9780471303091

Enzyme Kinetics : Behavior and Analysis of Rapid Equilibrium and Steady-State Enzyme Systems

by
  • ISBN13:

    9780471303091

  • ISBN10:

    0471303097

  • Format: Paperback
  • Copyright: 1993-05-06
  • Publisher: Wiley-Interscience

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Summary

Covers enzyme kinetics from its most elementary aspects to such modern subjects as steady-state, multi-reactant kinetics and isotope exchange. Offers an understanding of the behavior of enzyme systems and the diagnostic tools used to characterize them and determine kinetic mechanisms. Illustrates and explains current subjects such as cumulative, concerted and cooperative feedback inhibition and metal ion activation.

Table of Contents

Introduction---Enzymes As Biological Catalysts
The Discovery of Enzymes and the Development of Enzymology
1(3)
Life, Energy, and Coupled Reactions
4(1)
Enzymes as Catalysts
5(2)
The Active Site
7(2)
Three-Point Attachment
9(1)
The Flexible Enzyme-Induced Fit Hypothesis
10(2)
Factors Responsible for the Catalytic Efficiency of Enzymes
12(2)
Enzyme Kinetics
14(4)
References
15(3)
Kinetics of Unireactant Enzymes
The Henry Equation and the Michaelis-Menten Equation
18(4)
General Rules for Writing Velocity Equations for Rapid Equilibrium Systems
22(3)
The Van Slyke Equation
25(1)
The Briggs-Haldane Steady-State Approach
25(4)
Reversible Reactions---Effect of Product on Forward Velocity
29(5)
Haldane Relatioship Between Kinetic Constants and the Equilibrium Constant
34(3)
Specific (or Relative or Reduced) Substrate Concentration and Velocity
37(1)
Velocity Versus Substrate Concentration Curve
38(1)
Reaction Order
39(5)
Graphical Determination of Km and Vmax
44(10)
Lineweaver-Burk Reciprocal Plot: 1/v versus 1/[S]
46(1)
Substrate Concentration Range
46(1)
Labeling the Axes of Reciprocal Plots
46(4)
Graphical Analysis as a Method of Solving Simultaneuous Equations
50(1)
Effect of Impure Substrate on Km and Vmax
50(1)
Eisenthal, Cornish-Bowden Plot and New Dixon Plot
51(2)
Log v Versus Log [S] Plot
53(1)
Integrated Form of the Henri-Michaelis-Menten Equation
54(10)
Integrated Rate Equation Assuming No Product Inhibition (Kms ≪ Kmp) and that Keq Is Very Large
54(3)
Determination of Km and Vmax from [S] and v
57(2)
Integrated Rate Equation Where Kmp ≌ Kms and Keq Is Very Large
59(2)
Integrated Rate Equation Where Kmp ≌ Kms and Keq Is Not Very Large
61(3)
Multiple Enzymes Catalyzing the Same Reaction
64(8)
Kinetic Behavior at High Enzyme Concentrations
72(5)
Enzyme Assays
77(12)
Initial Velocity as a Function of [E]t
78(1)
Enzyme Units and Specific Activities---Quantitating [E]t
78(1)
Turnover Number
79(1)
Quantitation of [E]t Using the Integrated Velocity Equation
80(1)
Reporting Data
80(1)
Enzyme Purification
81(2)
Determination of v
83(1)
Assays with Auxillary Enzymes
83(2)
Kinetics of Coupled Assays
85(4)
Effects of Endogenous Substrates
89(11)
References
97(3)
Simple Inhibition Systems
Competitive Inhibition (Simple Intersecting Linear Competitive Inhibition)
100(25)
Effect of Concentration Range on Degree of Inhibition
106(1)
Reciprocal Plot for Competitive Inhibition Systems
107(1)
Replots of Slope and Kmapp Versus [I]
108(1)
Dixon Plot for Competitive Inhibition: 1/v versus [I]
109(2)
General Principles
111(1)
Integrated Rate Equation in the Presence of a Competitive Inhibitor
112(1)
Competitive Inhibition and Total Velocity with Mixed Alternative Substrates
113(5)
Apparent Competitive Inhibition by Carrier Dilution (Isotope Competition)
118(2)
Competitive Product Inhibition Where [S] + [P] is Constant (Regulation Via ``Energy Charge'')
120(5)
Noncompetitive Inhibition (Simple Intersecting Linear Noncompetitive Inhibition)
125(11)
General Principles
132(1)
