Chp. 21-1 Chemistry 121 Winter 2009 LA Tech Introduction to Organic Chemistry and Biochemistry Instructor Dr. Upali Siriwardane (Ph.D. Ohio State) E-mail:

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Chp Chemistry 121 Winter 2009 LA Tech Introduction to Organic Chemistry and Biochemistry Instructor Dr. Upali Siriwardane (Ph.D. Ohio State) Office: 311 Carson Taylor Hall ; Phone: ; Office Hours: MTW 9:00 am - 11:00 am; TR 9: :00 am & 1:00-2:00 pm. December 19, Test 1 (Chapters 12-14) January 2 Test 1 (Chapters 15-16) February 6 (Chapters 17-19) February 27, (Chapters 20 & 22) March 2, 2009, Make Up Exam: Bring Scantron Sheet 882-E Chemistry 121(01) Winter 2009

Chp Chemistry 121 Winter 2009 LA Tech Chapter 21. Enzymes and Vitamins Sections

Chp Chemistry 121 Winter 2009 LA Tech Chapter 21. Enzymes and Vitamins 21.1 General Characteristics of Enzymes 21.2 Nomenclature and Classification of Enzymes 21.3 Enzyme Structure 21.4 Models of Enzyme Action 21.5 Enzyme Specificity 21.6 Factors That Affect Enzyme Activity 21.7 Enzyme Inhibition 21.8 Regulation of Enzyme Activity: Allosteric Enzymes 21.9 Regulation of Enzyme Activity: Zymogens Antibiotics That Inhibit Enzyme Activity Medical Uses of Enzymes Vitamins Water-Soluble Vitamins Fat-Soluble Vitamins

Chp Chemistry 121 Winter 2009 LA Tech Chapter 21. Enzymes Nomenclature and Classification Activation Energy Enzyme-Substrate Interaction Cofactors and Coenzymes Effect of pH and Temperature Regulation of Enzyme Activity

Chp Chemistry 121 Winter 2009 LA Tech Biological Catalysts Typically very large proteins Permit reactions to to “go” to conditions that the body can tolerate Can process millions of molecules per second Are very specific-react with one or only a few types of molecules (substrates).

Chp Chemistry 121 Winter 2009 LA Tech Enzyme Nomenclature Naming is easy compared to other organic compounds Name is based on:-What it reacts with -how it reacts -add -ase- ending Examples lactase enzyme that reacts with lactose pyruvate decarboxylase remove carboxyl group from pyruvate

Chp Chemistry 121 Winter 2009 LA Tech Classification of Enzymes Oxidoreductases: catalyze oxidation-reduction. Transferases: transfer of functional groups. Hydrolases: catalyze hydrolysis reactions. Lyases: catalyse the removal of chemical groups. Isomerases: catalyze isomerization reactions. Ligases: catalyze formation of chemical bonds, join two molecules

Chp Chemistry 121 Winter 2009 LA Tech Effect of Enzyme on Activation Energy Enzyme change how a reaction will proceed. This reduces the activation energy It makes it easier

Chp Chemistry 121 Winter 2009 LA Tech Effect of Enzyme on Activation Energy

Chp Chemistry 121 Winter 2009 LA Tech Effect of Substrate Concentration For non-catalyzed reactions Reaction rate increase with concentration Enzyme catalyzed reactions Also increase but only to a certain point V max V max Maximum velocity V max At V max, the enzyme is working as fast as it can

Chp Chemistry 121 Winter 2009 LA Tech Effect of Substrate Concentration

Chp Chemistry 121 Winter 2009 LA Tech Characteristics of Enzyme Active Sites Catalytic siteCatalytic site Where the reaction actually occurs. Binding site Area that holds substrate in proper place. Enzyme uses weak, non-covalent interactions to hold the substrate in place based on alkyl (R) groups of amino acids. Shape is complementary to the substrate and determines the specificity of the enzyme. Sites are pockets or clefts on enzyme surface.

