07 August 2017

Lecture #4: Hemoglobin



Hemoglobin is an iron–bearing protein contained within the erythrocytes. It is a respiratory protein which serves as the main component of red blood cells. It is a conjugated protein that serves as the vehicle for the transportation of oxygen and carbon dioxide. It is a chromoprotein consisting of 35% solid material in the red cells. A chromoprotein is a compound of a protein molecule and a non–protein pigment.


Structure of hemoglobin


Hemoglobin is composed of one molecule of globin, a basic protein and four molecules of heme, an organic compound of iron. It has an approximate molecular weight of 68,000. It is believed to be elliptical in shape.



The molecule of hemoglobin is composed of two identical half–molecules, each containing two different peptide chains, designated alpha and beta.  The alpha consists of 141 amino acid residues and the beta chain, 146 amino acid residues. The precise organization of these amino acids is vital to a normal molecule, and one substitution along the amino acid chain known to alter the hemoglobin function and result in a group of disease called “hemoglobinopathies.”


Formation of hemoglobin


Synthesis of hemoglobin begins in the erythroblast and continuous throughout the normoblastic stage. Even when young RBC leaves the bone marrow and pass into the blood stream they continue to form hemoglobin for a few days. Thus, hemoglobin formation does not depend upon a specific structure of the bone marrow but, instead, is an intrinsic ability of the early red blood cells themselves.

From tracer studies with isotopes, it is known that hemoglobin is synthesized mainly form acetic acid and glycine. It is believed that acetic acid is changed into alpha–glutaric acid, and then 2 molecules of this combine with one molecule of glycine to form a pyrrole compound. In turn, 4 pyrrole compounds combine to form a protoporphyrin compound. One of the protoporphyrin compound, known as as the protoporphyrin III, then combines with iron to form the heme molecule. Finally, 4 heme molecules combine with one molecule of globin to form hemoglobin


A.      1 alpha–ketoglutaric acid + glycine -------> pyrrole
B.      4 pyrrole ---------> protophorphyrin
C.      Protoporphyrin III + Fe ------------> heme
D.     4 heme + globin ------> hemoglobin


Accessory substances needed for formation of hemoglobin


In addition to amino acid and iron, which are needed directly for formation of hemoglobin molecule, a number of other substances act as catalyst or enzymes during different stages of hemoglobin formation. These are:

a.      Copper
b.      Pyridoxine
c.       Cobalt
d.      Nickel
The above mentioned substances serve mainly to emphasize the fact that hemoglobin formation results from a series of synthesis reactions, each of which depends upon appropriate building materials and also upon appropriate controlling catalyst and enzymes.


Function of hemoglobin:


1. Transport oxygen to body tissues.
2. Removes carbon dioxide, a product of metabolism, from the body tissues
3. Act as the most important buffer in the blood


Normal hemoglobin:


The heme group is identical in all variants of human hemoglobin. The protein part of the molecule (globin) consists of four polypeptide chains. At least three distinct hemoglobin types are found postnatally in normal individuals, and the structure of each has been determined.


1. Hemoglobin A1 (HbA1) – the major normal adult hemoglobin present in more than 95% of normal adults. The polypeptide chains of the globin part of the molecules are

Two identical alpha chains
Two identical beta chains

2. Hemoglobin A2 (HbA2) – a normal adult hemoglobin which constitutes less than 35% of the total hemoglobin. The polypeptide chains are:

Two alpha chains
Two beta chains

3. Hemoglobin A3 (HbA3) – a degradation product of HbA2 which comprises of 5 – 15% of the total adult hemoglobin. The polypeptide chains are:

Two alpha chains
Two beta chains

4. Embryonic hemoglobin – these are found in normal human embryos and fetuses with a gestational age of less than three months:

Hb Gower – 1   –      composed of 2 zeta and 2 epsilon chain
Hb Gower – 2   –      composed of 2 alpha and 2 epsilon chains
Hb Portland – 1 –     composed of 2 zeta and 2 gamma chains

5. Fetal hemoglobin – HbF is the major Hb of the fetus and newborns. The polypeptide chains are: 2 alpha and 2 gamma chains


Reactions of normal hemoglobin


After traveling through the pulmonary arteries in the lungs, the blood becomes oxygenated in the capillaries, where the oxygen in the lung diffuses into the blood. Oxygenated hemoglobin is referred to as oxyhemoglobin (HbO2). The binding of the oxygen to the hemoglobin molecule is rather loose compared to other more stable chemical bonds.

