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Biochemistry

PROPERTIES OF TRIACYLGTYCEROLS

1. Hydrolysis : Triacylglycerols undergo stepwise enzymatic hydrolysis to finally liberate free fatty acids and glycerol.

The process of hydrolysis, catalysed by lipases is important for digestion of fat in the gastrointestinal tract and fat mobilization from the adipose tissues.

2. Saponification : The hydrolysis of triacylglycerols by alkali to produce glycerol and soaps is known as saponification.

3.Rancidity: Rancidity is the term used to represent the deterioration of fats and oils resulting in an unpleasant taste. Fats containing unsaturated fatty acids are more susceptible to rancidity.

Hydrolytic rancidity occurs due to partial hydrolysis of triacylglycerols by bacterial enzymes.

Oxidative rancidity is due to oxidation of unsaturated fatty acids.

This results in the formation of unpleasant products such as dicarboxylic acids, aldehydes, ketones etc.

 

Antioxidants : The substances which can prevent the occurrence of oxidative rancidity are known as antioxidants.

Trace amounts of antioxidants such as tocopherols  (vitamin E), hydroquinone, gallic acid and c,-naphthol are added to the commercial preparations of fats and oils to prevent rancidity. Propylgallate, butylatedhydroxyanisole (BHA)  and butylated hydroxytoluene (BHT) are the antioxidants used in food preservation.

Lipid peroxidation in vivo: In the living cells, lipids undergo oxidation to produce peroxides and free radicals which can damage the tissue. .

The free radicals are believed to cause inflammatory diseases, ageing, cancer , atherosclerosis etc

Iodine number : lt is defined as the grams (number)  of iodine absorbed by 100 g of fat or oil. lodine number is useful to know the relative

unsaturation of fats, and is directly proportional to the content of unsaturated fatty acids

Determination of iodine number will help to know the degree of adulteration of a given oil

Saponification number : lt is defined as the mg  (number) of KOH required to hydrolyse (saponify) one gram of fat or oiL

Reichert-Meissl (RM)  number: lt is defined as the number of ml 0.1 N KOH required to completely neutralize the soluble volatile fatty acids distilled from 5 g fat. RM number is useful in testing the purity of butter since it contains a good concentration of volatile fatty acids (butyric acid, caproic acid and caprylic acid).

Acid number : lt is defined as the number of mg of KOH required to completely neutralize free fatty acids present in one gram fat or oil. In normal circumstances, refined oils should be free from any free fatty acids.

The pH scale

An acidic solution is one in which [H+ ] > [OH- ]

•In an acidic solution, [H+ ] > 10-7 , pH < 7.

•A basic solution is when [OH- ] > [H+ ].

•In a basic solution, [OH- ] > 10-7 , pOH < 7, and pH >7.

• When the pH = 7, the solution is neutral.

•Physiological pH range is 6.5 to 8.0

 

Riboflavin: Vitamin B2

Riboflavin, or vitamin B2, helps to release energy from foods, promotes good vision, and healthy skin. It also helps to convert the amino acid tryptophan (which makes up protein) into niacin.

RDA Males: 1.3 mg/day; Females: 1.1 mg/day

Deficiency : Symptoms of deficiency include cracks at the corners of the mouth, dermatitis on nose and lips, light sensitivity, cataracts, and a sore, red tongue.

Polyprotic Acids

• Some acids are polyprotic acids; they can lose more than one proton.

• In this case, the conjugate base is also a weak acid.

• For example: Carbonic acid (H2CO3 ) can lose two protons sequentially.

• Each dissociation has a unique Ka and pKa value.

Ka1 = [H+ ][HCO3 - ] / [H2CO3]

Ka2 = [H+ ][CO3 -2 ] / [HCO3-

Note: (The difference between a weak acid and its conjugate base differ is one hydrogen)

Growth hormone

Growth hormone (GH or HGH), also known as somatotropin or somatropin, is a peptide hormone that stimulates growth, cell reproduction and regeneration in humans.

Growth hormone is a single-chain polypeptide that is synthesized, stored, and secreted by somatotropic cells within the lateral wings of the anterior pituitary gland.

Regulation of growth hormone secretion

Secretion of growth hormone (GH) in the pituitary is regulated by the neurosecretory nuclei of the hypothalamus. These cells release the peptides Growth hormone-releasing hormone (GHRH or somatocrinin) and Growth hormone-inhibiting hormone (GHIH or somatostatin) into the hypophyseal portal venous blood surrounding the pituitary.

