Chemistry - Imperial College London

Department of Chemistry Undergraduate Syllabuses_2005–06

This publication refers to the session 2005–06. The information given, including that relating to the availability of courses, is that current at the time of going to press, October 2005, and is subject to alteration. © Imperial College London 2005 For details of postgraduate opportunities go to www.imperial.ac.uk/pgprospectus.

242

Chemistry Interests in chemistry at Imperial College cover physical, organic, inorganic, analytical, polymer and biological chemistry and chemical crystallography, as well as intersectional and medical topics. The Department of Chemistry is housed partly in a modern building on the south side of the College precinct, and partly in the original, refurbished Royal College of Science building. We provide teaching facilities for about 360 undergraduates. There are two large teaching laboratories for first, second and third year work, and three specialised laboratories for advanced final year work, two lecture theatres, and two seminar rooms. Microcomputer workstations and terminals connected to the College, other computer systems and the internet are available for use by undergraduates and research workers. Details of postgraduate opportunities can be found in the online Postgraduate Prospectus at www.imperial.ac.uk/pgprospectus.

Undergraduate courses At the undergraduate level, single Honours (S) and joint Honours (J) courses are offered. For students entering in 2005, single Honours courses are offered leading to the Master in Science (MS) degree of the University of London, and joint Honours courses leading to the Bachelor of Science (BS) degree of the University of London. Joint Honours courses (BJ) are all BSc, and are given in conjunction with Imperial’s Tanaka Business School (M). Chemistry (C) courses may include a period of study at another European university (A) or working in industry (I) for a whole academic year or for five months (C/A or C/I). Courses are three, four or five years long: the letters following the length indicate the content of successive years of the course. Some courses require particular specialisation, e.g. in the final year of the Medicinal Chemistry courses, or a specific first year option, e.g. medicinal biology for Medicinal Chemistry, Chemical Engineering for Fine Chemicals Processing or a language for research abroad courses. Further information on undergraduate courses can be obtained from the Admissions Tutor, Dr Edward Smith, Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ. The courses are: F100 Chemistry (BS, 3: C, C, C or C/A or C/I) F103 Chemistry (MS, 4: C, C, C, C or C/A or C/I) F104 Chemistry with Research Abroad (MS, 4: C, C, C, A) F105 Chemistry with a Year in Industry (MS, 5: C, C, C, I, C) F124 Chemistry with Medicinal Chemistry (MS, 4: C, C, C, C) F125 Chemistry with Medicinal Chemistry and a Year in Industry (MS, 5: C, C, C, I, C) F1D4 Chemistry with Conservation Science (MS, 4: C, C, C, C) F1H8 Chemistry with Fine Chemicals Processing (MS, 4: C, C, C, C) F1HV Chemistry with Fine Chemicals Processing with a Year in Industry (MS, 5: C, C, C, A, C) F1N2 Chemistry and Management (BJ, 3: C, C, M) F1NF Chemistry with Management (BJ, 4: C, C, C, M) F1NG Chemistry and Management with a Year in Industry (BJ, 4: C, C, I, M) FN11 Chemistry with Management and a Year in Industry (BJ, 5: C, C, C, I, M) The university regulations for BSc degrees in science involve division of the course into ‘course units’. The three-year courses have 12 course units, four in each year. To qualify for a degree a student must complete and satisfy the examiners in courses totalling at least nine units. Both four and five-year courses have 16 units, since no units are awarded for the industrial year of the Year in Industry courses. Students must complete and pass a total of 13 out of the 16 units to qualify for a degree. BSc graduates are awarded the BSc degree with Honours of the University of London. MSci graduates are awarded the BSc or MSci degree with Honours of the University of London and the Associateship of the Royal College of Science. Students intending to take Chemistry as the principal subject of their degree must normally have

chemistry

243

satisfied the general university entrance requirements and the individual course requirements in terms of passes at Advanced level in the GCE examination, as indicated in the Undergraduate Prospectus online at www.imperial.ac.uk/p2729.htm#4.

First and second years of all courses listed above There are first year lecture courses in the three major branches of chemistry: organic (C.101), inorganic (C.102) and physical (C.103). A laboratory course (C.104) first introduces common experimental techniques, with separate exercises in arrow pushing and spectral interpretation. This is followed by two further practical sessions covering synthetic techniques and physical experiments. Students also have lectures and classes in mathematics (Theoretical methods in chemistry). All students take an ancillary course in either mathematics or physics or medicinal biology or a humanities option. Students on courses F124 and F125 take medicinal biology; those on F104 the appropriate language. Students on F1H8 or F1HV take chemical engineering. Other students choose any one of these courses (except chemical engineering). The second year is mostly devoted to chemistry, together with a course in computing C.270. The session includes sectional courses C.201, C.202 and C.203. Students take practical courses in each branch: C.255, C.260 and C.265. Students on Research Abroad courses continue with their language studies.

Third year: Chemistry, Chemistry with Management (four-year) and Chemistry with Management and a Year in Industry (five-year) There are two sections: Advanced chemistry theory IIIA (C.310, autumn term), and Advanced chemistry theory IIIB (C.320, spring term). Each section offers lecture courses totalling about 144 lectures on advanced topics in organic, inorganic, physical and analytical chemistry. Students take the 11 courses of the autumn term (IIIA), and choose nine in the spring term (IIIB). The structure of the IIIB examinations requires students to choose courses covering more than one branch of chemistry. Students also choose two courses of advanced chemistry practical work (C.316, or C.326, or C.336), which provide 11–15 weeks’ training in the autumn and spring terms in advanced techniques in two of the three specialist laboratories (organic, inorganic or physical). A literature report (C.360) is written on a topic chosen from a list including recent advances or applications of chemistry, or related science, supervised by a member of staff. BSc students present a report for the lay reader, written in a journalistic style. An additional subject is chosen in a field outside chemistry. The following courses are expected to be available in 2005–06: language and other courses offered by the Humanities Programme, a number of options from Tanaka Business School, Mathematics, Medicinal chemistry (in association with the Faculty of Medicine), Conservation (in association with the Victoria & Albert Museum/Royal College of Art). Chemistry with Fine Chemicals Processing students take a chemical engineering ancillary course. Chemistry with Medicinal Chemistry students take mainly the organic lectures, the medicinal chemistry additional subject (weighted at 0.5 unit), the organic laboratory course and either the physical or inorganic laboratory courses. Their literature reports will be on topics of pharmacological or medical significance. Students on the Conservation Science course take two of the specialist chemistry laboratories and normally a conservation science literature report.

Socrates exchange scheme in Europe Final year students (except Chemistry with Medicinal Chemistry) can take part in a Socrates-Erasmus exchange scheme: they carry out half their final year research exercise (February to June) at ETH, Zürich, ESPCI (Paris), Paris Sud (Orsay), Ecole Polytechnique (Paris), Ecole Normale Supérieure (Paris), Louis Pasteur (Strasbourg), Hannover, Marburg, Erlangen, Munich, Valencia, Leiden, Milan, or Oslo. (Research Abroad students spend the summer term of their third year, part of the summer vacation and the autumn term of their fourth year at one of these universities, see page 245.) Incoming exchange and other students not registered for an Imperial College degree may take any combination of the undergraduate courses. They normally take all or part of the final year of the single Honours course and/or a research project. Non-UK students who study at final year level or receive research training for an academic year and achieve good results may be eligible for the award of the Imperial College International Diploma (ICID).

244

undergraduate syllabuses

The arrangement of course units is shown below:

FIRST YEAR (all courses) C.100 Foundation course C.101 Organic chemistry I C.102 Inorganic chemistry I C.103 Physical chemistry I C.104 Chemistry coursework I (C.110, problems including theoretical methods) Additional subject MC.1 MB.1

Unit value 0.55 0.55 0.55 0.55 1.30

Mathematics or PC.1 Physics or Humanities or Language or Fine chemicals processing Medicinal biology 0.5

SECOND YEAR C.201 C.202 C.203 C.210

Organic chemistry II Inorganic chemistry II Physical chemistry II Chemistry coursework II C.225, C.260, C.265, C.270

0.75 0.75 0.75 1.75

THIRD YEAR (F103, F104, F105, F124, F125, F1H8) C.310 Advanced chemistry theory, IIIA C.320 Advanced chemistry theory, IIIB Any two of C.316, C.326 Advanced chemistry, practical work or C.336 C.360 Literature report on a topic in chemistry or extended literature report Additional subject (see above) Humanities: language Humanities: other Management Mathematics Medicinal chemistry Chemical engineering

1 1 1 0.25 0.5 0.5 0.5 0.5 0.5 0.5 0.75

THIRD YEAR (F100, F1NF, FN11) C.301, C.302, C.303 C.304, C.305, C.306, C.307 C.316 or C.326 or C.336 C.350 C.360 Additional subject as above

As above As above As above Research exercise in chemistry Literature report for a lay reader

1 1 0.5 0.5 0.25/0.5 0.75/0.5

Students choosing an ancillary subject with half-unit weighting take the extended literature report.

