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Proses-Karbohidrat -2

Proses-Karbohidrat -2

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PROSES KONVERSI KIMIAWI PADA BAHAN YANG MENGANDUNG KARBOHIDRAT

TEKNOLOGI PROSES

Bahan Mentah

Pengubahan y Kimiawi/ biokimiawi,atau y Fisik

Produk

Daftar Konversi Kimiawi Utama
1. Asetilasi 2. Alkoholisis 3. Alkilasi 4. Aminasi dengan reduksi 5. Aminolisis 6. Aromatisasi atau Siklisasi 7. Kalsinasi 8. Karboksilasi 9. Penyabunan 10. Pembakaran 11. Kondensasi 12. Dehidrasi 13. Dinitrifikasi 14. Dekomposisi ganda 15. Elektrolisis 16. Esterifikasi 17. Fermentasi 18. Reaksi Friedel Crafts 19. Halogenasi 20. Hidroformilasi 21. Hidrogenasi 22. Dehidrogenasi 23. Hidrogenolisis 24. Hidrolisis 25. Hidrasi. 26. Pertukaran ion 27. Isomerisasi 28. Netralisasi 29. Nitrasi 30. Oksidasi 31. Polimerisasi 32. Pirolisis 33. Reduksi 34. Pembentukan Silikat 35. Sulfonasi 36. Dsb.

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 Pati C6H12O6 + C6H12O6
monosakarida

Isomerisasi Glukosa Fruktosa C12H22O11 + H2O
disakarida air

monosakarida

Hidrolisis Xilan Asam Xilosa

Dehidrasi furfural 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 -dekstrorotari - + 66.5o

Inversi

Gula invert - levorotari - - 19.8o

Fruktosa + melibiosa Rafinosa
Asam lemah maltase

Galaktosa + sukrosa Hidrolisis Disakarida + air Pengaruh panas Gula dipanaskan

monosakarida

karamelisasi

Tingkat kemanisan relatif gula Gula Fruktosa Gula invert Sukrosa Glukosa Maltosa Galaktosa Laktosa Kemanisan relatif (%) 170 130 100 75 30 30 15

Tingkat kemanisan berbagai sugar alcohol
Pemanis Manitol Sorbitol Xilitol Arabinitol Isomaltitol Laktitol Maltitol L-sorbosa D-xilosa Laktulosa Tingkat kemanisan (%) [sukrosa 100%] 40-50 40-50 100 ~100 50 30 ~90 60-80 50 ~60 Sumber bahan baku/ proses Hidrogenasi fruktosa Hidrogenasi glukosa Hidrogenasi xilosa Hidrogenasi arabinosa Hidrogenasi isomaltulosa Hidrogenasi laktosa Hidrogenasi maltosa Proses fermentasi glukosa Hidrolisis hemiselulosa Isomerisasi laktosa

Tingkat kemanisan relatif berbagai pemanis sintetis Pemanis Sukrosa Sodium siklamat Dulcin (p-etoksifenilurea) Saccharine L-aspartil-L-fenilalanin metil ester 1-n-propoksi-2-amino-4nitrobenzen Kemanisan relatif (b/b.) 1 15-31 70-350 240-350 250 4100

Tingkat kemanisan relatif pemanis alami
Pemanis alami Monellin Thaumatins Miraculin Steviosida Osladin Phylloducin Glycyrrhizin Sumber Pulp dari Dioscorephyllum cumminsii Buah Thaumatococcus daniellii Buah Synsepalum dulcificum Daun Stevia rebaudiana Polypodium vulgare Hydragea macrophylla Akar Glycyrrhiza glabra 300 3000 200-300 50 Kemanisan relatif (sukrosa 1) 3000 2000

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 Rendaman

Air

Endapan Pati

Pengendapan

Suspensi Pati

Penyaringan

Supernatan

Ampas

Pengeringan

Penggilingan

Pati

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

Jagung Pembersihan Perendaman SO2

Suspensi pati Separasi hidrosiklon lembaga

Air perendaman encer Evaporasi

Suspensi pati-serat

Penggilingan , pencucian dan penyaringan

Suspensi lembaga Ekstraksi minyak

Suspensi pati-gluten

Pemisahan

Gluten Minyak jagung Ampas Pakan hewan

Pati

A

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

A

Hidrosiklon pencuci pati

Pati bersih

Perlakuan kimiawi Filtrasi dan pengeringan

Konversi pati dengan asam enzim netralisasi

Filtrasi dan pemurnian

Evaporasi dan pemurnian Kristalisasi

Produk pati

Pemasakan

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

Grinding

Malt adjunct (beras/jagung)

