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Thursday, 7 May 2015

CHEMICALS REACTIONS AND TYPES

Photo by: ggw1962

Chemical Reactions 3282A chemical reaction is a process in which one set of chemical substances (reactants) is converted into another (products). It involves making and breaking chemical bonds and the rearrangement of atoms. Chemical reactions are represented by balanced chemical equations, with chemical formulas symbolizing reactants and products. For specific chemical reactants, two questions may be posed about a possible chemical reaction. First, will a reaction occur? Second, what are the possible products if a reaction occurs? This

Sulfur reacting to heat.
Sulfur reacting to heat.

entry will focus only on the second question. The most reliable answer is obtained by conducting an experiment—mixing the reactants and then isolating and identifying the products. We can also use periodicity, since elements within the same group in the Periodic Table undergo similar reactions. Finally, we can use rules to help predict the products of reactions, based on the classification of inorganic chemical reactions into four general categories: combination, decomposition, single-displacement, and double-displacement reactions.
Reactions may also be classified according to whether the oxidation number of one or more elements changes. Those reactions in which a change in oxidation number occurs are called oxidation–reduction reactions . One element increases its oxidation number (is oxidized), while the other decreases its oxidation number (is reduced).

Combination Reactions

In combination reactions, two substances, either elements or compounds, react to produce a single compound. One type of combination reaction involves two elements. Most metals react with most nonmetals to form ionic compounds. The products can be predicted from the charges expected for cations of the metal and anions of the nonmetal. For example, the product of the reaction between aluminum and bromine can be predicted from the following charges: 3+ for aluminum ion and 1− for bromide ion. Since there is a change in the oxidation numbers of the elements, this type of reaction is an oxidation–reduction reaction:
2Al ( s ) + 3Br 2 ( g ) → 2AlBr 3 ( s )
Similarly, a nonmetal may react with a more reactive nonmetal to form a covalent compound. The composition of the product is predicted from the common oxidation numbers of the elements, positive for the less reactive and negative for the more reactive nonmetal (usually located closer to the upper right side of the Periodic Table). For example, sulfur reacts with oxygen gas to form gaseous sulfur dioxide:
S 8 ( s ) + 8O 2 ( g ) → 8SO 2 ( g )
A compound and an element may unite to form another compound if in the original compound, the element with a positive oxidation number has an accessible higher oxidation number. Carbon monoxide, formed by the burning of hydrocarbons under conditions of oxygen deficiency, reacts with oxygen to form carbon dioxide:
2CO ( g ) + O 2 ( g ) → 2CO 2 ( g )
The oxidation number of carbon changes from +2 to +4 so this reaction is an oxidation–reduction reaction.
Two compounds may react to form a new compound. For example, calcium oxide (or lime) reacts with carbon dioxide to form calcium carbonate (limestone):
CaO ( s ) + CO 2 ( g ) → CaCO 3 ( s )

Decomposition Reactions

When a compound undergoes a decomposition reaction, usually when heated, it breaks down into its component elements or simpler compounds. The products of a decomposition reaction are determined largely by the identity of the anion in the compound. The ammonium ion also has characteristic decomposition reactions.
A few binary compounds decompose to their constituent elements upon heating. This is an oxidation–reduction reaction since the elements undergo a change in oxidation number. For example, the oxides and halides of noble metals (primarily Au, Pt, and Hg) decompose when heated. When red solid mercury(II) oxide is heated, it decomposes to liquid metallic mercury and oxygen gas:
2HgO ( s ) → 2Hg ( l ) + O 2 ( g )
Some nonmetal oxides, such as the halogen oxides, also decompose upon heating:
2Cl 2 O 5 ( g ) → 2Cl 2 ( g ) + 5O 2 ( g )
Other nonmetal oxides, such as dinitrogen pentoxide, decompose to an element and a compound:
2N 2 O 5 ( g ) → O 2 ( g ) + 4NO 2 ( g )
Many metal salts containing oxoanions decompose upon heating. These salts either give off oxygen gas, forming a metal salt with a different nonmetal anion, or they give off a nonmetal oxide, forming a metal oxide. For example, metal nitrates containing Group 1A or 2A metals or aluminum decompose to metal nitrites and oxygen gas:
Mg(NO 3 ) 2 ( s ) → Mg(NO 2 ) 2 ( s ) + O 2 ( g )
All other metal nitrates decompose to metal oxides, along with nitrogen dioxide and oxygen:
2Cu(NO 3 ) 2 ( s ) → 2CuO ( s ) + 4NO 2 ( g ) + O 2 ( g )
Salts of the halogen oxoanions decompose to halides and oxygen upon heating:
2KBrO 3 ( s ) → 2KBr ( s ) + 3O 2 ( g )
Carbonates, except for those of the alkali metals, decompose to oxides and carbon dioxide.
CaCO 3 ( s ) → CaO ( s ) + CO 2 ( g )
A number of compounds—hydrates, hydroxides, and oxoacids—that contain water or its components lose water when heated. Hydrates, compounds that contain water molecules, lose water to form anhydrous compounds, free of molecular water.
CaSO 4 · 2H 2 O ( s ) → CaSO 4 ( s ) + 2H 2 O ( g )
Metal hydroxides are converted to metal oxides by heating:
2Fe(OH) 3 ( s ) → Fe 2 O 3 ( s ) + 3H 2 O ( g )
Most oxoacids lose water until no hydrogen remains, leaving a nonmetal oxide:
H 2 SO 4 ( l ) → H 2 O ( g ) + SO 3 ( g )
Oxoanion salts that contain hydrogen ions break down into the corresponding oxoanion salts and oxoacids:
Ca(HSO 4 ) 2 ( s ) → CaSO 4 ( s ) + H 2 SO 4 ( l )
Finally, some ammonium salts undergo an oxidation–reduction reaction when heated. Common salts of this type are ammonium dichromate, ammonium permanganate, ammonium nitrate, and ammonium nitrite. When these salts decompose, they give off nitrogen gas and water.
(NH 4 ) 2 Cr 2 O 7 ( s ) → Cr 2 O 3 ( s ) + 4H 2 O ( g ) + N 2 ( g )
2NH 4 NO 3 ( s ) → 2N 2 ( g ) + 4H 2 O ( g ) + O 2 ( g )
Ammonium salts, which do not contain an oxidizing agent, lose ammonia gas upon heating:
(NH 4 ) 2 SO 4 ( s ) → 2NH 3 ( g ) + H 2 SO 4 ( l )

