Proses-Karbohidrat - 2
Proses-Karbohidrat - 2
Proses-Karbohidrat - 2
Pengubahan
Bahan Kimiawi/
Mentah Produk
biokimiawi,atau
Fisik
Daftar Konversi Kimiawi Utama
1. Asetilasi 14. Dekomposisi ganda 26. Pertukaran ion
2. Alkoholisis 15. Elektrolisis 27. Isomerisasi
16. Esterifikasi 28. Netralisasi
3. Alkilasi
17. Fermentasi 29. Nitrasi
4. Aminasi dengan 18. Reaksi Friedel - 30. Oksidasi
reduksi Crafts 31. Polimerisasi
5. Aminolisis 19. Halogenasi 32. Pirolisis
20. Hidroformilasi 33. Reduksi
6. Aromatisasi atau
21. Hidrogenasi 34. Pembentukan
Siklisasi 22. Dehidrogenasi Silikat
7. Kalsinasi 23. Hidrogenolisis 35. Sulfonasi
8. Karboksilasi 24. Hidrolisis 36. Dsb.
25. Hidrasi.
9. Penyabunan
10. Pembakaran
11. Kondensasi
12. Dehidrasi
13. Dinitrifikasi
Karbohidrat (Hydrates of carbon),
sebagian mempunyai rumus empiris : Cn(H2O)n
n = 3 - ribuan
Penggolongan Karbohidrat :
1. Monosakarida
(n=5 Pentosa, n=6 heksosa, n=7 heptaosa)
Paling sederhana : 3 C gliseraldehida
dihidroksiaseton
Hidrolisis Isomerisasi
Pati Glukosa Fruktosa
Hidrolisis Dehidrasi
Xilan Xilosa furfural
Asam H2SO4
Sukrosa (Saccharose)
Fruktosa + melibiosa
Asam lemah
Rafinosa
maltase
Galaktosa + sukrosa
Hidrolisis
Disakarida + air monosakarida
Pengaruh panas
Gula dipanaskan karamelisasi
Tingkat kemanisan relatif gula
Gula Kemanisan
relatif (%)
Fruktosa 170
Gula invert 130
Sukrosa 100
Glukosa 75
Maltosa 30
Galaktosa 30
Laktosa 15
Tingkat kemanisan berbagai sugar alcohol
Pemanis Tingkat kemanisan (%) Sumber bahan baku/
[sukrosa 100%] proses
Manitol 40-50 Hidrogenasi fruktosa
Sorbitol 40-50 Hidrogenasi glukosa
Xilitol 100 Hidrogenasi xilosa
Arabinitol ~100 Hidrogenasi arabinosa
Isomaltitol 50 Hidrogenasi isomaltulosa
Laktitol 30 Hidrogenasi laktosa
Maltitol ~90 Hidrogenasi maltosa
L-sorbosa 60-80 Proses fermentasi glukosa
D-xilosa 50 Hidrolisis hemiselulosa
Laktulosa ~60 Isomerisasi laktosa
Tingkat kemanisan relatif berbagai pemanis sintetis
Pemanis Kemanisan relatif
(b/b.)
Sukrosa 1
Sodium siklamat 15-31
Dulcin (p-etoksifenilurea) 70-350
Saccharine 240-350
L-aspartil-L-fenilalanin metil 250
ester
1-n-propoksi-2-amino-4- 4100
nitrobenzen
Tingkat kemanisan relatif pemanis alami
Kemanisan
Pemanis alami Sumber relatif
(sukrosa 1)
Monellin Pulp dari Dioscorephyllum 3000
cumminsii
Thaumatins Buah Thaumatococcus 2000
daniellii
Miraculin Buah Synsepalum dulcificum
Greencorn
Rye
Spelt
Barley
Sorgum
Oats
Maize
Ekstraksi Pati
dari sumber biji-bijian
Air
Air
Air
Rendaman
Supernatan Ampas
Suspensi
lembaga Suspensi pati-gluten
Ekstraksi minyak
Pemisahan
Gluten Pati
Minyak Ampas Pakan
jagung hewan
A
Diagram blok garis besar
pengolahan produk-produk
yang berasal dari jagung (Corn
Products Refining Corp. and A
Dorr-Oliver) (lanjutan)
Kristalisasi
Dekstrin dan gum
Pemasakan
Air panas Uap
bertekanan
dan dingin
A
Hop Pemasakan di
ketel bir
Bir Pembotolan
Pendinginan
Penutupan,
pasteurisasi dan
Khamir Penumbuhan awal pelabelan
Kompresi
Filtrasi
Penyimpanan di tangki
A
Diagram alir proses pembuatan bir
(Shreve dan Brink, 1984)
Kacang-kacangan sumber karbohidrat