THIRD YEAR (F1D4) C.301, C.302, C.303 C.304, C.305, C.306, C.307 Any two of C.316, C.326 or C.336 C.360 Additional subject

As above As above As above Literature report (conservation) as above Conservation science

Unit value 1 1 1 0.5 0.5

245

chemistry

FOURTH YEAR (F103, F124, F105, F1D4) C.410 Advanced chemistry theory IVA C.420 Advanced chemistry theory IVB C.450 Research exercise in chemistry, proposal and oral examination

0.75 0.75 2/0.25/0.25

FOURTH YEAR (F104) Option 1 The fourth year is spent abroad at another European university Extended research exercise 2.50 Humanities project 1 Oral examination 0.50 OR Option 2 The third/fourth part-year is spent abroad at another European university Research exercise 2 Humanities project 1 Chemistry IVB examination 0.75 Oral examination 0.25

Tutorials and problem classes All students are expected to participate in tutorials and problem classes as well as the formal lectures and periods of laboratory work outlined below. In the first and second year each student is linked with three tutors, covering the broad fields of physical, organic and inorganic chemistry respectively, each of whom the student sees every week. In addition to the three academic tutors, a personal tutor takes an interest in the welfare of each student and is available to help in case of difficulties not connected with the material of the course. Problems classes are normally timetabled for one or two hours per week during the first and second years. They are used for setting and discussion of problems based on the subject matter of the course, particularly in physical and organic chemistry. Third and fourth year lecture courses carry tutorials with the lecturer concerned. Personal tutorials continue into the third year.

Examinations and assessment Examinations are held in the first and second years, in the spring and summer terms. The papers set are listed below.

FIRST YEAR Foundation I Inorganic chemistry I Chemical engineering or

Organic chemistry I Medicinal biology or Mathematics or

Physical chemistry I Physics or Humanities

SECOND YEAR Physical chemistry IIA and IIB Organic chemistry IIA and IIB Inorganic chemistry IIA and IIB The computing course taken by all second year students is assessed by coursework. Language courses are assessed by oral performance and by a test. Assessments on practical work require the submission of reports on the work completed and samples of any substances prepared. Students in years one, two and three (MSci only) who fail course units in the normal examinations may take resit papers in late August. Students must reach certain minimum standards of overall performance in both theory and coursework in the first and second years in order to continue into the following year. In the third year, assessment on the theory units is based on examinations in January (advanced chemistry

246


theory IIIA), and May (IIIB). Three papers are held for each unit. Assessment of the research exercise for F100, F1NF and FN11 is based on a research report, and a poster presentation of the work. The literature report is assessed by two members of staff. Language courses are assessed by written work and tests. The award of Honours is based upon a suitably weighted assessment of marks obtained for the 16 course units of the MSci course, including contributions from University examinations, tests and assessment of coursework. For Year Abroad students, the results for the exchange year are also taken into account. Students on three-year courses (12 course units) must pass nine units to qualify for a degree; those on courses with 16 units must pass 13 to qualify.

Syllabuses FIRST YEAR

C.100 Foundation course 1.F1 Atomic and molecular structure (16 lectures: Professor Robb (8), Dr Lickiss (8), plus 4 hours of problem classes: Professor Robb (2), Dr Lickiss (2)) Bohr atom, hydrogen spectrum, particle-wave duality, orbitals, wave function, quantisation, quantum numbers, spin, hydrogenic atoms, radial and angular functions, radial distribution function, angular shapes of s,p,d,f orbitals, Pauli exclusion principle, Aufbau principle, screening penetration and effective nuclear charge, Hund’s rule, trends in atomic size, ionisation energies, electron affinity, electronegativity, polarisability and polarising powers. Lewis theory, hypervalence, VSEPR model, valence bond theory applied to homodinuclear, heterodinuclear and polyatomic molecules, hybridisation, simple molecular orbital (MO) theory, linear combination of atomic orbitals (LCAO) method. Hybridisation, sigma and pi orbitals and bonds in organic molecules, MOs over delocalised systems (polyenes, benzene). 1.F2 Reactivity and characterisation (four lectures: Dr Smith (2), Professor Welton (2)) Reaction types such as nucleophilic addition, electrophilic substitution, oxidative addition, insertion etc. and the spectroscopic techniques used to determine organic and inorganic structures. 1.F3 Aromatic chemistry (five lectures plus a one-hour problem class: Dr Smith) Electrophilic substitution, nucleophilic substition and radical reactions of diazonium salts. 1.F4 Chemical equilibria (14 lectures by: Dr Durrant (7) and Dr Kucernak (7) plus 3 hours of problem classes. Introduction to Thermodynamics: work, temperature, systems, 1st Law, heat, state and path functions. Implications of 1st Law: enthalpy, calorimetry, Hess's Law. Entropy: direction of spontaneous change, disorder, 2nd Law, statistical view of entropy. Development of idea of free energy from entropy, application to physical equilibria. Chemical equilibria, molar free energy, chemical potential, dependence upon concentration, activity, ln Keq = -DG/RT, temperature dependence. Colligative properties: Raoult's Law, thermodynamics of freezing-point depression. Acids and Bases: pH, buffer action, pK. Acids-Base strengths, acidity and basicity of solvents, acid-base reactions, oxoacids, polybasic acids, entropic effects, electrostatic effect, buffers. Electrochemistry and Redox Reactions: half-reactions, oxidation/reduction potential, electrochemical cell, reversibility, reference electrodes, Nernst Equation, chemical potential from Nernst equation. Electrolysis, reductions, oxidations, commercial examples of electrochemical systems. Energetics – utilising chemical energy in biological and chemical systems: bioenergetics and fuel cells. 1.F5 Chemical kinetics (10 lectures: Dr Taylor) Classification of reactions by phase. Stoichiometry. Reaction rates. Orders of reaction. Experimental methods. Slow and fast reactions. Stopped-flow methods for fast reactions. Determination of rate laws by initial slopes method. First order reactions: Integrated rate equation. Half lives. Examples. Radioactive decay. Second order reactions: Integrated second order rate equation. Half lives. Isolation method of determining orders. Acid-base catalysis. Elementary reactions. Molecularity and order. Termolecular steps. Temperature variation of reaction rates and rate constants. Activation energies. Enthalpies of reaction. Unimolecular gas reactions. Lindemann-Hinshelwood mechanism. Complex reactions. Chain reactions. Radicals. Explosions. Collision theory. Experimental results and theoretical calculations. Encounter pairs in solution. Electrostatic effects in ionic reactions. Reactive cross sections. Cross-beam experiments in the gas phase. Harpoon mechanisms.

chemistry

247

1.FM Mathematics (5 lectures: Professor Quirke)

C.101 Organic chemistry I DR A.C. SPIVEY, PROFESSOR S.E. GIBSON, DR D.C. BRADDOCK, PROFESSOR D. BLACKMOND 34 lectures. 1.O1 Stereochemistry (3 lectures: Dr Spivey) Hybridisation and shape, stereogenic centres and other stereogenic elements, CIP priority rules, enantiomers and diastereomers, consequences of molecular symmetry for synthesis and spectroscopy. 1.O2 Alkanes, alkenes and alkynes (8 lectures: Professor Gibson) Chemistry and reactions of alkanes, alkenes and alkynes arenas. 1.O3 Haloalkanes, alcohols and amines (11 lectures: Dr Braddock) Chemistry of haloalkanes, alcohols and amines. Aliphatic nucleophilic substitution reactions and their mechanisms. 1.O4 Chemistry of the carbonyl and carboxyl groups (12 lectures: Professor Blackmond) Nucleophilic addition to the carbonyl group. Reaction with electrophiles at the alpha-carbon via enols and enolates. Nucleophilic substitution at the carboxyl group via addition-elimination.

C.102 Inorganic chemistry I DR C.K. WILLIAMS, DR M. HII, DR R. DAVIES 27 lectures. 1.I1 Characterisation of inorganic compounds (10 lectures: Dr Williams) Brief revision of principles of spectroscopic techniques. Applications of IR, Raman and NMR spectroscopy to inorganic compounds. Introduction to mass spectrometry and its application to inorganic chemistry. 1.I2 Coordination chemistry (8 lectures: Dr Hii) Introduction to the language and principles of coordination chemistry. The crystal field approximation and its use to interpret spectroscopic and magnetic properties. Formation of complexes, nomenclature and role of ligands and isomerism in coordination compounds. 1.I3 Periodicity and inorganic reactivity (eight lectures: Dr Davies) An overview of the properties, bonding and structures of the main group (s- and p- block) elements and their compounds. Particular emphasis is on the observed trends and their origins both down the Groups and across the Periods.

C.103 Physical chemistry I PROFESSOR R.H. TEMPLER, PROFESSOR A. DE MELLO, DR I. GOULD, PROFESSOR D.R. KLUG 33 lectures. 1.P1 Molecular interactions and dynamics (9 lectures: Professor Templer) Molecules as point particles, centre of mass. Force, acceleration, rate of change of linear momentum, conservation of linear momentum during collisions. Electrostatic force, principle of superposition, the dipole. Electrostatic field and field lines, work in an electrostatic field, electrostatic potential energy and potential, equi-potential maps. Conservation of energy, simple harmonic oscillator. Rotational dynamics, torque, moments of inertia, angular momentum and its conservation, rotational energy. 1.P2 Spectroscopy (eight lectures plus one problem class: Professor de Mello, ) Reiteration of basic quantum mechanics, Schrödinger equation and wave functions, electromagnetic radiation, quantisation of molecular energy, translational, rotational, vibrational and electronic energies, energy levels, Beer’s law, Boltzmann distribution, microwave spectroscopy, rigid and non-rigid rotors, infrared and Raman spectroscopy, harmonic and anharmonic oscillators. NMR spectroscopy, spin quantum number, gyromagnetic ration, Zeeman effect, chemical shift, integration, coupling, Pascal triangle, Karplus relationship. Ultraviolet visible spectroscopy, absorption of light, electronic transitions, infrared spectroscopy, Hooke’s law 1.P3 Measurement and mechanism in physical chemistry (8 lectures: Dr Gould) Spatial and temporal dimensions inherent in chemistry and physical processes. Relationship between structure, function, mechanism, measurement and design. Integration of theoretical material from the first year physical course with physical measurement. Links between quantum mechanics, thermodynamics, molecular dynamics, spectroscopy and kinetics with real chemical systems. 1.P4 Quantum chemistry I (8 lectures: Professor Klug)

248


Particle-wave duality: particle properties of electromagnetic waves and wave properties of matter—de Broglie waves. Matter waves: mathematical form of the wave function for free particle-interpretation in terms of probability. Particle in a box. Heisenberg uncertainty principle. Schrödinger wave equation. Particle moving in a circle. Application of Schrödinger wave equation to hydrogen atom. One-dimensional harmonic oscillator. Quantum mechanical tunnelling.