Penimbangan Pemasakan bertekanan

Diagram blok proses pembuatan bir

Air panas dan dingin

Uap A

Hop

Pemasakan di ketel bir Bir Pendinginan Pembotolan

Khamir

Penumbuhan awal

Penutupan, pasteurisasi dan pelabelan

Fermentasi (40-58 oF)

Bir dalam botol / kaleng CO2

Pendinginan dan penyimpanan di tangki timbun (32 oF)

Filtrasi

Kompresi

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 pencucian

Pemarutan

Pengepresan

Air Cucian

Ampas

Pengeringan

Endapan

Pengendapan

Suspensi pati

Air

Penggilingan

Pati

Ekstraksi Pati dari Sumber Batang
Bahan Baku Pembersihan Pemotongan Pembelahan

Air

Penokokan

Penyaringan

Suspensi Pati

Pemerasan

Empulur

Ampas dan Kotoran

Ampas dan Kotoran

Suspensi Pati

Pengendapan

Endapan Pati

Pengeringan

Pati

Inulin
Linear polilfruktan berikatan dengan ikatan F-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 Pencucian Supernatan

Residu

Sentrifuse

A

Proses Produksi Pati Termodifikasi (Food Thickener)
A

Supernatan Air Pengadukan

Supernatan

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 3-20 48-63

Aplikasi Stabilizer, thickener, filler, lem dan pasta Permen keras, mencegah higroskopis, fermentasi Soft drink, fermentasi Industri pengalengan, soft drink, produk susu Soft drink, bahan baku industri pangan

Hidrolisis Pati 1. Enzimatis 2. Hidrolisis Asam

Maltodekstrin Sirup Maltosa

Sirup Glukosa Sirup Fruktosa Sirup Campuran

96-98 42-63

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 Amilodekstrin Erithrodekstrin Achrodekstrin Amilopektin Biru tua, hitam Biru Merah Tidak berwarna Merah-violet

Sumber gula : tebu, bit, aren, nipah, dll

Tebu

Diagram blok pembuatan gula tebu kasar

Hasil samping : Bagase

Penggilingan

Jus tebu Boiler Pencampuran Kristal bibit Filtrasi 1 Kapur

A

Filtrat kental

Kristalisasi Filtrat keruh Sentrifugasi Filtrasi 2

Filtrat jernih

Gula kasar mutu tinggi

Molase 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

Pemvakuman

Diagram blok pembuatan gula tebu murni

Kristalisasi

Penghalusan dan aerasi

Penyaringan

Gula halus

Pengeringan hingga membentuk granular

Gula putih

kadar gula tinggi

Kadar gula rendah

Pencampuran

Molase akhir

Diagram alir pembuatan gula tebu murni (Shreve dan Brink, 1984)

A Uap H2O Molase Dephlegmator Penimbangan Air Pengenceran Sterilisasi molase Penyiapan kultur khamir Fermentasi (NH4)2SO4 Bir Kondensor Separator Minyak fusel H2O Pemurnian

Kolom pemisah Dephlegmator Kondensor

H2SO4

Aldehid

Uap

Alkohol 95%

Air

Pembuangan CO2 Penukar panas Destilasi A

CO2

Diagram blok proses dalam industri alkohol

Slop

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  Batang pisang  Bagas tebu Bahan baku berpotensi lainnya

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)
E-amilase 1.75 U/g pati

Likuifikasi 95oC, 180 menit Sakarifikasi (60oC, pH 4.5, 72 jam)

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

Fermentasi skala lab

Bioetanol Fermentasi bioetanol skala pabrik

Fermentasi Larutan Gula Menjadi Etanol

Broth

Fermentor Etanol

NUTRISI
Nutrisi yang ditambahkan : ‡ ‡ ‡ (NH4)2SO4 5.19 g/l KH2PO4 1.53 g/l MgSO4 0.55 g/l Sumber nutrisi lainnya : ‡ ‡ NPK 0.04% (b/v) ZA 0.15% (b/v)

STARTER
Inokulum : 1. Ragi Komersial 2. Biakan Saccharomyces

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

Filter tank

Evaporating tank

PILOT PLANT BIOETANOL-IPB

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 : F-D-glukopiranosa, F-D-manopiranosa (2) Arabinogalaktan Monomer : E-D-galaktopiranosa. F-D-glukopiranosa (3) Xilan Monomer : F-D-xilopiranosa, ikatan F-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

kayu

Kapas

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 Agar Alginat Karagenan Gum arabic Komponen Penyusun Poligalaktosa Asam manuronat & guluronat Poligalaktosa ester asam sulfat Sumber Rumput laut alga merah Gracalaria Alga coklat Laminaria Alga merah Chondus crispus Exudate tanaman Acacia Senegal Exudate tanaman Astragalus