Umbi-umbian sumber pati : ganyong, gembili, uwi, suweg,
kentang, talas, kimpul, dll
Air
Penggilingan Pati
Ekstraksi Pati
dari Sumber Batang Air
Sodium Sulfat
Pengadukan pada T= 45 oC
Sodium Hidroksid dan
propilen oksid
Pengadukan pada t=24
jamT= 45 oC
Sentrifuse
Endapan Supernatan
Pencucian Residu
Sentrifuse
A
Proses Produksi Pati Termodifikasi
(Food Thickener)
A
Supernatan Supernatan
Air
Pengadukan
A
Proses Produksi Pati Termodifikasi
(Food Thickener)
A
Sentrifuse
Endapan Supernatan
Pengeringan
Penggilingan
Penggilingan
Penyaringan
Pati
termodifikasi
Produk Hidrolisis Pati DE Aplikasi
Hidrolisis Pati Maltodekstrin 3-20 Stabilizer, thickener, filler,
1. Enzimatis lem dan pasta
Sirup Maltosa 48-63 Permen keras, mencegah
2. Hidrolisis higroskopis, fermentasi
Asam
Sirup Glukosa 96-98 Soft drink, fermentasi
Sirup Fruktosa - Industri pengalengan,
soft drink, produk susu
Sifat dekstrin :
- Larut dalam air, tidak larut dalam alkohol
- Mempunyai gugus karbonil bebas senyawa pereduksi
- Memberikan respon warna terhadap Iodine berbeda
Jenis Pati/Dekstrin Respon warna terhadap iodin
Amilosa Biru tua, hitam
Amilodekstrin Biru
Erithrodekstrin Merah
Achrodekstrin Tidak berwarna
Amilopektin Merah-violet
Sumber gula : tebu, bit, aren, nipah, dll
Tebu
Diagram blok pembuatan
gula tebu kasar
Hasil samping :
Penggilingan
Bagase
Jus tebu
A
Kapur
Boiler
Pencampuran
Filtrat kental
Kristal bibit
Filtrasi 1
Kristalisasi
Filtrat keruh
Sentrifugasi
Filtrasi 2
Filtrat jernih
Gula kasar Molase
mutu tinggi akhir
Pemanasan dan evaporasi
A
Diagram alir pembuatan gula tebu mentah
(Shreve dan Brink, 1984)
Gula kasar
Air Pencairan
Cairan dan
sirup
Diagram blok pembuatan
Pemvakuman gula tebu murni
Penghalusan dan
Kristalisasi Penyaringan
aerasi
Pemurnian
H2O
Molase
Fermentasi
Uap Alkohol 95%
(NH4)2SO4
Bir
CO2
Air Pembuangan CO2 Diagram blok proses dalam
industri alkohol
Penukar
panas
Destilasi Slop
A
Diagram alir proses dalam industri alkohol
(Shreve dan Brink, 1984)
BIOETANOL
Substitusi bahan bakar bensin
Rumus kimia (C2H5OH)
Penampakan : cairan tidak berwarna, jernih, mudah
menguap, berbau khas alkohol, berfase cair pada suhu
kamar, mudah terbakar dan dapat dibuat dari biomassa
maupun fraksi minyak bumi
Bahan berpati
Ketela pohon
Sagu
Sorghum
Jagung
Kentang manis
Bahan
berpati
Hidrolisis (Asam/enzim)
Larutan Gula
Fermentasi
Bioetanol
Pengaturan pH 5.2
Likuifikasi -amilase
95oC, 180 menit 1.75 U/g pati
Sakarifikasi Glukoamilase
(60oC, pH 4.5, 72 jam) 0.3 U/g pati
Larutan Gula
Pati Sagu
Konversi pati menjadi gula
Hidrolisis Asam
Pembuatan suspensi pati 30%
dalam air
Pengaturan pH 2 dengan
HCL 0.1%
Hidrolisis
121oC, 60 menit
Larutan Gula
Fermentasi Larutan Gula Menjadi Etanol
Pasteurisasi
Fermentasi skala lab
85oC, 5 menit
Starter
10-15% (v/v)
Fermentasi
7 hari, suhu 25-30oC
Destilasi
Bioetanol
Broth
Fermentor
Etanol
NUTRISI STARTER
Inokulum
Inkubasi
Ragi komersial : 24 jam
Biakan murni : 48 jam
Starter
Destilasi
Bertujuan untuk pemisahan etanol
dari komponen lain (terutama air)
Destilasi menghasilkan etanol
dengan kadar alkohol 95%.