C.104 Chemistry coursework I Foundation laboratory (about 60 hours: Dr Smith and others) Held during the autumn term, comprising instruction thin layer chromatography, recrystallisation, atmospheric distillation, pH measurements and ultraviolet absorption spectroscopy. 1.FM Mathematics (6 1-hour classes: Professor Quirke) Series, logarithms, exponentials, approximation methods. Minimisation and maximisation methods, application of integration methods to quantum mechanics and chemical kinetics. Complex algebra: relaxation methods in kinetics and spectroscopy. First- and second-order differential equations. Statistics in the laboratory, normal distribution of errors. Sequential processes. Thermodynamic problems with two or more variables, partial differentiation. Vectors. Matrices. Physical chemistry laboratory (about 60 hours: Professor A. de Mello and physical chemistry staff ) A five-week course held during the spring term providing instruction in the basic principles and techniques of physical chemistry. Synthesis laboratory (about 48 hours: Dr Steinke) A four-week course during the summer term, illustrating the basic preparative techniques of organic and inorganic chemistry. Mathematics laboratory (about 36 hours: Dr Bresme)

SECOND YEAR

C.201 Organic chemistry PROFESSOR D. CRAIG, PROFESSOR A. ARMSTRONG, DR R.V. LAW, PROFESSOR H.S. RZEPA, DR E.H. SMITH, DR A.C. SPIVEY 52 lectures. 2.O1 Organic synthesis (20 lectures: Professor Craig, Professor Armstrong) Formation of carbon-carbon bonds, principle and strategy. Use of organometallic reagents and carbanions, reduction, oxidation, protecting groups. Strategy of organic synthesis. 2.O2 Introduction to stereoelectronics (5 lectures: Dr Spivey) Orbital interactions, conformation and stereoelectronics of hydrocarbons and selected functional groups (anomeric effetcs, gauche effects, etc.), ionic rearangements (e.g. Beckmann, Wagner-Meerwein, pinacol, semipinacol and alpha-hydroxyketone), fragmentations (e.g. Beckmann, Grob, Eschenmoser), eliminations, substitutions, additions to alkenes (trans-diaxial) and carbonyl compounds (Burgi-Dunnitz), deprotonation alpha to carbonyl. 2.O3 NMR spectroscopy (6 lectures: Dr Law) Zeeman interactions, nuclear spin, energy levels, populations and Boltzmann distributions, isotopic abundance, origins of chemical shift, origins of J-coupling (scalar coupling), coupling patterns, effect of chiral centres, nuclear Overhauser effect, dipolar couplings, spatial connectivity, laboratory frame, rotating frame, rf pulses, vector representation, relaxation, linewidths, spin-lattice (T1), spin-spin (T2), dynamic NMR, spin exchange, time domains and frequency domains, Fourier transforms, twodimensional NMR spectroscopy. 2.O4 Pericyclic reactions (6 lectures: Professor Rzepa) Pericyclic reaction. Woodward-Hoffmann rules. Electrocyclic, cycloaddition, sigmatropic and ‘ene’ reactions. 2.O5 Heteroaromatics (6 lectures: Dr Spivey) The chemistry of pyrroles, thiophenes, furans, oxazoles, imidazoles, thiazoles, isoazoles, pyrazoles, isothiazoles, pyridines, quinolines, isoquinolines and indoles. 2.O6 Alicyclic chemistry and non-aromatic heterocycles (10 lectures: Dr Smith) Sources of strain in rings. Synthesis and unique properties of small and medium rings. Conformational analysis. Synthesis and reactions of small-ring non-aromatic heterocycles.

chemistry

249

C.202 Inorganic chemistry DR M. HILL, DR G. BRITOVSEK, DR T. HUNT, DR M. SHAFFER, DR P.D. LICKISS, PROFESSOR V.C. GIBSON 48 lectures. 2.I1 Main group chemistry (8 lectures: Dr Hill) Organometallic compounds of the main group elements, in particular those of groups 1, 2, 13 and 14. Ionic versus covalent bonding in such compounds. Some industrial uses of organoaluminium and organosilicon compounds. Main group clusters, particularly boron hydrides, their structures, preparation and reactivity. Classification of structures according to electron counting rules. Compounds isoelectronic to boranes. Group trends in main group chemistry, concentrating on groups 15 and 16. Oxidation state, the inert pair effect, reactivity and structure. Use of group 15 and 16 compounds as ligands in transition metal chemistry. 2.I2 Transition metal chemistry (8 lectures: Dr Britovsek) A molecular orbital description of metal-ligand binding is developed and used to interpret characteristic properties of transition metal complexes including colour, magnetism and ligand substitution processes. These ideas are then used to interpret the descriptive chemistry of representative triads from across the transition series. 2.I3 Molecular orbitals in inorganic chemistry (8 lectures by Dr Hunt) 2.I4 Crystal and molecular architecture (8 lectures: Dr Shaffer) Introduction to crystallography: lattices, symmetry considerations, Miller indices, motifs, close-packing, simple inorganic structures, coordination polyhedra, common defects, significance of atomic/ionic radii, relevance to diffraction (structural characterisation), surfaces, and fundamental properties. Brief discussions of both amorphous and more complex molecular materials. 2.I5 Introduction to organometallic chemistry (8 lectures: Professor Gibson) The nature of the metal-carbon bond is discussed across the periodic table, illustrating the diverse effect of the metal. Foci include alkyl, carbonyl, alkene and arene complexes, their synthesis, structure, bonding, reactivity and industrial significance. 2.16 NMR methods in inorganic chemistry (8 lectures: Dr Lickiss) General principles of NMR spectroscopy. CW versus FT methods. Introduction to FIDs and their manipulation. Glossary of terms: d, J, g, I, sensitivity, relaxation. Chemical shifts and coupling constants for common spin half nuclei (1H, 19F, 31P) in organic and organometallic compounds. 13C NMR spectra. Construction of coupling partners for a general nucleus using Pascal’s triangle. Defining spin systems. Variation of chemical shift and coupling constants for less common nuclei around the periodic table, detailed examination of group 14. Choice of NMR standards. Variation of chemical shifts with coordination number and oxidation state. Satellites, spectra and effects of low abundance spin half nuclei. Fluxionality. Quadrupolar nuclei eg 11B, 14N, 33S. Introduction to solid state NMR spectroscopy. Gases. Paramagnetic compounds and the NMR method for determining magnetic susceptibility.

C.203 Physical chemistry PROFESSOR J.M. SEDDON, DR C.P. WILDE, PROFESSOR T. JONES, DR F. BRESME, DR J.R. DURRANT 50 lectures. 2.P1 Interfacial thermodynamics (10 lectures: Professor Seddon) This part of the course (see also 2.P4) first reviews the laws of thermodynamics, with particular emphasis on the free energy. It then applies these concepts to analysing phase transitions. The behaviour of liquids and liquid mixtures is then described, with examples of binary and ternary phase diagrams. The last part of the course is concerned with surface and interfacial tension, and their consequences for a range of effects such as droplet nucleation (cloud formation), capillary action and self assembly of molecules such as surfactants and lipids into liquid crystals and membranes. 2.P2 Electrochemistry and electrochemical kinetics (10 lectures: Dr Wilde) Ionic interactions in solution, activity and chemical potential. Finding activity coefficients using DebyeHuckel theory. Transport properties of ions. Motion in an electric field-conductivity, variation of molar conductivity for strong and weak electrolytes and factors affecting ionic motion. Mobilities and transport

