PROSES KONVERSI KIMIAWI PADA

BAHAN YANG MENGANDUNG

KARBOHIDRAT
 TEKNOLOGI PROSES

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

2. Oligosakarida (2-10 unit monosakarida)

3. Polisakarida (> 10 unit monosakarida)

Homopolisakarida, Heteropolisakarida
Karbohidrat  sumber energi utama bagi aktivitas
manusia selain protein dan lemak
Indonesia : 80-90% sumber energi dari karbohidrat
 pangan pokok beras, jagung, sagu
USA : 46% karbohidrat, 42% lemak, 12% protein
Sumber karbohidrat
-Sumber Nabati : Hasil fotosintesa
-Sumber Hewani : biosintesis glikogen & sintesa
kimiawi lain
 Konversi Kimiawi pada karbohidrat

Glukosa komersial dihasilkan dari proses hidrolisis pati

(C6H10O5)n + n H2O n C6H12O6

Hidrolisis Isomerisasi
Pati Glukosa Fruktosa

C6H12O6 + C6H12O6 C12H22O11 + H2O

monosakarida monosakarida disakarida air

Hidrolisis Dehidrasi
Xilan Xilosa furfural
Asam H2SO4
Sukrosa (Saccharose)

Sumber : tebu (Saccharum officinarum) dan bit (Beta vulgaris)

Gula invert : hasil reaksi hidrolisis sukrosa menghasilkan

campuran glukosa dan fruktosa, dikatalisis oleh
enzim invertase atau asam
 Sukrosa Inversi Gula invert
-dekstrorotari - levorotari
- + 66.5o - - 19.8o

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

Steviosida Daun Stevia rebaudiana 300

Osladin Polypodium vulgare 3000

Phylloducin Hydragea macrophylla 200-300

Glycyrrhizin Akar Glycyrrhiza glabra 50

 Bahan Hasil Pertanian sumber
Karbohidrat
 Biji-bijian sumber pati : gandum, cantel,
sorgum, jali-jali, jagung, jawawut, dll
Serealia Buckwheat
Wheat

Greencorn
Rye
Spelt

Barley
Sorgum

Oats
Maize
 Ekstraksi Pati
dari sumber biji-bijian
Air

Bahan Baku Pembersihan Penggilingan Perendaman Penapisan

Air
Air
Rendaman

Endapan Pati Pengendapan Suspensi Pati Penyaringan

Supernatan Ampas

Pengeringan Penggilingan Pati

Diagram blok garis besar
pengolahan produk-produk
Jagung
yang berasal dari jagung (Corn
Products Refining Corp. and
Dorr-Oliver) Pembersihan

Air Perendaman SO2

Suspensi pati Air perendaman Suspensi pati-serat

encer
Separasi hidrosiklon
lembaga Evaporasi Penggilingan , pencucian dan
penyaringan

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)

Hidrosiklon pencuci pati

Pati bersih Perlakuan kimiawi

Filtrasi dan pengeringan

Konversi pati dengan asam enzim netralisasi

Filtrasi dan Evaporasi dan Produk pati Pemasakan

pemurnian pemurnian

Kristalisasi
Dekstrin dan gum

Sirup jagung Sentrifugasi dan pengeringan

Dekstrosa gula dan sirup

jagung
 Diagram alir garis besar pengolahan produk-produk yang berasal dari jagung
(Corn Products Refining Corp. and Dorr-Oliver di dalam Shreve dan Brink, 1984)
Malt barley Malt adjunct
Grinding
(beras/jagung)
Diagram blok proses
Penimbangan pembuatan bir

Pemasakan
Air panas Uap
bertekanan
dan dingin
A

Hop Pemasakan di
ketel bir
Bir Pembotolan

Pendinginan
Penutupan,
pasteurisasi dan
Khamir Penumbuhan awal pelabelan

Fermentasi (40-58 oF)

Bir dalam botol /
kaleng

Pendinginan dan penyimpanan di CO2

tangki timbun (32 oF)

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

Ganyong Kimpul Talas

Gembili Uwi Suweg

 Ekstraksi Pati Ubi Kayu
Air Air

Bahan Baku Pengupasan dan Pemarutan Pengepresan

pencucian

Air Cucian Ampas

Pengeringan Endapan Pengendapan Suspensi pati

Air

Penggilingan Pati
 Ekstraksi Pati
dari Sumber Batang Air

Bahan Pemotongan Pembelahan Penokokan

Pembersihan
Baku

Penyaringan Suspensi Pemerasan Empulur

Pati

Ampas dan Ampas dan

Kotoran Kotoran

Suspensi Pengendapan Endapan Pengeringan Pati

Pati Pati
Inulin
Linear polilfruktan berikatan dengan ikatan -2,1 glikosidik

Sumber Inulin : Jerusalem Artichoke, umbi dahlia, akar chicory,

dan dandelion

Sifat : - sedikit larut dalam air panas

- mudah dihidrolisis oleh asam
- Tidak berfungsi sebagai sumber nutrisi
- Sumber HFS (dengan inulinase)
Proses Produksi Pati Termodifikasi
(Food Thickener)
Pati cassava 50 %

