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Chapter 21 Biochemistry
Lipids
chemicals of the cell that are insoluble in water,
but soluble in nonpolar solvents fatty acids, fats, oils, phospholipids, glycolipids, some vitamins, steroids, and waxes structural components of cell membrane
because they dont dissolve in water
Fatty Acids
carboxylic acid (head) with a very long
hydrocarbon side-chain (tail) saturated fatty acids contain no C=C double bonds in the hydrocarbon side-chain unsaturated fatty acids have C=C double bonds
monounsaturated have 1 C=C polyunsaturated have more than 1 C=C Tail
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2
Head
O C OH
Fatty Acids
Stearic Acid C18H36O2 a saturated fatty acid
O CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 C OH
Fatty Acids
CH2 CH2
OH
CH2 O O O
O C O C O C
ester linkage
CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3 CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3 CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3
OH
CH2 CH2
CH2 OH Glycerol
Tristearin
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Triglycerides
triglycerides differ in the length of the fatty acid sidechains and degree of unsaturation
side chains range from 12 to 20 C most natural triglycerides have different fatty acid chains in the triglyceride, simple triglycerides have 3 identical chains warm-blooded animal fat solids
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Phospholipids
Esters of glycerol Glycerol attached to 2 fatty acids and 1 phosphate group Phospholipids have a hydrophilic head due to
phosphate group, and a hydrophobic tail from the fatty acid hydrocarbon chain part of lipid bilayer found in animal cell membranes
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Phosphatidyl Choline
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Lipid Bilayer
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Glycolipids
similar structure and properties to the
phospholipids the nonpolar part composed of a fatty acid chain and a hydrocarbon chain the polar part is a sugar molecule
e.g., glucose
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Glucosylcerebroside
(found in plasma membranes of nonneural cells)
HO
CH2 OH HC HC OH C HO H O O CH CH OH
H CH C CH N CH2
H C C O
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Steroids
characterized by 4 linked carbon
rings mostly hydrocarbon-like dissolve in animal fat mostly have hormonal effects serum cholesterol levels linked to heart disease and stroke levels depend on diet, exercise, emotional stress, genetics, etc. cholesterol synthesized in the liver from saturated fats
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Steroids
CH3 OH
CH3 CH3 CH3 CH3 CH3 HO
CH3
testosterone
CH3 OH
cholesterol
HO
estrogen b-estradiol
Tro, Chemistry: A Molecular Approach 20
Carbohydrates
carbon, hydrogen, and oxygen ratio of H:O = 2:1
same as in water
contain carbonyl groups and alcohol groups the many polar groups make simple carbohydrates
soluble in water
blood transport
Classification of Carbohydrates
hydroxycarbonyls - have many OH and one C=O
aldose when C=O is aldehyde, ketose when C=O is ketone
names of mono and disaccharides all end in ose monosaccharides - cannot be broken down into
simpler carbohydrates
triose, tetrose, pentose, hexose
Saccharides
Carbohydrate Glucose (mono) Fructose (mono) Galactose (mono) Sucrose (disac) Maltose (disac) Lactose (disac) Starch (poly) Cellulose (poly) Formula Source C6H12O6 blood, plants, fruit, honey C6H12O6 plants, fruit, honey C6H12O6 C12H22O11 sugar cane & beets, maple syrup, fruits & veggies C12H22O11 partial hydrolysis of starch C12H22O11 milk (5%) potatoes, corn, grains cell wall of plants
Optical Activity
there are always
several chiral carbons in a carbohydrate resulting in many possible optical isomers
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H C HOH2C
OH O C H
HO C HOH2C
H O C H
D-(d)-Glyceraldehyde
H HOH2C HO H C C H OH O
L-(l)-Glyceraldehyde
H HOH2C H C C H OH OH O
D-(l)-Erythrose
O C H H C C OH OH H
D-(l)-Threose
O C H HO C C OH H H
CH2OH
Tro, Chemistry: A Molecular Approach
CH2OH
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Ring Structure
H O
O
H OH
OH H
HO
H CH2OH
Ribose
H OH
H OH
HO H HO H
OH H
CH2OH H
Glucose
HO H
H OH
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Cyclic Monosaccharides
oxygen attached to second last carbon
bonds to carbonyl carbon
acetal formation
convert carbonyl to OH
transfer H from original O to carbonyl O
