Chemistry 121(01) Winter 2009 Introduction to Organic Chemistry and Biochemistry Instructor Dr. Upali Siriwardane (Ph.D. Ohio State) E-mail: upali@chem.latech.edu Office: 311 Carson Taylor Hall ; Phone: 318-257-4941; Office Hours: MTW 9:00 am - 11:00 am; TR 9:00 - 10:00 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 Winter 2009 LA Tech Chp. 21-1 Chapter 21. Enzymes and Vitamins Sections Chemistry 121 Winter 2009 LA Tech Chp. 21-2 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 21.10 Antibiotics That Inhibit Enzyme Activity 21.11 Medical Uses of Enzymes 21.12 Vitamins 21.13 Water-Soluble Vitamins 21.14 Fat-Soluble Vitamins Chemistry 121 Winter 2009 LA Tech Chp. 21-3 Chapter 21. Enzymes Nomenclature and Classification Activation Energy Enzyme-Substrate Interaction Cofactors and Coenzymes Effect of pH and Temperature Regulation of Enzyme Activity Chemistry 121 Winter 2009 LA Tech Chp. 21-4 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). Chemistry 121 Winter 2009 LA Tech Chp. 21-5 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 Chemistry 121 Winter 2009 LA Tech Chp. 21-6 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 Chemistry 121 Winter 2009 LA Tech Chp. 21-7 Effect of Enzyme on Activation Energy • Enzyme change how a reaction will proceed. • This reduces the activation energy • It makes it easier Chemistry 121 Winter 2009 LA Tech Chp. 21-8 Effect of Enzyme on Activation Energy Chemistry 121 Winter 2009 LA Tech Chp. 21-9 Effect of Substrate Concentration • For non-catalyzed reactions Reaction rate increase with concentration • Enzyme catalyzed reactions Also increase but only to a certain point Vmax Maximum velocity At Vmax, the enzyme is working as fast as it can Chemistry 121 Winter 2009 LA Tech Chp. 21-10 Effect of Substrate Concentration Chemistry 121 Winter 2009 LA Tech Chp. 21-11 Characteristics of Enzyme Active Sites • Catalytic 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. Chemistry 121 Winter 2009 LA Tech Chp. 21-12 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 Lets review each step Chemistry 121 Winter 2009 LA Tech Chp. 21-13 The Players Chemistry 121 Winter 2009 LA Tech Chp. 21-14 Formation of Enzyme-substrate Complex Chemistry 121 Winter 2009 LA Tech Chp. 21-15 Formation of the Transition State Chemistry 121 Winter 2009 LA Tech Chp. 21-16 Formation of the Enzyme-Product Complex Chemistry 121 Winter 2009 LA Tech Chp. 21-17 Chemistry 121 Winter 2009 LA Tech Chp. 21-18 Chemistry 121 Winter 2009 LA Tech Chp. 21-19 Chemistry 121 Winter 2009 LA Tech Chp. 21-20 Chemistry 121 Winter 2009 LA Tech Chp. 21-21 Chemistry 121 Winter 2009 LA Tech Chp. 21-22 Chemistry 121 Winter 2009 LA Tech Chp. 21-23 Chemistry 121 Winter 2009 LA Tech Chp. 21-24 Chemistry 121 Winter 2009 LA Tech Chp. 21-25 Chemistry 121 Winter 2009 LA Tech Chp. 21-26 Chemistry 121 Winter 2009 LA Tech Chp. 21-27 Chemistry 121 Winter 2009 LA Tech Chp. 21-28 Chemistry 121 Winter 2009 LA Tech Chp. 21-29 Chemistry 121 Winter 2009 LA Tech Chp. 21-30 Chemistry 121 Winter 2009 LA Tech Chp. 21-31 Chemistry 121 Winter 2009 LA Tech Chp. 21-32 Chemistry 121 Winter 2009 LA Tech Chp. 21-33 Chemistry 121 Winter 2009 LA Tech Chp. 21-34 Chemistry 121 Winter 2009 LA Tech Chp. 21-35 Chemistry 121 Winter 2009 LA Tech Chp. 21-36 Chemistry 121 Winter 2009 LA Tech Chp. 21-37 Chemistry 121 Winter 2009 LA Tech Chp. 21-38 Chemistry 121 Winter 2009 LA Tech Chp. 21-39 Chemistry 121 Winter 2009 LA Tech Chp. 21-40 Chemistry 121 Winter 2009 LA Tech Chp. 21-41 Chemistry 121 Winter 2009 LA Tech Chp. 21-42 Chemistry 121 Winter 2009 LA Tech Chp. 21-43 Chemistry 121 Winter 2009 LA Tech Chp. 21-44 Chemistry 121 Winter 2009 LA Tech Chp. 21-45 Chemistry 121 Winter 2009 LA Tech Chp. 21-46 Chemistry 121 Winter 2009 LA Tech Chp. 21-47 Chemistry 121 Winter 2009 LA Tech Chp. 21-48 Chemistry 121 Winter 2009 LA Tech Chp. 21-49 Chemistry 121 Winter 2009 LA Tech Chp. 21-50 Chapter Twenty One Chemistry 121 Winter 2009 LA Tech Enzymes and Vitamins Chp. 21-51 Enzymes and Vitamins cont’d ← CO 21.1 © Mark E. Gibson / CORBIS Chemistry 121 