Sodium Sulfat
Pengadukan pada T= 45 oC
Sodium Hidroksid dan
propilen oksid
Pengadukan pada t=24
jamT= 45 oC

Netralisasi dengan HCl

Sentrifuse

Endapan Supernatan

Pencucian Residu

Sentrifuse

A
Proses Produksi Pati Termodifikasi
(Food Thickener)
A

Supernatan Supernatan
Air
Pengadukan

Penambahan sodium hidroksid sampai pH

11-11,8

Penambahan Posporous oksiklorid dan

diaduk 30 mnt

Netralisasi dengan HCl

Pencucian 2 kali dengan air

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

Sirup Campuran 42-63 Soft drink, bahan baku

industri pangan
 Proses produksi HFCS
(High Fructose Corn Syrup)
 Proses Produksi Dekstrin
Hidrolisat parsial dari pati, hasil kerja enzim, asam dan panas
Senyawa antara dalam sintesis pati

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

Adsorban Filtrasi Air pencuci

panas

Cairan dan
sirup
Diagram blok pembuatan
Pemvakuman gula tebu murni

Penghalusan dan
Kristalisasi Penyaringan
aerasi

Gula halus Pengeringan hingga

membentuk granular Gula putih

kadar gula Kadar gula Pencampuran Molase akhir

tinggi rendah
Diagram alir pembuatan gula tebu murni
(Shreve dan Brink, 1984)
 A
Uap

Pemurnian
H2O
Molase

Dephlegmator Separator Minyak

Penimbangan fusel

Air Pengenceran Kondensor Kolom H2O

pemisah

H2SO4 Sterilisasi molase Dephlegmator

Aldehid

Penyiapan kultur khamir

Kondensor

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 baku bioetanol Sugar contain material

 Tebu
 Nira nipah
 Nira sorghum manis
 Nira aren
 Molase

Cellulose contain material

 Kayu
 Jerami Bahan baku
 Batang pisang berpotensi lainnya
 Bagas tebu
PROSES PRODUKSI

Prinsip : Fermentasi dengan bantuan mikoorganisme

dimana bahan baku (gula sederhana/glukosa) diubah
menjadi etanol
Produksi Bioetanol

Bahan
berpati

Hidrolisis (Asam/enzim)

Larutan Gula

Fermentasi

Bioetanol

Produksi bioetanol dari pati sagu

 Konversi pati menjadi gula
Pati
Hidrolisis Enzim

Pembuatan suspensi pati 30%

dalam CaCO3 200 ppm

Pengaturan pH 5.2

Gelatinisasi (105oC, 5 menit)

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

Hidrolisis asam skala pabrik

Penetralan dengan NaOH 1 N

Larutan Gula
 Fermentasi Larutan Gula Menjadi Etanol

Larutan gula 25-35 Brix

Penambahan nutrisi dan

pengaturan PH 3.9-4

Pasteurisasi
Fermentasi skala lab
85oC, 5 menit
Starter
10-15% (v/v)
Fermentasi
7 hari, suhu 25-30oC

Destilasi

Bioetanol

Fermentasi bioetanol skala pabrik

 Fermentasi Larutan Gula Menjadi Etanol

Broth

Fermentor

Etanol
 NUTRISI STARTER

Nutrisi yang ditambahkan : Inokulum :

• (NH4)2SO4 5.19 g/l 1. Ragi Komersial
• KH2PO4 1.53 g/l 2. Biakan Saccharomyces
• MgSO4 0.55 g/l
Sumber nutrisi lainnya :
• NPK 0.04% (b/v)
• ZA 0.15% (b/v)

Ragi komersial Biakan S.cerevisiae

Persiapan Starter

Inokulum

Pemindahan ke medium GYE steril

1 g ragi komersial/20 ml
1 jarum ose biakan/20 ml

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)

Destilasi skala pabrik

Molecular Sieve
• Bahan yang digunakan sebagai absorben untuk gas dan cairan
• Dapat menyerap air hingga 22% dari berat bahan adsorben
• Molecular sieve : alumunium silikat, zeolit, carbon aktif, clays

zeolit

Molecular sieve plant Molecular sieve skala

kecil

PSA
Bahan baku

Slurry tank Liquifiying tank Saccharifiying tank

Filter press Clarifiying tank Fermentor

Etanol

PILOT PLANT BIOETANOL-IPB

Filter tank Evaporating tank
Bahan berlignoselulosa : serat, kayu,
tongkol jagung, tkks, pelepah, dll
Lignoselulosa : bahan hasil pertanian yang mengandung
(1) Lignin, (2) Hemiselulosa, (3) selulosa

Fungsi Lignin
- Mengikat sel-sel tanaman satu dan lainnya
- Sebagai pengisi dinding sel sehingga tanaman menjadi
menjadi keras, teguh dan kaku

Hemiselulosa, terdiri atas :

(1) Glukomanan
Monomer : -D-glukopiranosa, -D-manopiranosa
(2) Arabinogalaktan
Monomer : -D-galaktopiranosa. -D-glukopiranosa
(3) Xilan
Monomer : -D-xilopiranosa, ikatan -1,4 glikosidik
Selulosa
Senyawa utama dalam struktur jaringan tanaman
Dalam dinding sel bergabung dengan lignin dan hemiselulosa

Sumber selulosa  berbeda kekuatan dan ketahanannya

Co. Serat kayu, flax, kapas (>90% selulosa)
Dietary fiber

benang

Pulp & kertas Kapas

kayu
 Xilitol
 Termasuk gula alkohol dengan lima karbon (1,2,3,4,5 pentahydroxy
pentane) dengan formulasi molekul C5H12O5.