250


numbers for ions. Motion as a result of a concentration gradient-diffusion. Links between diffusion coefficient and transport numbers. The influence of diffusion and migration in controlling properties/output of batteries. Potential and potential differences at the electrode solution interface. Electrochemical equilibrium at an electrode-definition and the Nernst equation. Electrochemical kinetics, the effect of potential on current. Concepts of overpotential and exchange current density, factors influencing exchange current density at an electrode. The Butler-Volmer equation. The balance between the rate of electron transfer and the rate of reactant supply to an electrode. Electrode reactions controlled by reactant supply, the rotating disc electrode and currents limited by diffusion. 2.P3 Electronic properties of solids (10 lectures: Professor Jones) Classification of solids: molecular, ionic, covalent, metallic, complex solids, comparison between bonding in molecules and solids, introduction to energy bands. Bonding in metals: free electron theory (one-dimensional, three-dimensional), Fermi level, Fermi sphere, density of states, UV photoelectron spectroscopy, effects of temperature, Fermi-Dirac distribution. Band theory; effects of periodic lattice and breakdown of free electron theory, nearly free electron model (onedimensional), band gaps, band structure, Brillouin zones. LCAO approach to bonding in solids: Bloch functions, one-dimensional linear chain (monatomic and binary), extension to two-dimensional (surfaces) and three-dimensional (bulk), examples of band structures for metals and insulators, optical spectroscopy, direct and indirect band gaps. Semiconductors: elemental and compound semiconductors, intrinsic and extrinsic behaviour, band gaps, doping, carrier concentrations, position of Fermi level and effects of temperature, p-n junctions. Band theory and complex molecular solids: low dimensional conductors, molecular metals. 2.P4 Statistical thermodynamics (10 lectures: Dr Bresme) This part of the course (see also 2.P1) provides a basic introduction to statistical thermodynamics. The theoretical framework introduced at the beginning of the course is used to explain and predict the equilibrium macroscopic properties of atomic and molecular gases as well as chemical equilibrium. An introduction to the liquid state and computer simulations of liquids is made at the end of the course. 2.P6 Photochemistry (10 lectures: Dr Durrant) Molecular photophysics: the course starts by building upon students’ understanding of quantum mechanics to describe the fundamental process of molecular light absorption and emission: Jablonski diagram, singlet and triplet states, transition dipoles and oscillator strength, electronic and vibronic transitions, Franck Condon factors, intersystem crossing, perturbation theory. Brief consideration will be given to the Einstein coefficients and lasers. Molecular photochemistry: excimers and exciplexes, photoisomerisation, excitation energy transfer and photoinduced electron transfer. Experimental studies of photochemistry: steady state and time-resolved techniques. The course will use a range of examples of photochemical systems, including photosynthesis, singlet oxygen damage and PDT, photoelectrochemistry and semiconductor photocatalysis.

C.210 Chemistry coursework II C.255 Physical chemistry laboratory course (part of C.210) (about 80 hours: Dr Taylor and others) A course of about four weeks in the summer term covering a wide range of physical chemistry. Experiments offered include some using modern equipment such as stopped flow, Fourier transform infrared (FTIR), thermogravimetric analysis, gas liquid chromatography and kinetic ultraviolet spectrophotometry. C.260 Synthesis laboratory course (part of C.210) (about 140 hours: Dr Braddock, Dr Davies and others) A course in two sessions of three and four weeks dealing with the preparation and purification of advanced chemicals and study of their properties and reactions. The second session consists of short synthesis projects. C.270 Chemical information technology (part of C.210) (5 lectures: Professor Rzepa, plus about 15 hours practical using computer workstations) The course covers the application of computer technology to chemical information retrieval and molecular modelling. Theoretical methods in chemistry II (part of C.210) (six one-hour lectures: Professor Harrison)

chemistry

251

THIRD YEAR

C.310 Advanced chemistry theory IIIA C.301 Organic chemistry A (part of C.310) DR J.H.G. STEINKE, PROFESSOR S.E. GIBSON, PROFESSOR A.D. MILLER, PROFESSOR D. BLACKMOND 24 lectures. 3.O1 Polymers: the essential guide (6 lectures: Dr Steinke) The aim of this course is to provide the student with a guide to the fundamental aspects of polymer synthesis and fundamental polymer properties covering all basic polymerisation mechanisms and methodologies to access linear and branched polymer architectures. 3.O2 Biological chemistry (7 lectures: Dr Miller) The structures of biological molecules, illustrating how analytical and spectroscopic techniques help us to understand the nature of these complex systems. The primary, secondary, tertiary and quaternary structures of proteins, DNA, and RNA. Complex oligosaccharide architecture and (briefly) lipids and their complex phase behaviour. This course is a foundation for the final year of Chemistry with Medicinal Chemistry as well as an invaluable biological chemistry background for students wishing to enter synthetic organic chemistry as their main study option. 3.O3 Organometallic complexes in organic synthesis (6 lectures: Professor Gibson) Applications of transition metals in organic synthesis will be discussed in detail in order to illustrate the breadth and depth of this rapidly expanding, exciting and synthetically useful area of organic chemistry. 1. The reactivity of arene chromium tricarbonyl complexes—a case study of the dramatic changes in reactivity that metal complexation may lead to. Fundamental properties will be examined and then synthetic applications will be presented. 2. The use of allyl palladium complexes in organic synthesis—an important catalytic transformation. The theory of the catalytic cycle will be discussed, applications presented and approaches to asymmetric versions of the reaction described. 3. Promotion of unusual cycloaddition reactions by transition metals—[2+2+2], [3+2], [4+4] and other cycloadditions will be presented and some of their applications in target molecule work will be described. 4. The use of palladium to promote coupling reactions—several important coupling processes will be defined. In particular, the Heck reaction will be addressed in some detail and elegant applications of this commonly used reaction will be presented. 5. Chromium-carbene centred reactions—the Dötz benzannulation reaction and the Hegedus photochemical reaction. The theory of these reactions will be discussed before some recent applications are presented. 6. Cobalt alkyne complexes in organic synthesis—this lecture will focus on cationic chemistry developed by Nicholas and the Pauson-Khand reaction. 3.O4 Introduction to physical organic chemistry (5 lectures: Professor Blackmond) This module highlights a selection of topics, touched upon briefly in other organic chemistry modules, concerning how physical aspects of organic chemistry relate to reactivity of organic molecules. The emphasis is on relating the topics under study to the modern experimental methods currently being developed for investigating these phenomena. 1. Review of structure and bonding. 2.Kinetics and thermodynamics. 3. Solutions and solvation. 4. Acid-base chemistry. 5. Energy diagrams and reaction rate laws. 6. Linear free energy relationships. 7. Reaction mechanisms. 8. Introduction to catalysis

252


C.302 Inorganic chemistry A (part of C.310) DR G. BRITOVSEK, DR P.D. LICKISS, PROFESSOR V.C. GIBSON, DR M. SHAFFER 25 lectures. 3.I1 Inorganic mechanistics and catalysis (6 lectures: Dr Britovsek) Coordination-sphere reorganisations: innersphere isomerisations of four- and six-coordinate complexes. Migratory insertions and eliminations: regiochemical and stereochemical aspects of carbonylation and decarbonylatin. A-, b- and more remote hydrogen-migrations; other carbon-migrations. Oxidative additions: concerted and stepwise mechanisms forming M-H bonds. Concerted and stepwise mechanisms forming M-C bonds; stereochemical probes. Reductive eliminations: stereochemical and regiochemical aspects. Extramolecular attack on ligand: addition to coordinated alkenes and polyenes; Gree/Davies/Mingos ‘rules’; addition to coordinated CO; the water-gas shift reaction; ‘insertion’ of SO2. 3.I2 Advanced main group (6 lectures: Dr Lickiss) Why is multiple bonding in compounds of the lower main group elements rare? Synthetic strategies to overcome the problems and the use of bulky ligands to stabilise multiply-bonded species. Borazenes and phosphazenes. The chemistry of the gases of group 18. How can the ‘inert’ nature of such elements be overcome? The chemistry and structures of the halogens and the interhalogens. CFCs and related compounds. Cluster compounds of the p-block elements. Carboranes, Zintl ions, sulfur nitrogen compounds, etc. 3.I3 Advanced organometallic chemistry (7 lectures: Professor Gibson (four), Dr Britovsek (three)) Topics of organometallic chemistry:the nature of the metal-carbon multiple bond, metal complexes containing p-cyclic ligands and activation of C-H bonds by metal complexes. The fundamental chemistry and some of the applications to catalysis, organic synthesis and material science for each topic. During the first half of the course, the nature of the metal-carbon multiple bond. Complexes with M-C double bonds (alkylidenes). Fischer and Schröck carbenes and study: their synthesis, structure and bonding, reactivity and applications to organic synthesis (e.g. cyclisation reactions) and catalysis (e.g. olefin metathesis). Complexes with metal-carbon triple bond (their synthesis, reactivity and applications). A description of alkylidenes and alkylidynes in bridged-assisted cluster assembly (m-CR2 and m3-CR groups). Organometallic complexes of cyclic p-compounds (CnHn). Sandwich complexes and half-sandwich complexes with cyclopentadienyl and arene groups are the central point . Besides the synthesis, structure and reactivity of these complexes some of their applications to catalysis and material sciences. The activation of C-H bonds by metal complexes. This very topical problem in organometallic chemistry is discussed giving particular attention to cyclometallation reactions (intramolecular C-H addition) and intermolecular oxidative addition of alkanes to metal centres. Examples and relevance to catalysis.

C.303 Physical chemistry A (part of C.310) PROFESSOR T.S. JONES, PROFESSOR D.R. KLUG, DR J. DE MELLO 24 lectures. 3.P1 The chemistry of solid surfaces (8 lectures: Professor Jones) Chemical analysis of solid surfaces: surface sensitivity and electron spectroscopy, X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), secondary ion mass spectroscopy (SIMS). The study of well-defined single crystal surfaces: atomic arrangement at surfaces, singular surfaces, stepped surfaces, surface reconstruction, low energy electron diffraction (LEED), electronic work function, scanning tunnelling microscopy (STM), atomic force microscopy (AFM). Gas adsorption at solid surfaces, the Langmuir adsorption isotherm, heats of adsorption, sticking probabilities, physisorption, chemisorption, work function changes upon adsorption. Characterisation of adsorbed molecules: structural studies (LEED, STM) electronic spectroscopies (UPS), vibrational spectroscopies (RAIRS, HREELS). 3.P2 Molecular reaction dynamics (8 lectures: Professor Klug) Mechanisms of bond breakage and formation and other reactions such as electron and proton transfer. Experimental techniques for studying reaction mechanisms and theoretical tools for interpreting these measurements. 3.P3 Quantum chemistry (8 lectures: Dr de Mello) This course applies quantum mechanics to atoms and molecules with a view to understanding, at a quantum level, chemical and physical properties such as bonding, reactivity, photochemistry and

chemistry

253

magnetism. The basic principles will be introduced using simple illustrative atoms and molecules (e.g. H, He, H2, ethene and benzene), and will be generalised to more complex systems without formal proof. The primary objective of this course is to provide a broad understanding of concepts in quantum chemistry rather than a formalised treatment of the subject.