Single-Displacement Reactions

In a single-displacement reaction, a free element displaces another element from a compound to produce a different compound and a different free element. A more active element displaces a less active element from its compounds. These are all oxidation–reduction reactions. An example is the thermite reaction between aluminum and iron(III) oxide:
2Al ( s ) + Fe 2 O 3 ( s ) → Al 2 O 3 ( s ) + 2Fe ( l )
The element displaced from the compound is always the more metallic element—the one nearer the bottom left of the Periodic Table. The displaced element need not always be a metal, however. Consider a common type of single-displacement reaction, the displacement of hydrogen from water or from acids by metals.
The very active metals react with water. For example, calcium reacts with water to form calcium hydroxide and hydrogen gas. Calcium metal has an oxidation number of 0, whereas Ca 2+ in Ca(OH) 2 has an oxidation number of +2, so calcium is oxidized. Hydrogen's oxidation number changes from +1 to 0, so it is reduced.
Ca ( s ) + 2H 2 O ( l ) → Ca(OH) 2 ( aq ) + H 2 ( g )
Some metals, such as magnesium, do not react with cold water, but react slowly with steam:
Mg ( s ) + 2H 2 O ( g ) → Mg(OH) 2 ( aq ) + H 2 ( g )
Still less active metals, such as iron, do not react with water at all, but react with acids.
Fe ( s ) + 2HCl ( aq ) → FeCl 2 ( aq ) + H 2 ( g )
Metals that are even less active, such as copper, generally do not react with acids.
To determine which metals react with water or with acids, we can use an activity series (see Figure 1), a list of metals in order of decreasing activity. Elements at the top of the series react with cold water. Elements above hydrogen in the series react with acids; elements below hydrogen do not react to release hydrogen gas.
The displacement of hydrogen from water or acids is just one type of single-displacement reaction. Other elements can also be displaced from their compounds. For example, copper metal reduces aqueous solutions of ionic silver compounds, such as silver nitrate, to deposit silver metal. The copper is oxidized.
Cu ( s ) + 2AgNO 3 ( aq ) → Cu(NO 3 ) 2 ( aq ) + 2Ag ( s )
The activity series can be used to predict which single-displacement reactions will take place. The elemental metal produced is always lower in the activity series than the displacing element. Thus, iron could be displaced from FeCl 2 by zinc metal but not by tin.

Figure 1. Activity series.
Figure 1. Activity series.
ACTIVITY SERIES
Li
K These metals will displace hydrogen gas from water
Ba
Ca
Na
Mg
Al
Zn These metals will displace hydrogen gas from acids
Fe
Cd
Ni
Sn
Pb
H
Cu
Hg These metals will not displace hydrogen gas from water or acids
Ag
Au

Double-Displacement Reactions

Aqueous barium chloride reacts with sulfuric acid to form solid barium sulfate and hydrochloric acid:
BaCl 2 ( aq ) + H 2 SO 4 ( aq ) → BaSO 4 ( s ) + 2HCl ( aq )
Sodium sulfide reacts with hydrochloric acid to form sodium chloride and hydrogen sulfide gas:
Na 2 S ( aq ) + 2HCl ( aq ) → 2NaCl ( aq ) + H 2 S ( g )
Potassium hydroxide reacts with nitric acid to form water and potassium nitrate:
KOH ( aq ) + HNO 3 ( aq ) → H 2 O ( l ) + KNO 3 ( aq )
These double-displacement reactions have two major features in common. First, two compounds exchange ions or elements to form new compounds. Second, one of the products is either a compound that will separate from the reaction mixture in some way (commonly as a solid or gas) or a stable covalent compound, often water.
Double-displacement reactions can be further classified as precipitation, gas formation, and acid–base neutralization reactions.

Precipitation Reactions

Precipitation reactions are those in which the reactants exchange ions to form an insoluble salt—one which does not dissolve in water. Reaction occurs when two ions combine to form an insoluble solid or precipitate. We predict whether such a compound can be formed by consulting solubility rules (see Table 1). If a possible product is insoluble, a precipitation reaction should occur.
A mixture of aqueous solutions of barium chloride and sodium sulfate contains the following ions: Ba 2+ ( aq ), Cl ( aq ), Na + ( aq ), and SO 4 2− ( aq ). According to solubility rules, most sulfate, sodium, and chloride salts are soluble. However, barium sulfate is insoluble. Since a barium ion and sulfate ion could combine to form insoluble barium sulfate, a reaction occurs.

