1. New Applications of Broadband Rotational Spectroscopy Wednesday 18 th April 2012 ERC Starting Grant Presentation Nicholas R. Walker (Left) The CP-FTMW spectrometer re-located to Newcastle University (Right) Some components of the instrument. 1.

2. 2003-2011 Royal Society University Research Fellowship, University of Bristol. 2012 1996-2003 Worked at 5 different institutions in Europe and North America. 48 peer-reviewed articles and achieved an h- index of 21. Susanna Stephens, Nicholas Walker and the CP-FTMW spectrometer in Newcastle. Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker Career Background 2.

3. 1946 - First high resolution microwave spectroscopic measurements. 3 1. G.G. Brown et al., Rev. Sci. Instr. 79, 053103 (2008) 1981 – cavity FT-MW spectroscopy (Balle and Flygare). Frequency / MHz 80001200016000 Frequency / MHz 2006 – Construction of the chirped-pulse Fourier transform microwave spectrometer (Pate 1 ). Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker The Broadband Advantage

4. 80001000012000140001600018000 Frequency / MHz Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker Measurement bandwidth Time required for data acquisition 1MHz 14 hours 11GHz 48 minutes Balle Flygare FTMW CP-FTMW* * G.G. Brown et al., J. Mol. Spec., 238 200 (2006) 4. The Broadband Advantage 138501386013870 Frequency / MHz

5. Microwave spectroscopy Theory Infrared spectroscopy Objectives Address problems outside of traditional boundaries of microwave spectroscopy. Metal ion solvation Role of metals in biochemistry Chemical analysis Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker Methodology Pd, C 2 H 4, C 2 H 2 5.

6. Theme 2 – Microscopic Ion Solvation N.R. Walker, R.R. Wright and A.J. Stace, J. Am. Chem. Soc. 121, 4837- 4844 (1999) N.R. Walker, R.S. Walters, G.A. Grieves and M.A. Duncan, J. Chem. Phys. 121, 10498-10507 (2004) Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker Ni + (CO 2 ) 5 Ni + (CO 2 ) 4 Ni + (CO 2 ) 3 6.

7. A. Mizoguchi, Y. Ohshima and Y. Endo, J. Chem. Phys. 135, 064307 (2011) H 2 O  AgCl: N.R. Walker and co- workers, Angew. Chem. Int. Ed. 49, 181- 183 (2010) H 2 O  AgF: N.R. Walker and co-workers, J. Mol. Spectrosc. 267, 163-168 (2011) Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker 7. Theme 2 – Microscopic Ion Solvation

8. Key Collaborators BH Pate (Virginia) W Jaeger (Alberta) M Schnell (Hamburg) MA Duncan (Georgia) BJ Howard, SR MacKenzie (Oxford) Tew, Legon, Western (Bristol) Other Competitors Alonso (Valladolid) Endo (Tokyo) WorldEurope Strategic Collaborations DJ Tozer (Durham) 8.

9. Concluding Remarks PI has an outstanding track record of success achieved through work at 5 different institutions in the U.K. and North America. State-of-the-art, globally unique instrument proven through many published works since mid-2010. Wide range of problems of contemporary importance. Expansive programme can only be pursued because of the speed and power of CP-FTMW spectroscopy. Newcastle University have committed funding for a postgraduate studentship to the proposed work. I will welcome questions. Thank you for your attention. Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker 9.