C.320 Advanced chemistry theory IIIB C.304 Organic chemistry B (part of C.320) PROFESSOR A. ARMSTRONG, DR E.H. SMITH, PROFESSOR A.G.M. BARRETT, PROFESSOR D. CRAIG, PROFESSOR D.G. BLACKMOND, DR R.V. LAW 48 lectures. 3.O5 Reactive intermediates—2 (carbenes, nitrenes, photochemistry) (8 lectures: Professor Armstrong, Dr Smith) Carbenes: generation, rearrangements, C-H and Het-H insertion, cyclopropanation, cyclopropanation with rearrangements, ylide formation and reactions. Nitrenes: generation, rearrangements, C-H insertions, aziridination, aziridination with rearrangement. Photochemistry: generation of photochemically excited states (direct and indirect population methods), non-chemical fates of excited states, [2+2] cycloadditions (olefin-olefin, carbonyl-olefin, enone-olefin), carbonyl reactivity (Norrish type 1+2 reactions), enone rearrangements, aromatic cycloadditions, singlet oxygen generation and reactivity. 3.O6 Carbohydrate chemistry (8 lectures: Professor Barrett) Nomenclature including definitions of pentose, hexose, aldose and hexose. Reactions of carbohydrates such as oxidations, reductions, homologation (ascent) and degradation (descent). Stereochemical correlations. Cyclisations of D-glucose and related systems including the formation of furanoses and pyranoses. Formation of glycosides by condensation with alcohols; kinetic and thermodynamic control. The anomeric effect. Protection of carbohydrates by esterification, etherification and condensation with benzaldehyde and acetone. Selective transformations of partially protected carbohydrates. Sulfonate esters, keto-sugars, unsaturated sugars and amino-sugars. Applications of carbohydrates as building blocks in synthesis. 3.O8 Advanced stereochemistry (8 lectures: Professor Craig) Review of principles of chirality: meso compounds, C2 symmetry, points of inversion. Axial and planar chirality. CIP notation. Enantiotopicity, diastereotopicity. Projections: Newman, saw-horse, Haworth, Fischer. Wedge/dash notation. Cram’s rule. Felkin-Anh model. Cieplak model of axial versus equatorial attack in cyclic systems. Stereoelectronic effects. Understanding stereochemical outcome of pericyclic processes, aldol reactions, addition to carbonyl groups, enolate alkylation. Cyclic and extended transition-states. Macrocyclic stereocontrol. Case-studies of stereoselectivity in synthesis, including the total synthesis of natural products. 3.O9 Molecular modeling (8 lectures: Professor Rzepa) The course introduces the principal methods for qualitative and quantitative modelling of organic molecules, their structure and their reactivity. Molecular mechanics methods are introduced, along with definitions of force fields, and the procedures for geometry optimisation. A brief summary is given of how molecular orbital theories such as Huckel can be evaluated using computer programs and are applied to problems organic selectivity. Semi-empirical and ab initio molecular orbital theories are introduced and applied to transition state modelling, electronic structure and properties. 3.O10 Polymers (8 lectures: Dr Law) Polymer synthesis (~80 per cent): latest generation Ziegler catalysts, metallocenes, ‘non-metallocenes’ and late transition metal systems for alpha-olefin polymerisations. Well-defined ROMP initiators for the synthesis of block copolymers, comb polymers, conducting materials. Living atom transfer free radical polymerisation. Living anionic and cationic polymerisations. Synthesis of novel polymer topologies (helices, cyclics, two-dimensional architectures, etc.), aspects of polymer chirality, polymer (solid-phase) supports, polymeric enzyme-mimics. Polymer characterisation (~20 per cent): understanding the molecular structure of polymeric materials is essential as they are directly related to the macroscopic physical properties. They are intrinsically difficult to characterise. The problems of characterisation and strategies involved in overcoming them. Synthesis

254


and characterisation of electron, proton and ion conducting polymers. Electron, proton and ion conduction mechanisms. Applications of conducting polymers in light-emitting polymers, fuel cells and batteries. 3.O11 Catalytic reaction kinetics in organic synthesis (8 lectures: Professor Blackmond) Asymmetric catalysis. Streamlining the costs of manufacture and waste disposal in an ever more competitive market. Pharmaceutical research and production operates in a dynamic arena where the challenges and constraints are quite different from those in basic chemicals or petrochemicals. Understanding how a reaction works. Reaction kinetics; Reaction Progress Kinetic Analysis, a new tool based on powerful new experimental methods for obtaining accurate kinetic data. Kinetics can be understood as a language that tells us how the molecules are behaving during the reaction.

C.305 Inorganic chemistry B (part of C.320) DR M. HILL, DR N.J. LONG, DR R. DAVIES, DR A.G. TAYLOR, PROFESSOR T. WELTON 40 lectures. 3.I6 Lanthanide and actinide chemistry (8 lectures: Dr Hill) Electronic structures of the lanthanides, their oxidation states and coordination numbers. Lanthanide contraction. Binary compounds. Coordination complexes. Organometallic compounds of lanthanides, magnetic and spectral properties, including luminescent properties, NMR shift reagents. Actinides: occurence, radiochemical formation and applications. Coordination numbers and oxidation states. Electronic and magnetic properties. The ‘super-actinides’ (elements 104–111): their formation, possibility of existence of higher elements. 3.I7 Metals in medicine (8 lectures: Dr Davies) A detailed overview, including many specific examples, of the use of inorganic pharmaceuticals in medicine for both therapeutic and diagnostic applications. Topics include chelation therapy, anti-cancer drugs (especially those based on platinum), radiopharmaceuticals for diagnostic and therapeutic applications, neutron capture therapy and MRI contrast agents. 3.l8 Advanced electronic spectroscopy (8 lectures by Dr Taylor) 3.I9 Chemistry of macrocycles (8 lectures: Dr Long) How the reactivity of organic ligands may be controlled by interaction with a metal through ‘normal’ donor atoms. The use of metals to control the formation and reactivity of cyclic molecules containing domains suitable for metal binding. Molecular self-assembly and the chemistry of metal-coordinating macrocycles and calixarenes. Critique of the uses and applications of these fascinating species. 3.I10 Solvent and solvent effects in chemistry (8 lectures: Professor Welton) Properties of liquids relevant to their use as solvents for synthesis and spectroscopy. How solvents can affect solute species and reactivities. Classification of liquids by physical properties, chemical properties and empirical parameters.

C.306 Physical chemistry B (part of C.320) DR A. KORNYSHEV, PROFESSOR R.H. TEMPLER, PROFESSOR J.M. SEDDON, DR J. DE MELLO, PROFESSOR N. QUIRKE 40 lectures. 3.P4 Introduction to molecular biophysics (8 lectures: Professor Kornyshev) An introduction to the physical aspects of biological phenomena at the molecular level. The course will include introductions to: protein folding and function; DNA structure, conformation and function; biosynthesis of proteins; ion and molecular transport across membranes; bioenergetics; neurons and propagation of nerve signals; motion and biomolecular machines; molecular bioengineering. 3.P7 Structure of matter (8 lectures: Professor Seddon) Properties of X-rays and neutrons; scattering by atoms: X-ray atomic scattering factors and neutron scattering lengths; definition of scattering vector; phase difference and interference; scattering from molecules and groups of molecules: form factors, structure factors and effect of centrosymmetry; phase problem of crystallography; Fourier transforms, delta functions and convolution; amplitude and intensity calculations for model structures and lattices; effects of thermal and static disorder; lattices and reciprocal lattices; diffraction conditions and Ewald sphere; translational order: long-range, quasi-long-

chemistry

255

range, and short range; layer structures: liquid crystals, polymers and Langmuir-Blodgett films; methods of phasing the Bragg peaks: contrast variation and swelling experiments; electron density profiles; structure of mesoporous materials templated via self-assembly. 3.P8 Lyotropics (8 lectures: Professor Templer) The polar/apolar interface, why oil and water do not mix. Amphiphilic molecules, reducing interfacial tension. Aggregation and self-assembly, the critical micelle concentration, detergent action. Micelles, the energetics of spherical and rod micelles. The fluid lamellar phase, stabilising inter-lamellar forces, the van der Waals attraction, hydration repulsion, electrostatic repulsion and fluctuation repulsion. Local intermolecular forces, the desire for curvature, biological relevance. 3.P9 Molecular electronics (8 lectures: Dr de Mello) Organic semiconductors are highly attractive commercial materials, which are finding increasing application in a wide range of electronic devices. This lecture course compares the properties of organic electronics with more conventional inorganic devices, and investigates their use in emissive displays, solar cells, lasers and transistors. 3.P10 Nature at the nanoscale: insights from molecular simulation (8 lectures: Professor Quirke) What is modelling? Overview, examples and research/industrial applications. Potentials and potential energy surfaces: graphics, energy minimisation and complex molecules. Modelling at T>OK. The molecular simulation algorithms, Monte Carlo and molecular dynamics. Applications to problems in physisorption, wetting, and transport of molecules and electrons in nanoscale structures.

