GPAT: Syllabus

PHYSICAL CHEMISTRY

Composition & physical states of matter:
Intermolecular forces & their impact on the state of the matter. Various physical properties of matter, dipole moment, dielectric constant, Van Der Waal’s equation & critical phenomenon, liquefaction of gases, aerosols.
Colligative Properties:
The liquid state, vapor pressure, ideal & real solutions. Raoult’s law, elevation of boiling point, depression of freezing point, osmotic pressure, determination of molecular weight based on colligative properties.
Thermodynamics:
First, second & third law of thermodynamics. Thermochemical laws, isothermic & adiabatic processes, reversible processes, work of expansion, heat content, enthalpy, heat capacity. Gibb’s & Helmholtz equation & chemical potential.
Refractive index:
Refractive index, specific refractivity, molar refractivity, refractometers.
Solutions:
Solubility, factors affecting solubility, solubility curves. Types of solutions, effect of co-solvency, pH & other factors on solubility. Solubility of gases in liquids, liquids in liquids, & solids in liquids, critical solution temperature, law of partitioning & its applications. Solute-solvent interactions. Expression of the concentration of pharmaceutical solutions & calculations. Molarity, molality, mole fraction & percentage expressions.
Electrochemistry:
Properties of electrolyte solutions, electrolysis. Faraday’s law of electrolysis, electron transport, electrical cell, single electrode potential, concentration cells, half-cells & half-cell potential, types of half cells, sign convention, Nernst equation, salt bridge, electromotive series, standard potential, SHE. Measuring the relative voltage of half cells, Calculation of standard potential. Reference & indicator electrodes. Standard oxidation-reduction potential.
Ionic equilibrium:
Theory of conductivity, equivalent conductance, mobility of ions, specific conductance.
Kinetics:

Order of reactions, derivation & internal form of rate laws, molarities of reaction, derivation of rate constants.

PHYSICAL PHARMACY

Matter, properties of matter
States of matter, change in the state of matter, latent heat and vapor pressure, sublimation- critical point, eutectic mixtures, gases, aerosols- inhalers, relative humidity, liquid complexes, liquid crystals, glasses state, solid crystalline and amorphous polymorphism.
Micromeritics and powder rheology
Particle size and distribution, average particle size number and weight distribution, particle number, methods of determining particle size and volume, optical microscopy, sieving, sedimentation, determining surface areas, permeability, adsorption, derived properties of powders, porosity, packing arrangement densities, bulkiness and flow properties.
Surface and interfacial phenomenon
Liquid interface, surface and interfacial tensions, surface free energy, measurement of surface and interfacial tension, spreading coefficient, adsorption and liquid interfaces, surface active agents, HLB classification, solubilization, detergency, absorption at solid interfaces, solid gas and solid-liquid interfaces, complex films, electrical properties of interfaces.
Viscosity and rheology
Newtonian systems, law of flow, kinematics viscosity, effect of temperature, non- Newtonian systems, pseudoplastics, dilatant, plastic, thixotropy in formulations, determination of viscosity and thixotropy by capillary, falling ball, rotational viscometer, application of theology in pharmacy
Dispersion systems
Colloidal dispersions: Definition, types, properties of colloids, protective colloids, application of colloids in pharmacy.

Suspensions and emulsions: Interfacial properties of suspended particles settling in suspension, theory of sedimentation, effect of Brownian movement, sedimentation of flocculated particles, sedimentation parameters, wetting of particles, significance of electrical properties in dispersions, controlled flocculation, flocculation in structured vehicles, rheological considerations, emulsions: types, theories, physical stability.

 

Complexation
Classification of complexes, methods of preparations and analysis, applications
Buffer
Buffer equations and buffer capacity in general. Buffers in pharmaceutical systems, preparations and stability, buffered isotonic solutions. Measurements of tonicity calculations and methods of adjusting isotonicity.
Solubility
Miscibility-influence of foreign substances three component systems;

·       dielectric constant and solubility,

·       solubility of solids in liquids

·       ideal and non-ideal solutions

·       solvation and association in solutions

·       solubility of salts in water

·       solubility of slightly soluble and weak electrolyte

·       calculating solubility of weak electrolytes as influenced by pH, influence of solvents on the solubility of drugs

·       combined effect of pH and solvents, distribution of solutes between immiscible solvents, effect of ionic dissociation and molecular association on partition, extraction, preservatives action of weak acids in emulsions, drug action and distribution coefficient.

Concepts of dissolution and diffusion

ORGANIC CHEMISTRY

General principles
A brief review of classification & sources of organic compounds, sp3, sp2, sp hybridization, sigma & pi- bonds, bond lengths, bond angles & bond energies along with their significance in reactions should be carried out. An overview of bond polarization, hydrogen bonds, inductive effects, resonance, and hyperconjugation be taken. Concept of homolytic & heterolytic bond fission, acidity & basicity with different theories should be covered briefly. Ease of formation

& order of stabilities of electron deficient & electron rich species along with the reasons for the same should be covered. Relationships between energy content, stability, reactivity & their importance in chemical reactions should be covered. Calculations for determining empirical & molecular formula should be covered.

Different classes of compounds
The following classes of compounds should be taught in detail with respect to their IUPAC / systematic nomenclature, industrial [wherever applicable] & laboratory methods of preparations, physical properties & chemical reactions with emphasis on reaction mechanisms [arrow based] & stereochemistry [wherever applicable].

