MEDICAL CHEMISTRY Topics of the Examination General chemistry 1. -

Basic terms of chemistry Elements, compounds, mixtures The molar concept The laws of chemistry

2.

Periodic classification of the elements

3. -

Chemical bonds Bonding interactions as a function of electronegativity differences Non-bonding interactions

4. -

Chemical equations Writing and balancing chemical equations Molecular, ionic, redox and thermochemical equations

5. -

The gaseous state Kinetic gas theory Gas laws

6. -

The liquid and the solid state Phase transitions; phase diagram of water Types of crystal lattices; supercooled liquids (amorphous solids)

7. -

Solutions I Solubility of gases in liquids Solubility of liquids in liquids Partition of a solute between two immiscible solvents

8. -

Solutions II Concentration of solutions Solubility of solids in liquids; solubility curves

9. -

Colligative properties of dilute solutions I Raoult's law Freezing-point depression Boiling-point elevation

10. -

Colligative properties of dilute solutions II The osmotic phenomenon Osmotic concentration and osmotic pressure Biological importance of osmosis

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11. -

Electrolytes Distinction between electrolytes and non-electrolytes The two types of electrolytes Electrolytic dissociation; degree of dissociation Determination of degree of dissociation from conductivity measurements

12. -

Acid-base theories Arrhenius's theory The theory of Brřnsted and Lowry Lewis's theory

13. Acids, acid anhydrides, acyl groups, acid halides, bases and base anhydrides - Definitions with examples 14. Salts and thio compounds - Definition and classification of salts (with examples) - Definition of thio compounds (with examples) 15. Chemical kinetics I - Definition of reaction rate, rate constant and half-life - Rate laws of zero-, first- and second-order reactions 16. -

Chemical kinetics II Reaction mechanism: collision theory, transition state, activation energy Temperature dependence of reaction rates Rate-determining step of complex (multistep) reactions

17. -

Chemical kinetics III Catalysis Definition; catalysts and inhibitors Homogeneous and heterogeneous catalysts (with examples) The Michaelis-Menten mechanism of enzyme action

18. -

Chemical equilibria Definition and classification of chemical equilibria The interpretation of the mass-action law (a kinetic approach) Altering equilibrium conditions (Le Châtelier's principle with examples)

19. Electrolytic equilibria - Electrolytic dissociation as an equilibrium - Relationship between the degree of dissociation and dissociation constant 20. Heterogeneous equilibria - Precipitate formation as an equilibrium - Solubility product

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21. Amphoteric character - Definition and examples - Isoelectric point 22. -

Self-ionization of water; pH, pOH Definition of pH pH of strong and weak electrolytes Methods of pH measurement

23. -

Buffer solutions Definition The Henderson-Hasselbalch equation Buffer capacity Physiological buffer systems (bicarbonate and phosphate)

24. Hydrolysis of salts - Qualitative aspects (with examples) 25. -

Acid-base indicators Definition; the mechanism of change in colour Indicator exponent; colour-change interval Acid-base titrations; interpretation of titration curves

26. -

Electrochemistry Redox reactions; oxidation number (with examples) Electrode processes (half-cell reactions: anode, cathode) Electrode potentials Standard hydrogen electrode; standard potentials; the electrochemical series

27. -

Galvanic cells Explanation of the function of a voltaic cell Nernst equation; electromotive force Classification of electrodes (first- and second-kind, ion-selective membrane electrodes)

28. Concentration cells - Definition; calculation of e.m.f. - Measuring pH with concentration cell and with glass electrode 29. Redox potential - Definition; function of redox electrodes - Predicting the direction of redox reactions by comparison of standard redox potentials 30. -

Electrolysis Conductivity of electrolytes Electrolysis of NaCl solution; anodic and cathodic, primary and secondary processes Faraday's law

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31. -

Elements of thermodynamics I Thermodynamic system The first law of thermodynamics Expansion work; enthalpy Exothermic and endothermic reactions Hess's law (with an example)

32. Elements of thermodynamics II - Definition of entropy (S); The second law of thermodynamics - Free enthalpy and equilibrium 33. -