Table 1.
Table 1.
SOME SOLUBILITY RULES FOR INORGANIC SALTS IN WATER
Compound Solubility
Na + , K + , NH 4 + Most salts of sodium, potassium, and ammonium ions are soluble.
NO 3 All nitrates are soluble.
SO 4 2− Most sulfates are soluble. Exceptions: BaSO 4 , SrSO 4 , PbSO 4 , CaSO 4 , Hg 2 SO 4 , and Ag 2 SO 4 .
Cl , Br , I , Most chlorides, bromides, and iodides are soluble. Exceptions: AgX, Hg 2 X 2 , PbX 2 , and HgI 2 .
Ag + Silver salts, except AgNO 3 , are insoluble.
O 2− , OH Oxides and hydroxides are insoluble. Exceptions: NaOH, KOH, NH 4 OH, Ba(OH) 2 , and Ca(OH) 2 (somewhat soluble).
S 2− Sulfides are insoluble. Exceptions: salts of Na + , K + , NH 4 + and the alkaline earth metal ions.
CrO 4 2− Most chromates are insoluble. Exceptions: salts of K + , Na + , NH 4 + , Mg 2+ , Ca 2+ , Al 3+ , and Ni 2+ .
CO 3 2− , PO4 3− , SO 3 2− , SiO 3 2− Most carbonates, phosphates, sulfites, and silicates are insoluble. Exceptions: salts of K + , Na + , and NH 4 + .
BaCl 2 ( aq ) + Na 2 SO 4 ( aq ) → BaSO 4 ( s ) + 2NaCl ( aq )

Gas-Formation Reactions

A double-displacement reaction should also occur if an insoluble gas is formed. All gases are soluble in water to some extent, but only a few gases [HCl ( g ) and NH 3 ( g )] are highly soluble. All other gases, generally binary covalent compounds, are sufficiently insoluble to provide a driving force if they are formed as a reaction product. For example, many sulfide salts will react with acids to form gaseous hydrogen sulfide:
ZnS ( s ) + 2HCl ( aq ) → ZnCl 2 ( aq ) + H 2 S ( g )
Insoluble gases are often formed by the breakdown of an unstable double-displacement reaction product. For example, carbonates react with acids to form carbonic acid (H 2 CO 3 ), an unstable substance that readily decomposes into water and carbon dioxide. Calcium carbonate reacts with hydrochloric acid to form calcium chloride and carbonic acid:
CaCO 3 ( s ) + 2HCl ( aq ) → CaCl 2 ( aq ) + H 2 CO 3 ( aq )
Carbonic acid decomposes into water and carbon dioxide:
H 2 CO 3 ( aq ) → H 2 O ( l ) + CO 2 ( g )
The net reaction is:
CaCO 3 ( s ) + 2HCl (aq) → CaCl 2 ( aq ) + H 2 O ( l ) + CO 2 ( g )
Sulfites react with acids in a similar manner to release sulfur dioxide.

Acid-Base Neutralization Reactions

A neutralization reaction is a double-displacement reaction of an acid and a base. Acids are compounds that can release hydrogen ions; bases are compounds that can neutralize acids by reacting with hydrogen ions. The most common bases are hydroxide and oxide compounds of the metals. Normally, an acid reacts with a base to form a salt and water. Neutralization reactions occur because of the formation of the very stable covalent water molecule, H 2 O, from hydrogen and hydroxide ions.
HCl ( aq ) + NaOH ( aq ) → NaCl ( aq ) + H 2 O ( l )
Recognizing the pattern of reactants (element or compound, and the number of each) allows us to assign a possible reaction to one of the described classes. Recognizing the class of reaction allows us to predict possible products with some reliability.

CHEMICAL BOUNDING

Chemical Bond Types


Overview
Ionic Bonds
An ionic bond is formed by the attraction of oppositely charged atoms or groups of atoms. When an atom (or group of atoms) gains or loses one or more electrons, it forms an ion. Ions have either a net positive or net negative charge. Positively charged ions are attracted to the negatively charged 'cathode' in an electric field and are called cations. Anions are negatively charged ions named as a result of their attraction to the positive 'anode' in an electric field.
Every ionic chemical bond is made up of at least one cation and one anion.
Ionic bonding is typically described to students as being the outcome of the transfer of electron(s) between two dissimilar atoms. The Lewis structure below illustrates this concept.


ionic NaCl

For binary atomic systems, ionic bonding typically occurs between one metallic atom and one nonmetallic atom. The electronegativity difference between the highly electronegative nonmetal atom and the metal atom indicates the potential for electron transfer.
Sodium chloride (NaCl) is the classic example of ionic bonding. Ionic bonding is not isolated to simple binary systems, however. An ionic bond can occur at the center of a large covalently bonded organic molecule such as an enzyme. In this case, a metal atom, like iron, is both covalently bonded to large carbon groups and ionically bonded to other simpler inorganic compounds (like oxygen). Organic functional groups, like the carboxylic acid group depicted below, contain covalent bonding in the carboxyl portion of the group (HCOO) which itself serves as the anion to the acidic hydrogen ion (cation).

HCOOH
Covalent
A covalent chemical bond results from the sharing of electrons between two atoms with similar electronegativities A single covalent bond represent the sharing of two valence electrons (usually from two different atoms). The Lewis structure below represents the covalent bond between two hydrogen atoms in a H2 molecule.

H2
h2b
Dot Structure
Line Structure
Multiple covalent bonds are common for certain atoms depending upon their valence configuration. For example, a double covalent bond, which occurs in ethylene (C2H4), results from the sharing of two sets of valence electrons. Atomic nitrogen (N2) is an example of a triple covalent bond.
Double Covalent Bond

Double Bond


Triple Covalent Bond

N2
N2b
The polarity of a covalent bond is defined by any difference in electronegativity the two atoms participating. Bond polarity describes the distribution of electron density around two bonded atoms. For two bonded atoms with similar electronegativities, the electron density of the bond is equally distributed between the two atom is This is a nonpolar covalent bond. The electron density of a covalent bond is shifted towards the atom with the largest electronegativity. This results in a net negative charge within the bond favoring the more electronegative atom and a net positive charge for the least electronegative atom. This is a polar covalent bond.
Polar Bond

Coordinate Covalent

A coordinate covalent bond (also called a dative bond) is formed when one atom donates both of the electrons to form a single covalent bond. These electrons originate from the donor atom as an unshared pair.