Reciprocal Plot for Noncompetitive Inhibition Systems
132(1)
Replots of Slope 1/s and 1/Vmax, Versus [I]
133(1)
Dixon Plot for Noncompetitive Inhibition: 1/v Versus [I]
134(1)
Integrated Rate Equation in the Presence of a Noncompetitive Inhibitor
135(1)
Uncompetitive Inhibition (Simple Linear Uncompetitive Inhibition)
136(7)
Reciprocal Plot for Uncompetitive Inhibition
141(1)
Replots of 1/Vmax, and 1/Kmapp Versus [I]
141(2)
Dixon Plot for Uncompetitive Inhibition: 1/v Versus [I]
143(1)
Integrated Rate Equation in the Presence of an Uncompetitive Inhibitor
143(1)
Effects of Contaminating Inhibitors on the Initial Velocity Versus Enzyme Concentration Plot
143(7)
Other Factors Producing Nonlinear v Versus [E]t Plots
147(1)
Contaminating Inhibitors in the Substrate
147(3)
Tightly Bound Inhibitors
150(11)
References
159(2)
Rapid Equilibrium Partial and Mixed-Type Inhibition
Partial Competitive Inhibition (Simple Intersecting Hyperbolic Competitive Inhibition)
161(5)
Partial Noncompetitive Inhibition (Simple Intersecting Hyperbolic Noncompetitive Inhibition)
166(4)
Mixed-Type Inhibition
170(32)
Linear Mixed-Type Inhibition
170(8)
Hyperbolic Mixed-Type Inhibition
178(4)
Intersection Points in Mixed Inhibition Systems
182(10)
Two-Site Model for Partial Inhibition
192(4)
Apparent Partial or Mixed-Type Inhibition Resulting from Multiple Enzymes
196(2)
Reduction of Steady-State Velocity Equation to Rapid Equilibrium Form
198(4)
Reciprocal Plot Nomenclature
202(1)
Interaction Between Inhibitor and Substrate
203(5)
Other Methods of Plotting Enzyme Kinetics Data
208(19)
The Hanes-Woolf Plot: [S]/v Versus [S]
210(1)
The Woolf-Augustinsson-Hofstee Plot: v Versus v/[S]
210(4)
The Eadie-Scatchard Plot: v/[S] Versus v
214(1)
The Eadie-Scatchard Plot: v/[S] Versus v
214(4)
The Scatchard Plot for Equilibrium Binding Data: [S]b/[S]f Versus [S]b or [S]b/[S]f[E]t Versus [S]b/[E]t
218(2)
Isotope Competition in Equilibrium Ligand Binding
220(4)
References
224(3)
Enzyme Activation
Nonessential Activation
227(15)
General Scheme for Nonessential Activation
227(4)
Inhibitor Competitive with Nonessential Activator
231(1)
Nonessential Activation By Two Competing Activators that Alter Only Ks
232(2)
Nonessential Activator Acts as Deinhibitor (Anti-inhibitor)
234(6)
``Energy Charge'' Regulation: [I] + [A] Pool Is Constant
240(2)
Substrate-Activator Complex Is the True Substrate
242(32)
Only SA Binds to the Enzyme
245(5)
SA and S Bind to the Enzyme
250(5)
SA and A Bind to the Enzyme
255(3)
SA, S, and A Bind to the Enzyme
258(5)
A Is an Essential Activator
263(4)
A Is a Nonessential Activator; Only SA Binds to the Catalytic Site
267(3)
Both S and SA Are Substrates (ES and ESA Are Catalytically Active)
270(2)
References
272(2)
Rapid Equilibrium Bireactant and Terreactant Systems
Random Bireactant Systems
274(46)
Initial Velocity Studies
274(9)
Inhibitor Competes With One Substrate
283(10)
I Is a Nonexclusive Inhibitor
293(6)
Product Inhibition in Rapid Equilibrium Random Bireactant Systems
299(10)
Substrate Inhibition in Rapid Equilibrium Random Systems
309(11)
Ordered Bireactant Systems
320(10)
Random Terreactant Systems
330(7)
Ordered and Hybrid Random-Ordered Terreactant Systems
337(5)
Rules for Predicting Inhibition Patterns in Rapid Equilibrium Systems
342(4)
References
344(2)
Multisite and Allosteric Enzymes
Enzymes With Multiple Catalytic Sites
346(39)
Noncooperative Sites
346(7)
Allosteric Enzymes---Cooperative Binding
353(2)
Adair-Pauling Simple Sequential Interaction Model
355(1)
Interaction Factors
355(3)
A Note on Terminology Regarding ``Interaction Factors''
358(2)
A Simplified Velocity Equation for Allosteric Enzymes---The Hill Equation
360(2)
Sigmoidicity of the Velocity Curve
362(1)
Inflection Point of the Velocity Curve
