- 열역학 : 물질내의 물리적 화학적 변화를 동반하는 에너지변환을 연구하는 학문

- 생체에너지론 : 생물체내 에너지변환을 연구

- 생화학반응의 3 가지 중요한 인자 : 엔탈피 ( 총 열함량 ), 엔트로피 ( 무질서 ),
자유에너지 ( 화학적 일을 하는데 이용할 수 있는 에너지 )
- 자유에너지 : 화학반응의 자발성을 가름함

4.1 열역학
- 제 1 법칙 : 우주의 총 에너지는 일정 , 단지 한 형태에서 다른 형태로 전환될 수 있다 .
- 제 2 법칙 : 우주의 무질서가 증가함 , 화학반응은 무질서도가 증가하는 방향으로
-3 법칙 : 완전한 결정고체의 온도가 절대온도 영도 (0K) 에 근접할 때 무질서도는 0 에
근접하게 된다 .
-1,2 법칙은 생물계내의 에너지변환에 사용
- 우주 ( 시스템과 주위 ) 에서 열과 에너지변환
- 시스템 ?
열린 시스템 : 물질과 에너지는 시스템과 주위 사이에 교환됨
닫힌 시스템 : 에너지만 교환
- 글루코스분자의 에너지함량은 같다 : 일과 열로 변환

From McKee and McKee, Biochemistry,

International Fifth Edition, © 2012
Oxford University Press
 Energy
Chapter 4
Overview
 Section 4.1: Thermodynamics
 Section 4.2: Free Energy
 Section 4.3: The Role of ATP

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.1:
Thermodynamics
 Energy is the basic constituent of the universe
 Energy is the capacity to do work
 In living organisms, work is powered with the energy
provided by ATP
 Thermodynamics is the study of energy transformations
that accompany physical and chemical changes in matter
 Bioenergetics is the branch that deals with living
organisms

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.1:
Thermodynamics
 Three laws of thermodynamics:
 First Law of Thermodynamics—Energy cannot be created nor
destroyed, but can be transformed
 Second Law of Thermodynamics—Disorder always increases
 Third Law of Thermodynamics—As the temperature of a
perfect crystalline solid approaches absolute zero, disorder
approaches zero

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.1:
Thermodynamics

 Bioenergetics is especially important in understanding

biochemical reactions
 These reactions are affected by three factors:
 Enthalpy—total heat content
 Entropy—state of disorder
 Free Energy—energy available to do chemical work

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.1:
Thermodynamics
 First two laws are powerful
biochemical tools
 Thermodynamic transformations take
place in a universe composed of a
system and its surroundings
 Energy exchange between a system
and its surroundings can happen in
two ways: heat (q) or work (w)
 Work is the displacement or movement
of an object by force
Figure 4.1 A Thermodynamic
Universe

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
(1) 제 1 법칙
-ΔE = q + w ( 시스템의 에너지변화 = 주위로부터 시스템에 의해 흡수된 에너지 +
주위에 의해 시스템에 행해진 일 )
-( 화학자 ) H= E + PV ( 엔탈피 = 압력 - 부피일 )
- ΔH = ΔE ( 일정한 압력의 생화학반응에서 ): 생물계의 총에너지의 변화가 시스템에
의해 방출 혹은 흡수된 에너지와 같음
- ΔH<0, 발열반응 , ΔH>0, 흡열반응
- ΔH 반응 = ΣΔH 생성물 – ΣΔH 반응물
- 문제 4.1-2

- (2) 제 2 법칙
- 반응이 일어나는지의 예측 , 자발적인지 ?
- 모든 자발적인 반응과정은 우주의 총 질서를 증가시키는 방향으로 일어난다 ( 그림
4.2)
- 휘발유연소시 탄소원자들이 무작위로 분산된다 ( 그림 4.3)
- 엔트로피 (S): 자발적인 반응에 대해 양성

From McKee and McKee, Biochemistry,

International Fifth Edition, © 2012
Oxford University Press
 Section 4.1:
Thermodynamics
 First Law of Thermodynamics
 Expresses the relationship between internal energy (E) in a
closed system and heat (q) and work (w)
 Total energy of a closed system (e.g., our universe) is
constant
 DE = q + w
 Unlike a human body, which is an open system
 Enthalpy (H) is related to internal energy by the equation: H
= E + PV
 DH is often equal to DE (DH = DE)