L-arabinosa, L-rhamnosa, D-galaktosa, asam Dglucoronat Gum tragacanth Campuran polisakarida asam, unit asam galakturonat, D-galaktosa, L-fucose, D-xylose, Larabinosa Locust bean gum Rantai manosa, dan unit galaktosa Xantan Rantai utama selulosa, rantai cabang galaktosa

Locust bean (carob bean) dari Ceratonia siliquia Mikroba Xanthomonas 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 Ketoses Aldoses Disaccharides amd polysaccharides Reducing (hemiacetals) Non-reducing (acetals)

Hexoses

Ability to react with Ag 2O + NH3 + H2O Pentoses

Examples: OH HO OH OH CHO OH

*

*
OH

*

*
OH

*
OH O

*
OH

An aldohexose, 2 4 = 16 stereoisomers

A ketopentose, 2 2 = 4 stereoisomers

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 H

O OH CH 2OH

H HO

O H CH 2OH

D-glyc D-key

ldehyde L-key

-glyceraldehyde

E ery 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)
H H HO H H Ha orth projections O OH H OH OH CH 2OH CH 2OH OH H H OH H HO OH H OH E-Glucose (E-D-glucopyranose) CH 2OH O OH H H OH H HO H H OH F-Glucose (F-D-glucopyranose)

Open orm of glucose Epimers H+ or OHH H HO H HOH 2C OH O OH H OH H H+ or OH-

CH 2OH OH H H HO H OH

H HO

CH 2OH OH H H H OH ot ischer projections!

O

H OH O

H OH H

Example 2: Cyclization of ribose
O OH OH OH CH2OH CH2OH O H H H OH H OH OH E-Ribose (E-D-Ribofuranose) CH2OH O OH H H H H OH OH F-Ribose (F-D-Ribofuranose)

H H H H

Open form of ribose H+ or OHH+ or OH-

H H H HOH2C OH

O OH OH H HO

CH2OH H H H OH H HO OH O

CH2OH H H H OH OH O H

Example 3: Cyclization of fructose
CH2OH O HO H H OH H OH CH2OH Open form of fructose H+ or OHCH2OH HO H HOH2C OH O H OH H CH2OH H OH HO H OH H O CH2OH HO H OH H CH2OH CH2OH H OH H+ or OHCH2OH O CH2OH H HO OH H OH H E-Fructose E-D-fructofuranose) CH2OH OH O H HO H OH H CH2OH F-Fructose F-D-fructofuranose)

O

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 H HO H H

O OH H OH OH CH 2OH Ca(OH)2 H2 O

H H HO H H

O OH H OH OH CH 2OH

H HO HO H H

O H H OH OH CH 2 OH

CH 2 OH

+

+

Glucose Enolization OH

O HO H H OH H OH CH 2 OH Fructose, 30%

Recovered glucose, 67%

Mannose, 2%

H

OH HO H H OH H OH CH 2 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

A glycoside hydroxyl CH 2OH OH H H OH H HO OH H OH E-D-Glucopyranose (a hemiacetal)
+

HCl, CH 3OH

CH 2 OH OO H H OH H HO H H OH

CH 3

+

CH 2OH OH H H OH H HO O H OH

CH 3

MethylF-D-glucopyranoside (a glycoside (an acetal)

H

CH 2 OH OH H H OH H + HO O H H OH H

CH 2OH O H + H OH H C H HO H OH

HO

CH 3

CH 2 OH CH 2OH + OH OO H H H H H+ OH H OH H + HO HO H O H OH H OH

CH 3

H CH 3

O Another example of a glycoside:

OH

O CH 2 OH OH

H 3CO

O H

OH H H O

O

Doxorubicin (an anticancer drug)

H HO

CH 3

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 OH HO HH H OH H OH OH OCH3 H 3CO OH (CH3O)2SO2 HH H H OCH3 NaOH OCH3 H 3CO OCH3 H3CO O OCH3 HH H H H OCH3 OCH3

