1. An Introduction W.T. Winter wtwinter@syr.edu 215 Jahn Lab; x6876

2. Overview Monosaccharides? Oligosaccharides? Polysaccharides Glycoproteins and Proteoglycans

3. Carbohydrates Are Chiral Molecules D L Glyceraldehyde Typically but not always L – amino acids D - sugars Hence, these molecules have a measurable optical rotation, which depends upon both the monomer residues and their conformation

4. Next to last carbon determines D or L New carbon is added as C1 Fisher Formulas

6. A Way to Explore Monosaccharides John Maser at Leeds has developed a “Monosaccharide Browser” the site is http://www.beechtreecommon.org/bioche mistry/monosaccharide/ http://www.beechtreecommon.org/bioche mistry/monosaccharide

7. Epimers Differ by Configuration at One Chiral Center D-glucoseC2 epimerD-mannose C3 epimerD-allose C4 epimerD-galactose C5 epimerL-idose

8. Sugars Prefer To Be Cyclic

9. Hemiacetals and Cyclization Group

10.  -D-Glucose In nature, open chain forms are rare. NMR has shown that all 5 coexist with the pyranose forms occurring 99% of the time, furanose about 0.5% each and a trace of open chain  and  are “anomers and differ in configuration at the new chiral center formed in the cycle

11. Pyranose Ring Shapes Pyranose rings can form chair and boat conformers 1 C 4 4 C 1

12. Sucrose 1-2 linked alpha glucose, beta fructose Sources sugar cane sugar beet

13. Polysaccharides Polysaccharides consist of sugar residues linked into a polymer. Polysaccharides, unlike proteins or nucleic acids, are not always linear in sequence The most abundant biomolecules in nature-about 10 12 tons of cellulose are synthesized each year Functions: structural, food storage, cell surfaces, extracellular matrices.

14. Polysaccharides May Be the Most Diverse Biomolecules From one 6 carbon hexopyranose sugar such as glucose, you can make 11 different disaccharides and 8 of those lead to infinite polymers From one amino acid or nucleotide you can make only a single dimer.  -D-Glucose  -D-Glucose

15. Cellulose: Structural polysaccharide from glucose Microfibrils of cellulose Wood cell (fiber) cell walls are made of cellulose + lignin and hemicelluloses Also found in some bacteria, algae, fungi, seed hairs, and animals (tunicates or sea squirts) n ~ 5000-10000

16. Starch: a-D-Glucose polymer found as an energy storage material in foods Amylopectin Amylose Unlike cellulose, starch can be metabolized by humans. Starches provide the bulk of the energy we obtain from grains, potatoes etc.

17. Extracellular Matrix: Hyaluronic acid A regular copolymer of N-acetyl glucosamine and Glucuronic Acid (as a metal salt)

18. HA cont Found in: synovial fluid (knee, shoulder ) Vitreous humor (eye- used in reconstructive eye surgery) Skin – small amounts in all connective tissues

19. Connective Tissues- fibrous proteins, polysaccharides, and proteoglcans

20. Other Structural Polysaccharides Mannans – some algae Alginic acids – many algae Chitin- insects, crustaceans (shrimp shell), fungi.