Winter 2009 LA Tech Chp. 21-52 Enzymes and Vitamins ← Fig. 21.1 Bread dough rises as a result of the action of yeast enzymes. Steven Needham / Envision Chemistry 121 Winter 2009 LA Tech Chp. 21-53 Enzymes and Vitamins cont’d Table 21.1 Chemistry 121 Winter 2009 LA Tech Chp. 21-54 Enzymes and Vitamins cont’d → Fig. 21.2 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. Chemistry 121 Winter 2009 LA Tech Chp. 21-55 Enzymes and Vitamins cont’d Fig. 21.3 The lock-and-key model for enzyme activity. Chemistry 121 Winter 2009 LA Tech Chp. 21-56 Enzymes and Vitamins cont’d Fig. 21.4 The induced-fit model for enzyme activity. Chemistry 121 Winter 2009 LA Tech Chp. 21-57 Enzymes and Vitamins cont’d ← Fig. 21.5 A schematic diagram representing amino acid R group interactions that bind a substrate to an enzyme active site. Chemistry 121 Winter 2009 LA Tech Chp. 21-58 Enzymes and Vitamins cont’d → Fig. 21.6 A graph showing the effect of temperature on the rate of enzymatic reaction. Chemistry 121 Winter 2009 LA Tech Chp. 21-59 Enzymes and Vitamins cont’d → CC 21.1 Meckles / Ottawa / Photo Researchers Chemistry 121 Winter 2009 LA Tech Chp. 21-60 Enzymes and Vitamins cont’d ← Fig. 21.7 A graph showing the effect of pH on the rate of enzymatic reaction. Chemistry 121 Winter 2009 LA Tech Chp. 21-61 Enzymes and Vitamins cont’d → CC 21.2 © Leonard Lessin / Peter Arnold, Inc. Chemistry 121 Winter 2009 LA Tech © Leonard Lessin / Peter Arnold, Inc. Chp. 21-62 Enzymes and Vitamins cont’d → Table 21.2 Chemistry 121 Winter 2009 LA Tech Chp. 21-63 Enzymes and Vitamins cont’d → Fig. 21.8 A graph showing the change in enzyme activity with a change in substrate concentration. Chemistry 121 Winter 2009 LA Tech Chp. 21-64 Enzymes and Vitamins cont’d ← Fig. 21.9 A graph showing the change in reaction rate with a change in enzyme concentration for an enzymatic reaction. Chemistry 121 Winter 2009 LA Tech Chp. 21-65 Enzymes and Vitamins cont’d CAG 21.1 Chemistry 121 Winter 2009 LA Tech Chp. 21-66 Enzymes and Vitamins cont’d → Fig. 21.10 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). Chemistry 121 Winter 2009 LA Tech Chp. 21-67 Enzymes and Vitamins cont’d ← Fig. 21.11 The difference between a reversible competitive inhibitor and a reversible noncompetitive inhibitor. Chemistry 121 Winter 2009 LA Tech Chp. 21-68 Enzymes and Vitamins cont’d → Fig. 21.12 Conversion of zymogen to a proteolytic enzyme. Chemistry 121 Winter 2009 LA Tech Chp. 21-69 Enzymes and Vitamins cont’d CAG 21.2 Chemistry 121 Winter 2009 LA Tech Chp. 21-70 Enzymes and Vitamins cont’d ← Fig. 21.13 Structures of selected sulfa drugs in use today as antibiotics. Chemistry 121 Winter 2009 LA Tech Chp. 21-71 Enzymes and Vitamins cont’d → Fig. 21.14 Structures of selected penicillins in use today as antibiotics Chemistry 121 Winter 2009 LA Tech Chp. 21-72 Enzymes and Vitamins cont’d Fig. 21.15 Selective binding of penicillin to the active site of transpeptidase. Chemistry 121 Winter 2009 LA Tech Chp. 21-73 Enzymes and Vitamins cont’d → Table 21.3 Chemistry 121 Winter 2009 LA Tech Chp. 21-74 Enzymes and Vitamins cont’d → CC 21.3 Chemistry 121 Winter 2009 LA Tech Chp. 21-75 Enzymes and Vitamins cont’d → Table 21.4 Chemistry 121 Winter 2009 LA Tech Chp. 21-76 Enzymes and Vitamins cont’d → Fig. 21.16 Drawing of a blood sample. Saturn Stills / SPL / Photo Researchers Chemistry 121 Winter 2009 LA Tech Chp. 21-77 Enzymes and Vitamins cont’d ← Fig. 21.17 Rows of cabbage plants. © Jeff Greenberg / Peter Arnold, Inc. Chemistry 121 Winter 2009 LA Tech Chp. 21-78 Enzymes and Vitamins cont’d → Fig. 21.18 The quantity of vitamin D synthesized by exposure of the skin to sunlight varies with latitude, exposure time, and skin pigmentation. Melissa Grimes-Guy / Photo Researchers Chemistry 121 Winter 2009 LA Tech Chp. 21-79 Enzymes and Vitamins cont’d → Table 21.5 Chemistry 121 Winter 2009 LA Tech Chp. 21-80 Enzymes and Vitamins cont’d → Table 21.6 Chemistry 121 Winter 2009 LA Tech Chp. 21-81 Enzymes and Vitamins cont’d → Table 21.7 Chemistry 121 Winter 2009 LA Tech Chp. 21-82