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ENERGETIKA

METABOLISME
I Wayan Sweca Yasa
Pengertian Energetika
 Perubahan energi yang terjadi dalam proses atau
reaksi
 Sistem : Bagian dari alam semesta yang menjadi
pusat perhatian kita dengan batas-batas yang jelas,
misal proses katabolisme pd umbi..pelunakan buah,
perubahan tekstur daging ikan
 Lingkungan : Bagian di luar sistem
 Antara sistem dan lingkungan dapat terjadi
pertukaran energi atau materi
Jenis Sistem
Berdasarkan pertukaran ini, dapat dibedakan 3
macam sistem :
1. Sistem tersekat : yang dengan lingkunganya tidak
dapat tukar-menukar energi atau materi
2. Sistem tertutup : yang dengan lingkungannya dapat
tukar-menukar energi saja, materi tidak
3. Sistem terbuka : yang dengan lingkungannya dapat
tukar-menukar energi atau materi
Keadaan Sistem
 Ditentukan oleh sejumlah parameter atau variabel
 Sifat variabel :
1. Intensif : tidak bergantung pada ukuran sistem
2. Ekstensif : bergantung pada ukuran sistem
Termo Kimia

HPT = Hukum Pertama Termodinamika


Hubungan antara ΔU
dan ΔH
Perhitungan Entalpi (ΔH)
Hukum Kedua Termodinamika
Entropi pada Reaksi Kimia
Fungsi Energi Bebas (ΔG)
Jenis Reaksi Kimia yang Terjadi pada
berbagai Jalur Reaksi Metabolisme
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1. Oksidasi-Reduksi(Redox)
2. Pembentukan dan pemutusan ikatan C-C
3. Penyusunan kembali, isomerisasi atau eliminasi
4. Pemindahan gugus
5. Reaksi radikal bebas
Reaksi Redox
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 Oksidasi – kehilangan elektron, mendapatkan


oksigen, kehilangan hidrogen
 Hidrogenase
 Oksidase
 Catatan : perbedaan keadaan teroksidasinya atom
C
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Ikatan C-C
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 Pemutusan ikatan
 Homolitik(1 elektron utk setiap atom)
 Heterolitik (kedua elektron dr satu atom)
 Penarikan
 Nukleofil (Menarik muatan + )
 Elektrofil (Menarik muatan – )
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Tipe umum reaksi
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 Memanfaatkan gugus karbonil : C=O


 + atom Karbon; - pada atom Oksigen
 Gugus reaktif dalam :
 Kondensasi Aldol
 Kondensasi Claisen
 Dekarboksilasi
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Reaksi Internal
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 Perangkaian kembali, isomerisasi, eliminasi


 Gugus
 Ikatan
 Atom
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Pemindahan Gugus
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 Gugus yang berpindah


 Asil
 Glikosil
 Fosforil
 Fosfat = Pi
 Pirofosfat = PPi
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Radikal Bebas
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 Elektron tidak berpasangan


 Paling sering terjadi
1. Jalur Utama dalam Sel

• Bahan bakar metabolit


Zat gizi utama yang dikonsumsi mamalia:
(1) Karbohidrat – sumber energi
(2) Protein - sumber asam amino utk sintesis
protein dan energi
(3) Lemak – triasillglisero sumber energi dan
lemak utk sistesis membran sel
Gambar 10.5

• Ringkasan
Jalur
Katabolisme
Katabolisme Senyawa
sebagai sumber energi

• Tiga jenis senyawa yg mrp media penghasil


energi
(1) Asetil CoA
(2) Nukleoside trifosfat (e.g. ATP)
(3) Ko-enzim tereduksi (NADH, FADH2, QH2)
Kemampuan Mereduksi

• Elektron ko-enzim tereduksi mengalir ke arah O2


• Memproduksi sebuah aliran proton flow dan
membuat perbedaan tekanan antar membran
• Fosforilasi Oksidatif mrp proses reaksi
berpasangan :
ADP + Pi ATP
Pembentukan wadah dan organ
metabolisme
• Pembentukan wadah proses metabolisme
memungkinkan:
- memisahkan kumpulan (pool) metabolit dalam sel
- beroperasinya scr simultan jalur metabolik yg
berlawanan
- metabolit menumpuk di satu tempat
- regulasi enzim scr terkoordinasi
• Contoh: enzim mensistesis asam lemak (sitosol),
enzim memecah asam lemak (mitokondria)
Gambar. 10.6 Wadah tempat metabolit
2 Termodinamika and Metabolisme

A. Perubahan Energi Bebas

• Free-energy change (DG) is a measure of the


chemical energy available from a reaction
DG = Gproducts - Greactants
• DH = change in enthalpy
• DS = change in entropy
Hubungan antara Energi Bebas dan Entropi

• Both entropy and enthalpy contribute to DG


DG = DH - TDS
(T = degrees Kelvin)
-DG = a spontaneous reaction in the
direction written
+DG = the reaction is not spontaneous
DG = 0 the reaction is at equilibrium
The Standard State (DGo) Conditions

• Reaction free-energy depends upon conditions


• Standard state (DGo) - defined reference conditions
Standard Temperature = 298K (25oC)
Standard Pressure = 1 atmosphere
Standard Solute Concentration = 1.0M
• Biological standard state = DGo’
Standard H+ concentration = 10-7 (pH = 7.0) rather
than 1.0M (pH = 1.0)
B. Equilibrium Constants and
Standard Free-Energy Change

• For the reaction: A + B C+D

DGreaction = DGo’reaction + RT ln([C][D]/[A][B])

• At equilibrium: Keq = [C][D]/[A][B] and


DGreaction = 0, so that:

DGo’reaction = -RT ln Keq


C. Actual Free-Energy Change Determines
Spontaneity of Cellular Reactions

• When a reaction is not at equilibrium, the


actual free energy change (DG) depends
upon the ratio of products to substrates
• Q = the mass action ratio

DG = DGo’ + RT ln Q
Where Q = [C]’[D]’ / [A]’[B]’
3. Energi Bebas ATP

• Energy from oxidation of metabolic fuels is


largely recovered in the form of ATP
Table 10.1
Gambar 10.7

• Hidrolisis
ATP
Gambar 10.8 Complexes between ATP and Mg2+
ATP mrp senyawa “kaya energi”

• A large amount of energy is released in the


hydrolysis of the phosphoanhydride bonds of
ATP (and UTP, GTP, CTP)
• All nucleoside phosphates have nearly equal
standard free energies of hydrolysis
Energy of phosphoanhydrides

(1) Electrostatic repulsion among negatively


charged oxygens of phosphoanhydrides of ATP
(2) Solvation of products (ADP and Pi) or (AMP
and PPi) is better than solvation of reactant ATP
(3) Products are more stable than reactants
There are more delocalized electrons on ADP, Pi
or AMP, PPi than on ATP
Peranan Metabolisme ATP

• Senyawa kaya energi dpt mendorong reaksi


biosintesis
• Reaksi ini diikat oleh reaksi antara berenergi (B-
X) spt di bawah ini :
A-X + B A + B-X
B-X + C B + C-X
Sintesis Glutamine butuh Energi ATP
A. Phosphoryl-Group Transfer

• Phosphoryl-group-transfer potential - the ability


of a compound to transfer its phosphoryl group
• Energy-rich or high-energy compounds have
group transfer potentials equal to or greater than
that of ATP
• Low-energy compounds have group transfer
potentials less than that of ATP
Table 10.3
B. Production of ATP by
Phosphoryl-Group Transfer

• Metabolites with high phosphoryl-group-transfer


potentials can donate a phosphoryl group to ADP
to form ATP
• Energy-rich compounds are intermediates in
catabolic pathways
• Energy storage compounds can be energy-rich
Fig 10.9 Relative phosphoryl-group-transfer
potentials
Fig 10.10 Transfer of the phosphoryl group
from PEP to ADP

• Phosphoenolpyruvate (PEP) (a glycolytic


intermediate) has a high P-group transfer potential
• PEP can donate a P to ADP to form ATP
Phosphagens: Energy-rich storage molecules in
animal muscle

• Phosphocreatine (PC) and phosphoarginine (PA)


are phosphoamides
• Have higher group-transfer potentials than ATP
• Produced in muscle during times of ample ATP
• Used to replenish ATP when needed via creatine
kinase reaction
Fig 10.11 Structures of PC and PA
C. Nucleotidyl-Group Transfer

• Transfer of the nucleotidyl group from ATP is


another common group-transfer reaction
• Synthesis of acetyl CoA requires transfer of an
AMP moiety to acetate
• Hydrolysis of pyrophosphate (PPi) product
drives reaction to completion
Fig 10.12 Synthesis of acetyl CoA

(continued next slide)


Fig. 10.12 (continued)
10.8 Thioesters Have High Free Energies of
Hydrolysis

• Thioesters are energy-rich compounds (10.22)


• Acetyl CoA has a DGo’ = -31 kJ mol-1 (10.23)
Succinyl CoA Energy Can Produce GTP
10.9 Reduced Coenzymes Conserve Energy from Biological
Oxidations

• Amino acids, monosaccharides and lipids are


oxidized in the catabolic pathways
• Oxidizing agent - accepts electrons, is reduced
• Reducing agent - loses electrons, is oxidized
• Oxidation of one molecule must be coupled with
the reduction of another molecule
Ared + Box Aox + Bred
A. Free-Energy Change Is Related
to Reduction Potential

• The reduction potential of a reducing agent is


a measure of its thermodynamic reactivity
• The electromotive force is the measured
potential difference between two half-cells
• Reference half-cell reaction is for hydrogen:
2H+ + 2e- H2
Fig 10.13 Diagram of an electrochemical cell

• Electrons flow
through external
circuit from Zn
electrode to the
Cu electrode
Standard reduction potentials and free energy

• Relationship between standard free-energy


change and the standard reduction potential:

DGo’ = -nFDEo’

n = # electrons transferred
F = Faraday constant (96.48 kJ V-1)
DEo’ = Eo’electron acceptor - Eo’electron donor
Actual reduction potentials (DE)

• Under biological conditions, reactants are not


present at standard concentrations of 1 M
• Actual reduction potential (DE) is dependent
upon the concentrations of reactants and
products
DE = DEo’ - (RT/nF) ln ([Aox][Bred] / [Ared][Box] )
Tugas kelompok
1. Proses pencoklatan roti
2. Proses proses pengerasan kulit roti
3. Proses pencoklatan buah salak terkupas
4. Proses pencoklatan ubi goreng
5. Proses pengasaman acar (saurkrout)
6. Proses kerenyahan saurkrout
7. Proses perubahan warna kulit udang saat digoreng
8. Proses kekakuan ikan segera setelah ditangkap
9. Proses melunaknya buah pepaya masak
10. Proses memudarnya warna hijau daun kangkung saat dimasak
11. Proses ketahanan warna kangkung tetap hijau saat dimasak
12. Proses perubahan warna daging selama penyimpanan
13. Proses perubahan flavor terasi
14. Proses perubahan tekstur daging kuring
15. Proses perubahan tekstur nasi dimasak dengan magic jar!
16. Proses perubahan warna nasi dimaska dengan magic jar
17. Proses perubahan bau dan rasa tape ketan

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