10. Theme 1 objective: Determine precisely all bond lengths and angles in isolated species of M n  (C 2 H 4 ), M n  (C 2 H 2 ), M n -CCH and M n -CH 2 where M=Ni, Pd, Pt. Theme 2 objective: Determine the geometries of (H 2 O) n  AgCl and (H 2 O) n  AgF where n=1-6 to characterise the emerging solvent environment and identify whether the structures of these complexes follow divergent trends (with increasing n) even at these small sizes of unit. Subsequent experiments will use the same methodology to explore the microscopic solvation of CuCl, CuF, AuCl and AuF Theme 3 objective: D etermine precisely bond lengths and angles in complexes formed between the ionic copper atom of a copper chloride molecule and one or more glycine or imidazole molecules. Equivalent interactions involving alanine, histidine and cysteine will be characterised in subsequent experiments. IR and MW spectra of the complexes will be analysed to determine vibrational band shifts and characterise the structures. Theme 4 objective: Spectrometer will be coupled with gas chromatography to demonstrate new measurement dimension for the technique. The instrument will be used to distinguish the chemicals present in wine and fruit juice. Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker

11. Year 1Measure and analyse MW spectra of M  C 2 H 4 and M  C 2 H 2 where M is nickel, palladium or platinum. Write automation programmes Measure and analyse MW spectra of (H 2 O) n  AgCl, (H 2 O) n  AgF (where n=2,3) Construct slit nozzle. Install laser to obtain IR spectra of metal ion- solvent complexes. Obtain IR spectra of (H 2 O) n  AgCl, (H 2 O) n  AgF (where n=2,3) Year 2Measure and analyse MW and IR spectra of MCCH, MCH 2 where M=Ni, Pd, Pt. DFT calculations Measure MW and IR spectra of (H 2 O) n  AgCl, (H 2 O) n  AgF (where n=4,5,6). DFT calculations Modify instrument to generate complexes containing amino acids. Measure and analyse MW and IR spectra of (gly)  CuCl and (imid)  CuCl. Obtain MW and IR spectra of (gly) n  CuCl, (imid) n  CuCl where n=2,3. DFT calculations Project Plan Postgrad. 1 Postgrad. 2 Postgrad. 3 Postdoctoral researcher

12. Year 3Measure and analyse MW spectra of M 2  C 2 H 4, M 2  C 2 H 2, M 3  C 2 H 4, M 3  C 2 H 2, M 2 CCH, M 2 CH 2, M 3 CCH, M 3 CH 2, Measure MW and IR spectra of (H 2 O) n  CuCl, (H 2 O) n  CuF (where n=4,5,6) Measure and analyse MW and IR spectra of (ala)  CuCl, (cys)  CuCl and (hist)  CuCl. DFT calculations Measure and analyse MW and IR spectra of (hist) n  CuCl (n=2,3,4) (ala) n  CuCl (n=3,4) and (cys) n  CuCl. (n=3,4) Year 4Thesis write-up Measure and analyse MW and IR spectra of (ala) n  CuCl and (cys) n  CuCl. (n=1,2) Measure MW and IR spectra of (H 2 O) n  AuCl, (H 2 O) n  AuF (where n=1-6) Year 5 Thesis write-upConstruct GC-CP- FTMW spectrometer and trial performance for analysis of wine and juice. Postgrad. 1 Postgrad. 2 Postgrad. 3 Postdoctoral researcher

13. Cost CategoryYear 1Year 2 2 Year 3 2 Year 4 2 Year 5 2 Total (Y1-5) 2 Direct Costs: Personnel: PI36,74577,23280,02682,91885,910362,831 Senior Staff Post docs47,34150,51553,90457,51161,366270,637 Students17,32435,86037,11628,7569,883128,939 Other Total Personnel:101,410163,607171,046169,185157,159762,407 Other Direct Costs: Equipment136,611140,835 277,446 Consumables48,02028,01128,99130,00631,062166,090 Travel6,2376,4546,6806,9147,15733,442 Publications, etc Other Total Other Direct Costs:190,868175,30035,67136,92038,219476,978 Total Direct Costs:292,278338,907206,717206,105195,3781,239,385 Indirect Costs (overheads): Max 20% of Direct Costs58,45667,78141,34341,22139,076247,877 Subcontracting Costs:(No overheads) 3,400 3,5203,68010,600 Total Costs of project:(by year and total)350,734410,088248,060250,846238,1341,497,862 Requested Grant:(by year and total)350,734410,088248,060250,846238,1341,497,862 For the above cost table, please indicate the % of working time the PI dedicates to the project over the period of the grant: 90% Budget