After hemoglobin loses its oxygen to the various tissue of the body, it become known as reduced hemoglobin


Oxyhemoglobin – by virtue of its iron, oxyhemoglobin, a compound that gives the bright red color to oxygenated blood in the arteries. It is the presence of oxyhemoglobin passing through capillaries near the body surface that gives the pinkness to the skin and varying degrees of redness to mucous membranes and the lips.


Reduced hemoglobin – is hemoglobin that has given up its oxygen and is blue in color rather than red. Under normal conditions not enough reduced hemoglobin is formed for the blue color to be visible, and blood in the systemic veins merely appears dark red in color. However, various diseases or abnormalities related to the cardiovascular and respiratory systems may result in the presence of such large quantities of reduced hemoglobin in the capillaries that the skin and mucous membrane have a distinctly blue color, this condition is called cyanosis.


Hemoglobin derivatives


The two physiologic hemoglobins, the oxyhemoglobin and the reduced hemoglobin, are readily converted to a series of compounds through the action of acids, alkalies, oxidizing and reducing substances, heat and other agents.

1. Hemiglobin (Hi) or Methemoglobin (MHb) or Ferrihemoglobin

Hi is a derivative of hemoglobin in which the ferrous ion is oxidized to the ferric state. This abnormal form of oxidized Hb is chocolate brown in color.

2. Sulfhemoglobin

In vitro and in the presence of oxygen, hemoglobin reacts with hydrogen sulfide to form a greenish derivative of hemoglobin called sulfhemoglobin. It may form in response to an oxidant stress; further change can result in denaturation and precipitation of hemoglobin as Heinz bodies.

SHb cannot transport oxygen, but it can combine with CO2 to form carboxyhemoglobin (HbCO).

3. Carboxyhemoglobin

Hemoglobin which combines with carbon monoxide results in the formation of brilliant cherry red colored carboxyhemoglobin (HbCO). The chief sources of CO gas are gasoline moors, illuminating gas, gas heaters, defective stoves and the smoking tobacco.


Abnormal hemoglobin and nomenclature


Abnormal hemoglobin is formed if there is a permanent structural rearrangement of molecular composition of the hemoglobin. The abnormal hemoglobin may or may not produce a disease state. When it is associated with a disease process, the condition is termed hemoglobinopathy.

1. Hemoglobin Bart’s – an abnormal variant of HbF

2. Hemoglobin H – the hemoglobin that moves fastest toward the anode in hemoglobin electrophoresis. It is often found in association with an alpha chain disorder and with thalassemia minor.

3. Hemoglobin C – abnormal Hb wherein the substitution of amino acid is in the sixth position of the beta chain.

4. Other hemoglobin was assigned letters of the alphabet, then geographical names, or both.

The sequence of eight amino acids in the Beta – peptide chain of Hb showing the substitution abnormality in hemoglobin S and C:

Amino Acid Sequence

Hb
A
S
C
1
Valine
Valine
Valine
2
Histidine
Histidine
Histidine
3
Leucine
Leucine
Leucine
4
Threonine
Threonine
Threonine
5
Proline
Proline
Proline
6
Glutamic acid
Valine
Lysine
7
Glutamic acid
Glutamic acid
Glutamic acid
8
Lysine
Lysine
Lysine


Destruction of hemoglobin


When a red cell fragments, its hemoglobin is immediately released into the plasma. Very soon, this phagocytized by the reticuloendothelial cells, which split the heme portion from the globin molecule. The result is a straight chain of four pyrrole nuclei, which is the basic structure of bile pigments. The first pigment formed is biliverdin, but this is rapidly reduced to bilirubin. These products are gradually released into the plasma.

Bilirubin is insoluble in water, but it combines firmly with plasma proteins in which form it is soluble and is transported throughout the body. On reaching the liver, the liver cells remove bilirubin from the protein and conjugate approximately 80% of it with glucuronic acid to form bilirubin glucuronide. This is highly soluble in water and is normally secreted by the liver cells into the bile. An additional 10% is conjugated with sulfate to form the soluble bilirubin sulfate, and the final 10% is conjugated with other solubilizing substances, all of which are similarly excreted.

It is bilirubin in the bile that gives it its greenish yellow color and any failure of the liver to excrete bile causes increased quantities of bilirubin in the body fluids. These in turn produce a yellow color (jaundice) in the skin. Obviously, the more rapid the destruction of RBC, the greater also will be the amount of bilirubin in the body fluids.

In forming the bile pigments, the reticuloendothelial cells remove iron from heme and this is immediately released into the iron pool of the body. The iron can then be reused for formation of additional Hb or other substances.


*********


Hemoglobinometry – the measurement of the concentration of hemoglobin in blood.