+

3. Complete acylation

OH OAc AcO OH OH HO Acetic anhydride H H H HH H H OH OAc H Py OH OH OAc AcO

+

OAc AcO O OAc H H H H H OAc OAc

4. Oxidation to aldonic acids
H H HO H H O OH H OH OH CH 2OH Glucose H HO H H COOH OH H OH OH CH 2OH

Br2, H2O CaCO3

Gluconic acid

5. Oxidation to aldaric acids
H H HO H H O OH H OH OH CH2OH Glucose H HO H H COOH OH H OH OH COOH

HNO3, H2O 60 oC

Glucaric acid

6. Reduction to alditols
H H HO H H O OH H OH OH CH2OH Glucose H HO H H CH2 OH OH H OH OH CH2 OH

Na H4, H2O

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

H HO H H

O H OH OH CH2OH Arabinose HCN OHH HO H H

CN OH H OH OH CH2OH HO HO H H

CN H H OH OH CH2OH

+

Gluconitrile 29

Manonitrile 51

H2, Pd / BaSO4, Pressure H H HO H H O OH H OH OH CH2OH H2O, H+ H H HO H H NH OH H OH OH 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

Disaccharides and polysaccharides are composed from two or more cyclic monosaccharides. If the saccharide contains at least one semi-acetal group, it is a reducing sugar due to the equilibrium with the open form, which actually reacts with the Tolence reagent. Saccharides-acetales do not react with Tolence reagent, because they do not equilibrate with the open form in the alkaline conditions. Examples:
A semi-acetal fragment OH OO OH H OH H H H H OH OH H OH H OH H OH H OH H+, H2O OH O OH H OH OH H H H OH Galactose OH O H H OH H HO H OH Glucose

+

OH

E-Lactose (F-D-galactopyranosido-E-D-glucopyranose) A reducing sugar

OH H OH H OH H O HO H OH HO O H HO H OH OH H

H+, H2O

OH O H H OH H HO H OH Glucose

HO OH

+

H

O H HO OH H

OH OH

Fructose

Sucrose (E-D-glucopyranosido-F-D-fructofuranoside) A non-reducing sugar

Polysaccharides
OH H OO H OH H H HO H OH OH H OH H OH H OH H OH H+, H2O OH O H H OH H HO H OH Glucose

OH

+

Cellubiose (built from F-fragments of glucose)

OH H OH H OH H HO O H OH Maltose

Site of branching OH H OH H OH H OH H OH

H+, H2O

OH O H H OH H HO H OH Glucose

OH

+

Amilopectin is a water soluble component of starch, built from E-fragments of glucose with high extent of branching Amilose is a water unsoluble component of starch, built from E-fragments of glucose with almost no branching Cellulose is a water unsoluble polymer, built from F-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 Pyrimidine OH N N OH Uracil (U) N H O NH O

N N H N

N

Purine NH 2 N N OH Cytosin (C) N H NH 2 N O

The point of attachment to RNA OH H 3C N N H 3C OH N H Thymine (T) O NH O

The point of attachment to DNA or RNA

O F NH N The point of attachment to DNA O

H Fluorouracil (an anticancer drug)

H2N N N H Adenine (A) The point of attachment to DNA or RNA N N N N H

HO N N NH2 N N H

O NH N NH2

Guanine (G) The point of attachment to DNA or RNA

Complimentarity of pyrimidine and purine bases
A O H N N N N N H A A D D A A D D H H N O CH3 H T H N N N N H D A A H O N O N H H N N N H G C H

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 F -D-ribose or F -D-2'-deoxyribose
HO O H H OH
Examples: H2 N N N N H 3C O NH N O

OH H H OH

HO O H H OH H H

OH H

HO O H H OH
Adenosine

N

HO O H H OH H H

H
H

OH

H 2'-Deoxythymidine

Nucleotides are esters of nucleosides and phosphoric acid
Examples: HO HO P O N H 2N HO N HO N P O H 3C N O NH O

O O H H OH OH H

N

O O H H OH H H

H

H

Adenosine-5 -phosphate

2 -Deoxythymidine-5 -phosphate

HO O O O P O P OH P O N

H 2N N N HO O P O N H 2N N N

O O H H
OH OH

N

H
H

O O P H 2O, enzyme OH HO

O H H OH OH H

N

+
H

OH

OH

H 3 PO 4

+ energy

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 HO P O N H2 N N N HO HO P O O H3C N NH O

O O H H O
HO P

N

O O H H H
H2 N N N N O HO

H
H

H

OH
O

H
P O H3 C

O NH N O

O O H H OH OH H

N

O O H H H OH H

H

H

RNA is a polynucleotide, formed from ribophosphates of adenine, uracil, cytosine and guanine

DNA is a polynucleotide, formed from deoxyribophosphates of adenine, thymine, 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 N I
+

S CH 3 N H3C COOH N CH 3 H3C N I
+

CH 3

CH 3

COOH

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