4/24/2016

BIOMOLECULES:
CARBOHYDRATES AND LIPIDS

BIO20 - Introduction
to Biomimetics Prof. Ureah Thea A. Sevilla

Challenges to Engineers and Scientist

Designs that bring tangible solutions to some of the

worlds most pressing sustainability problems:
Foodsecurity
Human safety

Applications of biomimetics in manufacturing,

products, shipping industries and medicine
Robotics, including the development of human-like
robots

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Specific Problem Areas where Biomimicry

Can Be Involved
Energy efficient movement on water
Energy efficient movement in rugged terrain
Mechanical energy storage, short duration high
impact energy in/output -- long lasting low impact
energy in/output
Navigation
Active lumination in darkness
Detection of victims in catastrophes
Prevention of personal attacks

Biomimetics for Engineering Design

Using biomimetics for engineering design involves a

number of steps:
Search for relevant analogies
Proper analysis of the biological solutions

Interpretation and identification of design principles

Design of the desired artifacts

A biomimetics search can be done using different

sources of biological information specifically
biomolecular features.

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Biomolecules: Carbohydrates and Lipids

What properties do Carbohydrates and Lipids

have that makes them relevant in the innovation
of technology or in biomimetics?

Biological Functions of Carbohydrates

Generally, carbohydrates are the immediate sources of
energy
Carboydrates form structural tissues in plants and in
microorganisms ( e.g. cellulose, lignin, murein)

Other functions:
intermediates in the biosynthesis of other basic
biochemical entities (fats and proteins)
associated with other entities such as glycosides,
vitamins and antibiotics)
participate in biological transport, cell-cell recognition,
activation of growth factors, modulation of the immune
system

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Carbohydrate Structure
The simple carbohydrates - Monosaccharides consist
of carbon, hydrogen and oxygen in a 1:2:1 ratio
(CH2O)n.
They are divided into polyhydroxyaldehydes and

polyhydroxyketones.
Generally monosaccharides are polar molecules.

Classifications of Carbohydrates

Monosaccharides Oligosaccharides
Glucose (aldose) Fructose (ketose) Disaccharides
Sucrose

Maltose

Lactose

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Oligosaccharides
Oligosaccharides are formed from linking two or
more sugar units together by a glycosidic bond.
Common oligosaccharide disaccharides

Sucrose linkage of glucose and fructose

Oligosaccharides
Maltose linkage of two glucose molecules

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Oligosaccharides
Lactose linkage of galactose and glucose

Lactose

Infants produce lactase to

hydrolyze the disaccharide to
monosaccharides.
Some adults have low levels of
lactase. This leads to lactose
intolerance. The ingested lactose
is not absorbed in the small
intestine, but instead is fermented
by bacteria in the large intestine,
producing uncomfortable volumes
of CO2.

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Polysaccharides
homoglycans (starch, cellulose, glycogen, inulin)
heteroglycans (gums, mucopolysaccharides)
characteristics:
polymers (MW from 200,000)
White and amorphous products (glassy)
not sweet
not reducing (do not give the typical aldose or ketose reactions)
form colloidal solutions or suspensions

Starch
most common storage polysaccharide in plants
composed of 10 30% a-amylose and 70-90%
amylopectin depending on the source
the chains are of varying length, having molecular
weights from several thousands to half a million

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Amylose and amylopectin are the 2 forms of starch. Amylopectin

is a highly branched structure, with branches occurring every 12
to 30 residues

Starch in Plant Cell

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Glycogen
also known as animal starch
stored in muscle and liver
present in cells as granules (high MW)
contains both a(1,4) links and a(1,6) branches at
every 8 to 12 glucose unit
complete hydrolysis yields glucose
glycogen and iodine gives a brown color
hydrolyzed by both a and b-amylases and by
glycogen phosphorylase

Glycogen in Animal Cell

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Cellulose
Polymer of b-D-glucose attached by b(1,4) linkages
Yields glucose upon complete hydrolysis
Partial hydrolysis yields cellobiose
Most abundant of all carbohydrates
Cotton flax: 97-99% cellulose
Wood: ~ 50% cellulose
Gives no color with iodine
Held together with lignin in woody plant tissues

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Structure of cellulose

Inter- and Intra-chain Hydrogen Bonding of

Glucose in Cellulose

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Products obtained from cellulose

Microcrystalline cellulose : used as binder-disintegrant

in tablets
Methylcellulose: suspending agent and bulk laxative
Oxidized cellulose: hemostat
Sodium carboxymethyl cellulose: laxative
Cellulose acetate: rayon; photographic film; plastics
Cellulose acetate phthalate: enteric coating
Nitrocellulose: explosives; collodion (pyroxylin)

Chitin

chitin is the second most abundant

carbohydrate polymer
present in the cell wall of fungi and in the
exoskeletons of crustaceans, insects and spiders
chitin is used commercially in coatings (extends
the shelf life of fruits and meats)

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Exoskeleton of butterfly.

