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148 Cards in this Set

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What are the goals of wet milling?

To anatomically separate the germ and pericarp


To isolate the starch and protein

How must maize be physically modified for wet milling?

* Kernel hydration


* Plasticization of hull and germ


* Swell germ


*Chemically modify endosperm protein to release starch

Name two aspects unique to maize wet milling

* Effluent recovery - water leaves the system only as stem


*Counter-flow water movement

Describe "steeping"

In the process of wet milling maize, kernels are steeped in tanks at high temperature and SO2 with XS water running counter current

Function of SO2 in steeping

*Control fermentation


*Modify proteins by cleaving disulfide bonds

Describe the fermentation that occurs during steeping

Lactobacillus produces lactic acid early in production, reducing pH and inhibiting other bacteria

What happens to the germ in maize wet milling?

It is released in the first and second grind mills (function is to release germ and not to reduce the endosperm)


The germ is recovered using density-based hydrocyclones

After the germ has been removed in maize wet milling, what is the next step?

The fiber, protein and starch is separated in the third grind using double disk attrition mills which grind finely

What happens to the fiber in maize wet milling?

About 8-15% of the initial dry weight of the kernel is fiber


Insoluble fiber is caught as an "over" and then goes to the dewatering press then to the feed dryer

How is the starch and protein recovered in maize wet milling?

Soluble starch and proteins are separated based on density differential using continuous, sequential centrifuges or hydroclones


Higher density starch sinks out (underflow)


Starch is purified through washing/hydrocloning then dried

What happens to the protein recovered in maize wet milling?

Separated from starch using hydroclones (less dense than starch)


Protein in concentrated and dried, may be combined with steep solids


Referred to as corn "gluten"

Name four differences between wheat and maize wet milling

1. Wheat milling primarily produces vital wheat gluten


2. Starch is the primary product of maize milling, but secondary product for wheat milling


3. Wheat milling starts with flour, maize with whole kernel


4. Wheat process differences: no counter flow, no concentration of steep, no SO2

What materials are used to start the wet wheat milling process?

Low grade flours such as clear or high extraction


Higher quality flour can be used, but is more expensive


Whole wheat flour is more difficult to process


Flour is first made into a thick batter / weak dough

What is the first process step of wet wheat milling?

Washing/kneading


Goal is to form gluten (protein self-associates and starch will separate)


Creates water-soluble slurry

What happens in wet wheat milling after the washing step?

Product is screened


Through: starch, solubles, water


Retained: crude "gluten"

How is the soluble starch isolated in wet wheat milling?

Isolated using centrifuges, hydroclones, starch tables, or sieves


Goal: remove remaining gluten


Then dry (explosion hazard)

What are the grades of wheat starch?

Prime - valuable, mostly large lenticular granules


B - mostly small and/or damaged granules, also includes cell walls and WU arabinoxylans

How is wheat gluten isolated?

After screening it is critical to retain functional properties ("vital")


Drying must be well calculated as heat damage will reduce functionality

What are the basic steps in wet milling rice?

* Protein and starch is very tightly associated, must be dissociated by steeping at alkaline pH


* Recover starch using centrifuge, drying is similar to wheat starch


*Protein must be neutralized

What are the major characteristics of wheat germ oil?

Very minor presence in marketplace


Oil is highly unsaturated, so very perishable


High in vitamin E

What are the two major cereal oils?

Rice bran oil - byproduct of solvent extracted bran


Maize germ oil - used in cooking and frying

How is maize oil produced?

Germ is flaked and steamed


Processed through expeller at high temperature and pressure


Several passes are made to achieve about 95% recovery


Residue = foots (used for feed, solvent extracted)

What are the two ways oil can be extracted from maize germ?

Expeller - problem with overheating the oil


Extraction - use large volumes of hexane in a sealed system, high recovery and good quality

What process steps are used to further treat crude maize oil?

Particulate removal


Alkali treatment


Bleaching


Winterization


Deodorizing

How are particulates removed from crude maize oil?