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Glucose
aka blood sugar, grape
sugar, and dextrose aldohexose = sugar containing aldehyde group and 6 carbons source of energy for cells
5 to 6 grams in blood stream supply energy for about 15 minutes
Tro, Chemistry: A Molecular Approach 29
Fructose
aka levulose, fruit sugar ketohexose = sugar
containing ketone group and 6 carbons sweetest known natural sugar
HOH2C H H OH H
OH CH2OH OH
O HOH2C
HO H CH2OH
HO H
Tro, Chemistry: A Molecular Approach
H OH
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Galactose
occurs in brain and
nervous system only difference between glucose and galactose is spatial orientation of groups on C4
Glucose
Tro, Chemistry: A Molecular Approach 31
Sucrose
also known as table sugar, cane
sugar, beet sugar glucose + fructose = sucrose a - 1:2-linkage involves aldehyde group from glucose and ketone group from fructose
gyclosidic link
nonreducing
Tro, Chemistry: A Molecular Approach 32
Sucrose
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disaccharides into monosaccharides hydrolysis is the addition of water to break glycosidic link
under acidic or basic conditions
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Polysaccharides
aka complex carbohydrates polymer of monosaccharide units bonded
together in a chain the glycosidic link between units may be either a or b
in a, the rings are all oriented the same direction in b, the rings alternate orientation
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made of glucose rings linked together give only glucose on hydrolysis starch
main energy storage medium digestible, soft, and chewy 1,4 - a link amylose and amylopectin
amylopectin chains branch
cellulose
not digestible fibrous, plant structural material 1,4 - b link allows neighboring chains to H-bond
resulting in rigid structure
glycogen
structure similar to amylopectin, except highly branched used for excess glucose storage in animal muscles
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Proteins
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Amino Acids
a-amino acids about 20 amino acids found in proteins 10 synthesized by humans, 10 essential each amino acid has 3 letter abbreviation glycine = Gly high melting points generally decompose at temp > 200C good solubility in water less acidic than most carboxylic acids and less basic than most amines
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Amino Acids
building blocks of proteins main difference between amino acids is the side
chain
R group
some R groups are polar, others are nonpolar some polar R groups are acidic, others are basic some R groups contain O, others N, and others
S some R groups are rings, other are chains
Tro, Chemistry: A Molecular Approach 41
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CH3 C H2N H O OH
NH H2N N H H2 C
H2 C H C C H2 NH2
O OH
NH2 O
NH2 OH O O
OH
NH2 OH O
C C H H2
C C H H2
Arginine Arg H2 C O NH2 C C H H2 O Glutamine Gln NH2 H2 C H C H3C C H CH CH3 O Isoleucine Ile O OH HO
O H2C NH2
Glycine Gly
H2 C O H2 C H C C H2 NH2
OH
C C H H2 Histidine His
OH
NH2
Leucine Leu
Lysine Lys
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H3C S
H2 C
NH2 C C H H2
OH
O
HC HC
H C C H CH
H2 O C H OH C NH2
H2C
H2 C H C
O H2 C H CH C OH HO NH2
Methionine Met
OH C H3C H H C NH2
Phenylalanine Phe
C NH H2 Proline Pro
Serine Ser
O OH HC
H H C C C H
H2 C H C N H Tryptophan Trp CH
NH2
Threonine Thr
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Optical Activity
the a carbon is chiral on the amino acids
except for glycine
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Protein Structure
the structure of a protein is key to its function most proteins are classified as either fibrous or globular fibrous proteins have linear, simple structure
insoluble in water used in structural features of the cell
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amino acids in the polypeptide link COOH group of first to NH2 of second
loss of water, condensation form an amide structure peptide bond
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H2N CH R2
C OH
H2O
peptide bond
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Secondary Structure
short range repeating patterns found in protein chains maintained by interactions between amino acids that
are near each other in the chain formed and held by H-bonds between NH and C=O a-helix
most common
b-pleated sheet many proteins have sections that are a-helix, other sections are b-sheets and others are random coils