The hemoglobin content of a solution may be estimated by:

a. Measurement of its color through the color of the blood.
b. A method based on specific gravity of the blood.
c. By its power of combining with oxygen
d. By its iron content
e. By converting hemoglobin into one of several compounds and comparing the resulting compound with a known standard either visually or photoelectrically.


Different methods of hemoglobin determination


1. Specific gravity method or Copper Sulfate method


In this method, drop of blood are allowed to fall into 16 small bottles containing copper sulfate solution of increasing specific gravity readings.

a. If the drop of blood falls in a few seconds, it has a greater specific gravity than the solution

b. If the drop of blood rises in a few second, it has a lower specific gravity than the solution

c. If the drop of blood remains suspended for about 15 seconds and then falls, more or less it has the same specific gravity as the solution

Note:   This method is used by blood banks as a screening test for blood donors.


2. Gasometric method


Oxygen capacity method

Principle:         

Hemoglobin will combine with and liberate a fixed quantity of oxygen.The blood is hemolyzed with saponin and the oxygen is collected and measured in a Van Slyke apparatus.

Note:   

The oxygen combining capacity of blood is 1.34 ml O2 per gram of hemoglobin. The volume of oxygen is corrected for temperature and pressure and the hemoglobin concentration is determined with the use of the following formula:

Volume of oxygen / 100 ml blood   =   Grams of Hb/100 ml blood
                        1.34

Grams of Hb/100 ml blood x 10                     =          Grams of Hb / liter of blood

Note:   This method was formerly used to calibrate or standardize instruments for hemoglobin determination
          
   
3. Chemical method


Hemoglobin may be measured by determining the iron content of whole blood. Based on the molecular structure, the iron content of hemoglobin is 0.347%. Thus, 1 gram or 1000 mg of Hb contains 3.47 mg or iron. The concentration of hemoglobin in blood is calculated by dividing the iron content (mg/dl) by 3.47

Wong’s method

Principle:        

Iron is detached from the hemoglobin by treating the blood with concentrated sulfuric acid in the presence of potassium persulfate. The protein are precipitated with tungstic acid and filtered off. The iron content of the filtrate is determined in a colorimeter and the Hb value is calculated with the following formula:

mg iron / 100 ml               =          grams of Hb / 100 ml blood
           3.47

Grams of Hb / 100 ml x 10     =          grams of Hb / liter

Note:   This method has been used for calibrating various hemoglobinometers


4.      Colorimetric method


a. Visual colorimetric method

(1)   Direct matching method

Principle:        

The color of fresh blood is compared with a series of colored standards representing known quantities of hemoglobin.

The procedure employed in the following are based on the principle of direct matching method:

(a)   Tallquist method
(b)   Dare’s method
(c)    Spencer’s method

(2)   Acid hematin method

Principle:        

Blood is mixed with 0.1 N HCl. This hemolyzes the red cells and converts the hemoglobin to a brownish yellow solution of acid hematin. The acid hematin is then compared with a colored glass standard (Comparator Block)

The procedures employed in the following are based on the principle of Acid Hematin method:

(a)   Sahli – Hellige method
(b)   Haden – Hausser method
(c)    Sahli – Adams method
(d)   Osgood – Haskin method
(e)   Haldane method
(f)     Newcomer method

(3)   Alkali hematin method

Principle:        

Blood is mixed with 0.1 N NaOH. The solution is then boiled. The hemoglobin is then converted to a blue–green solution of alkaline hematin. The color of the solution is then compared with a known standard or in a colorimeter

Note:              

This method will not accurately measure the hemoglobin of an infant, because infant’s blood contains alkali resistant fetal hemoglobin (HbF)

The principle of Alkali – hematin method is used in the following:

(a)   Standard method using Gibson and Harrison’s standard solution
(b)   Clegg and King method

b.      Photoelectric method

(1)   Oxyhemoglobin method

Principle:        

Blood is mixed with either 0.1% sodium carbonate or 0.007 N Ammonium hydroxide solution. This converts the Hb to oxyhemoglobin. The depth of the resulting color is then measured in a photometer with a green filter (540 nm) and 0.007 N ammonium hydroxide as a blank

(2)   Cyanmethemoglobin method (MHbCN method) or Hemiglobincyanide (HiCN) method

Principle:        

Blood is diluted with Drabkin’s solution which contains ferricyanide and Cyanide. The potassium ferricyanide oxidizes hemoglobin to hemiglobin and potassium cyanide provides cyanide ions to form hemiglobincyanide, which has a broad absorption maximum at a wavelength of 540 nm. The absorbance of the solution is measured in a Photometer or spectrophotometer at 540 nm and compared with that of a standard HiCN solution.

