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KARBOHIDRAT

Tim Pengampu MK KBHP


Perikanan UGM
Apa itu karbohidrat?

Klasifikasi karbohidrat?

Apa itu ikatan alfa dan beta?


Pengertian

a. mengandung unsur-unsur:
C, H dan O
b. terdapat 75%.
c. hidrat dari karbon;

dalam senyawa tersebut perbandingan antara H dan O


sering 2 berbanding 1 seperti air.
Co/ C6H12O6 --- C6(H2O)6
C12H22O11 --- C12 (H2O)11
CnH2nOn --- Cn (H2O)n.
Karbohidrat

Gugus Fungsi Jumlah Atom Unit Monomer

n Category Monosakarida
Aldosa
3 Triose Disakarida
Ketosa 4 Tetrose
Oligosakarida
5 Pentose
6 Hexose Polisakarida

7 Heptose
8 Octose
Gugus Fungsi
aldosa ketosa
Atom C3 gliserosa dihidroksiaseton
C4 eritrosa eritrulosa
C5 ribosa ribulosa
C6 glukosa fruktosa
Aldosa dan Ketosa
Jumlah Atom

n Category
3 Triose
4 Tetrose
5 Pentose
6 Hexose
7 Heptose
8 Octose

7
Unit Monomer

Monosakarida Disakarida Polisakarida


Mudah larut Mudah Larut Rantai panjang dan
bercabang
Manis Manis > 10 gula
Co/ Glukosa, Berikatan dengan Tidak berasa/pahit
Galaktosa, fruktosa, gugus -OH
ribosa, deoksiribosa
Co/ Maltosa, sukrosa, Sulit larut air
Laktosa
Co/ Selulose, Kitin, glikogen,
amilum, amilase,
glukosaminoglikan
Most common monosacharides
Glukosa: Galaktosa: Fruktosa :
a. di dlm darah a. gula dalam susu a. Gula dalam
b. sumber ATP dlm dan yoghurt madu dan
respirasi seluler b. penyusun dr buah-buahan
c. dlm polimer: pati laktosa b. Penyusun
dan glikogen c. dlm polimer sbg sukrosa
d. Struktural : agar
selulosa
Apa bedanya
Glukosa,galaktosa dan
fruktosa
Furanosa
Chirality rules
1. Monosaccharides contain one or more asymmetric C-
atoms: get D- and L-forms, where D- and L-
designate absolute configuration
2. D-form: -OH group is attached to the right of the
asymmetric carbon
3. L-form: -OH group is attached to the left of the
asymmetric carbon
4. If there is more than one chiral C-atom: absolute
configuration of chiral C furthest away from carbonyl
group determines whether D- or L-
from
http://ntri.tamuk.edu/cell/carb
ohydrates.html)
Beda bentuk L dgn D pd monosakarida
Pembentukan cincin piranosa dari
heksosa

16
C O
1

OH
2

HO
3

OH
4

OH
5

CH2OH
6
O
C

OH
HO
OH
OH
CH2OH
O
C

OH
HO
OH
OH
CH2OH
CH2OH
OH

C O

HO
OH

OH
CH2OH
OH

C O

HO
OH

OH
CH2OH

C O

HO
OH

OH
CH2OH

HO
OH OH α

OH
CH2OH

HO
OH OH

OH
CH2OH

C O

HO
OH

OH
CH2OH
OH

C O

HO
OH

OH
CH2OH
OH

C O

HO
OH

OH
CH2OH

C O

HO
OH

OH
CH2OH

O OH
β
C

HO
OH

OH
6 CH2OH

5 O

C OH

HO
4
1
OH
3 2

OH
Pembentukan cincin furanosa

31
32
Kemungkinan orientasi gugus -OH 33
Konformasi apa?

34
Konformasi kursi dan kapal
Cincin piranosa  tdpt
dlm konformasi:
• Kursi
• Kapal

Atom2 dlm cincin


piranosa  mempy 2
orientasi:
• axial
• equatorial
35
OLIGOSAKARIDA
Oligosakarida
Ikatan glikosida antar monosakarida akan
membentuk  oligosakarida dan polisakarida
Oligosakarida yg paling sederhana  Disakarida
Dlm proses Ikatan
penggabungan 2 alpha
monomer tst  H2O
akan dibebaskan
C12H22O11 =
2 C6H12O6 − H2O

37
• Ikatan glikosida  terbentuk dari eliminasi air
antara gugus hidroksil dari suatu monosakarida
berbentuk siklis dengan gugus hidroksil senyawa
yang lain.