C.307 Analytical chemistry (part of C.320) PROFESSOR A. DE MELLO 8 lectures. 3.An3 Sensing and detection Lectures are focused on modes of detection for analytical processes. Detection protocols include fluorescence spectroscopy, absorption spectroscopy, electrochemistry and mass spectrometry. Particular attention is paid to ultra-high sensitivity detection with respect to chromatography and electrophoresis.

C.316 Advanced physical chemistry laboratory DR J. DE MELLO AND OTHERS About 100 hours. Spectroscopic techniques: Fourier transform infrared spectroscopy of gases, studies of hydrogen bonding in solution using infrared and nuclear magnetic resonance spectroscopies, visible absorption spectra of a thermochromic compound. Photochemistry: fluorescence quenching and excited state complex formation. Electrochemistry: cyclic voltammetry and use of rotating electrode. Kinetics: kinetic isotope effects and kinetics of a fast reaction by the stopped flow method. Adsorption and catalysis: adsorption isotherms and determination of surface area, characterisation of zeolite surface acidity by temperature programmed desorption of ammonia, kinetics of the nickel catalysed methanation reaction. Solid state chemistry: high temperature oxide superconductors. Polymer chemistry: copolymerisation of styrene and methyl methacrylate. Gas liquid chromatography: quantitative analysis of hydrocarbon mixtures. Liquid crystals: synthesis and characterisation by microscopy, calorimetry and diffraction. Monte Carlo calculations: simulation of liquid.

C.326 Advanced inorganic chemistry laboratory DR P. LICKISS AND OTHERS About 100 hours. Techniques: vacuum line techniques, handling of unstable compounds, reactions on a small scale. Instrumental methods: NMR, normal and resonance laser-Raman spectroscopy, infrared spectroscopy. Special topics: bioinorganic reactions, main group synthesis, ultrasound, homogeneous catalysis. Development projects. The four-week course is usually taken by students who have worked in another laboratory in the autumn term. They undertake a suitable selection of experiments from the main course, e.g. either handling air-

256


sensitive compounds or bioinorganic or spectroscopic techniques.

C.336 Advanced organic chemistry laboratory DR A.C. SPIVEY AND OTHERS About 200 hours. Training in techniques of organic chemistry. Purification and separation: flash and thin-layer chromatography, fractional distillation, sublimation, reactions under inert atmosphere, computer assisted modelling. Analysis: infrared, ultraviolet, nuclear magnetic resonance, mass spectrometry, absorption spectrometry, advanced identifications.

C.350 Research exercise in chemistry (F100, F1NF and FN11 only) This is a practical or theoretical project performed under the supervision of a member of staff. A list of projects is available in all the main fields of chemistry; guidance is given to ensure selection of a topic suited to individual experience and skills. Work on the project commences early in the spring term. For certain types of work the initial stages will involve learning new techniques to be applied in the project work. Assessment, based on a research report, will be by two members of staff. In addition, when appropriate, the assessment will include credit for a short seminar on the subject of the exercise.

C.360 Literature report The literature report covers a topic of current or historical interest in chemistry or chemical technology. Medicinal chemistry students choose a topic of pharmacological or medical significance. Conservation science students choose a conservation topic. After reading the original scientific literature, students write a critical report under the supervision of a member of staff. BSc students present a report for the lay reader, written in a journalistic style.

FOURTH YEAR

C.410 Advanced chemistry theory IVA C.401 Organic chemistry (part of C.410) PROFESSOR A.D. MILLER, DR A.C. SPIVEY, DR P. GAFFNEY, DR D.C. BRADDOCK 4.O1 Biological molecular recognition (8 lectures: Professor Miller) An overview of molecular recognition theories followed by a discussion about the techniques used to study molecular recognition events. A number of case studies in molecular recognition illustrate how diverse molecular recognition processes can be and emphasise their fundamental importance. 4.O2 Biosynthesis and biotransformations (8 lectures: Dr Spivey) Biosynthesis: the pathways and mechanisms used by natural systems to generate selected examples of the major classes of non-polymeric natural products: fatty acids and prostaglandins; polyketide antibiotics; terpenes and steroids; medicinal alkaloids. Biotransformation: the use of whole organisms or isolated enzymes as reagents for stereocontrolled organic synthesis: lipases and related hydrolytic enzymes; redox enzymes; aldolases and related C-C bond forming enzymes. 4.O3 Synthesis of phosphorylated biomolecules (8 lectures by Dr Gaffney) In the biological context phosphorus occurs almost exclusively as P(V) phosphoryl moieties. However, these groups are incompatible with many common procedures in multi-step organic syntheses. So there is a prolific literature for how to incorporate them into synthetic biomolecules, usually in a protected form, and then to perform global deprotection. The main biological arenas in which phosphorus is found are DNA/RNA, phospho-proteins, phospholipids and sugar-based phosphates. Significantly amongst these heavily poly-functional molecules, mutually incompatible protective group strategies have had to be devised to address different synthetic compromises. Hence the wider application of protective groups will be a continuous Leitmotif to the course. Furthermore, there are several artificial analogues of phorsphoryl species that have found prominence in bio-assays and as enzyme inhibitors.

chemistry

257

4.O4 Combinatorial and solid phase synthesis (6 lectures: Dr Braddock) Introduction: the drug discovery process; solution and solid phase combinatorial chemistry; split and mix synthesis; parallel methods; serial techniques (deconvolution); what is diversity? Solid phase synthesis: peptide synthesis progressing to small molecule synthesis; phage display; types of support; functionalisation of polystyrene resins; linker technologies; tagging systems; examples of libraries prepared. Solution phase synthesis: parallel synthesis; example of libraries prepared; multi-component condensations; the use of solid phase reagents and scavenger methodologies. Automation and other issues: the use of robotics, spectroscopic methods, screening issues, diversity analysis. The use of combi-chem for the discovery of materials and catalysts. 4.O5 Advanced heterocyclic chemistry (8 lectures: Dr Braddock) Introduction and synthetic case study, e.g. Viagra. Imazoles, thiazoles and oxazoles; synthesis and strategic use in synthesis illustrated by Muscoride A and Thiangazole. General preparation of heterocycles. Cyclisation reactions: (i) heteroatom in ring; ring closing metathesis, enyne metathesis, McMurry reaction, cationic cyclisations, anionic cyclisations (ii) heteroatom as nucleophiles. Cycloadditions.

C.402 Inorganic chemistry (part of C.410) DR J.H.G. STEINKE, DR C.K. WILLIAMS, DR M. SHAFFER, DR R. DAVIES, DR M. HII 4.I2 Supramolecular chemistry of nanomaterials (8 lectures: Dr Steinke) Supramolecular chemistry has developed over the last two decades as an interdisciplinary area which studies the chemistry beyond the molecule. It involves investigating systems (both found in nature and designed in labs) in which the most important feature is that the components are held together by intermolecular forces and not by covalent bonds. Some of the topics covered are: supramolecular assembly of nanoparticles and metal complexes, molecular machines and switches, large cavities as ‘nanoreactors’, chemical sensors, self-assembly, artificial photosynthesis 4.I3 Green chemistry (8 lectures: Dr Williams) Design, development and evaluation processes of green chemistry. Following an introduction and evaluation of the 12 principles of green chemistry, the areas covered include the use of renewable resources as chemical feedstocks, atom economy, green solvents, catalysis and biocatalysis, greener reagents or products and biodegradable materials. 4.I4 Nanotubes (8 lectures: Dr Shaffer) Structure, synthesis, properties and applications of a range of high aspect ratio nanoparticles. Carbon nanotubes, other types of tubular materials, based both on carbon (such as nano-peapods) and other layer materials (e.g. BN, WS2), as well as solid nanorods of metals and, in particular, compound semiconductors. 4.I5 Modern applications of inorganic chemistry in industry (8 lectures: Dr Davies, Dr Hii and others) An overview of how inorganic chemistry is used in industry, lectures by invited speakers from the chemical industry on their specialist areas. The areas covered vary from year to year although previous topics have included olefin dimerisation catalysts, ethylene polymerisation, the chemistry of light olefin production, fuel cell systems, silicones—their chemistry and applications, automotive pollution control and catalytic process design.

