
 Hormones fructose-1,6-bisphosphates
 Secondary Messenger Systems (brings messages from (kasi nagkaron ng 2
external that is binded to the receptor going to the ultimate phosphate groups)
effect)  REGULATES:
o Adenylyl cyclase – enzyme o ATP and citrate
o Phosphatidylinositol system – kind of lipid o Adenosine
monophosphate –
GLYCOLYSIS present in a low
- Breakdown of glucose energy state;
- Ten (10) steps provides feedback
- Products: pyruvate, ATP, NADH but it does not inhibit
but rather activate
this enzyme;
decreases the

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 activity of PFK-1
o Fructose 2,6-
bisphosphate – it is
a metabolite that
promotes glycolysis
while inhibiting
gluconeogenesis
4. Aldolase  Enzyme that breaks fructose
1,6-bisphophate
 Catalyzes the cleavage of
fructose, 1,6-bisphosphate to
form glyceraldehyde 3-
phosphate and
dihydroxyacetone phosphate
5. Triose phosphate  Only glyceraldehyde 3-P
isomerase gets to proceed with
glycolysis
 Turns ketone into aldehyde
 Converts Dihydroxyacetone
phosphate to
glyceraldehyde-3-Phosphate
ENERGY PAY-OFF
1. Glyceraldehyde 3-  Produces NADH
phosphate  First redox reaction in
dehydrogenase glycolysis because aldehyde
becomes carboxylic acid
 Uses inorganic phosphate
2. Phosphoglycerate  Produces ATP
kinase
Substrate level phosphorylation
- When the substrates of the
pathway generates ATP
- Phenomenon when substrate
cell can create ATP
- When ATP is produced
directly from a substrate
rather than from the
reduction of O2 in the
electron transport chain
3. Phosphoglycerate  
mutase
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4. Enolase 
5. Pyruvate kinase  Produces ATP
 Irreversible
 Fructose-1,6-bisphophate
increases the rate of reaction
of pyruvate kinase
Pyruvate Dehydrogenase
- Three enzyme complex
- Enzyme that oxidizes pyruvate (3 carbon compound) to Acetyl
CoA (2 carbon compound)
 FIVE COENZYMES
 Lipoic acid
 Thiamine – vitamin b1
 FAD – flavin adenine dinucleotide; vitamin b2 (riboflavin)
 NAD – vitamin b3 (thiasine or nicotinamide)
 Coenzyme A – vitamin b5 (pantothenic)
Krebs Cycle
 Central metabolic pathways to all the pathways of biomolecules
 Tricarboxylic acid cycle because it uses a metabolite that is a
tricarboxylic acid molecule
 Produces 3 NADH, 1 ATP & 1 FADH2 (for Acetyl CoA)
 Also called citric acid cycle
 Convergence of carbohydrate, amino acid, fatty acid catabolism
 Produces majority of ATP
 Aerobic
KREBS CYCLE REACTIONS
1. Citrate Synthase  Irreversible
 Catalyzes the condensation of
Acetyl CoA from pyruvate
dehydrogenase and oxaloacetate
to form citrate (which is TCA)
2. Acotinase  Isomerization of citrate molecule
o Citrate > isocitrate
3. Isocitrate  Irreversible
dehydrogenase  Removes carboxyl group
 Produces NADH
Releases CO2
 Decarboxylation – oxidative
reaction; for every oxidation there
 must be a reduction  Complex IV: Cytochrome oxidase (because oxygen will be
o NAD+ reduced to NADH attached here) H2O become O2
4. α-ketoglutarate  Produces NADH  Cytochrome c transfers electrons from Complex III to Complex
dehydrogenase  Release CO2 IV
complex  CO, CN-, NaN3: inhibit Complex IV
5. Succinate  Coupled to phosphorylation of  ATP synthase (Complex V)
thiokinase GDP (Guanosine Diphosphate) to  Chemiosmotic theory: H+ gradient drives ATP synthesis
GTP (Guanosine Triphosphate)  Glycolysis: 2 ATP, 2 NADH per glucose
 Substrate-level phosphorylation  Malate-aspartate shuttle
 Converts succinyl CoA to  Glycerol 3-phosphate shuttle
succinate  PDH: 1 NADH per pyruvate
 Phosphorylated succinyl CoA  Krebs: 1 GTP, 3 NADH, 1 FADH2 per acetyl CoA
which contains thiol bond by
nature of having CoA
6. Succinate  Produces FADH2 ADDITIONAL NOTES:
dehydrogenase  Complex II of ETC Glycogenesis – making of glycogen
 Dehydrogenation – another Glycogenolysis – breaking down of glycogen
redox reaction Pentose Phosphate Pathway – ribose, cellulose and ribulose (which
 Part of electron transport chain are made of 5 carbon sugar)
7. Fumarase  Phosphorylation – simple addition of phosphate to a given molecule
8. Malate  Produces final NADH (purpose: to trap molecule inside the cell and to activate it for further
dehydrogenase  Turn malate back into reaction)
oxaloacetate Glucose – a monosaccharide converted prior to their breakdown
o Oxaloacetate – 5 ATP molecules per glucose molecule from the PDH complex
Intermediate in the Krebs
cycle serves as the
acceptor of Acetyl CoA to
form citrate

ELECTRON TRANSPORT CHAIN

 Complex I: NADH dehydrogenase
o Rotenone, amyta
 block electron transfer from Complex I to CoQ
 compounds that prevent complex I from being
its electron to CoQ (inhibitor of complex I)
 Complex II: Succinate dehydrogenase; accepts FADH2
 Complex III: Ubiquinone: cytochrome c oxidoreductase
 Coenzyme Q transfers electrons from Complex I and II to
Complex III
 Antimycin A: blocks electron transfer within Complex III;
inihibitor of Complex III

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