38
Lactose:

Maltose:

from
http://ntri.tamuk.edu/
cell/carbohydrates.htm
Most common disacharides

40
Maltosa : Sukrosa : Laktosa :
hasil hidrolisis Dikenal sebagai Dikenal sebagai
pati gula meja  gula susu
t.d 2 glukosa yg diperoleh dr tebu t.d galaktosa dan
terikat dgn ikatan dan beet glukosa yg terikat
α 1-4 t.d. glukosa dan dgn cara C1 β gal
Hidrolisis  fruktosa yang – C4 glu
maltase terikat dgn cara Hidrolisis 
C1α glu - C2 β fru laktase / β
Hidrolisis  galaktosidase
sukrase /
invertase
Bahan Kemanisan Relatif

Sucrose Galaktosa
Glukosa
32
74
Fruktosa 173
Sukrosa 100
Maltosa 32
Laktosa 16
Sakarin 500x sukrosa
Aspartam 200x sukrosa
Silkamat 300x sukrosa

Saccharin
Aspartam
POLISAKARIDA
Polisakarida
• Merupakan polimer unit monosakarida
• Unit monomer bisa :
• homopolisakarida
• heteropolisakarida

• Berbeda antara satu dgn yg lain pada unit


penyusunnya, ikatan yg menghubungkan, rantai
cabang yg terbentuk

44
Common polysacharides
Polysaccharide Monomeric Linkages
Glycogen D-Glucose α 16 branches
Cellulose D-Glucose β14
Chitin N-Acetyl-D- β14
glucosamine
Amylopectin D-Glucose α 16 branches
Amylose D-Glucose α 1 4

46
Struktur polisakarida
Polysaccharides
• Starch and glycogen are storage molecules
• Chitin and cellulose are structural molecules
• Cell surface polysaccharides are recognition
molecules
Starch Composition
• Amylose. Linear a-1,4 glucose chain. DP: 180-320,
MW~106. Branch approximately every 200 glucose
units
• Amylopectin. Linear a-1,4 chain with an a-1,6
branch approximately every 20 glucose units.
MW~108
• Amylose: amylopectin ~ 1:3
– Waxy starches all amylopectin
– High amylose mutants up to 70% amylose
Amylose Structure
Amylopectin Structure
Amaranth starch Arrowroot starch Buckwheat starch
(Bar: 1 µm) (Bar: 20 µm) (Bar: 5 µm)

Cassava starch Corn starch Oat starch


(Bar: 10 µm) (Bar: 10 µm) (Bar: 5 µm)

Potato starch Rice starch Kidney bean starch


(Bar: 50 µm) (Bar: 2 µm) (Bar: 20 µm)
Granule Structure
Starch Gelatinization and Pasting,
Gelation, and Uglification

Go to Slide Show mode and click to begin


Starch granules contain both linear amylose
and branched amylopectin.
Timeline

You are here


Turn heat on
Raw, uncooked starch granules
heated in water
Swelling is evident
Notice loss of amylose from the granules
Some granules have collapsed.

Gelatinization and pasting are complete


Timeline

gelatinization

You are here


Turn heat off
Start to cool
Gelation
Now we start to cool.
Notice areas of association. These are
called junction zones.
This picture is not yet complete as we haven’t
accounted for the water in the system.
water
water

water

water water
water

This is a starch gel


Timeline

gelatinization gelation

You are here


Ideal texture
Uglification
WATER

This picture ignores swollen and collapsed


granules.

Junction zones will naturally enlarge over time or


in response to processes such as freezing.
WATER

+ WATER of SYNERESIS that has been


squeezed out of the gel structure

The texture gets very ugly when this happens.