Chp Chemistry 121 Winter 2009 LA Tech Steps in Enzymatic Reactions Enzyme and substrate combine to form a complex Complex goes through a transition state -which is not quite substrate or product A complex of the enzyme and the product is produced Finally the enzyme and product separate All these steps are equilibria All these steps are equilibria Lets review each step Lets review each step

Chp Chemistry 121 Winter 2009 LA Tech The Players

Chp Chemistry 121 Winter 2009 LA Tech Formation of Enzyme-substrate Complex

Chp Chemistry 121 Winter 2009 LA Tech Formation of the Transition State

Chp Chemistry 121 Winter 2009 LA Tech Formation of the Enzyme-Product Complex

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech

Chp Chemistry 121 Winter 2009 LA Tech Chapter Twenty One Enzymes and Vitamins

Chp Chemistry 121 Winter 2009 LA Tech Enzymes and Vitamins cont’d © Mark E. Gibson / CORBIS ← CO 21.1

Chp Chemistry 121 Winter 2009 LA Tech ← Fig Bread dough rises as a result of the action of yeast enzymes. Enzymes and Vitamins Steven Needham / Envision

Chp Chemistry 121 Winter 2009 LA Tech Table 21.1 Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech → Fig The active site of an enzyme is usually a crevice-like region formed as a result of the protein’s secondary and tertiary structural characteristics. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech Fig The lock-and-key model for enzyme activity. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech Fig The induced-fit model for enzyme activity. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech ← Fig A schematic diagram representing amino acid R group interactions that bind a substrate to an enzyme active site. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech → Fig A graph showing the effect of temperature on the rate of enzymatic reaction. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech Enzymes and Vitamins cont’d Meckles / Ottawa / Photo Researchers → CC 21.1

Chp Chemistry 121 Winter 2009 LA Tech ← Fig A graph showing the effect of pH on the rate of enzymatic reaction. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech Enzymes and Vitamins cont’d © Leonard Lessin / Peter Arnold, Inc. → CC 21.2

Chp Chemistry 121 Winter 2009 LA Tech → Table 21.2 Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech → Fig A graph showing the change in enzyme activity with a change in substrate concentration. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech ← Fig A graph showing the change in reaction rate with a change in enzyme concentration for an enzymatic reaction. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech Enzymes and Vitamins cont’d  CAG 21.1

Chp Chemistry 121 Winter 2009 LA Tech → Fig A comparison of an enzyme with a substance at its active site (a) and an enzyme with a competitive inhibitor at its active site (b). Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech ← Fig The difference between a reversible competitive inhibitor and a reversible noncompetitive inhibitor. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech → Fig Conversion of zymogen to a proteolytic enzyme. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech Enzymes and Vitamins cont’d CAG 21.2

Chp Chemistry 121 Winter 2009 LA Tech ← Fig Structures of selected sulfa drugs in use today as antibiotics. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech → Fig Structures of selected penicillins in use today as antibiotics Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech Fig Selective binding of penicillin to the active site of transpeptidase. Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech → Table 21.3 Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech → CC 21.3 Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech → Table 21.4 Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech → Fig Drawing of a blood sample. Enzymes and Vitamins cont’d Saturn Stills / SPL / Photo Researchers

Chp Chemistry 121 Winter 2009 LA Tech ← Fig Rows of cabbage plants. Enzymes and Vitamins cont’d © Jeff Greenberg / Peter Arnold, Inc.

Chp Chemistry 121 Winter 2009 LA Tech → Fig The quantity of vitamin D synthesized by exposure of the skin to sunlight varies with latitude, exposure time, and skin pigmentation. Enzymes and Vitamins cont’d Melissa Grimes-Guy / Photo Researchers

Chp Chemistry 121 Winter 2009 LA Tech → Table 21.5 Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech → Table 21.6 Enzymes and Vitamins cont’d

Chp Chemistry 121 Winter 2009 LA Tech → Table 21.7 Enzymes and Vitamins cont’d