Coordinate Formula

Both the ammonium ion and hydronium ion contain one coordinate covalent bond each. A lone pair on the oxygen atom in water contributes two electrons to form a coordinate covalent bond with a hydrogen ion to form the hydronium ion. Similarly, a lone pair on nitrogen contributes 2 electrons to form the ammonium ion. All of the bonds in these ions are indistinguishable once formed, however.

Ammonium
Hydronium
Ammonium (NH4+)
Hydronium (H3O+)
Network Covalent


Some elements form very large molecules by forming covalent bonds. When these molecules repeat the same structure over and over in the entire piece of material, the bonding of the substance is called network covalent. Diamond is an example of carbon bonded to itself. Each carbon forms 4 covalent bonds to 4 other carbon atoms forming one large molecule the size of each crystal of diamond.
Diamond
Silicates, [SiO2]x also form these network covalent bonds. Silicates are found in sand, quartz, and many minerals.
Quartz

Metallic

The valence electrons of pure metals are not strongly associated with particular atoms. This is a function of their low ionization energy. Electrons in metals are said to be delocalized (not found in one specific region, such as between two particular atoms).

Since they are not confined to a specific area, electrons act like a flowing “sea”, moving about the positively charged cores of the metal atoms.

  • Delocalization can be used to explain conductivity, malleability, and ductility.
  • Because no one atom in a metal sample has a strong hold on its electrons and shares them with its neighbors, we say that they are bonded.
  • In general, the greater the number of electrons per atom that participate in metallic bonding, the stronger the metallic bond.
Hydrogen bond
A hydrogen bond is a weak type of force that forms a special type of dipole-dipole attraction which occurs when a hydrogen atom bonded to a strongly electronegative atom exists in the vicinity of another electronegative atom with a lone pair of electrons. These bonds are generally stronger than ordinary dipole-dipole and dispersion forces, but weaker than true covalent and ionic bonds

NUCLEOTIDES HEREDITORY DETERMINANT

NUCLEOTIDES(HEREDITARY DETERMINANT)


                    











    

Nucleotides 3834Nucleotides are the subunits that are linked to form the nucleic acids ribonucleic acid (RNA) and deoxyribonucleic acid (DNA), which serve as the cell's storehouse of genetic information. Free nucleotides play important roles in cell signaling and metabolism , serving as convenient and universal carriers of metabolic energy and high-energy electrons.
All nucleotides are composed of three parts: a five-carbon sugar, a phosphate, and a nitrogen-rich structure called a nitrogenous base. The sugar can be ribose, which is found in ribonucleotides and RNA, or deoxyribose, which is found in deoxyribonucleotides and DNA. The only difference between these two sugars is that deoxyribose has one fewer oxygen atom than ribose. The five carbon atoms in the sugar are numbered sequentially. To distinguish these carbon atoms from those of the nitrogenous base, which are also numbered, they are designated as 1 (prime), 2 , and so on.
There are five nitrogenous bases. The so-called pyrimidines (cytosine, thymine, and uracil) are smaller, having only one ring structure. The larger purines (adenine and guanine) have two rings. Adenine, guanine, and cytosine are found in both ribonucleotides and deoxyribonucleotides, while thymine occurs only in deoxyribonucleotides and uracil only in ribonucleotides.
The phosphate group is bonded to the 5 carbon of the sugar (see Figure 2), and when nucleotides are joined to form RNA or DNA, the phosphate of one nucleotide is joined to the sugar of the next nucleotide at its 3 carbon, to form the sugar-phosphate backbone of the nucleic acid. In a free nucleotide, there may be one, two, or three phosphate groups attached to the sugar, as a chain of phosphates attached to the 5 carbon.
Three nucleotides merit special consideration because of their specialized roles in cellular function. These are adenosine triphosphate (ATP), flavin adenine dinucleotide (FAD), and nicotinamide adenine dinucleotide (NAD + ). Most biosynthetic reactions require energy, which is usually supplied by ATP. When ATP is hydrolyzed to ADP (adenosine diphosphate) or AMP (adenosine monophosphate), energy is released. By coupling this energy release to a reaction requiring energy, that reaction can be made to occur. Since ATP is so frequently used this way, it is commonly called the "energy currency of the cell."
Adenine-containing molecules are also important coenzymes, serving to carry chemical functional groups that are needed for enzyme activity. Three important adenosine-containing coenzymes are coenzyme A (CoA), FAD, and NAD + . CoA carries acetyl groups into the Krebs cycle (the central metabolic pathway in mitochondria ), and FAD and NAD + carry high-energy electrons from the Krebs cycle to the electron transport system , where their energy is used to synthesize ATP from ADP and inorganic phosphate.
Another adenine-based molecule is important in cellular signaling. When a hormone binds at a cell-surface receptor, it often promotes the production of cyclic AMP (cAMP) inside the cell. In cAMP, the phosphate group is joined to the 3 and 5 carbons of the ribose, forming a small ring structure.
The molecular structures of the five nitrogenous bases.
The molecular structures of the five nitrogenous bases.
A nucleotide consists of a nitrogen-containing base, a 5-carbon sugar, and one or more phosphate groups. The sugar dipicted is ribose. Deoxyribose has an H instead of an OH in the boxed position.
A nucleotide consists of a nitrogen-containing base, a 5-carbon sugar, and one or more phosphate groups. The sugar dipicted is ribose. Deoxyribose has an H instead of an OH in the boxed position.
cAMP can activate or suppress various cell processes, thereby serving as an intracellular signal and messenger that responds to hormone binding.