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a-Helix
amino acid chain wrapped in a tight coil with
the R groups pointing outward from the coil the pitch is the distance between the coils the pitch and helix diameter ensure bond angles are not strained and H-bonds are as strong as possible
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a-Helix
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b-Pleated Sheet
extended chain forms a zig-zag pattern chains linked together by H-bonds silk
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Tertiary Structure
hydrophobic interactions
between large, nonpolar R groups
salt bridges
between acidic and basic R groups
Tro, Chemistry: A Molecular Approach 58
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Cysteine
the amino acid cysteine performs a
unique function in protein structure cysteine units on remote parts of the peptide chain can react together, forming a disulfide bond the disulfide bond ties parts of the chain together, contributing to the tertiary structure
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Quaternary Structure
many proteins are composed of multiple amino
acid chains the way the chains are linked together is called quaternary structure interactions between chains the same as in tertiary structure
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Nucleic Acids
carry genetic information DNA molar mass = 6 to 16 million amu RNA molar mass = 20K to 40K amu made of nucleotides
phosphoric acid unit 5 carbon sugar cyclic amine (base)
Nucleotide Structure
each nucleotide has 3 parts a cyclic pentose, a
phosphate group, and an organic aromatic base the pentoses are ribose or deoxyribose the pentoses are the central backbone of the nucleotide the pentose is attached to the organic base at C1 and to the phosphate group at C5
OH O P OH O O CH2 H H OH H
O N H H
NH2
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Sugars
HOH2C H H OH H H
OH H
HOH2C H H OH
O
H OH
OH H
Deoxyribose
Ribose
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Bases
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Organic Bases
NH2 N N N N H H2N N N OH N N H O N N H NH2 CH CH O HN N H CH O CH3 O HN N H O CH CH
Adenine
Guanine
Cytosine
Thymine
Uracil
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Bases
Purine Bases
Pyrimidine Bases
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Nucleotide Formation
HOH2C H H OH H H
OH H
H N N
N N NH2
HOH2C H H OH
O
H H H
N N
N N NH2
H2O
NH2 N N N
NH2
O HO P OH O
O HO P OH OH
HOH2C
O
H OH H H
N
H
H2 C
H H OH
N N
O
H H
N
H
H2O
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O O P P O O O O
4 C C4 1 2
5 O 5 O H H C 2C 2
Base Base C 1C H
H HC 3 C H
2 CH
CH
O
O
OH H
O
O Base C4
O H2C 5
O H2C 5
Base O 1C C 43 2 1 C H H HC 3 CH 2 H H HC CH
OH H
OH H
Tro, Chemistry: A Molecular Approach 71
Linking Nucleotides
OH O P OH O O CH2 H H OH H O N H H N NH2
OH O P OH O O CH2 H H H O O P O OH CH2 H H OH H
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O N H H
NH2
+
OH O P OH O O CH2 H H OH H
Tro, Chemistry: A Molecular Approach
+ H2O
O O N H H N NH2
O N H H
NH2
Nucleotide Chain
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Chromosomes
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DNA
RNA
ribonucleic acid sugar is ribose one of the following amine bases
adenine (A) guanine (G) cytosine (C) uracil (U)
DNA Structure
DNA made of two strands linked together
by H-bonds between bases strands are antiparallel
one runs 3 5, other runs 5 3
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Base Pairing
base pairing generates the
Thymine
O
helical structure H3C in DNA, the complementary bases hold strands together HC by H-bonding N H allow replication of strand
H
N O H
H Adenine N N NH N N
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DNA Replication
when the DNA is to be replicated, the region to
be replicated uncoils this H-bond between the base pairs is broken, separating the two strands with the aid of enzymes, new strands of DNA are constructed by linking the complementary nucleotides to the original strand together
Tro, Chemistry: A Molecular Approach 82
DNA Replication
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Protein Synthesis
transcription translation in nucleus, DNA strand at gene separates and a
complementary copy of the gene is made in RNA
messenger RNA = mRNA
Protein Synthesis
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