Photochemistry The quantum theory of light Excitation; photolysis and photosynthesis Quantum yield (ozone formation) Photoinduced chain reaction (HCl formation) The photographic process

34. -

Colloidal systems I Definition of the colloidal state Classification of colloids (with examples) Preparation and stability of different colloidal systems

35. -

Colloidal systems II Physical characteristics of colloids Tyndall effect, Brownian motion, electric and high-surface phenomena Surfactants Macromolecular colloids Dialysis, electrophoresis, gel-permeation chromatography Organic chemistry

1. -

Alkanes The sp3-hybridized C atom General formula (names of the first ten members) IUPAC nomenclature, structural isomerism Physical properties and chemical reactions Conformations of ethane and n-butane

2. -

Cycloalkanes General formula Physical and chemical properties Conformation of the 3-, 4-, 5- and 6-membered rings

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3. -

Alkenes and alkynes The sp2- and sp-hybridized C atom General formula IUPAC nomenclature Chemical reactions

4. -

Dienes Classification of dienes (the arrangement of the double bonds) 1,2- and 1,4-addition

5. -

Alkyl halides Names, preparation and uses Substitution (SN) and elimination (E) reactions

6. -

Alcohols Definition, classification, nomenclature Physical and chemical properties Alcohols of practical importance

7. -

Ethers Definition, grouping, nomenclature Physical and chemical properties Ethers of practical importance

8. -

Organic sulphur compounds Thiols, thioethers and derivatives Definition, naming, classification Physical and chemical properties Thio compounds of practical importance

9. -

Aldehydes Structure of the carbonyl group; naming Redox, addition, condensation and polymerization reactions Tautomerism

10. -

Aliphatic ketones Structure of the carbonyl group; naming Redox, addition and condensation reactions Tautomerism

11. -

Aliphatic monocarboxylic acids Structure and names Preparation and chemical reactions Monocarboxylic acids of biochemical importance

12. Functional derivatives of carboxylic acids - Acyl groups - Formation and reactions of acid anhydrides, acid halides, amides, nitriles and esters

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13. -

Dicarboxylic acids Oxalic, malonic, succinic, glutaric and adipic acid Maleic and fumaric acid Inner anhydrides

14. Hydroxy and oxo carboxylic acids - The reactions of the OH and COOH groups; lactones - Important hydroxy and oxo carboxylic acids 15. Esters - Definition, classification, naming - Chemical properties 16. -

Aliphatic amines Definition, naming, grouping Physical and chemical properties Biologically important amines; neurotransmitters

17. -

Aromatic hydrocarbons I Structure of benzene; the Hückel's rule Aromatic character Grouping, naming and isomerism Isolated and fused polycyclic aromatics

18. -

Aromatic compounds II Physical properties of aromatic hydrocarbons Reactions of benzene Orientation of electrophilic aromatic substitution

19. -

Phenols, quinones and enols Classification of unsaturated OH compounds (enols, phenols, aromatic alcohols) Physical and chemical properties of phenols and quinones Important phenols and quinones

20. -

Aromatic oxo compounds and aromatic carboxylic acids Benzaldehyde, acetophenone, benzophenone and their reactions Benzoic acid, its chemical properties and derivatives Aromatic dicarboxylic acids

21. Aromatic amines - The physical and chemical properties of aniline (azo coupling included) - Aniline derivatives (acetanilide, sulphonamides, PAS) 22. -

Types of isomerism Definitions (isomerism; constitution, configuration, conformation) Structural (constitutional) isomerism Stereoisomerism: 2D and 3D geometrical isomerism; chirality. Diastereomers and enantiomers 23. Chirality I

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The phenomenon of optical activity; measurement of optical rotation Characterization of enantiomers and racemic mixtures Relative and absolute configurations

24. -

Chirality II Enantiomers and diastereomers (on the example of erythrose and threose) Stereoisomers of tartaric acid (meso isomers) Resolution of racemic mixtures