C.403 Physical chemistry (part of C.410) DR J.R. DURRANT, PROFESSOR T.S. JONES, PROFESSOR D. KLUG, PROFESSOR M. ROBB, DR S. YALIRAKI, PROFESSOR N. QUIRKE, PROFESSOR N. HARRISON, DR F. BRESME, PROFESSOR A. KORNYSHEV 4.P1 Single molecule spectroscopy (8 lectures: Dr Yaliraki) Basic fundamentals of single molecule spectroscopy and experimental description. Applications will include (i) Single molecule fluorescence experiments of biological systems: enzyme kinetics, protein dynamics (ii) Single molecule spectroscopy of quantum dot nanoparticles: blinking, stochastic switching (iii) Single molecule force-extension experiments. 4.P2 The theory of nanoscale structures: computer simulations and modelling (8 lectures: Professor Harrison) One of the fascinating features of nanoscale systems is the pervasive impact of quantum phenomena. This course will give an introduction to the important conceptual models used to understand electronic

258


states at the nanoscale and to explore how new chemistry emerges from them. Topics covered will include the quantization of conductance, interaction of molecules with surfaces, the operation of scanning tunneling microscopes and the behavious of quantum optical devices. This material will help to fill the gap between basic course work and the current research literature. 4.P3 Interfacial Science: from macroscale to nanoscale interfaces (8 lectures: Dr Bresme) This course covers the physical chemistry of interfacial systems (wetting and capillarity), with particular emphasis on wetting phenomena at the nanoscale. This area of research has undergone a dramatic development in the latest years, thanks to recent advances in experimental and theoretical methodologies that make possible the study of wetting phenomena at nanometer scale dimensions. In this course the theoretical approximations to investigate interfacial science phenomena will be presented. Applications to modern problems in science and technology are discussed with specific examples on nanomaterials, self assembly and micro-fluidics. 4.P4 Nanostructured semiconductor materials (8lectures: Professor Jones) Methods for fabricating and characterising nanostructured semiconductor materials. Revision of bulk semiconductor properties, epitaxial growth and semiconductor thin film deposition, monitoring semiconductor growth, electron diffraction, scanning probe techniques, electron microscopy, properties of low dimensional semiconductor structures, examples of quantum wells, wires and dots, application in electronic devices. 4.P5 Macromolecules and biopolymers (8 lectures: Professor Kornyshev) This course will address the principles of the physics of the most biologically important macromolecules, relating it with their structure and functionality. The course will include: statistical physics of polymers, interactions and non-ideal chains, structural chemistry of macromolecules, molecular symmetry applied to macromolecules, applications to protein and DNA structure, DNA denaturation and renaturation, DNA mechanics and topology and their functional importance. 4.P6 Optical and electrical properties of nanomaterials (8 lectures (4 each): Dr Durrant, Dr Yaliraki) Optical properties of inorganic nanomaterials, quantum confinement, quantum dots, core/shell structures. Examples of applications: pigments, photocatalysis. Optical properties of organic nanomaterials: Huckel theory for polymers, exciton theory for molecular aggregates. Examples of applications: colour photography. Electrical properties of nanomaterials: classical and semiclassical theories of transport. Mechanisms of quantum transport. Landauer formalism. Examples: quantum dots, atomic wires, molecular wires.

C.404 Analytical and interfacial chemistry (part of C.410) DR R.V. LAW, DR J.H.G. STEINKE, IRSL STAFF, PROFESSOR DAME J.S. HIGGINS (DEPARTMENT OF CHEMICAL ENGINEERING AND CHEMICAL TECHNOLOGY) 4.A3 Advanced polymers (7 lectures: Dr Williams (3), Dr Steinke (4)) Mechanism and applications of living polymerisation methods. Pd-catalysed synthesis of alternating copolymers. Well-defined ring-opening metathesis polymerisation (ROMP) initiators for the synthesis of block copolymers, comb polymers, conducting materials. Cu and Ru systems for living atom transfer free radical polymerisation. Immortal initiators for methylmethacrylate polymerisation. Living anionic and living cationic polymerisations. Modern synthetic approaches for the control of polymer architectures and advances in their molecular characterisation. Mechanistic and structural aspects of hyperbranched polymers. Design criteria and synthesis of biodegradable polymers. Recent developments in polymer recycling. 4.A5 Chemistry of medical imaging (7 lectures: IRSL staff ) Introduction to positron emission tomography (PET) and single photon emission computed tomography (SPECT); their sensitivity and specificity. The importance of these techniques in basic research in neurology, psychiatry, cardiology, oncology and drug discovery. Introduction to important basic concepts with regard to nuclear and radiochemistry. Methods for the production, isolation and measurement of key g- and positron-emitting isotopes, especially cyclotron methods for positron-emitters. Organic radiochemistry with short lived positron-emitters, such as 11C and 18F. The need for special chemical processes enabling the fast radiosynthesis, purification and analysis of radiochemicals for safe administration to human subjects. Role of classical organic chemistry in providing precursors than can be

chemistry

259

labelled efficiently and specifically. Future potential of the radiochemistry of positron emitting radiohalogens and radiocations for labelling macromolecules. Design of new radiopharmaceuticals. 4.A10 Polymers, Polymerisation Processes and Properties (9 lectures: Professor Dame J.S. Higgins, Dr A. Bismarck, Dr. C. Immanuel, Dr J.H.G. Steinke, Dr R. V. Law (Seminars, workshops, group problem solving, introduction to materials properties, analysis and processing). Please note that if you choose this course, then you only need to choose one other course for the IVA 1 examination paper. The course illustrates the complex interaction between chemistry and chemical engineering needed to produce a desirable polymer product. The course discusses the challenges of turning the initial milligram quantities of a polymer into an industrial product by considering the entire process covering monomer synthesis, polymerisation chemistry, polymer structure, function, morphology, processibility and environmental issues. A key feature of the course is the format in which chemists and chemical engineers will be tackling challenges in groups, working as teams thoughout the course, to promote mutual appreciation of each other's discipline through sharing of knowledge and expertise. The course participants will be introduced to a wide range of polymeric materials and their processing, ranging from bulk polymers to recent developments in biomedical and electronic materials and the challenges associated with their pilot scale and industrial production. The course consists of a combination of seminars, supervised team exercises, an experimental introduction to polymer characterisation techniques, processing and properties and includes speakers from industry.

C.420 Advanced chemistry theory IVB C.405 Organic chemistry (part of C.420) PROFESSOR A.G.M. BARRETT, PROFESSOR D. CRAIG, PROFESSOR R.J. LEATHERBARROW, PROFESSOR A. ARMSTRONG, AND GSK AND SYNGENTA STAFF 4.O6 Pharmaceuticals (6 lectures: GSK research staff ) Introduction to medicinal chemistry and related subjects in the pharmaceutical industry. An introductory lecture on the overall processes of the pharmaceutical industry from a chemistry perspective, beginning at the identification of new disease targets, through to the final marketing of a drug, and focuses on the issues and hurdles that need to be overcome at each stage. Changes underway in the industry to minimise the risks of failure at each stage are also described. Two case study lectures focus on recently developed drugs, illustrating their discovery and the medicinal chemistry challenges and hurdles that needed to be overcome. A further lecture covers the importance of understanding the pharmacokinetics and metabolism of drug substances, and looks at the effects of physical characteristics and chemical structure on these parameters. The fifth lecture provides an introduction to the chemical issues around process development of drug substances and scale up from research quantities through to manufacture of drug substances. The final session is on newer technologies now impacting on the industry, primarily looking at high throughput screening methods, the generation of compound libraries for screening and the introduction of combinatorial and parallel processing in chemistry at all stages of the drug discovery process. 4.O7 Chemistry of enzymes (8 lectures: Professor Leatherbarrow) Kinetics of enzymes, differences between ‘normal’ solution reactions and enzyme-catalysed ones. Advanced kinetics. Multi-substrate enzymes, allosteric behaviour. Regulation of enzyme action. General features of enzyme catalysis. Effects of pH, temperature, etc. Transition-state stabilisation as a general mechanism for enzyme action. Use of transition-state analogues as enzyme inhibitors. Protein engineering to study mechanism and alter specificity. Energetics of interactions involved in molecular recognition and protein stability. Case studies, mechanisms of serine proteinases, lysozyme, ribonuclease. Principles of structure-based drug design. Application to construction of new therapeutics. 4.O8 Advanced synthesis (7 lectures: Professor Barrett) Total synthesis of endiandric acids A, B, C and D (Nicolaou). Acetylene coupling; semi-hydrogenation; cascade electrocyclisations and cycloadditions; biomimetic synthesis. Total synthesis of rifamycin S (Masamune, Kishi). Assembly of ansa chains; stereo-controlled aldol reactions; chelation and non-chelation control; Pummerer chemistry; macrocyclisation.

260


Total synthesis of (-) roxaticin (Rychnovsky). Asymmetric hydrogenation; Brown allylboration; 1,3dioxanes in stereocontrolled 1,3-diol assembly; polyene construction; macrocyclisation. Total synthesis of (-) histrionicotoxin (Stork). Brown allylboration; epoxide spiroannulation and related reactions; (Z)-iodomethylenylation; Weinreb-Woodward-Vorbruggen amide synthesis; palladium catalysed coupling reactions. Strychnine: an overview of a recent total synthesis (Rawal). Pyrroline-diene Diels Alder reactions; allylation; palladium catalysed cyclisations; isostrychnine synthesis and conversion into strychnine. Total synthesis of gilvocarcin (Suzuki). Stereoselective C-glycoside synthesis; benzyne-furan cycloadditions; intramolecular palladium catalysed coupling chemistry. 4.O9 Advanced problems class (8 lectures: Professor Craig) This course complements many of the preceding and current organic chemistry courses. Circulated to all participants about a fortnight before any given class, the intricacies and finer details of the chemistry are discussed in the two-hour classes. 4.O10 The discovery of agrochemicals (6 lectures: Syngenta staff ) Introduction: fungicides and bactericides; herbicides; insecticides; plant growth regulators; targeting. Lead generation: random screening: DDT; pymetrozine; glyphosate. Analogue chemistry: aryloxyphenoxypropionate herbicides. Natural products: pyrethroids; strobilurins. Biorational design: juvenoids; pyruvate dehydrogenase; acetylcholinesterase. Lead clarification: bioisosteres; sulfonylurea herbicides. Lead optimisation—design strategies: structure-activity models; CoMFA; simplex optimisation; agrikinetic properties; propesticides; carbosulfan. Compound development—field trials; formulations; toxicology; paclobutrazole; environmental safety; patents. Process research route selection; flufenprox; process development, manufacture. 4.O11 Catalytic asymmetric synthesis (7 lectures: three by Professor Gibson and four by Professor Armstrong) Introduction and general principles of asymmetric catalysis: ligand accelerated catalysis, non-linear effects. Homogeneous asymmetric hydrogenation of olefins, carbonyls, imines and enamides. Asymmetric reduction of carbonyls and imines by non-hydrogenative methods. Asymmetric hydrogenX/olefin additions (hydrosilylation, hydroformylation). Asymmetric olefin oxidation: epoxidation, dihydroxylation, aminohydroxylation. Cyclopropanation. Asymmetric carbenoid reactions. Asymmetric transition metal catalysis in C-C bond forming reactions. Chiral Lewis acid catalysis: aldol reactions, cycloadditions, Mannich reactions, allylations. Asymmetric transition metal catalysis in C-C bond forming reactions. 4.O12 Solid phase peptide synthesis (8 lectures: Professor Leatherbarrow) The course will provide an overview of peptide chemistry, describing methods for their analysis and synthesis. Peptide chemistry is a key area of natural product chemistry, and has a large number of biological, medicinal and pharmaceutical applications. The importance of peptide chemistry is reflected in intense research interest within academic and industrial laboratories. Many key developments in modern chemistry, particularly the use of solid-phase synthetic methodologies, have come about from work in the peptide field.