 Pemanis rendah kalori (4 kal/g), indeks glukemik jauh lebih rendah

 tidak meningkatkan gula darah dan metabolisme tanpa insulin 
aman untuk penderita diabetes
Proses pembuatan xilitol
Rumput Laut sumber Karbohidrat

Rumput laut bernilai ekonomis

Struktur Kimiawi Polisakarida
(1) Homopolisarida
(2) Heteropolisakarida
(3) Senyawa konjugasi : gabungan dengan lipid & protein

Polisakarida dalam bahan pangan

(1) Pati (pati kasar, pregelatinisasi, pati termodifikasi)
(2) Selulosa dan turunan selulosa
(3) Ekstrak rumput laut (alginat, karagenan, agar, furcellaran)
(4) Gum dan lendir dari tanaman (arabik, karaya, tragacanth)
(5) Gum biji-bijian (locust bean dan guar)
(6) Ekstrak tanaman (pektin)
(7) Mikrobial gum (xanthan)
Klasifikasi Hidrokoloid Alami dari Tanaman

(1) Polisakarida Anionik dari Rumput Laut

Co. Agar, alginat, karagenan
(2) Polisakarida Anionik dari Exudate
Co. Arabic, ghatti, karaya, tragacanth
(3) Polisakarida non-ionik dari bijian
Co. Guar gum, locust bean gum,
(4) Polisakarida anionik hasil fermentasi
Co. Xantan, dekstran, gellan gum
Produk Hidrokoloid Alami
 Klasifikasi Hidrokoloid Alami dari Tanaman
Polisakarida Komponen Penyusun Sumber
Agar Poligalaktosa Rumput laut alga merah
Gracalaria
Alginat Asam manuronat & Alga coklat Laminaria
guluronat
Karagenan Poligalaktosa ester asam Alga merah Chondus
sulfat crispus
Gum arabic L-arabinosa, L-rhamnosa, Exudate tanaman
D-galaktosa, asam D- Acacia Senegal
glucoronat
Gum tragacanth Campuran polisakarida Exudate tanaman
asam, unit asam Astragalus
galakturonat, D-galaktosa,
L-fucose, D-xylose, L-
arabinosa
Locust bean Rantai manosa, dan unit Locust bean (carob
gum galaktosa bean) dari Ceratonia
siliquia
Xantan Rantai utama selulosa, Mikroba Xanthomonas
rantai cabang galaktosa campestris
Carbohydrates Chemical
Reaction
 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
 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

Monosaccharides Disaccharides amd polysaccharides

Ketoses Aldoses Reducing (hemiacetals) Non-reducing (acetals)

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

Every monosaccharide belongs to either D- or L-type

L- and D-monosacharides are enantiomers

 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
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

5. Oxidation to aldaric acids

H O
COOH
H OH H OH
HO H H N O 3, H 2O
HO H
H OH H OH
6 0 oC
H OH H OH
CH2OH COOH
Glucose Glucaric acid
 6. Reduction to alditols
H O
CH2OH
H OH H OH
HO H N aB H 4, H 2O
HO H
H OH H OH
H OH H OH
CH2OH CH2OH
Glucose Sorbitol

7. Oxidation by the Tolence reagent (Ag2O, NH3, H2O), producing Ag

a silver mirror reaction).

Because of the basic conditions, the reaction produces a messy mixture of

carbohydrate-based ammonium salts (mostly ammonium gluconate).
 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
 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

-L a c to se Galactose Glucose

(  - D - g a la c t o p y r a n o s id o -  - D - g lu c o p y r a n o s e )
A reducing sugar
 OH
H OH
H OH
OH H
O O HO OH
HO H +, H 2O H O
H
HO
H OH OH H OH + H
H HO
OH
O HO
H HO H OH OH H
H
OH H OH Glucose Fructose

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

Complimentarity of pyrimidine and purine bases

A T G C
H H
O N O H N
N

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

RNA is a polynucleotide, formed from DNA is a polynucleotide, formed from

ribophosphates of adenine, uracil, deoxyribophosphates of adenine, thymine,
cytosine and guanine cytosine and guanine
 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
Individual polynucleotide chains
interact due to the H-bonding
between complimentary bases,
forming double strained DNA
and RNA.

A sequence of three nucleotides

encodes incorporation of a specific
aminoacid to a protein.

The double strain DNA, discovered

by Watson, Wilkins and Crick
(1962 Nobel Prize), is the most
common, but not the only form
of DNA in living organisms.
 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
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.

Example of a DNA-sensitive dye:

S S
+
N CH3 N CH3
- +
I CH3 N CH3 N
-
H3C H3C I
COOH COOH