14. H 2 O  CuCl rapidly inverts on the timescale of molecular rotation. H 2 S  CuCl is rigidly pyramidal Recent Results C 2 H 4  AgCl. The C=C double bond in ethene lengthens by 0.0124 Å on attaching to AgCl (Similar for CuCl) (Owing to  * electron donation from C 2 H 4 to the metal) 1.914(1) Å2.062(6) Å 2.1531(3) Å2.0633(3) Å 78.052(6)  40.9(13)  2.2724(8) Å 2.1719(9) Å 1.354(40) Å These studies are further described in publications; Angew. Chem. Int. Ed., 49, 181-183 (2010) J. Chem. Phys., 134, 134305 (2011) J. Chem. Phys. 135, 014307 (2011) J. Chem. Phys. 135, 024315 (2011)

15. r (C=C) = 1.3518(4) Å 1 r (Ag-*) = 2.1719(9) Å r (Ag-Cl) = 2.2724(8) Å The r (C=C) bond distance is 0.013 Å longer than that found in free C 2 H 4. S.L. Stephens, D.P. Tew, V.A. Mikhailov, N.R. Walker and A.C. Legon,, J. Chem. Phys. 135, 024315 (2011) Pt  C 2 H 4 Pt  C 2 H 2 Pt  CCH C 2 H 4  AgCl Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker

16. What can we learn about biochemistry from gas phase spectroscopy? Molecular recognition Conformation Zwier and co-workers: Drive changes in conformation using infrared light and measure the efficiency of the isomerisation. B.C. Dian et al., Science, 296, 2369 (2002) N-acetyl-tryptophan methyl amide Alonso and co-workers: Use a combination of microwave spectroscopy and high accuracy theory to spectroscopically distinguish between different conformers of amino acids and carbohydrates. e.g., alanine (left) S. Blanco et al., J. Am. Chem. Soc., 126, 11675 (2004) Theme 3 – Copper Binding Sites in Enzymes Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker

17. Copper centre Coordination environmentExample Type I (T1Cu) 2  histidine (N atoms), 1  cysteine (S atom), in trigonal planar + 1 other axial ligand Plastocyanin Type II (T2Cu) Square planar coordination by N or N/O ligandsEnzymes Type III (T3Cu) Pair of Cu centres, 3  histidine Hemocyanin A (Cu A ) Pair of Cu atoms coordinate with 2  histidine, 1  methionine, backbone CO, 2  bridging cysteine ligands, Cytochrome c- oxidase B (Cu B )3  histidine in trigonal pyramidalCytochrome c- oxidase Histidine Cysteine Glycine Imidazole Alanine Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker

18. Theme 4 - Rotational Spectroscopy Beyond the Complexity Limit Task of assigning spectra becomes increasingly difficult when a sample contains many different chemicals. Technology behind broadband rotational spectroscopy advancing quickly. Broadband rotational spectroscopy distinguishes between molecules on the basis of their structure rather than their mass/charge ratio. Wednesday 18 th April 2012, ERC Proposal Presentation, Nicholas R. Walker

19. New Challenges and Opportunities Biology Analysis Conformational isomerisation of cyclopropane carboxaldehyde 1  Syn.Anti. 1) B.C. Dian, G.G. Brown, K.O. Douglass and B.H. Pate, Science, 320, 924 (2008) Molecular Dynamics  -D-fructofuranose

20. Laser ablation source informed by the designs currently used by Duncan and co-workers, Gerry and co-workers, Ziurys and co-workers. Laser ablation source

21. OC  AgI 8000 10000 12000 14000 16000 18000 Frequency/MHz CF 3 I 107 AgI 109 AgI AgI

22. OC  AgI 13200 13400 13600 13800 14000 14200 14400 Frequency / MHz 107 AgI 109 AgI OC  ICF 3 Exp. Sim. OC  107 AgI OC  109 AgI