Exoskeleton of Cicada.

Chitin used to make strong,

flexible surgical threads that
decomposes after the wound or
incision heal.

Molting and
shedding off of
exoskeleton of
Cicada

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Linear structures of cellulose and chitin

(2 most abundant polysaccharides)

Gums
widely used in the food and pharmaceutical industry
used as: suspending agents, gelling agents, thickening
agents, emulsifiers, foam stabilizers, crystallization
inhibitors, adhesives, binding agents
agar, tragacanth, karaya, carrageenan, guar gum,
gum arabic (acacia), furcellaran, sodium alginate,
locust bean gum

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Iranian gum tragacanth showing the spiny shrub.

A ribbon of gum exuding from the exposed upper taproot.

Powdered gum tragacanth.

Gum tragacanth

Applications to Biomimetics
Chitosan has been used in many medical applications.
It serves as biomimetic material of anti-hemoglobin
antibodies to create an imprinted recognition surface
of hemoglobin beads.
Glycocalyx-mimetic peptoid that serve as biofouling
surfaces

Hyun Ok Ham, et al., J. Am. Chem. Soc., 2013, 135 (35), pp 1301513022

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Applications to Biomimetics
Polysaccharide admixture (cement)
Chitosan

Xanthan Gum

Welan

Succinoglucan

Curdlan - industrial applications include adsorption

of heavy metals and admixture to concrete.

Studies on chitosan as an admixture for cement-based materials:

Assessment of its viscosity enhancing effect and complexing ability for
heavy metals (M. Lasheras-Zubiate, I. Navarro-Blasco, J. M. Fernndez and J. I. Alvarez,
Journal of Applied Polymer Science, 2010)

Chitosan was proved to act as a thickener in cement

mixtures.
Chitosans of different molecular weights were assessed
as cement admixtures to modify the rheological
properties of a fresh cement paste. The highest
molecular weight chitosan showed the greatest
effectiveness taking into account its combined role as
heavy metal retainer and thickener. In addition, a clear
interaction between this high molecular weight chitosan
and cement particles was also demonstrated.

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Welan gum: Microbial production, characterization, and

applications (Varinder Kaur, Manav B. Bera, Parmjit S. Panesar, Harish
Kumar, J.F. Kenned, Int. Journ. of Biological Macromolecule, 2014)

Welan is an environment friendly natural

exopolysaccharide, produced fermentatively.
Structurally, it is composed of l-mannose, l-
rhamnose, d-glucose, and d-glucuronic acid.
It is available commercially to use in cement
compositions.
It also has commercial applications in oil-well
drilling.
Present review is focused on welan gum production,
purification, recovery and conformational
characterization of welan gum.

Lipids
Lipids are compounds of biological origin that dissolve in
nonpolar solvents such as chloroform and diethyl ether
Lipids include a variety of structural types, represented by the
following examples:

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Biological Function of Lipids

provide energy reserves, predominantly in the form
of triacylglycerols.
serve as structural components of biological
membranes.

Basic Unit of Lipids: Fatty Acids

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Physical Properties of Fatty Acids

FACTORS affecting FA properties
Length of hydrocarbon chain
Degree of unsaturation
Solubility to water
- FAs have poor solubility in H2O
*the longer the FA chain and fewer double bonds, the lower its
solubility in water.
Ex: Arrange the ff. FAs accdg. to increasing solubility in water:
16:0; 20:0; 18:0; 16:19
Melting point
unsaturated FAs have lower MP than saturated FAs.

Numerical Common Name Structure Melting temp.,

Symbol C
14:0 Myristic acid CH3(CH2)12COOH 53.9
16:0 Palmitic acid CH3(CH2)14COOH 63.1
16:19 Palmitoleic acid CH3(CH2)5CH=CH(CH2)7COOH 0.5
18:0 Stearic acid CH3(CH2)16COOH 69.6
18:19 Oleic acid CH3(CH2)7CH=CH(CH2)7COOH 13.4
18:29,12 Linoleic acid CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH 5
18:39,12,15 Linolenic acid CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7 11
COOH
20:45,8,11,14 Arachidonic acid CH3(CH2)3(CH2CH=CH)4(CH2)3COOH 49.5

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Physical Properties of Fatty Acids

% Fatty Acid
State at RT Saturated Unsaturated
25C C4-C12 C14 C16 C18 C16 + C18
Olive oil Liquid <2 <2 13 3 80
Butter Solid (soft) 11 10 26 11 40
Beef fat Solid (hard) <2 <2 29 21 46