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.1:
Thermodynamics
 First Law of Thermodynamics Continued
 If DH is negative (DH <0) the reaction gives off heat:
exothermic
 If is DH positive (DH >0) the reaction takes in heat from its
surroundings: endothermic
 In isothermic reactions (DH =0) no heat is exchanged
 Reaction enthalpy can also be calculated:
 DHreaction = SDHproducts  SDHreactants
 Standard enthalpy of formation per mole (25°C, 1 atm) is
symbolized by DHf°

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.1:
Thermodynamics

 As a result of spontaneous
processes, matter and energy
become more disorganized
 Gasoline combustion
 The degree of disorder is
measured by the state function
entropy (S)

Figure 4.3 Gasoline Combustion

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
4.2 자유에너지
- 엔트로피측정의 불가능 , 자유에너지를 유도
- ΔS= ΔS 주위 + ΔS 시스템
- ΔS 주위는 특정 화학적 또는 물리적 변화가 일어나는 동안 K 온도에 대해 교환된
열의 양 : = -ΔH/T
- -T ΔS 우주 = ΔH - T ΔS 시스템
- -T ΔS 우주는 깁스자유에너지변화 또는 ΔG 라 함
- ΔG= ΔH - T ΔS
- 그림 4.4: 자유에너지 변화는 ΔS 우주가 양성일 때 음성인데 , 이는 자발적인
반응이 자유에너지감소 (exergonic) 반응임을 나타낸다 .
- ΔG=0 면 그 반응은 평형상태임

(1) 표준자유에너지
- 표준자유에너지 ΔG0 는 용질 1.0M 농도 , 1.0 기압 , 250C 에서 일어나는 반응
- 자유에너지변화는 반응의 평형상수와 관련 ( 정반응과 역반응의 반응속도가
동일할 때 )
- 평형상태 (ΔG=0) 에서 ΔG0= -RTlnKeq
- Keq 를 알면 ΔG0 계산가능
- ΔG0’: 대부분 생화학반응은 pH7.0 부근에서 일어나고 , 생체에너지론에서 1M
용질표준에서 일어나므로 이같이 표기
- 문제 4.3 From McKee and McKee, Biochemistry,
International Fifth Edition, © 2012
Oxford University Press
 Section 4.1:
Thermodynamics
Figure 4.2 A Living Cell as a
Thermodynamic System

 Second Law of Thermodynamics

 Physical or chemical changes resulting in a release of
energy are spontaneous
 Nonspontaneous reactions require constant energy input
 All spontaneous processes occur in the direction that
increases disorder

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.1:
Thermodynamics
 Second Law of Thermodynamics Continued
 Entropy change for the universe is positive for every
spontaneous process
 DSuniv = DSsys + DSsurr
 Living systems do not increase internal disorder; they increase the
entropy of their surroundings
 For example, food consumed by animals to provide energy
and structural materials needed are converted to disordered
waste products (i.e., CO2, H2O and heat)
 Organisms with a DSuniv = 0 or equilibrium are dead

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.2: Free Energy

 Free energy is the most definitive

way to predict spontaneity
 Gibbs free energy change or DG
 Negative DG indicates spontaneous
and exergonic
 Positive DG indicates
nonspontaneous and endergonic
 When DG is zero, it indicates a
process at equilibrium
Figure 4.4 The Gibbs
Free Energy Equation

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.2: Free Energy

 Standard Free Energy Changes

 Standard free energy, DG°, is defined for reactions at 25°C,1
atm, and 1.0 M concentration of solutes
 Standard free energy change is related to the reactions
equilibrium constant, Keq
 DG° = -RT ln Keq
 Allows calculation of DG° if Keq is known
 Because most biochemical reactions take place at or near pH
7.0 ([H+] = 1.0  10-7 M), this exception can be made in the 1.0
M solute rule in bioenergetics
 The free energy change is expressed as DG°′

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
(2) 짝지어진반응 ( 연관반응 )
- 화학반응에서 자유에너지 값은 연속반응에서 덧셈이 가능 ( 문제 4.4-5)
- 그림 4.5 은 연관반응의 예 : 부분적으로는 가능하지 않지만