DIGESTIVE STARCH AND AMYLASE


alpha-amylase

Digestion of starch and alpha-amylase

Factors affecting relationship between starch and alpha-amylase

Fig. 1 – Spaghetti
Amylose and amylopectin, the two families of homopolysaccharides constituting starch, during their biosynthesis within vegetable cells, are deposited in highly organized particles called granules.
Granules have a partially crystalline structure and diameter ranging from 3 to 300 µm.
The access of the alpha-amylase, the enzyme that catalyzes the breakdown of amylose and amylopectin into maltose, maltotriose, and alpha-dextrins or alpha-limit dextrins, to carbohydrates making up granules varies as a function of:
  • amylose-amylopectin ratio;
  • temperature and packaging of amylose and amylopectin;
  • granules-associated proteins;
  • presence of fibers.

Amylose-amylopectin ratio

Starch for foodstuff use is obtained from various sources, the most important of which are corn (normal, waxy or high amylose content), potatoes, rice, tapioca and wheat.
Depending on botanical origin, molecular weight, degree of branching, and amylose-amylopectin ratio will vary.
Generally, there is 20-30% amylose and 70-80% amylopectin, even if there are starches with high amylose or amylopectin content (e.g. waxy corn). These differences justify the existence of starches with different chemical-physical characteristics and, to a certain extent, different digestibility.
  • corn: 24% amylose, 76% amylopectin;
  • waxy corn: 0,8% amylose, 99.2% amylopectin;
  • Hylon VII corn: 70% amylose, 30% amylopectin;
  • potatoes: 20% amylose, 80% amylopectin;
  • rice: 18.5 amylose, 81.5% amylopectin;
  • tapioca: 16.7% amylose, 83.3% amylopectin;
  • wheat: 25% amylose, 75% amylopectin.

Temperature and packaging of amylose and amylopectin

The chains of amylose, and to a lesser extent ramifications of amylopectin, thanks to the formation of hydrogen bonds with neighboring molecules and within the same molecules, have the tendency to aggregate. For this reason, pure amylose and amylopectin are poorly soluble in water at below 55 °C (131°F), and are more resistant to alpha-amylase action (resistant starch).
However, in aqueous solution, these granules hydrate increasing in volume of about 10%.
Above 55°C (131°F), the partially crystalline structure is lost, granules absorb further water, swell and pass to a disorganized structure, that is, starch gelatinization occurs, by which starch assumes an amorphous structure more easily attachable by alpha-amylase.

Granules-associated proteins

In granules, starch is present in association with proteins, many of which are hydrophobic, that means with low affinity for water. This association have the effect to hinder the interaction, in the intestinal lumen, between alpha-amylase, a polar protein, and the polysaccharides making up starch granules.
The physical processes to which cereals undergo before being eaten, such as milling or heating for several minutes, change the relationship between starch and the associated proteins, making it more available to α-amylase action.

Fibers

Alpha-amylase activity may also be hindered by the presence of nondigestible polysaccharides, the fibers: cellulose, hemicellulose and pectin.

Conclusions

The presence of inhibitors, of both chemical and physical type, hinders starch digestion, even when pancreatic α-amylase secretion is normal. This means that a part of starch, ranging from 1% to 10%, may escape the action of the enzyme, being then metabolized by colonic bacteria.
Refined starch is instead hydrolyzed efficiently, even when there is an exocrine pancreatic insufficiency (EPI), condition in which alpha-amylase concentration in gut lumen may be reduced to 10% of the normal.

GLYCOGEN:DEFINATION,STURUCTURE AND FUNCTIONS

Glycogen StructureGlycogen: definition, structure and functions


What is glycogen?

Fig. 1 – Glycogen Structure
Glycogen is an homopolysaccharide formed by units of glucose. Chemically similar to amylopectin, and therefore sometimes referred to as animal starch, compared to the latter it is more compact, extensively branched and larger, reaching a molecular weight up to 108 Da corresponding to about 600000 glucose molecules.
As in the amylopectin, glucose units in the main chain and in the lateral chains are linked by α-(1→4) glycosidic bonds. Lateral chains are joined to the main chain by an α-(1→6) glycosidic bond; unlike amylopectin branches are more frequent, approximately every 10 glucose units (rather than every 25-30 as in amylopectin) and are formed by a smaller numbers of glucose units.
Glycogen is located in the cytosol of the cell in the form of hydrated granules of diameter between 1 to 4 µm and forms complexes with regulatory proteins and enzymes responsible for its synthesis and degradation.

Functions of glycogen

Glycogen, discovered in 1857 by French physiologist Claude Bernard, is the storage form of glucose, and therefore of energy, in animals in which it is present in the liver, muscle (skeletal and heart muscle) and in lower amounts in nearly all the other tissues and organs.
In humans it represents less than 1% of the body’s caloric stores (the other form of caloric reserve, much more abundant, is triacylglycerols stored in adipose tissue) and is essential for maintaining normal glycemia too.
It represents about 10% of liver weight and 1% of muscle weight; although it is present in a higher concentration in the liver, the total stores in muscle are much higher thanks to its greater mass (in a non-fasting 70 kg adult male there are about 100 g of glycogen in the liver and 250 g in the muscle).
  • Liver glycogen stores is a glucose reserve that hepatocyte releases when needed to maintain a normal blood sugar levels: if you consider glucose availability (in a non-fasting 70 kg adult male) there is about 10 grams or 40 kcal in body fluids while hepatic glycogen can supply, also after a fasting night, about 600 kcal.
  • In skeletal and cardiac muscle, glucose from glycogen stores remains within the cell and is used as an energy source for muscle work.
  • The brain contains a small amount of glycogen, primarily in astrocytes. It accumulates during sleep and is mobilized upon waking, therefore suggesting its functional role in the conscious brain. These glycogen reserves also provide a moderate degree of protection against hypoglycemia.
  • Glycogen has a specialized role in fetal lung type II pulmonary cells. At about 26 weeks of gestation these cells start to accumulate glycogen and then to synthesize pulmonary surfactant, using it as a major substrate for the synthesis of surfactant lipids, of which dipalmitoylphosphatidylcholine is the major component.
Glycogen: Dipalmitoylphosphatidylcholine
Fig. 1 – Dipalmitoylphosphatidylcholine