Essential Fatty Acids

Not synthesized by the body
Precursors for long chain FAs (>16C)

Examples:
Linoleic acid
Arachidonic acid

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Common Dietary Fatty Acids

Saturated Fatty Acids
12:0 Lauric acid
14:0 Myristic acid
8:0 14:0 Medium chain FA (virgin coconut oil)

Monounsaturated Fatty Acids (MUFA)

18:1 Oleic acid (cis-FA; olive oil)
18:1 Elaidic acid (trans-FA; hydrogenated fats)

Common Dietary Fatty Acids

Polyunsaturated Fatty Acids (PUFA)
Omega-6
18:2 Linoleic acid (essential FA)
20:4 Arachidonic acid (in peanut oil; precursor for prostaglandin
and thromboxane)
Omega-3
18:3 Linolenic acid (essential FA)
20:5 Eicosapentanoic acid (EPA; help reduce cholesterol level)
22:6 Docosahexanoic acid (DHA; help reduce cholesterol level)

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Trans Fats
Trans fats
Partiallyhydrogenated vegetable oils formed by a
chemical hydrogenation process
Double bond straightens the molecule

Pack tightly; solid at room temperature

Triacylglycerols
TAGs consist of three FAs attached to a glycerol
backbone.
Oils from plants and fats of animal origin are
triacylglycerols
Oils are generally liquids at room temperature, fats
are solid

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Biological Functions of Triacylglycerols

Triacylglycerols are primarily used as an energy
reserve in animals
When they are metabolized they yield more
than twice the amount of energy per gram that
carbohydrates do
Fats are a form of long-term energy storage,
whereas carbohydrates are a source of rapid-
release energy

Biological Functions of Triacylglycerols

Saponification of Triacylglycerols
Basic hydrolysis of triacylglycerols yields salts of carboxylic
acids and glycerol

Chapter 23

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Biological Functions of Triacylglycerols

Salts of long-chain carboxylic acids are called soaps

In water, soaps exist in soluble spherical clusters called
micelles
Micelles have the hydrophilic carboxylate group of the fatty
acid salt on the outside exposed to water

Biological Functions of Triacylglycerols

Soaps clean by incorporating greasy (hydrophobic) dirt molecules

into the hydrophobic alkyl portion of micelles
The polar carboxylate groups of the soap micelles serve to suspend the
micelle in water so that it (with the enclosed dirt molecules) can be washed
away

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Phospholipids
Phospholipids are a class
of lipids that are a major
component of all cell
membranes as they can
form lipid bilayers.

The Cell Membrane

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Semi-permeable Membrane

A Gases (such as oxygen B Other solutes

and carbon dioxide), small
Lipid
nonpolar molecules, and
Bilayer
water cross a bilayer freely.
(molecules and ions)
cannot cross a lipid
bilayer on their own.

Fig. 5-6, p. 82

Fluid Mosaic Model of Cell Membrane

Proteins and substances such as cholesterol become embedded

in the bilayer, giving the membrane the look of a mosaic.

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Plasma membranes are primarily lipid bilayers with associated

proteins and glycolipids

Cholesterol is also a major component of plasma membranes

APPLICATIONS TO BIOMIMETICS

Biomimetic membranes may provide an alternative

to current Reverse osmosis and Nanofiltration
membranes e.g. for industrial separation and
wastewater treatment.

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APPLICATIONS TO BIOMIMETICS
Lipid Membranes in Biosensors
The lipid bilayers provide a matrix for biological

interactions and transduction.

The lipid bilayer closely mimics a cellular
membrane, creating an impermeable
barrier around the wire, yet this barrier
can incorporate membrane proteins.

Device schematics showing an ion channel

embedded in the lipid bilayer covering the
silicon nanowire (SiNW). S and D denote
source and drain electrodes and Vg is the
applied gate voltage.
Noy, A., Misra, N., Martinez,J. (2009) Lipid-coated
nanowires enable small-scale bioelectronics.

References:
Yosef Bar Cohen, Biomimetics Biologically Inspired
Technologies, CRC press, 2006.
Hyun Ok Ham, et al., J. Am. Chem. Soc., 2013, 135 (35), pp
1301513022
Varinder Kaur, Manav B. Bera, Parmjit S. Panesar, Harish
Kumar, J.F. Kenned, Int. Journ. of Biological Macromolecule,
2014
M. Lasheras-Zubiate, I. Navarro-Blasco, J. M. Fernndez and J.
I. Alvarez, Journal of Applied Polymer Science, 2010
Torben Lenau, Biomimetics as a Design Methodology, Intl Conf.
on Engg Des. Stanford Univ., 2009
Voet and Voet, Biochemistry 2nd ed. Wiley Publication (2004).

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