362(3)
Lineweaver-Burk Plot for Allosteric Enzymes
365(2)
Eadie-Scatchard Plot for Allosteric Enzymes
367(4)
The Hill Plot---Logarithmic Form of the Hill Equation
371(3)
Summary of Differen Uses of the Symbol n
374(1)
Effect of Interaction Strengths on the Velocity Curve
375(2)
Negative Cooperativity
377(5)
Interaction that Affects Vmax
382(3)
Inhibition and Activation in Multisite Systems
385(19)
Pure Competitive Inhibition, Exclusive at Both Substrate Sites (``Ligand Exclusion'')
385(2)
Inhibition Competitive at Two Sites
387(2)
General Equation for the Two-Site Pure Competitive System
389(1)
Partial Competitive Inhibition
390(8)
Substrate Activation
398(3)
Multiple Essential Activator Sites
401(2)
Cooperative Essential Activation
403(1)
The General Sequential Interaction Model of Koshland, Nemethy, and Filmer (Restricted Interactions Between Sites)
404(17)
Dimer Model
407(4)
Tetramer Models
411(4)
Nonidentical Subunits
415(1)
Inhibition and Activation---A Dimer Model
416(3)
Independent Binding Model
419(2)
Summary
421(1)
The Symmetry Model of Allosteric Enzymes (The Concerted Transition Model of Monod, Wyman, and Changeux)
421(39)
Derivation of the General Velocity Equation
422(5)
Exclusive Ligand Binding
427(1)
Effect of L and c on Cooperativity
428(3)
V Systems
431(1)
Mixed K and V Systems
432(1)
Comparison and Formal Equivalence of the Sequential and Concerted Models
432(2)
Inhibition in Exclusive Binding K Systems
434(6)
Activation in Exclusive Binding K Systems
440(5)
Horn-Bornig Plot to Determine n and L (When c = 0)
445(4)
Combinations of Alternative Effectors
449(1)
Competitive Inhibition
450(1)
Nonexclusive Substrate and Effector Binding
451(1)
Determination of KST, KSR, and c in Nonexclusive K Systems
452(2)
Determination of n
454(1)
Determination of L' and L
455(1)
Consequences of Nonexclusive Ligand Binding
455(2)
General and Hybrid Models
457(3)
Alternative Kinetic Explanations for Sigmoidal Responses
460(5)
References
462(3)
Multiple Inhibition Analysis
Multiple Sites for a Given Inhibitor
465(9)
Hill Equation and Hill Plots for Multisite Inhibition
470(4)
Inhibition by Mixtures of Different Inhibitors
474(32)
Pure Competitive Inhibition by Two Different Exclusive Inhibitors
474(5)
Noncompetitive and Mixed-Type Inhibition by Two Different Mutually Exclusive Inhibitors
479(2)
Cooperative (Synergistic) Pure Competitive Inhibition by Two Different Nonexclusive Inhibitors
481(7)
Cooperative (Synergistic) Noncompetitive Inhibition by Two Different Nonexclusive Inhibitors
488(4)
Cooperative (Synergistic) Uncompetitive Inhibitors
492(1)
I Is Competitive and X Is Noncompetitive With Respect to S
493(2)
Two Partial Inhibitors
495(3)
Concerted (Multivalent) Inhibition by Two Different Inhibitors
498(6)
References
504(2)
Steady-State Kinetics of Multireactant Enzymes
The King-Altman Method of Deriving Steady-State Velocity Equations
506(9)
Uni Uni Reactions
506(9)
Isomerization of Central Complexes
515(1)
Simplification of Complex King-Altman Patterns
515(8)
General Rules for Defining Kinetic Constants and Deriving Velocity Equations
523(11)
Cleland Nomenclature
523(1)
Maximal Velocities and Keq
523(1)
Michaelis Constants
523(1)
Inhibition Constants
524(1)
Isoinhibition Constants
525(1)
Velocity Equation for the Forward Direction
525(1)
Velocity Equation for the Reverse Direction
526(1)
Haldane Equations
527(1)
A Shortcut for Obtaining Velocity Equations
528(1)
Rate Constants
528(1)
Distribution Equations
528(2)
Alternative Nomenclature
530(3)
Kslope and Kint Nomenclature
533(1)
Iso Uni Uni System (Mobile Carrier Model of Membrane Transport)
534(10)
Ordered Uni Bi and Ordered Bi Uni Systems
544(16)
Complete Velocity Equation---Product Inhibition
551(6)
Calculation of Rate Constants
557(3)