Perlu dilakukan pengeringan
(dehidrasi)
zeolit
PSA
Bahan baku
Etanol
Fungsi Lignin
- Mengikat sel-sel tanaman satu dan lainnya
- Sebagai pengisi dinding sel sehingga tanaman menjadi
menjadi keras, teguh dan kaku
benang
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
Outline
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
Carbohydrates
A b ilit y t o r e a c t w it h A g 2 O + N H 3 + H 2O
Hexoses Pentoses
E x a m p le s :
OH OH OH
OH
HO CHO
* * * * *
* OH
OH OH OH O
A n a ld o h e x o s e , 2 4 = 1 6 s t e r e o is o m e r s A k e t o p e n t o s e , 2 2 = 4 s t e r e o is o m e r s
Outline
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
H O H O
H OH HO H
CH2OH CH2OH
D-glyceraldehyde L-glyceraldehyde
D-key L-key
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
All cyclic forms of monosaccharides are cyclic hemiacetals. The cycle are
preferred
forms and contain either 6 atoms (pyranoses) or 5 atoms (furanoses)
Haworth projections
H O
H OH CH2OH CH2OH
H OH H O OH
HO H H H
OH H OH H
H OH HO OH HO H
H OH H OH H OH
CH2OH -Glucose (-D-glucopyranose) -Glucose (-D-glucopyranose)
Open form of glucose
Epimers
+ -
H +
or O H - H or O H
H O
CH2OH CH2OH
H OH OH OH
H H H H H O
HO H
HO HO
H OH
H H OH O H H OH H
HOH2C H OH OH
OH Not Fischer projections!
Example 2: Cyclization of ribose
O
H
CH2OH CH2OH
H OH O H O OH
H H H H
H OH H OH H H
H OH OH OH OH OH
CH2OH -Ribose (-D-Ribofuranose) -Ribose (-D-Ribofuranose)
Open form of ribose
+ -
H +
or O H - H or O H
H O CH2OH CH2OH
H H H H H O
H OH
HO HO
H OH
H OH O H OH H
HOH2C H OH OH
OH
Example 3: Cyclization of fructose
CH2OH
O CH2OH CH2OH
O CH2OH O
OH
HO H H HO H HO
H OH H OH H
OH H OH H CH 2OH
H OH
CH2OH -Fructose (-D-fructofuranose) -Fructose (-D-fructofuranose)
Open form of fructose
+ -
H +
or O H - H or O H
CH 2OH
O CH2OH CH 2OH
HO H H OH CH2OH H OH O
H OH HO HO
HOH2C H H H O H H
OH CH2OH
OH OH
Outline
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
H O H O H O CH2OH
H OH
C a (O H )2 H OH HO H O
HO H HO H HO H
H OH H 2O + HO H +
H OH H OH H OH
H OH H OH H OH
H OH
CH2OH CH2OH CH2OH
CH2OH
Glucose
Recovered glucose, 67% Mannose, 2% Fructose, 30%
Enolization
H OH
OH
HO H
H OH
H OH
CH2OH
Outline
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
A glycoside hydroxyl
CH2OH CH2OH CH3 CH2OH
H OH H OO H OH
H C l, C H 3 O H H H
H
OH H
HO
OH H
H
+ OH H
HO OH HO O
H OH H OH H OH CH3
- D - G lu c o p y r a n o s e ( a h e m ia c e t a l) M e t h y l - D - g lu c o p y r a n o s id e ( a g ly c o s id e ( a n a c e t a l)
+
H
CH3
CH2OH CH2OH CH2OH + CH2OH
H OH H O HO CH3 OH
H OO H
H
OH H
H
OH H C H
+
H H+ H
+ OH H OH H H
HO O HO HO H HO +
H O
H OH H OH H OH H OH
H CH3
O
O OH
CH2OH
A n o t h e r e x a m p le o f a g ly c o s id e :
OH
O OH H O
H3CO
H
H O
CH3
D o x o r u b ic in ( a n a n t ic a n c e r d r u g ) H
HO H
NH2
Outline
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
1. Alkylation at the glycoside position (see the previous slide)
2. Complete alkylation
OH OCH3 OCH3
H3CO H3CO O OCH3
HO OH (C H 3O )2S O OH
HH H
2
HH H HH H +
H OH N aO H H OCH3 H H
OH OH OCH3 OCH3
H3CO OCH3
3. Complete acylation
OH OAc OAc
AcO AcO O OAc
HO OH A c e t ic a n h y d r id e OH
H H H
H
H H
OH
H H + H
H H
H
Py H OAc
OH OH OAc OAc
AcO OAc
4. Oxidation to aldonic acids
H O
COOH
H OH H OH
HO H B r2, H 2O
HO H
H OH H OH
C aC O 3
H OH H OH
CH2OH CH2OH
Glucose Gluconic acid
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
CN CN
H O
H OH HO H
HO H H CN HO H HO H
H OH H OH H OH
H OH
O H -
+
H OH H OH
CH2OH CH2OH CH2OH
Arabinose Gluconitrile 29% Manonitrile 51%
H 2, P d / B aS O 4,
P ressu re
H O NH
H
H OH H OH
+
HO H H 2O , H
HO H
H OH H OH
H OH H OH
CH2OH CH2OH
Glucose
Outline
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
saccharides and polysaccharides are composed from two or more cyclic
onosaccharides. If the saccharide contains at least one semi-acetal group,
s a reducing sugar due to the equilibrium with the open form, which
tually reacts with the Tolence reagent. Saccharides-acetales do not react with
lence reagent, because they do not equilibrate with the open form in the
kaline conditions.