Filter press

Describe the alkali treatment used on crude maize oil

Short time necessary to prevent saponification


Converts free FA and polar lipids to water soluble salts

Describe bleaching of crude maize oil

Pigments/flavors adsorbed by acid activated clay

Describe winterization of crude maize oil

Rapidly cool oil, hold, and filter


Removes those molecules that are insoluble at low temperatures to prevent clouding

Describe deodorization of crude maize oil

Vacuum distill at high temp to remove volatile compounds (flavors, aromas, color)

How is maize oil packaged?

UV-intercepting material inhibits rancidity

Starch in plants

Temporarily in leaf, long term in endosperm


Granules formed in amyloplasts

How is starch chemistry different from typical polymer chemistry

Branched polymer is crystalline


Linear is amorphous

How are starches used outside of the food industry?

textiles


pharma


paper


wallboard, drilling mud

What are the sources of starch?

cereal grains


roots and tubers


fruits


lentils/beans/peas

Mineral component of starch

phosphorus from phospholipids in cereals


not covalently linked to starch polymer (it is in potato)


Nitrogen at low levels from lipid and protein

What is the major component of starch

alpha-D-glucose


referred to as dextrose in industry

Describe the two forms of glucose

Open chain = aldehyde, reduces Cu++, a reducing sugar, basis for assays


Ring form = hemiacetal, cannot reduce Cu++

Linkages of starch vs cellulose

Starch - alpha-1,4 linkage


Cellulose - beta-1,4 linkage

What is amylose

Minor polymer of starch


Usually 20-30%


Linear with alpha-1,4 linkages


80K-1000K MW; 500-6,000 AGU

What are the properties of amylose?

Strongly interacts with self and other CHO polymers


Results in strong gels and films


Stable helix: left handed, 6 AGU repeat that maximizes h-bonding opportunities intra chain and inter chain


Helix can trap molecules in the core (iodine, FA, alcohols)

What is a clathrate?

Complex of amylose helix and molecule trapped within

How are clathrates used?

FA clathrate - reduce granular swelling, viscosity


Iodine - used to quantitate amylose

What is amylopectin

major glucose polymer (70-80%)


Branches with individual alpha-1,4 linkages with branch points at alpha-1,6 linkage


Very large 100,000K MW, 600,000 AGU


Highly branched (about 5% of bonds)

Describe the branching structure of amylopectin

A chains = outer chains with no branches and no free reducing groups


B chains = at least 1 branch point and no free reducing group


C chains = at least one branch point and contains the ONLY reducing group for the entire molecule

How does amylopectin interact?

with self and other molecules primarily with A chains (h-bonding, entanglement)


Basis of granular structure and integrity

What is the typical amylose:amylopectin

Ratio generally consistent within plant species


Normal cereals 18-33% amylose


Rice has large variation, more amylose=less sticky

What is considered "waxy"?

Essentially 100% amylopectin

What is considered "high amylose"?

Up to 70% amylose

How are starch granules organized?

About 30% is crystalline, rest is amorphous


Many small crystalline regions = crystallites


Regularly arranged in granule as shown by birefringence

What is birefringence?

light and dark regions when viewed under polarized light


pattern indicates crystal arrangement


in starch = Maltese cross with arms crossing at hilum


There is NO direct correspondence of light and dark to crystalline and amorphous

Why are starch granules so insoluble?

Interactions of h-bonding


Crystallites are very organized, no room for H2O


Amylopectin ties together

How are starch granules disrupted?

crystallites must be melted


replace intermolecular h-bonding with water h-bonding


energy is required

Relationship of amylopectin and crystallites

Amylopectin and not amylose is important for crytallites


Amylose is not necessary for birefringence

What is the French-Kainuma model

Granule grows radially, shown in growth rings


length of crystallites limited by max length of amylopectin chains

How does starch behave in XS water at RT?

About 30% absorption


Slight granular swelling


Water uptake and swelling is reversible


Birefringence and crystallinity not lost


Solubility not changed

How does starch behave in XS water at elevated temps?