•         Alkanes [including cyclic compounds]

•         Alkenes [including cyclic compounds]

•         Alkynes [only open-chain compounds]

•         Aliphatic hydroxyl compounds

•         Alkyl halides

•         Aldehydes & Ketones

•         Carboxylic acids

•         All functional derivatives of carboxylic acids.

Protection & deprotection of groups
Introduction to protection & deprotection of functional groups. Two examples each for amino, hydroxyl, & carbonyl groups. The significance of these in syntheses should be explained.
Aromaticity & chemistry of aromatic compounds
Concept of aromaticity, Huckel’s rule & its use in determining the aromatic/non-aromatic character of a compound. A brief coverage of structure of benzene. Detailed coverage of electrophilic & nucleophilic aromatic substitution reactions. Reactivity & orientation in these reactions. Reactivity & orientation in mono- & disubstituted benzenes. Benzyne mechanism.
Different aromatic classes of compounds
The following classes of compounds with respect to their IUPAC / systematic nomenclature, industrial [wherever applicable] & laboratory methods of preparations, physical properties & chemical reactions with emphasis on reaction mechanisms [arrow based] & stereochemistry [wherever applicable].

•         Aromatic hydrocarbons.

•         Phenolic compounds.

•         Aromatic & aliphatic amines.

•         Diazonium salts.

•         Aromatic nitro- compounds, aryl halides, & ethers.

Polycyclic aromatic hydrocarbons
Syntheses & reactions with mechanisms of bi & tricyclic fused carbocyclic rings like naphthalene, anthracene, & phenanthrene.
Carbonyl Chemistry
Carbonyl chemistry involving group conversions & their reaction mechanisms along with stereochemistry wherever applicable.

•         Wolf-Kishner reduction & Huang-Minlong modification.

•         Reduction of arylsulfonyl hydrazine/hydrazones to alkanes. c. Bamford Steven reaction.

•         DCC Oxidation of alcohol.

•         Michael addition / 1,4-addition / conjugate addition. f. Mannich condensation / reaction.

•         Robinson annulation.

•         Stobbe condensation.

•         Darzen’s glycidic ester synthesis.

•         Beckmann rearrangement.

•         Baeyer Villiger rearrangement.

•         Curtius, Wolff, & Lossen rearrangements.

•         Willgerodt rearrangement.

•         Pinacol-pinacolone rearrangement.

•         Methylene transfer reactions. Use of diazomethane & sulphur ylides in the same.

•          Mono- & dialkylations in 1,3-dicarbonyl compounds.

•         Formation & use of enol ethers, enol acetates & enamines as protective groups & in regiospecific alkylations.

Heterocyclic Chemistry
IUPAC Nomenclature of heterocyclic rings [3-10 membered] containing O, S, & N atoms. Nomenclature of above rings containing mono-, di-, & multiple [same or different] heteroatoms should also be covered. Nomenclature of 2 & 3 fused rings containing mono-, di-, & multiple heteroatoms [same or different] should also be covered. Syntheses & reactions of three to six- membered rings in detail. Syntheses of five & six-membered rings containing mono- or any di- heteroatoms [O, S, & N]. Syntheses of quinoline, isoquinoline, benzoxazole, benzothiazole, & benzimidazole, benzotriazole, and benzothiazole.
Bridged rings
Bridged ring systems & their nomenclature.C8, C9, C11 bridged bicyclic alkanes. Chemistry of hexamine, morphan, biperiden, amantadine, diazabicyclo octane.
Kinetic & thermodynamic control
Kinetic & thermodynamic control of sulfonation, enolate anion formation & alkylation of enamine reactions.
Stereochemistry
Stereochemistry. Chirality & asymmetry [introduction of the same to S, P, & N]. Definition & classification [different types of isomerisms]. Enantiomers, diastereomers. Enantiomerism & diastereomerism. Meso compounds & their optical activity. Stereochemistry in acyclic compounds. Newman projection formulae & their significance. Conformational analysis of n- butane. Absolute & relative configuration. Assigning R & S configuration based on Cahn Ingold

& Prelog system. Racemic mixture- its definition & resolution. Definitions of terms stereoselective, stereospecific, Enantiomeric excess & diastereomeric excess. Stereochemistry in cyclic systems. Conformations of cyclohexane. Cis-trans relationship in cyclohexane. Prediction of stability of different conformations of 1, 2- 1,3- & 1,4- disubstituted cyclohexanes. Effect of multiple substitutions on the stability of cyclohexane conformations. Chair conformations of cis-, & trans-decalins, perhydrophenanthrenes, & a tetracyclic steroidal nucleus. An introduction to atropisomerism.

Carbohydrates
Carbohydrates. Definition & classification. D & L nomenclature in sugars. Different ways of drawing / representing a sugar molecule [including cyclic Structure], interconversion of these representations. Anomers & epimers. Mutarotation. Reactions of glucose. Chain extension & chain reduction of a sugar.
Amino acids & proteins
Amino acids & proteins. Definition & classification. D & L Amino acids, natural, essential, & non- essential amino acids. Denaturation, Strecker, Gabriel phthalimide methods for the preparation of amino acids. Peptide bond & its formation. Two protective groups each, for -NH2 & -COOH functionalities during protein synthesis. Sequencing of a protein by chemical & enzymatic methods.
Pericyclic reactions
Pericyclic reactions. Concept of HOMO & LUMO. Drawing of HOMO & LUMO of 1, 3-butadiene, allylic cation, radical & anion, & 1, 3, 5-hexatriene, Diel’s-Alder & retro Diel’s Alder reaction.