Absorbance of test sample     x          Concentration of standard (mg/dl)    x   251
Absorbance of standard                                  100 mg

=          Hb (g/dl)

Drabkin’s reagent

Potassium ferricyanide                       –          0.200 g
Potassium cyanide                              –          0.050 g
Dihydrogen potassium phosphate      –          0.140 g
Non–ionic detergent
            Storox                                      –          0.5 ml
            Tritron                                     –          1.0 ml
Distilled water q.s.ad.                         –          1000 ml

The solution should be clear and pale yellow, have a pH of 7.0 to 7.4 and give a reading of zero when measured in the photometer at 540 nm against water blank. This reagent should be kept in ambered colored bottle.

Note:  

The HiCn method is the method of choice, being considered as the most accurate and reliable method.

a. Most forms of hemoglobin (Hb, HbO2, Hi and HbCO2, but not SHb) are measured
b. The test sample can be directly compared with HiCN standard
c. Readings can be made at the convenience of the operator because of the stability of the diluted samples. The solution of HiCN is the most stable among the hemoglobin derivatives.

Errors in hemoglobinometry

1. Errors inherent in the sample

a. Blood sample collected through improper venipuncture
b. Blood sample collected through improper skin or capillary puncture technique

2. Errors inherent in the method

3. Errors inherent in the equipment

a. The accuracy of the equipment is not uniform
b. Unmatched cuvettes
c. Improper standardization of the photometer or colorimeter

4. Operator’s error – the so called human errors

Human errors can be reduced by good training, understanding the clinical significance of the test and the necessity for a dependable method, adherence to oral and written instructions and familiarity with the equipment and with the sources of error. The technologist who is interested in the work will be less prone to make errors than others.


Normal values


                        Conventional unit                             S.I. unit

Men                 14 – 18 g / 100 ml blood                    140 – 180 g/l
Women           12 – 16 g / 100 ml blood                    120 – 160 g/l
Children          14 – 26 g / 100 ml blood                    140 – 260 g/l


Test for hemoglobin derivatives and abnormal hemoglobin pigments


1. Shaking (naked eye examination)

Shaking of normal whole blood in the air for 15 minutes imparts to it a bright red color as the Hb is converted to HbO. The blood is cherry red when the pigment is HbCO in carbon monoxide poisoning. The color is chocolate brown in methemoglobinemia (HiCN) and mauve lavender in sulfhemoglobinemia

2. Spectrophotometric identification of hemoglobin

The various hemoglobins have characteristic absorption spectra, which can easily be determined with a spectrophotometer

3. Katayama’s test – the patient’s blood is mixed with fresh orange colored ammonium sulfide and then viewed with a hand spectroscope. Then the spectra of the unknown and the known pigments may be compared in the spectroscope.

4. Examination of plasma or serum for methemalbumin

Methemalbumin is also known as the Fairley’s pigment. In this protein, the ferrous iron is oxidized to ferric state and is bound to albumin.

Schumm’s test:

The plasma or serum is covered with a layer of ether and mixed saturated yellow ammonium sulfide. The mixture is then viewed with a hand spectroscope. If methemalbumin is present, a relatively intense narrow absorption band will be seen in the green filter at 558 nm.

5. Hemoglobin electrophoresis – this the single most useful laboratory test for detection and identification of abnormal hemoglobin.

Hemoglobin molecule in an alkaline solution have a net negative charge and move toward the anode in an electrophoretic system at a speed proportional to the strength of their charge. Those with electrophoretic mobility greater than that of HbA at pH 8.6 in barbital buffer are known as “fast hemoglobin” and these include Hb Barts and the two fastest, HbH and Hb1. HbC is the slowest of the common hemoglobins.

6. Determination of fetal hemoglobin

a. Alkali Denaturation Test

Singer and Chernoff’s method

Fetal hemoglobin resists alkali denaturation, while adult hemoglobin does not. A hemolysate is alkalinized and then neutralized and the denatured adult Hb is precipitated by ammonium sulfate. A filtrate will then contain only alkali resistant hemoglobin, which is measured and expressed as a percentage of the total.

Normal values:      Adults              0.5 – 0.8%
                              1 year old        1%

HbF is increased in thalassemia major, sickle cell disease, and in hereditary persistence of fetal hemoglobin.

b. Acid – Elution Test
Kleihauer, Braun and Betke method

The identification of cells containing HbF depends upon the fact that they resist acid–elution to a greater extent than do normal cells, thus, they appear as isolated darkly–staining cells among a background of pale–staining ghost cells. Hemoglobin other than HbF are eluted from the red cells on air dried blood film by citric acid phosphate buffer (pH 3.3)

7. Test to detect the presence of HbS (Test for Sickling)


For details, please refer to the topic on sickle cell anemia under the Chapter – Red Cell Disorders 




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