Simultaneous irreversible changes


* granular swelling


* water uptake


* Birefringence lost


*crytallinity lost


*system viscosity increases


Occurs at specific and characteristic temp

Define solubilization

Starch granule dissolves, starch molecules are lost to the water

What molecular changes occur during gelatinization?

h-bonds disrupted


molecules plasticize


amylose solubilizes

What two things are required for gelatinization?

1. heat - increases molecular motion


2. water - plasticizes the polymer

What occurs after gelatinization?

Pasting


*granule continues to swell


*granule is totally disrupted

What is retrogradation?

After gelatinized/pasted starch cools, molecules reassociate into ordered structure

How is a paste defined?

starch granules that have been heated sufficiently to:


1. lose birefringence


2. solublize part of the granule


*primarily or exclusively viscous

How is a gel defined?

Liquid-polymer system with some properties of solids (elasticity)


Small amount of solid will control a large amount of liquid

What are characteristics of starch gels?

Distance between the chains is large


water in the gel behaves like pure water


occurs at low conc of starch


more time and cooling leads to firmer gel

List three ways the gelatinization process can be measured

1. polarized light microscopy


2. DSC differential scanning calorimetry


3. recording viscometer

What does a viscoamylograph show?

starch in XS water with controlled heating, holding, and cooling


*Pasting


*Peak viscosity


*Shear thinning


*Set back

What regions can be identified in viscograph curve?

1. Pasting - granular swelling, dissolution, temp dependent


2. Cooking - no further solubilization w/o more temperature, decrease in viscosity attributed to shear thinning


3. Set Back - cooling, viscosity increases, more h-bonding as motion slows, gel may form if not stirred


4. Retrogradation - more h-bonding, syneresis

How do damaged starch granules behave?

Similar to gelatinized starch


More digestible


Less order/structure


More viscosity


More water absorption


More susceptible to amylase

Effect of alpha-amylase

Endo-hydrolase: randomly breaks a-1,4 links


Breaks both sides of a branch point w/in 2-3 AGU of a-1,6 link


"Liquifying"


produces dextrins - large molecular chunks


Givn time, will produce glucose


Amt naturally present in cereal flours varies

Effect of maltogenic amylase

Exo-hydrolase: breaks a-1,4 links at non-reducing end


Produces varying sizes of oligosaccharides

Effect of isoamylase

Endo-hydrolase: breaks a-1,6 link


debranching


Requires >3AGU

Effect of pullanase

Endo-hydrolase: breaks a-1,6 link


debranching


Requires >2 AGU

Effect of beta-amylase

Exo-hydrolase: breaks every other a-1,4 link @ non-reducing end


Cannot pass 1,6 branches


produces maltose


leaves b-limit dextrins

Effect of glucoamylase

Exo-hydrolase: breaks both a-1,4 and 1,6 links


Produces glucose


From non-reducing ends

List endo-hydrolases

alpha-amylase


isoamylase


Pullanase



List exo-hydrolases

Maltogenic amylase


beta-amylase


glucoamylase



What are the three primary methods of starch modification?

Chemical


Physical


Enzyme

What are the three ways starches are chemically modified?

acid-thinned


cross-linked


substituted

What are the two ways starches are physically modified?

pre-gelatinized


granular instant

How is starch acid modified?

Start with conc starch slurry


Add HCl at 1-3%, heat 50C X12-14 hours


Neutralize


*The amorphous regions are penetrated and hydrolyzed NOT the crystalline regions

Results of acid modification of starch

Reduced molecular weight


Intact crystalline structure


Intact granule


During gelatinization: less swelling, more fragmentation, increased temp range


During pasting: more solubilization, lower viscosity


RAPID GELATION


RIGID GELS

Types of cross-linking

1. Covalent bonding (inter polyer more important than intra)


2. diester cross-link (phosphate rxs with phosphoric acid)


3. ether cross-link (propyl rxn with epichlorohydrin)