Glycogen and foods

Glycogen is absent from almost all foods because after an animal is killed it is rapidly broken down to glucose and then to lactic acid; it should be noted that the acidity consequently to lactic acid production gradually improves the texture and keeping qualities of the meat. The only dietary sources are oysters and other shellfish that are eaten virtually alive: they contain about 5% glycogen.
In humans, accumulation of glycogen is associated with weight gain due to water retention: for each gram of stored glycogen 3 grams of water are retained.
References

PROTEIN DEFINATION AND CLASSIFICATION



Fig. 1 – Wheat
Gluten is not a single protein but a mixture of cereal proteins, about 80% of its dry weight (for example gliadins and glutenins in wheat grains), lipids, 5-7%, starch, 5-10%, water, 5-8%, and mineral substances, <2%.
It forms when components naturally present in the grain of cereals, the caryopsis, and in their flours, are joined together by means of mechanical stress in aqueous environment, i.e. during the formation of the dough.
The term is also related to the family of proteins that cause problems for celiac patients (see below).
Isolated for the first time in 1745 from wheat flour by the Italian chemist Jacopo Bartolomeo Beccari, it can be extracted from the dough by washing it gently under running water: starch, albumins and globulins, that are water-soluble, are washed out, and a sticky and elastic mass remains, precisely the gluten (it means glue in Latin).

Cereals containing gluten

It is present in:
  • wheat, such as:
durum wheat (Triticum durum); groats and semolina for dry pasta making are obtained from it;
common wheat or bread wheat (Triticum aestivum), so called because it is used in bread and fresh pasta making, and in bakery products;
  • rye (Secale cereale);
  • barley (Hordeum vulgare);
  • spelt, in the three species:
einkorn (Triticun monococcum);
emmer (Triticum dicoccum Schrank);
spelta (Triticum spelta);
  • khorasan wheat (Triticum turanicum); a variety of it is Kamut®;
  • triticale (× Triticosecale Wittmack), which is a hybrid of rye and common wheat;
  • bulgur, which is whole durum wheat, sprouted and then processed;
  • seitan, which is not a cereal, but a wheat derivative, also defined by some as “gluten steak”.
Given that most of the dietary intake of gluten comes from wheat flour, of which about 700 million tons per year are harvested, representing about 30% of the global cereal production, the following discussion will focus on wheat gluten, and mainly on its proteins.
Note: the term gluten is also used to indicate the protein fraction that remains after removal of starch and soluble proteins from the dough obtained with corn flour: however, this “corn gluten” is “functionally” different from that obtained from wheat flour.

Cereal grain proteins

Gluten
Fig. 2 – Cereal Grain Proteins
The study of cereal grain proteins, as seen, began with the work of Beccari. 150 years later, in 1924, the English chemist Osborne T.B., which can rightly be considered the father of plant protein chemistry, developed a classification based on their solubility in various solvents.
The classification, still in use today, divides plant proteins into 4 families.
  • Albumins, soluble in water.
  • Globulins, soluble in saline solutions; for example avenalin of oat.
  • Prolamins, soluble in 70% alcohol solution, but not in water or absolute alcohol.
    They include:
gliadins of wheat;
zein of corn;
avenin of oats;
hordein of barley;
secalin of rye.
They are the toxic fraction of gluten for celiac patients.
  • Glutelins, insoluble in water and neutral salt solutions, but soluble in acidic and basic solutions.
    They include glutenins of wheat.
Albumins and globulins are cytoplasmic proteins, often enzymes, rich in essential amino acids, such as lysine, tryptophan and methionine. They are found in the aleurone layer and embryo of the caryopsis.
Prolamins and glutelins are the storage proteins of cereal grains. They are rich in glutamine and proline, but very low in lysine, tryptophan and methionine. They are found in the endosperm, and are the vast majority of the proteins in the grains of wheat, corn, barley, oat, and rye.
Although Osborne classification is still widely used, it would be more appropriate to divide cereal grain proteins into three groups: structural and metabolic proteins, storage proteins, and defense proteins.

Wheat gluten proteins

Proteins represent 10-14% of the weight of the wheat caryopsis (about 80% of its weight consists of carbohydrates).
According to the Osborne classification, albumins and globulins represent 15-20% of the proteins, while prolamins and glutelins are the remaining 80-85%, composed respectively of gliadins, 30-40%, and glutenins, 40-50%. Therefore, and unlike prolamins and glutelins in the grains of other cereals, gliadins and glutenins are present in similar amounts, about 40%.
Technologically, gliadins and glutenins are very important. Why?
These proteins are insoluble in water, and in the dough, that contains water, they bind to each other through a combination of intermolecular bonds, such as:
  • covalent bonds, i.e. disulfide bridges;
  • noncovalent bonds, such as hydrophobic interactions, van der Waals forces, hydrogen bonds, and ionic bonds.
Thanks to the formation of these intermolecular bonds, a three-dimensional lattice is formed. This structure entraps starch granules and carbon dioxide bubbles produced during leavening, and gives strength and elasticity to the dough, two properties of gluten widely exploited industrially.
In the usual diet of the European adult population, and in particular in Italian diet that is very rich in derivatives of wheat flour, gliadin and glutenin are the most abundant proteins, about 15 g per day. What does this mean? It means that gluten-free diet engages celiac patients both from a psychological and social point of view.
Note: the lipids of the gluten are strongly associated with the hydrophobic regions of gliadins and glutenins and, unlike what you can do with the flour, they are extracted with more difficulty (the lipid content of the gluten depends on the lipid content of the flour from which it was obtained).