(3) 소수성효과의 재검토

4.3 ATP 의 역할
-ATP 의 가수분해로 자유에너지제공 ( 그림 4.6)
-ATP 의합성 : ADP 와 Pi( 오로토인산 또는 무기인산 ) 로부터 합성 ( 그림 4.7)
-ATP 는 아데닌 , 리보오스 , 삼인산으로 구성된 뉴클레오티드임 ( 그림 4.8)
두 개의 말단 인산기 (PO42-) 는 무수인산결합
-ATP 가수분해 , 인산기 전이전위 : 생체 내 전이 ( 표 4.1)
- 포스포엔올피루브산과 비슷한 전이전위 ( 그림 4.9)
- 무수인산결합 : 높은 에너지
- 왜 ATP 가수분해가 자유에너지감소반응인가 ?(115 페이지 ) ( 그림 4.10)

• ( 읽을거리 : 심해의 산화환원

- 에너지생성메카니즘 , 무기반응에 의한 에너지획득 - 리토트롭 등
- 질소화박테리아 , 유황박테리아 (H2S 의 산화 ))
From McKee and McKee, Biochemistry,
International Fifth Edition, © 2012
Oxford University Press
 Section 4.2: Free Energy
Figure 4.5 A Coupled Reaction

 Coupled Reactions
 Many reactions have a positive DG°′
 Free energy values are additive in a reaction sequence
 If a net DG°′ is sufficiently negative, forming the product(s) is
an exergonic process

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.2: Free Energy

Figure 4.5 A Coupled

Reaction

 Conversion of glucose-6-phosphate to fructose-1,6-

bisphosphate
 First step is endergonic (DG°′ = +1.7 kJ/mol) so the reaction
should not proceed

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.2: Free Energy

Figure 4.5 A Coupled

Reaction

 The second reaction is exergonic (DG°′ = -14.2 kJ/mol) due to

cleavage of ATP’s phosphoanhydride bond
 The overall DG°′ for the coupled reactions is negative (DG°′ = -
12.5 kJ/mol); therefore, the reaction does proceed in the
direction written at standard conditions

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.2: Free Energy

 The Hydrophobic Effect Revisited

 Understanding the spontaneous aggregation of nonpolar
substances is enhanced by understanding thermodynamic
principles
 The aggregation decreases the surface area of their contact
with water, increasing its entropy
 The free energy of the process is negative; therefore, it
proceeds spontaneously
 Spontaneous exclusion of water is important in membrane
formation and protein folding

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.3: The Role of ATP

Figure 4.6 Hydrolysis

of ATP

 Adenosine triphosphate is a nucleotide that plays an

extraordinarily important role in living cells
 Hydrolysis of ATP  ADP + Pi provides free energy

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.3: The Role of ATP

 Drives reactions of several

types:
1. Biosynthesis of
biomolecules
2. Active transport
across membranes
3. Mechanical work such
as muscle contraction

Figure 4.7 The Role of ATP

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.3: The Role of ATP

 Structure of ATP is ideally

suited for its role as universal
energy currency
 Its two terminal phosphoryl
groups are linked by
phosphoanhydride bonds
 Specific enzymes facilitate
ATP hydrolysis

Figure 4.8 Structure of ATP

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.3: The Role of ATP

Figure 4.9 Transfer of

Phosphoryl Groups

 The tendency of ATP to undergo hydrolysis is an example of

its phosphoryl group transfer potential
 ATP acts as energy currency, because it can carry phosphoryl
groups from high-energy compounds to low-energy
compounds
From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.3: The Role of ATP

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.3: The Role of ATP
Figure 4.10 Contributing Structure of the Resonance Hybrid of Phosphate

 Several factors need to be considered to understand why

ATP is so exergonic:
1. At physiological pH, ATP has multiple negative charges

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.3: The Role of ATP
Figure 4.10 Contributing Structure of the Resonance Hybrid of Phosphate

2. Because of resonance stabilization, the products of ATP

hydrolysis are more stable than resonance-restricted ATP
 Resonance is when a molecule has two or more alternative
structures that differ only in the position of their electrons

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press
 Section 4.3: The Role of ATP

3. Hydrolysis products of ATP are more easily solvated

4. Increase in disorder with more molecules

From McKee and McKee, Biochemistry, International Fifth Edition, © 2012 Oxford University Press