amples:
A semi-acetal fragment
OH OH OH OH
OH OO H OH H +, H 2O OH O H O
H H
H
OH H H
OH H OH H OH + OH H OH
H H OH H HO
H OH H OH H OH H OH
S u cro se
( - D - g lu c o p y r a n o s id o - - D - fr u c t o f u r a n o s id e )
A non-reducing sugar
Polysaccharides
OH OH OH
H OO H OH H +, H 2O H O
H H H
OH H OH H OH H OH +
HO H OH HO
H OH H OH H OH
Glucose
C e llu b io s e
( b u ilt fr o m - f r a g m e n t s o f g lu c o s e )
Site of branching
OH OH OH
H OH H OH H +, H 2O H O
H H H
OH H OH H OH H OH +
HO OH HO
O
H OH H OH H OH
Maltose Glucose
A m i lo p e c t i n is a w a t e r s o lu b le c o m p o n e n t o f s t a r c h , b u ilt f r o m - f r a g m e n t s o f g lu c o s e w it h
h ig h e x t e n t o f b r a n c h in g
A m i lo s e is a w a t e r u n s o lu b le c o m p o n e n t o f s t a r c h , b u ilt f r o m - f r a g m e n t s o f g lu c o s e
w it h a lm o s t n o b r a n c h in g
Cellulose is a water unsoluble polymer, built from -fragments of glucose with no branching
Outline
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
N N N
N N N
Pyrimidine
H Purine
OH O NH2 NH2
N NH N N
N OH N O N OH N O
Uracil (U) H Cytosin (C) H
The point of attachment to RNA
The point of attachment to DNA or RNA
OH O
H3 C H3 C
N NH O
F
N OH N O NH
H N O
The point of attachment to DNA H
Thymine (T)
Fluorouracil (an anticancer drug)
H2N HO O
N N N N
N NH
N N N N NH2 N N NH2
H H H
Adenine (A)
The point of attachment to DNA or RNA Guanine (G)
The point of attachment to DNA or RNA
H N N H N N N H N
CH3 H N N
N O O H
N H N H
N
H H
A A D
D D A
A
D A D A
Outline
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
Nucleosides are glycosides, formed by one of five above listed bases with
either -D-ribose or -D-2'-deoxyribose
HO HO
O OH O OH
H H H H
H H H H
OH OH OH H
Examples:
H2N
O
N N H3C
NH
HO N N
O HO N O
H H O
H H H H
OH OH H H
OH H
Adenosine
2'-Deoxythymidine
Nucleotides are esters of nucleosides and phosphoric acid
Examples:
HO H2N
HO O
O
HO P N N O
P H3C
HO NH
O N N
O O N O
H H O
H H H H
OH OH H H
OH H
Adenosine-5'-phosphate 2'-Deoxythymidine-5'-phosphate
HO H2N
O HO H2N
O P N N
O
O O O P N N
P N N
O O O
H H P N N
O OH H 2O , en zym e O
H
P OH
H HO OH H H + H3PO4 + energy
OH OH H H
O OH OH OH
Adenosinetriphosphoric acid (ATP) - a universal carrier of energy for all forms of life on the Earth
Nucleic acids are esters, formed from nucleotides
Examples of dinucleotides:
HO H2N HO O
O O H3 C
P N P NH
HO N HO
O N O N O
N
O O
H H H H
H H H H
O OH H2N O H O
O O H 3C
P N P
HO N HO NH
O N O N O
N
O O
H H H H
H H H H
OH OH OH H
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
Individual polynucleotide chains
interact due to the H-bonding
between complimentary bases,
forming double strained DNA
and RNA.
1. Classification of carbohydrates
2. Stereochemistry of open monosaccharides
3. Cyclic forms of monosaccharides
4. Base-catalyzed isomerisation of monosaccharides
5. Glycosides
6. Reactions of monosaccharides
7. Synthesis of monosaccharides
8. Disaccharides and polysaccharides
9. Pyrimidine and purine bases
10. Nucleosides and nucleotides
11. Structures of DNA and RNA
12. Fluorescent detection of nucleic acids
Fluorescent detection of nucleic acids is base on their ability to interact with
certain dyes and restrict internal rotation of chromophoric fragments around
conjugated bonds. It may reduce rotational dissipation of the light energy and
initiate fluorescence.
S S
+
N CH3 N CH3
- +
I CH3 N CH3 N
-
H3C H3C I
COOH COOH