Define DS

Degrees of substitution


Average number of crosslinks per AGU


Max for linear starch=DS3


Max for branched<DS3


For food applications: DS 0.01-0.1


*No change in gelatinization temp


*Significant change in paste/gel properties

Properties of cross-linked food starch

Less swelling at gelatinization


Less solubilization


Lower pasting viscosity


LESS SHEAR THINNING


INCREASED VISCOSITY IN ACID


shorter paste texture


slower retrogradation


INCREASED FREEZE-THAW STABILITY



How are starches substituted?

mono ester formation of phosphate groups


bulky


charged

Properties of substituted starch

starch polymers repel each other


More swelling and solubility at gelatinization


higher viscosity


greater shear-thinning


once soluble, phosphate groups inhibit inter-chain interaction and charges repel


LESS RETROGRADATION


INCREASED FREEZE-THAW STABILITY


at DS 0.7: gelatinization at RT (instant pudding)

Characteristics of pregelatinized starch

Pre-cooked


viscosity may change during storage, so reduced shelf life


May have slight visual grittiness


granule integrity has been lost

What is granular instant?

AKA cold water swelling


not pregelatinized


granule integrity maintained


smooth consistency (surface gloss)


freeze-thaw stable

Differences between pregelatinized and granular instant

Both hydrate quickly


Both cold water soluble


PG swells in cold water where GI is pre-swollen


PG may have grainy appearance where GI is smooth and glossy

Types of resistant starches

RS1 - starch is physically inaccessible


RS2 - granules are resistant


RS3 - retrograded starch


RS4 - chemically modified

Dextrose Equivalent

DE measures the % of glucosidic bonds that have been broken


Measures the number of reducing ends formed (C1)


DE= reducing power/wt of CHO X100


glucose = 100


maltose = 50


measures the number of breaks, not the size of polymers


indicates fermentability and sweetness

How are starches hydrolyzed?

Gelatinized first


Acid + heat = random hydrolysis, can generate off color/flavor (often used for thin pastes to further processing)


a-amylase


b-amylase

Maltodextrins

DE <20


Made with acid or acid+a-amylase


Useful as viscosity builder, fat extender

Intermediate DE syrup (42-70)

Acid thinned starch + a-amylase + b-amylase


properties depend on DE (70DE is complete, glu + stubs)


For high maltose: +pullanase +b-amylase

High DE syrup (92-95)

Sweeteners


start for HFCS


+glucoamylase

HFCS

glucose isomerase: glucose ->fructose


single pass = 42% fructose, iso-sweet with sucrose


Higher osmotic pressure than sucrose (higher aW)


More susceptible to brownign than sucrose

Essential AA and plant proteins

Lysine and tryptophan poorly represented

General structure of AA

NH2 - CH- R - COOH

Classification of proteins

Albumins - soluble in water


Globulins - soluble in salt water


Prolamins - soluble in 70% ethyl alcohol


Glutelins - soluble in dilute acid/base

Characteristics of albumins and globulins

enzymes (metabolic protein)


good AA balance


minor quantities in cereals


concentrated in aleurone, germ, pericarp

Characteristics of glutelins and prolamins

storage protein


major quantities in cereals


concentrated in endosperm


composition varies greatly b/w cereals

Wheat protein

8-16%


varies depending on genetics and env


protein made through dev, starch at end

How is a higher % protein wheat different from lower in composition?

Higher protein = lower proportion of albumins and globulins (total amount greater)

Proteins of gluten

When gluten is acid treated then extracted with EtOH and spun:


Soluble - gliadins


Precipitate - glutenins


gliadins (prolamins) and glutenins (glutelins) in equal amts

AA composition of gluten

35% glutamine (%P = Nx5.7) > hydrophobic side chains


14% proline


Low % basic AAs



Gliadins

single chain - three subunit types


moderate MW


NO inter-chain linking


STICKY


EXTENSIBLE

Glutenins

ELASTIC


RESILIANT


synthesized as monomers - two subunits (HMW and LMW)


polymerization between flowering and maturity


S-S bonds link subunits >> HUGE polymers


RESPONSIBLE FOR DOUGH STRENGTH/ELASTIC

Triticale protein

Forms weak dough

Rye protein

Second best AA balance


high level of albumins and globulins

Barley protein

high level prolamin (hordein)