25. Amino acids - Definition; functional groups; the 20 common amino acids found in proteins - Configuration; amphoteric character; chemical reactions 26. -

Peptides, polypeptides Grouping of the amino acids (with examples) The structure and detection of the peptide bond Sequence-determination methods Naturally occurring peptides and polypeptides

27. -

Proteins Definition; classification Primary, secondary, tertiary and quaternary structures The colloidal nature of proteins

28. Monosaccharides I - Definition and classification with examples - The most important monosaccharides (glucose, fructose, galactose, mannose, ribose and deoxyribose) - The structure and configuration of D-glucose - Mutarotation 29. Monosaccharides - The reactions of monosaccharides - Sugar derivatives (aminosugars, glycosides) 30. -

Disaccharides Definition, classification Chemical properties Cellobiose, maltose, lactose, saccharose

31. -

Polysaccharides Definition, classification, biological role Cellulose, starch, glycogen Other biologically important polysaccharides

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32. Lipids I - Definition, classification, biological role - Fats, oils and waxes 33. Lipids II - Prostaglandins - Phospholipids; the structure of animal cell membranes 34. -

Sterols The sterane (gonane) skeleton; numbering; stereochemistry Classification of steroids Ergosterol and the vitamin-D group

35. -

Cholesterol (Stereo)structure and reactions Outlined biosynthesis pathway Biological role

36. Bile acids - (Stereo)structure (cholanic acid; taurocholic and glycocholic acid) - Physiological role 37. Steroid hormones - Sex hormones - Adrenal hormones 38. Cardiac glycosides and their aglycons - Digitoxigenin, strofantidin 39. -

Terpenes Definition and classification Monoterpenes Diterpenes (vitamin A; phytol) Triterpenes (squalene)

40. Carotenoids - Definition; cis-trans isomerism - Lycopene, α- and β-carotene (provitamins), zeaxanthin 41. Simple heterocycles - Heteroaromaticity - Five- and six-membered heterocycles 42. Fused-ring heterocycles - Indole and derivatives - Quinoline, isoquinoline, acridine and derivatives

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43. Macro-heterocycles - Hem, hemoglobin, myoglobin, bile pigments - Chlorophyll a and b 44. -

Purine and derivatives Purine; numbering Hydroxypurines (hypoxanthine, xanthine and uric acid; lactam-lactim tautomerism) Purine alkaloids Purine bases

45. -

Nucleosides and nucleotides Citidine, uridine, thymidine, adenosine and guanosine Nucleotides High-energy nucleotides (ADP, ATP); AMP, cAMP

46. Nucleic acids - Primary and secondary structures of RNA and DNA - tRNS, mRNS and rRNS 47. -

Nucleotide coenzymes NAD and NADP FAD Coenzyme A

48. -

Carbonic acid derivatives Phosgene, carbamic acid, carbamide, thiocarbamide Urethanes, ureides, barbituric acid and barbiturates Guanidine, creatine, creatine phosphate, creatinine

49. -

Alkaloids Definition Tropane alkaloids Opium alkaloids Purine alkaloids Others (ephedrine, nicotine, coniine, mescaline, quinine, LSD)

50. -

Vitamins I Definition of essential macro- and micronutrients Fat-soluble vitamins Hypo- and hypervitaminosis

51. -

Vitamins II Definition of a coenzyme Water-soluble vitamins Hypovitaminosis

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52. Drugs - Aspirin, phenacetin, sulphanilamides, penicillines, cephalosporines, barbiturates, morphine, 5-fluorouracil, 6-mercaptopurine Bioinorganic chemistry 1. -

Complex compounds I Definition, structure, nomenclature

2. -

Complex compounds II Isomerism, complexes of living organisms

3. -

The evolution of inorganic and organic chemicals on Earth Three groups of essential elements. Biological functions of inorganic elements

4. -

Biological role of the alkali metals I Terrestrial distribution, in vivo, functions of sodium and potassium, Complexes of alkali metal ions

5. -

Biological role of alkali metals II Osmo-regulation, mechanisms of ion transport

6. 7.