Timeline
Retrogradation

gelatinization gelation uglification

You are here


Ugly texture
Syneresis
Carbohydrate in Marine Products

Tim Pengampu MK Kimia Biokimia


Hasil Perikanan
Departemen Perikanan, FPN UGM
Carrageenan
•fills cellulosic plant structure
Galactose
•contribute outstanding
functional properties to control
moisture, texture and stabilise
food systems

Cold water, kappa


and lambda type

Warm water,
Cold water, kappa
kappa and Iota
and lambda type
type
Kelarutan karaginan

Solubility of Kappa Iota Lambda


Carrageenan in

80 oC water Yes Yes Yes


20 oC water Na+ salt soluble Na+ salt soluble Yes
K+, Ca 2+ , and Ca 2+ salts swell to
NH4+ salts swell form thixotropic
dispersion
80 oC milk Yes Yes Yes
20 oC milk No No Thickens

50 % Sugar solution Hot No Yes


10 % Salt solution No Hot Hot
kappa

iota

lambda
Pembentukan Gel

Cool Cool

K+

Heat
Heat

Solution Gel Agregated Gel


Gel properties

Gel Properties Kappa Iota Lambda

Strongest gels With K+ With Ca2+ No gel


Gel Texture Brittle Elastic No gel
Re-gelation after share No Yes No
Syneresis Yes No No
Freeze –thaw stability No Yes Yes
Synergism with LBG Yes No No
Synergism with konjac flour Yes No No
Synergism with starch No Yes No
Acid Stability *)
Gels at pH > 3.5 Stable Stable Stable
Salt tolerance Poor Good Good

*) Hydrolysis in low pH systems accelerated by heat


V. FUNCTIONAL PROPERTIES

Kappa Iota Lambda


• Strong rigid gel • Elastic gels, • No gel random
• Some syneresis • Form helixe with Ca2+. distribution of polymer
• Form helix with K+ • Limited aggregation chains
• Ca2+ causes helices to contributes to elasticity
aggregate and the gel to
contract and become brittle
• Slightly opaque gel. • Clear gel • High viscosity
• Become clear with sugar • Freeze / thaw stable
• Approximately 25% ester • Approximately 32% ester • Approximately 35% ester
sulphate and 34% 3,6- AG sulphate and 30% 3,6- AG sulfate and little or no
3,6- AG
Agar
b-(1,3)-linked –D-galactose and a-(1,4)-linked 3,6-anhydro L-galactose
Alginate
Brown Seaweed (Phaeophyceae) :
• Laminaria (Japan, China, Korea)
• Undaria (Korea, China, Japan)
• Macrocystis
• Durvillaea
• Ascophylum
•Sargassum

Ascophylum nodosum Ascophylum nodosum


2. Raw Materials
Brown Seaweed (Phaeophyceae) :
• Laminaria (Japan, China, Korea)
• Undaria (Korea, China, Japan)
• Macrocystis
• Durvillaea
• Ascophylum
•Sargassum

Ascophylum nodosum Ascophylum nodosum


2. Raw Materials

Laminaria digitata Laminaria digitata Eclonia sp.


2. Raw Materials

Sargassum flavican Sargassum sp.


Ca menjadi jembatan

Ca - bridges
5. Functional Properties
(Gelling Agent)

Ion
Ca 2+
Chitin vs chitosan
Images of Chitin molecules [2]

6 6
• Chitin is a natural polysaccharide 4
5
4
5
1 1
2 2
• The 2nd abundant organic source on earth 3 3

• Structure similar to cellulose with hydroxyl


group replaced by acetamido group
• N-acetyl-glucosamine units in β-(1→4) linkage

• Chitosan is the N-deacetylated derivative of


chitin
• N-glucosamine units in β-(1→4) linkage/ poli
(2-amino-2deoksi-β-(1-4)-D-glukopiranosa)
• N-deacetylation of chitin into chitosan is
achieved by treating with 50% NaOH

Structure of Chitin, Chitosan, and Cellulose [1]

[1] Kohr E. Chitin: fulfilling a biomaterials promise. Elsevier Science, 2001


[2] http://invsee.asu.edu/Modules/yeast/structure.htm
Chitin Sources (W.H. Daly, 2015)

Crawfish/Crabs
Shrimp Fungi (A.niger,
Mucor sp.
Penicillium
Composition (Based upon Dry Weight) notatum)

Chitin 25-30% 30-40 15-40%

Protein 15% 35% 5-10%


CaCO3 55% 30% Glycans
Lipids 2-5% 5-10% 5-10%
Astaxanthin pigment!
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