C.406 Inorganic chemistry (part of C.420) DR N.J. LONG, DR P. LICKISS, PROFESSOR T. WELTON, DR P. HUNT 4.I6 Inorganic and organometallic polymers (8 lectures: Dr Long) The course describes a wide range of inorganic polymers concentrating on polyphosphazenes, polysilanes, polysiloxanes and organometallic polymers based on transition metals. Other materials mentioned in less detail will include BN, poly-sulfur and poly-phosphorus compounds. The following aspects of the polymers will be discussed; specific syntheses, polymer-specific spectroscopy (briefly), reactions of polymers, and the physical properties and applications of polymers. 4.I7 Ultrasound and Microwaves for Chemical Synthesis (8 lectures: Dr Lickiss) Sonochemistry - The physical basis for sonochemistry: generation of ultrasound, effects of frequency, power, dissolved gas, solvent, and cavitation. Equipment used for sonochemistry. Synthetic applications of ultrasound in organic and organometallic chemistry. Synthetic applications of ultrasound in inorganic and materials chemistry. Industrial applications of ultrasound. Recent years have also seen the

chemistry

261

increasing use of microwave activation as a means of increasing reaction rates. The heating effects of microwaves on food are well known and it has been found that microwave heating of polar solvents e.g. water can lead to rapid temperature increases, increased pressures and increased reaction rates. Practical applications of microwaves in synthetic chemistry will be discussed and comparisons made with sonochemistry. 4.I8 Ionic liquids (8 lectures: Dr Welton) Introduction to ionic liquids as solvents for synthesis and catalysis applications. Aspects of their structure and physical properties will be included to achieve a full understanding of their behaviour. The course assumes a knowledge of the material covered in the third year course Non-aqueous solvents. Lectures 1 and 2 What is an ionic liquid? Models of molten salts formation and the thermodynamics of melting. Structural influences on the melting point of a salt. Lectures 3 and 4 Physical properties of molten salts and ionic liquids, polarity, interionic bonding, structure. Lectures 5 and 6 Applications of ionic liquids to materials synthesis and stoichiometric organic reactions. Lectures 7 and 8 Applications of ionic liquids in catalysis. 4.I10 Exploring inorganic chemistry (8 lectures: Dr Hunt) How the results of calculations can be used to gain insight into reaction mechanisms, structure, bonding and spectra of inorganic systems. Topics selected from: catalysis, transition metal complexes, main group chemistry, molecular liquids, photochemistry, metallic clusters, metal-oxide surfaces. Molecular computational modelling as a compliment to synthesis and experimental characterisation.

C.407 Physical chemistry (part of C.420) DR I.R. GOULD, PROFESSOR D. KLUG, DR A.R. KUCERNAK, PROFESSOR A. KORNYSHEV, PROFESSOR M. ROBB 4.P7 Fuel Cells and Renewable Energy Systems (8 lectures: Dr Kucernak) Fuel Cells. How fuel cells work. Different types of fuel cells. Catalysts/Electrolytes/Fuels. Current capabilities/uses. Fuel cell stacks and systems. Limitations to the performance of fuel cells. Hydrogen as a fuel. Production of hydrogen: Electrolysis, Thermochemical Processes, Hydrocarbon reformation, Biosynthesis and Photochemical Processes. Storage, Transport, and Handling of Hydrogen. Dangers associated with hydrogen. 4.P8 Complex solids (8 lectures: Professor Kornyshev) Introduction to complexity. Deterministic and random fractals, fractal diagnostics and characterization. Fractal and non-fractal aggregation, evolution and growth. Percolation. Processes in complex aggregates (diffusion, reactions). Stochastic geometry and physical processes of composites. Composite electrodes and catalysts. Impedance of complex electrodes. Fluids in complex media. Ion conducting membranes. Biomolecular aggregates. 4.P9 Optical Methods in Biomolecular and Nano-Science (8 lectures: Professor Klug) The course will cover the fundamental principles of the interaction between light and molecules which provides the basis for all modern spectroscopies including NMR, EPR, Optical Absorbtion, Infra-Red spectroscopy, Raman Spectroscopy, Fluorescence, Near Field microscopy, Single molecule spectroscopy, time resolved spectroscopy. Molecular systems that will be covered include proteins and non-biological nanoparticles and the application of spectroscopies to analytical chemistry, microscopy, structure determination and dynamics. 4.P10 Mechanistic Photochemistry (8 lectures: Professor Robb) A photochemical mechanism involves understanding molecular evolution from light absorption to the appearance of ground state products. However photochemistry is complicated by the fact that a reaction path has two segments, one on the electronic excited state and one on the ground state. In addition there is always the competition between radiative pathways (fluorescence) and radiationless decay (internal conversion and inter system crossing). Our objective in this lectures is too understand the mechanistic concepts that appear to control photochemical and photo-physical behaviour in terms of molecular potential energy surfaces. Case studies will be discussed from femtochemistry, organic and inorganic photochemistry, photobiology, photochromic systems, and both synthetic and natural photostabilizers.

262


4.P11 Physical methods in Biological Chemistry (8 lectures: Dr Gould) A comprehensive review of how three dimensional and temporal data of biological chemistry is acquired, analysed and interpreted. X-ray and neutron diffraction, 2 and 3 D NMR, 1 and 2D IR/VIS spectroscopy, Atomic Force Microscopy.

C.408 Analytical and interfacial chemistry (part of C.420) DR R.V. LAW, PROFESSOR A. DE MELLO, PROFESSOR A.D. MILLER AND FACULTY OF MEDICINE STAFF 4.A7 Chemistry of gene therapy (6 lectures: Professor Miller) This lecture course begins with an overview of gene therapy research and then focuses upon the design and preparation of several distinctly different vector systems which are now being developed worldwide for human gene therapy in the future. 4.A8 Miniaturised analytical chemistry (8 lectures: Dr de Mello) The advantages of miniaturising conventional analytical technologies, separation and scaling theory. Microfabrication technologies: conventional micromachining technology novel polymeric microstructures. Applications: ultra-fast chemical separations, free flow electrophoresis, DNA analysis (sizing and sequencing), synchronised circular capillary electrophoresis. Applications (miniaturised chromatography): HPLC, gas chromatography and capillary electrochromatography. Detection: small volume detection systems for microchip applications. Chemical reactions on chip: chemical reactors, mixers, and sieves. Laboratories-on-a-chip: integrated analysis systems, combinatorial and diagnostic applications. 4.A9 Advanced NMR spectroscopy (7 lectures: Dr Law) Application of simple editing techniques (e.g. DEPT, INEPT) to small molecules. Brief theory of polarisation transfer. Nuclear Overhauser effect. Theory and application of NOE. Introduction to, and applications of, two-dimensional spectroscopy: NOESY and the spatial information derived from this. COSY and J-coupling and their variants. Other important two-dimensional experiments. Single and multiple bond carbon-proton correlation spectroscopy. Total correlation spectroscopy. Differences between solution and solid state NMR spectroscopy: line broadening interactions, strategies to suppress each type of interaction, dipolar decoupling, magic angle spinning (MAS), use of high field. Simple pulse sequences used in solid state NMR. Basic theory and techniques for sensitivity enhancement. Crosspolarisation. Bloch decay. Dipolar dephasing. Relaxation. Problems of observing protons in the solid state. Techniques for high abundance spin half nuclei, e.g. 1H and 19F. Multiple-pulse spectroscopy and line narrowing. CRAMPS and ultra-fast magic angle spinning. Methods for measuring distances in the solid state. Rotational resonance and REDOR/TREDOR. Examples of insoluble proteins and polymers. Two-dimensional NMR spectroscopy for the investigation of molecular motion.

C.450 Research exercise in chemistry (F103, F124, F105, F125, F1D4, F1H8, F1HV) Practical or theoretical project performed under staff supervision. A list of projects is available in all the main fields of chemistry and guidance is given to ensure selection of a topic suited to individual experience and skills. Lists of topics are handed out in the preceding March, selections submitted by early June and allocations are made by the end of June. Students prepare a short proposal on the project at the beginning of the autumn term and the research extends throughout the year. Assessment is based on a written project report, an oral presentation and the project proposal.