Maize protein

high level prolamins (zein), some cross linked


high leucine

Sorghum protein

similar to maize


more cross-linking

millet protein

similar to maize but more variable


relatively less leucine

oat protein

highest % protein of cereals


good AA balance


mostly globulins

Rice protein

lowest % protein of cereals


relatively good AA balance


difficult to solubilize

Proteases

serine protease


metalloprotease


aspartic protease


cysteine protease

What is required for viscoelasticity in dough?

protein must be at a temperature above its glass transition temperature

Regions of glass transition curve

glass


Tg = glass transition


leather


rubbery plateau


elastic flow


liquid flow

Modulus

stiffness of a material


stress/strain

Glass transition temperature

marks large modulus change


mdpt of temp between glassy and rubbery


varies with temp and moisture

Polymer behavior below Tg

backbone configs immobilized


no segmental motion or interaction


glass-like

Polymer behavior above Tg

Increased chain motion


inter-chain interaction increases


changes in properties:


heat capacity


modulus of elasticity

Importance of Tg in tempering

Toughen bran:


becomes leathery


proteins are amorphous, cellulose semi-crystalline


Mellow endosperm:


become rubbery


protein and NSPoly amorphous, cellulose semi-crystalline

Why do non-wheat prolamins not form viscoelastic doughs?

Zeins (maize) and kafirins (sorghum) exist as protein bodies


Zein doughs - viscoelastic at 40C or at RT if organic plasticizer added



Hemicellulose

nonstarch, noncellulose polysaccharide


vary widely in sugars, size


includes:


b-glucans


arabinoxylans


others

Lignin

assoc w/cellulose, hemicellulose


complex, diverse structure


crosslinks with hemicellulose

Arabinoxylan

hemicellulose in wheat


WU = fiber


WE = gum


arabinose + xylose + ferulic acid

Properties of water extractable arabinoxylan

increase absorption and viscosity


cross-link and gel w/oxidation


increased foam stability


form network reinforcing gluten

Properties of water unextractable arabinoxylan

not a true cellulose


increase absorption and viscosity


disrupts gluten film and foam stability

Arabinogalactan peptide

hemicellulose of wheat


involved in grain hardness/softness

Beta-d-glucan

famous in oats


hemicellulose of wheat


soluble fiber

Hemicelluloses of wheat

arabinoxylan WE, WU


arabinogalactan peptides


beta-d-glucan



hemicelluloses of rye

arabinoxylans


arabinogalactan peptides

hemicelluloses of barley

arabinoxylans (minor)


beta-d-glucan, WE and WU


*linear polymers: b-1,4 and b-1,3 glu


*highly viscous, gel forming


*FDA health claim

hemicelluloses of oats

beta-d-glucan


*slightly higher than barley


*FDA health claim

Nonstarch polysaccharide degrading enzymes

endoxylanases (wheat inhibitors)


lichenase


cellulase

Smaller saccharides of cereals

sucrose


glucose, fructose and combos


glucofructosan in wheat and barley


occasional galactose

Phytic acid

major phosphorus in cereals


chelates divalent cations, so phytase added to feeds of monogastrics

Where are most minerals, B vitamins?

aleurone

Fatty Acid definition

carboxylic acid with long hydrocarbon chains


even number of carbons in chain

monoglyceride naming

1 - end


2 - middle

diglyceride naming

1,2 - next to eachother


1,3 - ends

Primary type of lipid in cereals

nonpolar


unsaturated

Cereal high in tocopherol (vit E)

wheat

Cereals high in wax

maize


sorghum

Cereal with lipid in endosperm

oat

Cereal with lipid in bran

Rice

Two cereals with high lipases

oats


barley