part iv: carbohydratesnielssi/download/5. semester/biological chemistry … · carbohydrates in...
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Part IV: Carbohydrates
Biological Chemistry I: Nucleic Acids & Carbohydrates
Prof. Helma Wennemers
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• Occurrence and Importance in Nature • Nomenclature – anomeric effect • Structure
• Synthesis – Glycosylation – Protecting Groups • Functions
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Carbohydrates in Nature
15000 years ago (Spider cave, Valencia)
Structural Energy storage (Glycolysis)
Cellulose Chitin Amylose
OOHO
OH
OHO
O HOOH
OH
n
OOHO
HO
OH
OHO
OH
OH
n
O
poly α(1-4)-glucopyranose poly β(1-4)-glucopyranose
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Carbohydrates in Nature (cont.) Molecular Recognition
Neomycin
Blood type determinants Streptomycin
Antibiotics
O A
B AB
O OH
OHOH
H3C
O
OOR
OHHOOHO
HOHOO
OH
O OH
OHOH
H3C
O
OOR
OHHOOHO
HOAcHNO
OH
A B
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Carbohydrates in Nature (cont.) Molecular Recognition Leucozyte adhesion upon inflammation!
Sialyl Lewis x (sLex) - ligand for selectins
OH
O
HOAcHN
CO2HHO OH
OO
OH OH
OH
O
OO
OHOR
NHAc
O
OH
H3C
OHOH
N-Acetyl Neuraminsäure Galaktose N-Acetyl glukose
Fucose
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Emil Fischer (1852 – 1919)
.....studied with Adolf von Baeyer earned his PhD on phthalein dyes 1874 – Assistant instructor - discovered the first hydrazine base, phenylhydrazine 1881 – Professor of Chemistry at the University of Erlangen Gastritis problems force leave of absence and caused him to refuse a tempting offer to follow Victor Meyer at the ETH Zurich 1888 – Professor of Chemistry at the University of Würzburg 1892 – Chair of Chemistry at the University of Berlin 1902 – Nobel Prize in Chemistry for his work on sugar and purine syntheses
....according to his father: „Der Junge ist zum Kaufmann zu dumm, er soll studieren“
Emil Fischer. Aus meinem Leben. Berlin, 1922, S. 45 (Buch auf zeno.org)
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„In its early youth organic chemistry was so closely connected with biology. I do consider it not only possible but desirable, that the close connexion of chemistry and biology [....] should be reestablished, as the great chemical secrets of life are only to be unveiled by cooperative work.“
Emil Fischer, Faraday Lecture: Synthetic Chemistry in its Relation to Biology, J. Chem. Soc. 1907, 1749.
Emil Fischer (1852 – 1919)
http://www.nobel.se/chemistry/laureates/1902/fischer-bio.html Kunz, H. „Emil Fischer - Unequalled Classicist, Master of Organic Chemistry Research, and Inspired Trailblazer of Biological Chemistry“ Angew. Chem. Int. Ed.2002, 41, 4439-4451
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OOH
OH
CO2HAcNHHO OH
OH
Most Common Monosaccharides in Mammals
HOO
HO
CO2H
OH
HO
HOO
AcNH
OH
OH
HO
HOO
HO
OH
OH
HOHO
O
HO
OHHO
OH
HOO
HO OH
HO O OH
OHOH
H3COH
HOO
AcNH
OHHO
OH
Glucose (Glc) Galactose (Gal) Mannose (Man)
Xylose (Xyl) Fucose (Fuc) Glucuronic acid (GluA)
N-Acetylgalactosamine (GlcNAc)
N-Acetylglucosamine (GalNAc)
N-Acetylneuraminic acid Sialic acid (NANA)
HOO
OH
OH
HOOH
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Carbohydrates – Nomenclature
Fuc α-(1→2)Gal β-(1→3)GalNAc β-(1→3)Gal α-(1→4)Gal β-(1→4)Glc
O OH
OHOH
H3C
O
OO
OHHO
HOO
NHAcO
OHHOO
HO
OHHO
O
OH
OHO
HO O
OH
OH
HOO
OH
α α
β
β β reducing end
non-reducing end
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Cellulose β(1->4) glycosidic linkages
www.biologie.uni-hamburg.de/ b-online/e26/26a.htm courses.cm.utexas.edu/.../ ch339k/overheads-2.htm
Carbohydrates – Structure
OOHO
OH
OHO
O HOOH
OH
n
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Amylose and Amylopectin Amylose Amylopectin
additionally α(1->6) branches
Carbohydrates – Structure (cont.) α(1->4) glycosidic linkages
OOHO
HO
OH
OHO
OH
OH
n
O
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Glycoproteins
N-linked – via Asn
O-linked! via Ser or Thr
anti freeze glycopeptide
NH
O
O
HOO
AcNH
OH
NH
HOO
AcNH
OH
OOHOOH
O
HOO
HOHO
O
HOO
AcNH
OHO
O
O OH
OHOH
H3C
O
O
OHHO
HOHO
O
AcNH
OHO O
OH
OHHO
O
HOO
HOHO
O
HOO
AcNH
OHO
O
O OH
OHOH
H3C
O
O
OHHO
HOHO
O
AcNH
OHO O
OH
OHHO
O
H-type 2 Blood Group Determinant
Lactosamine Spacer
High Mannose Region Chitobiose
NH
O
HN
NH
O
O
OO
AcNH
OHHO
O
HOO
AcNH
OHHO
n
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Glycolipids
HOO
HO
OHHO
ONH
HOO 5
nn = 6,8,10,...
HOO
HO
OH
ONH
HOO 5
nn = 6,8,10,...
HO
e.g. Cerebrosides (belong to the group of glycosphingolipids)
in nerve cells
in liver, and spleen (Glc) tissue