Gliadins: extensibility and viscosity

Gluten
Fig. 3 – Wheat Grain Proteins
Gliadins are hydrophobic monomeric prolamins, of globular nature and with low molecular weight. On the basis of electrophoretic mobility in low pH conditions, they are separated into the following types:
  • alpha/beta, and gamma, rich in sulfur, containing cysteines, that are involved in the formation of intramolecular disulfide bonds, and methionines;
  • omega, low in sulfur, given the almost total absence of cysteine and methionine.
They have a low nutritional value and are toxic to celiac patients because of the presence of particular amino acid sequences in the primary structure, such as proline-serine-glutamine-glutamine and glutamine-glutamine-glutamine-proline.
Gliadins are associated with each other and with glutenins through noncovalent interactions; thanks to that, they act as “plasticizers” in dough making. Indeed, they are responsible for viscosity and extensibility of gluten, whose three-dimensional lattice can deform, allowing the increase in volume of the dough as a result of gas production during leavening. This property is important in bread-making.
Their excess leads to the formation of a very extensible dough.

Glutenins: elasticity and toughness

Glutenins are polymeric proteins, that is, formed of multiple subunits, of fibrous nature, linked together by intermolecular disulfide bonds. The reduction of these bonds allows to divide them, by SDS-PAGE, into two groups.
  • High molecular weight (HMW) subunits, low in sulfur, that account for about 12% of total gluten proteins. The noncovalent bonds between them are responsible for the elasticity and tenacity of the gluten protein network, that is, of the viscoelastic properties of gluten, and so of the dough.
  • Low molecular weight (LMW) subunits, rich in sulfur (cysteine residues).
    These proteins form intermolecular disulfide bridges to each other and with HMW subunits, leading to the formation of a glutenin macropolymer.
Glutenins allow dough to hold its shape during mechanical (kneading) and not mechanical stresses (increase in volume due to both the leavening and the heat of cooking that increases the volume occupied by gases present) which is submitted. This property is important in pasta making.
If in excess, glutenins lead to the formation of a strong and rigid dough.

Properties of wheat gluten

From the nutritional point of view, gluten proteins do not have a high biological value, being low in lysine, an essential amino acid. Therefore, a gluten-free diet does not cause any important nutritional deficiencies.
On the other hand, it is of great importance in food industry: the combination, in aqueous solution, of gliadins and glutenins to form a three-dimensional lattice, provides viscoelastic properties, that is, extensibility-viscosity and elasticity-tenacity, to the dough, and then, a good structure to bread, pasta, and in general, to all foods made with wheat flour.
It has a high degree of palatability.
It has a high fermenting power in the small intestine.
It is an exorphin: some peptides produced from intestinal digestion of gluten proteins may have an effect in central nervous system.

Gluten-free cereals

The following is a list of gluten-free cereals, minor cereals, and pseudocereals used as foods.
  • Cereals
corn or maize (Zea mays)
rice (Oryza sativa)
  • Minor cereals
    They are defined “minor” not because they have a low nutritional value, but because they are grown in small areas and in lower quantities than wheat, rice and maize.
Fonio (Digitaria exilis)
Millet (Panicum miliaceum)
Panic (Panicum italicum)
Sorghum (Sorghum vulgare)
Teff (Eragrostis tef)
Teosinte; it is a group of four species of the genus Zea. They are plants that grow in Mexico (Sierra Madre), Guatemala and Venezuela.
  • Pseudocereals.
    They are so called because they combine in their botany and nutritional properties characteristics of cereals and legumes, therefore of another plant family.
Amaranth; the most common species are:
Amaranthus caudatus;
Amaranthus cruentus;
Amarantus hypochondriacus.
Buckwheat (Fagopyrum esculentum)
Quinoa (Chenopodium quinoa), a pseudocereal with excellent nutritional properties, containing fibers, iron, zinc and magnesium. It belongs to Chenopodiaceae family, such as beets.
  • Cassava, also known as tapioca, manioc, or yuca (Manihot useful). It is grown mainly in the south of the Sahara and South America. It is an edible root tuber from which tapioca starch is extracted.
It should be noted that naturally gluten-free foods may not be truly gluten-free after processing. Indeed, the use of derivatives of gliadins in processed foods, or contamination in the production chain may occur, and this is obviously important because even traces of gluten are harmful for celiac patients.

Oats and gluten

Oats (Avena sativa) is among the cereals that celiac patients can eat. Recent studies have shown that it is tolerated by celiac patients, adult and child, even in subjects with dermatitis herpetiformis. Obviously, oats must be certified as gluten-free (from contamination).

LIPID,DEFINATION AND CLASSIFICATION



lipidsLipids: definition, classification and functions

What are lipids?

Fig. 1 – High Fat/Oil Foods
Lipids, together with carbohydrates, proteins and nucleic acids, are one of the four major classes of biologically essential organic molecules found in all living organisms; their amounts and quality in diet are able to influence cell, tissue and body physiology.
Unlike carbohydrates, proteins and nucleic acids they aren’t polymers but small molecules, with a molecular weights that range between 100 and 5000, and also vary considerably in polarity, including hydrophobic molecules, like triglycerides or sterol esters, and others more water-soluble like phospholipids or very short-chain fatty acids, the latter completely miscible with water and insoluble in non polar solvents.
The little or absent water-solubility of many of them means that they are subject to special treatments at all stages of their utilization, that is in the course of digestion, absorption, transport, storage and use.