GH release in the pituitary is primarily determined by the balance of these two peptides, which in turn is affected by many physiological stimulators (e.g., exercise, nutrition, sleep) and inhibitors (e.g., free fatty acids) of GH secretion.

Regulation

Stimulators of growth hormone (GH) secretion include peptide hormones, ghrelin, sex hormones, hypoglycemia, deep sleep, niacin, fasting, and vigorous exercise.

Inhibitors of GH secretion include somatostatin, circulating concentrations of GH and IGF-1 (negative feedback on the pituitary and hypothalamus), hyperglycemia, glucocorticoids, and dihydrotestosterone.

Clinical significance

The most common disease of GH excess is a pituitary tumor composed of somatotroph cells of the anterior pituitary. These somatotroph adenomas are benign and grow slowly, gradually producing more and more GH excess. The adenoma may become large enough to cause headaches, impair vision by pressure on the optic nerves, or cause deficiency of other pituitary hormones by displacement.

Factors regulating blood calcium level

(i) Vitamin D

(a) Vitamin D and absorption of calcium: Active form of calcium is calcitriol. Calcitriol enters intestinal wall and binds to cytoplasmic receptor and then binds with DNA causes depression and consequent transcription of gene code for calbindin. Due to increased availability of calbindin, absorption of calcium increases leading to increased blood calcium level.
(b) Vitamin D and Bone: Vitamin D activates osteoblast, bone forming cells & also stimulates secretion of alkaline phosphatase. Due to this enzyme, calcium and phosphorus increase.

(c) Vitamin D and Kidney: Calcitriol increase reabsorption of calcium and phosphorus by renal tubules.

 

(ii) Parathyroid  hormone (PTH)

Normal PTH level in serum is 10-60ng/l.

(a) PTH and bones: In bone, PTH causes demineralization. It also causes recreation of collagenase from osteoclast  leads to loss of matrix and bone resorption. As a result, mucopolysacharides and hydroxyproline are excreted in urine.

(b) PTH and Kidney: In kidney, PTH causes increased reabsorption of calcium but decreases reabsorption of phosphorus from kidney tubules.

(iii) Calcitonin Calcitonin decreases serum calcium level. It inhibits resorption of bone. It decreases the activity of osteoclasts and increases osteoblasts.

Hyper Calcemia When plasma Ca2+ level is more than 11mg/dl is called Hypercalcemia. It is due to parathyroid adenoma or ectopic PTH secreting tumor. calcium excreted in urine decreases excretion of chloride causing hyperchloremic acidosis.

Hypocalcemia Plasma calcium level less than 8mg/dl is called hypocalcemia. Tetany due to accidental surgical removal of parathyroid glands or by autoimmune disease. In tetany, neuromuscular irritability is increased. Increased Q-7 internal in ECG is seen. Main manifestation is carpopedal spasm. Laryngismus and stridor are also observed.

Nomenclature for stereoisomers: D and L designations are based on the configuration about the single asymmetric carbon in glyceraldehydes

 

For sugars with more than one chiral center, the D or L designation refers to the asymmetric carbon farthest from the aldehyde or keto group.

Most naturally occurring sugars are D isomers.

D & L sugars are mirror images of one another. They have the same name. For example, D-glucose and L-glucose

Other stereoisomers have unique names, e.g., glucose, mannose, galactose, etc. The number of stereoisomers is 2 n, where n is the number of asymmetric centers. The six-carbon aldoses have 4 asymmetric centers, and thus 16 stereoisomers (8 D-sugars and 8 L-sugars

An aldehyde can react with an alcohol to form a hemiacetal

Similarly a ketone can react with an alcohol to form a hemiketal

 

Pentoses and hexoses can cyclize, as the aldehyde or keto group reacts with a hydroxyl on one of the distal carbons

E.g., glucose forms an intra-molecular hemiacetal by reaction of the aldehyde on C1 with the hydroxyl on C5, forming a six-member pyranose ring, named after the compound pyran

The representations of the cyclic sugars below are called Haworth projections.

 

 

Fructose can form either: 

  • a six-member pyranose ring, by reaction of the C2 keto group with the hydroxyl on C6
  • a 5-member furanose ring, by reaction of the C2 keto group with the hydroxyl on C5.

 

 

Cyclization of glucose produces a new asymmetric center at C1, with the two stereoisomers called anomers, α & β

 

Haworth projections represent the cyclic sugars as having essentially planar rings, with the OH at the anomeric C1 extending either:

  • below the ring (α)
  • above the ring (β).

Because of the tetrahedral nature of carbon bonds, the cyclic form of pyranose sugars actually assume a "chair" or "boat" configuration, depending on the sugar

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