Distribution Equations
560(1)
Effect of Isomerizations
560(1)
Ordered Bi Bi System
560(31)
Initial Forward Velocity in the Absence of Products
564(1)
Other Methods of Plotting Data
565(9)
Complete Velocity Equation---Product Inhibition
574(12)
Kislope and Kiint
586(2)
Calculation of Rate Constants
588(1)
Distribution Equations
589(1)
Effect of Isomerizations
589(1)
Agreement of Kinetic Data With the Haldane Equations
589(2)
Partial Rapid Equilibrium Ordered Bi Bi System
591(2)
Theorell-Chance Bi Bi System
593(13)
Product Inhibition
595(2)
Rate Constants
597(7)
Distribution Equations
604(1)
Effect of Isomerizations
604(1)
Reduction of Ordered Bi Bi to Theorell-Chance
605(1)
Evaluating the Kinetic Significance of the Central Complexes
605(1)
Ping Pong Bi Bi System
606(19)
Initial Forward Velocity in the Absence of Products
608(4)
Haldane Equations
612(4)
Product Inhibition
616(5)
Distribution Equations
621(1)
Effect of Isomerizations
621(1)
Effect of Impure Substrates
621(1)
Prestedy-State ``Burst'' Phenomenon With Ping Pong Enzymes
621(2)
Ordered Bi Bi Systems That Appear to be Ping Pong
623(2)
Partial Rapid Equilibrium Ping Pong Bi Bi Systems
625(1)
Hybrid Ping Pong---Rapid Equilibrium Random (Two-Site) Bi Bi Systems
626(8)
Iso Bi Bi Systems
634(5)
Hybrid Theorell-Chance Ping Pong (and Iso Ping Pong) Systems
639(4)
Rapid Equilibrium Random Bi Bi Systems
643(3)
Steady-State Random Mechanisms
646(3)
Partial Rapid Equilibrium Random Bi Bi System
649(8)
Varieties of Nonhyperbolic Velocity Curves
657(8)
Random Bi Bi Systems
657(1)
Unireactant Systems
658(2)
Hybrid Ping Pong-Ordered and Ping Pong-Random Bi Bi Systems
660(5)
Ordered Ter Bi System
665(19)
Velocity Equation, Kinetic Constants, and Haldane Equations
665(2)
Rate Constants
667(1)
Distribution Equations
667(1)
Effect of Isomerizations
668(1)
Initial Velocity Studies in the Forward Direction
669(3)
Plots With Two Changing Fixed Substrates
672(2)
Varying Two Substrates Together
674(1)
Product Inhibition
675(5)
Reverse Direction---Ordered Bi Ter
680(3)
Reduction to Rapid Equilibrium Ordered Ter Bi
683(1)
Bi Uni Uni Uni Ping Pong Ter Bi System
684(15)
Reaction Sequence
684(1)
Velocity Equation, Kinetic Constants, and Haldane Equations
684(2)
Rate Constants
686(1)
Distribution Equations
686(1)
Effect of Isomerizations
687(1)
Initial Velocity Studies in the Forward Direction
687(3)
Plots With Two Changing Fixed Substrates
690(1)
Varying Two Substrates Together
691(1)
Product Inhibition Studies
692(4)
Reverse Direction---Uni Uni Uni Bi Ping Pong Bi Ter
696(2)
Multiple Inhibition Studies
698(1)
Alternate Designation---Uni Bi Uni Uni Ping Pong Bi Ter
699(1)
Ordered Ter Ter System
699(5)
Velocity Equation, Kinetic Constants, and Haldane Equations
699(3)
Rate Constants
702(1)
Distribution Equations
702(1)
Effect of Isomerizations
703(1)
Initial Velocity in the Forward and Reverse Directions
704(1)
Product Inhibition Studies
704(1)
Partial Rapid Equilibrium Ordered Terreactant Systems
704(2)
Ordered Terreactant Systems With Rapid Equilibrium Random Sequences
706(5)
Random A--B, Ordered C
706(4)
Ordered A, Random B-C
710(1)
Bi Uni Uni Bi Ping Pong Ter Ter System
711(8)
Reaction Sequence
711(3)
Velocity Equation, Kinetic Constants, and Haldane Equations
714(2)
Rate Constants
716(1)
Distribution Equations
716(1)
Effect of Isomerizations
716(1)
Initial Velocity Studies in the Forward Direction
717(1)
Product Inhibition Studies
717(2)
Bi Bi Uni Uni Ping Pong Ter Ter System
719(8)
Reaction Sequence
719(1)
Velocity Equation, Kinetic Constants, and Haldane Equations
720(2)
Rate Constants
722(1)
Distribution Equations
722(1)
Effect of Isomerizations
723(1)
Initial Velocity Studies in the Forward Direction
723(1)
Product Inhibition Studies
723(3)