Biological role of magnesium

8. -

Biological role of iron I Uptake, transport and storage of iron

9. -

Biological role of iron II Oxygen transport and storage by iron complexes

Biological role of calcium

10. Biological role of iron III - Iron complexes with catalytic function 11. Zinc-containing proteins 12. Biological significance of copper I - Menkes and Wilson diseases. The blue-copper proteins. Cytochrome c oxidase 13. Biological significance of copper II - Oxygen activating copper proteins. Cu and Zn-containing superoxide dismutase 14. Biological role of manganese and molybdenum 15. Biological role of nickel, vanadium and chromium 16. Bioinorganic chemistry of toxic metals I

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Lead, cadmium, thallium

17. Bioinorganic chemistry of toxic metals II - Mercury, aluminium and chromium as chromate 18. Platinum complexes in cancer therapy 19. Natural silicates and their biological effects 20. Synthetic silicates and silicones. Biomineralization 21. Biological functions of boron, arsenic and selenium 22. Biological functions of the halogens

STRUCTURES TO BE RECOGNISED

Organic and bioorganic chemistry To 26: glutathione, penicillin, carnosin To 27: α-helix, β-sheet, outlined structure of myoglobin To 30: saccharose, maltose, lactose, cellobiose To 31: cellulose, amylose, amylopectine, chondroitin-6-sulphate, hyaluronic acid, heparin To 32: oleic acid, linoleic acid, linolenic acid To 33: arachidonic acid, PGE2, PGA2, L-α-cephalin, lecithin, phosphatidyl serine, phosphatidyl inositol To 34: ergosterol, vitamin D2 and D3 To 36: steric structure of cholic acid To 37: testosterone, estrone, estradiol, progesterone, cortisol (hydrocortisone), aldosterone To 38: digitoxigenin, strophantidin To 39: IPP, limonene, geraniol, camphor, phytol, vitamin A, squalene To 40: β-carotene, α-carotene, Lycopene, zeaxanthin, vitamin A To 42: indoxyl, serotonin, papaverine, quinine, methylene blue, uric acid To 43: heme, bilirubin, biliverdin, chlorophyll To 44: hypoxanthine, xanthine, uric acid, caffeine, theophylline, theobromine, adenine, guanine To 45: citidine, uridine, thymidine, adenosine, guanosine, AMP, ADP, ATP, cAMP, AZT.

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To 46: DNA, RNA To 47: NAD, FAD, CoA. To 48: creatinine, creatine phosphate, barbituric acid To 49: atropine, cocaine, morphine, LSD, papaverine, quinine, theophylline, theobromine, caffeine, nicotine, coniine, mescaline, ephedrine To 50: β-carotene, vitamin A-, D2-, D3, E and K, ubiquinone (coenzyme-Q) To 51: vitamin B1, B2 and B6, folic acid, pantotheic acid, vitamin C To 52: Aspirin, phenacetin, sulfanilamide, penicillin, cephalosporin, barbiturates, morphine, AZT, 5-fluorouracil, 6-mercaptopurine

Bioinorganic chemistry To 1: Structure of [Co(EDTA)]To 4: Macrocyclic ligands, K+/nonactin, K+/valinomicin To 6: Chlorophyll, mechanism of phosphate hydrolysis To 8: Outlined structure of apoferritin To 9: Hem, myoglobin, hemoglobin To 10: Catalytic cycle of P-450 enzymes To 11: Zn2+ in the active centre of carboxypeptidase-A. The active centre of liver alcohol dehydrogenase. To 12: Co-ordination environment of the copper center in azurin... Path of electrons through cytochrome c oxidase To 13: Reversible oxygenation of hemocyanin Structure of dimetal center in Cu,Zn superoxide dismutase To 14: Supposed structure of Fe-S-Mo cofactor of nitrogenase and reaction mechanism To 15: Coordination environment of the Cr3+ center in the glucose tolerance factor To 19: Cross-linking between collagen chains in lung tissue To 20: Hypothetical model of silification To 21: The catalytic cycle of GSH peroxidase To 22: Structures of thyroid hormones