Classification of lipids

They may be classified based on their physical properties at room temperature (solid or liquid, respectively fats and oils), on polarity, or on their essentiality for humans, but the preferable classification is based on their structure.
Based on structure, they can be classified in three major groups.
  • Simple lipids
    They consist of two types of structural moieties.
    They include:
glyceryl esters that is esters of glycerol and fatty acids: e.g. triacylglycerols, mono- and diacylglycerols;
cholesteryl esters that is esters of cholesterol and fatty acids;
waxes which are esters of long-chain alcohols and fatty acids, so including esters of vitamins A and D;
ceramides that is amides of fatty acids with long-chain di- or trihydroxy bases containing 12–22 carbon atoms in the carbon chain: e.g. sphingosine.
  •  Complex lipids
    They consist of more than two types of structural moieties.
    They include:
phospholipids that is glycerol esters of fatty acids;
phosphoric acid, and other groups containing nitrogen;
phosphatidic acid that is diacylglycerol esterified to phosphoric acid;
phosphatidylcholine that is phosphatidic acid linked to choline, also called lecithin;
phosphatidylethanolamine;
phosphatidylserine;
posphatidylinositol;
phosphatidyl acylglycerol in which more than one glycerol molecule is esterified to phosphoric acid: e.g. cardiolipin and diphosphatidyl acylglycerol;
glycoglycerolipids that is 1,2-diacylglycerol joined by a glycosidic linkage through position sn-3 with a carbohydrate moiety;
gangliosides that is glycolipids that are structurally similar to ceramide polyhexoside and also contain 1-3 sialic acid residues; most contain an amino sugar in addition to the other sugars;
sphingolipids, derivatives of ceramides;
sphingomyelin that is ceramide phosphorylcholine;
cerebroside: they are ceramide monohexoside that is ceramide linked to a single sugar moiety at the terminal hydroxyl group of the base);
ceramide di- and polyhexoside that is linked respectively to a disaccharide or a tri- or oligosaccharide;
cerebroside sulfate that is ceramide monohexoside esterified to a sulfate group.
  •  Derived lipidsThey occur as such or are released from the other two major groups because of hydrolysis that is are the building blocks for simple and complex lipids.
    They include:
fatty acids and alcohols;
fat soluble vitamins A, D, E and K;
hydrocarbons;
sterols.
Classification adapted from: Bloor W.R. Proc Soc Exp Biol Med, 17, 138, 1920; Christie W.W. in “Lipid Analysis” Pergamon Press, Oxford, 1982; Pomeranz Y. and Meloan C.L. in “Food Analysis; Theory and Practice” 4th ed., AVI, Westport, Connecticut, 1994; Akoh C.C. and Min D.B. “Food lipids: chemistry, nutrition, and biotechnology” 3th ed. 2008.

Functions of lipids

  • They are stored in adipose tissue (triglycerides) and are one of the major energy source. Lipids are the best energy source for humans since at a parity of weight they provide the major part of calories: if carbohydrates, on average, gives 4 kcal/g, as proteins, lipids provide, on average, 9 kcal/g. Moreover, they can be present in foods without there are also fiber or water (for polysaccharides 2 g water/g) allowing to contain a great quantity of energy in a little weight.
    Mostly of Nutrition Organizations recommend that lipids must contribute up to 30% (with saturated fatty acids only less than 10%) of the total daily energy intake.
  • Some lipids are essential nutrients like fat-soluble vitamins A, (necessary for vision) and D (necessary for calcium metabolism), present in some fats and oils of animal origin, vitamin E (prevention of autoxidation of unsaturated lipids), present in vegetable oils, and vitamin K (normal clotting of blood) present in green leaves, essential fatty acids, in particular linoleic and α-linolenic acids, founders of the family of omega-6 and omega-3 fatty acids respectively.
  • During growth they are utilized as “bricks” for construction of biological membranes (phospholipids, cholesterol and glycolipids together with proteins), so contributing to construction of that barrier that separates intracellular environment from extracellular one and, inside cell, circumscribes organelles like mitochondria, Golgi apparatus or nucleus, and whose integrity is the basis of life itself; moreover they are also important for maintenance, physiochemical properties and repairing of cell membranes themselves.
  • Many hormones are lipids: steroid hormones, like estrogens, androgens and cortisol, are formed from cholesterol (essential also during embryogenesis), prostaglandins, prostacyclin, leukotrienes, thromboxanes, and other compounds (all eicosanids) from omega-3 and omega-6 polyunsaturated fatty acids with 20 carbon atoms.
  • On plasmatic cell membranes they can act as receptors, antigens and membrane anchors for proteins and can modify the structure, and therefore the functionality, of membrane enzymes.
  • Many lipids, like diacylglycerol, ceramides, sphingosine and platelet-activating factor act as regulators of intracellular processes.
  • There are fat deposits not accessed during a fast, classified as structural fat, the function of which is to hold organs and nerves in the right position protecting them against traumatic injuries and shock; fat pads on the palms and buttocks protect the bones from mechanical pressure.
  • A subcutaneous layer of fat is present in humans: it insulates the body reducing the loss of body heat and contributing to maintain body temperature.
  • On epidermis they are involved in maintaining water barrier.
  • They are electrical insulator of axon of neurons that are covered over and over again by plasmatic membranes of Swann cells, in peripheral nervous system, and of oligodendrocytes in central nervous system; these plasmatic membranes have a lipid content greater than that of the other cells. This lipoprotein coating is called myelin sheath.
  • On digestive tract they facilitate the digestive process depressing gastric secretion, slowing gastric emptying and stimulating biliary and pancreatic flow.
  • Bile salts (by-products of cholesterol) are natural detergents synthesized in the liver and secreted into bile. They solubilize phospholipids and cholesterol in the bile, permitting the secretion of cholesterol into the intestine (the excretion of both cholesterol and bile acids is the major way by which cholesterol is removed from the body). Bile salts also aid in the digestion and absorption of fat and soluble-fat vitamins in gut.
  • In many animals, some lipids are secreted into external environment and act as pheromones that attract or repel other organisms.
  • They affect the texture and flavor of food and so its palatability.
    Food manufacturers use fat for its textural properties, e.g. in baked goods fat increase the tenderness of the product. Chefs know that fat addiction add to the palatability of meal and increase satiety after a meal.