Reverse Direction---Uni Uni Bi Bi Ping Pong Ter Ter
726(1)
Hexa Uni Ping Pong System
727(9)
Velocity Equation, Kinetic Constants, and Haldane Equations
727(2)
Rate Constants
729(1)
Distribution Equations
729(1)
Effect of Isomerizations
730(1)
Initial Velocity Studies in the Forward Direction
730(1)
Product Inhibition Studies
731(5)
Summary of Nonrandom Terreactant Systems
736(4)
Other Possible Terreactant Systems
740(9)
Theorell-Chance Systems
740(1)
Terreactant Ping Pong Systems With Rapid Equilibrium Segments
741(1)
Terreactant Ping Pong Systems With Rapid Equilibrium Random Segments
742(2)
Hybrid (Two-Site) Rapid Equilibrium Random-Ping Pong Bi Bi Uni Uni System
744(5)
Quadreactant Systems
749(1)
General Rules for Predicting Initial Velocity Patterns
749(18)
Intercept Effects
750(1)
Exceptions to the Intercept Rule
750(1)
Slope Effects
751(1)
Effect of Irreversible Sequences
752(5)
Substrates That Add Twice
757(1)
Product Inhibition
757(1)
Establishing a Reversible Connection by Adding Another Product
758(1)
Modification of Slope and Intercept Rules for Steady-State Systems With Rapid Equilibrium Segments
759(8)
Dead-End Inhibition
767(16)
General Rules
779(1)
Multiple Inhibition Analysis
780(3)
Dead-End Inhibitors Versus Alternative Substrates
783(1)
Mixed Dead-End and Product Inhibition
783(10)
Velocity Equations
788(3)
Dead-End Complexes With the Normal Enzyme Form
791(2)
Inhibition by Alternative Substrates
793(20)
Ordered Bi Bi With Alternative A
793(5)
Ordered Bi Bi With Alternative B
798(4)
Alternative Substrates That Promote a Partial Reaction in an Ordered Sequence
802(1)
Ping Pong Bi Bi With Alternative Substrates
803(7)
Alternative Substrates That Promote a Partial Ping Pong Reaction Sequence
810(1)
Measurement of Common Product
811(2)
Inhibition by Alternative Products
813(5)
Substrate Inhibition
818(12)
Substrate Inhibition in an Ordered Bireactant System
819(7)
Substrate Inhibition in Ping Pong Systems
826(4)
A Review of Inhibition Systems
830(17)
Linear Inhibition
831(2)
Parabolic Inhibition
833(1)
Hyperbolic Inhibition
833(3)
More Complex Types of Nonlinear Inhibition Systems
836(5)
References
841(6)
Isotope Exchange
Ordered Bi Bi
847(6)
Random Bi Bi System
853(1)
Isotope Exchange During A Net Reaction
854(1)
Ping Pong Systems
855(5)
Determining Exchange Velocities
860(4)
Determining Keq
864(1)
Derivation of Isotope Exchange Velocity Equations
864(20)
References
882(2)
Effects of pH and Temperature
Effect of pH
884(42)
Effect of pH on Enzyme Stability
884(4)
System A1. All Forms of ``E'' Bind S; Only E``S Yields Product
888(5)
Plots of Vmaxapp Versus pH and 1/slope Versus pH
893(3)
Dixon-Webb Log Plots
896(2)
Correction for Ionization of the Substrate
898(4)
Varieties of pH Responses
902(1)
System A2. Only E'' Binds S; Only E``S Yields Product
902(2)
Treating H+ as a Substrate
904(3)
System A3. En and En+1 Bind S; Only EnS and En-1S Yield Product
907(6)
System A5. General System: All Forms of ``E'' Bind S; All Forms of ``E''S Yield Product
913(1)
A Diprotic System Where Successive pK Values of the Enzyme are Closer Than 3.5 pH Units
914(3)
Displacement of pK Values Under Nonrapid Equilibrium Conditions
917(3)
Effect of the Ionization of EP
920(3)
Limitations of pH Studies
923(1)
Choice of Buffers
924(1)
Ionic Strength Effects
924(2)
Effect of Temperature
926(17)
Temperature Effects on Enzyme Stability
926(3)
Identifying Prototropic Groups From ΔHion
929(1)
Effect of Temperature on Km and Ki
930(1)
The Collision Theory and the Arrhenius Equation---Energy of Activation
931(3)
Eyring Transition State Theory---Absolute Reaction Rates
934(7)
Thermodynamics of Enzyme Inactivation
941(1)
References
941(2)
Appendix Least Squares Method 943(2)
Index 945

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