Alex D. Bain Professor  B.Sc. (Toronto), M.Sc. (British Columbia), Ph.D. (Cambridge)

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Mailing Address: Dr A.D. Bain Department of Chemistry McMaster University Hamilton, Ont., Canada L8S 4M1 Office:         ABB-269A

Telephone: Voice (905) 525-9140, ext. 24524 FAX   (905) 522-2509       email: bain@mcmaster.ca

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Studies in Modern Pulse and Two-dimensional NMR

My research interests lie in the field of pulse and two-dimensional NMR and chemical exchange, including both theoretical simulations and practical applications. .

protein L.

Today, the normal, one-dimensional NMR spectrum is just a starting point for the investigation of the structure and dynamics of a molecule. We are beginning to exploit the full power of NMR spectroscopy, but we have just scratched the surface. This research aims at applying pulse NMR to such problems as structure determination, starting with a very firm theoretical foundation.

In particular, some of my current projects are as follows:

• Chemical exchange lineshapes. In an NMR spectrum, each nucleus has its own chemical shift. However, if there is dynamics in the system, the nuclei may exchange on the "NMR timescale". This gives an amazing variety of chemical exchange lineshapes, described in introductory outline. (Intro.pdf).
• Simulations. To simulate these lineshapes (example of fit), and to extract rates from them, we have written a suite of programs called MEXICO. As of April 2002, a new version (3.0) has been released. More details are given on a separate page.
• Investigation of chemical kinetics and slow exchange. NMR provides an excellent way of probing chemical reactions, since rates from s^-1 up to more than 10⁵ . Most chemical systems show dynamic behaviour, but much of this has been ignored in the past. Valuable information on mechanisms and the nature of the transition state can be obtained by NMR. My group has been developing new methods to measure theses rates in the slow, intermediate and fast exchange regions. Relaxation experiments for slow exchange (the CIFIT (manual) program, which you can download as a unix tar file or as a zip file) and bandshape methods for intermediate exchange are all under active investigation.
• NMR of quadrupolar nuclei. Nuclei with a spin > 1/2 can have strong interactions with electric field gradients at the nucleus. These interactions can be as large or larger than the Zeeman interaction with the static field. when the two interactions are comparable, then the usual perturbation theory approaches break down. In looking at this problem, we confront such issues as the rotating frame of reference and the calculation of spinning sidebands. An example of some code that implements the quadrupole calculation is given in the pdf file. This is abbreviated for display, but if you want the full code, please email me.
• Floquet theory. We used Floquet theory to simulate the spinning sidebands. In order to learn this useful technique, we wrote a program that does the classic Herzfeld and Berger/Maricq and Waugh sideband calculation with Floquet theory. A  listing is given here, and the full program is available on request.

 

The exchange projects involve a wide range of useful methods, and there is scope to concentrate on one or more of them. Starting from chemical synthesis, the work goes through running the actual spectra, fitting them with existing computer programs, on to developing and implementing new theory. In NMR, theory and experiment agree almost exactly, so a complete study is quite feasible.
 

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Recent Publications:

 

1. A.D. Bain, "NMR quadrupole Liouvillians for arbitrary spin. Exact symbolic expressions and perturbation solutions." Concepts Magn.Reson. 42 45-58 (2013).
2. T.L. Spencer, G.R. Goward, A.D. Bain, "Complete description of the interactions of a quadrupolar nucleus with a radiofrequency field. Implications for data fitting." Solid State Nucl.Magn.Reson. 53 20-26 (2013).
3. Z.Q. Zhu, M.Q. Salih, E. Fynn, A.D. Bain, C.M. Beaudry, "The garuganin and garugamblin diarylether heptanoids: Total synthesis and determination of chiral properties using dynamic NMR." J.Org.Chem. 78 2881-2896 (2013).
4. T.R. Field, A.D. Bain, "A dynamical theory of spin relaxation." Phys.Rev.E 87 022110 (2013).
5. C.K. Anand, A.D. Bain, A.T. Curtis, Z. Nie, "Designing optimal universal pulses using second-order, large-scale, nonlinear optimization." J.Magn.Reson. 219 61-74 (2012).
6. A.D. Bain, The NMR of quadrupolar nuclei. "Relationship between exact and perturbation solutions for spin-3/2." Chem.Phys.Lett. 531 267-271 (2012).
7. L.J.M. Davis, X.J. He, A.D. Bain, G.R. Goward, "Studies of lithium ion dynamics in paramagnetic cathode materials using 6Li 1D selective inversion methods." Solid State Nucl.Magn.Reson. 42 26-32 (2012).
8. J.S. Hartman, B. Berno, P. Hazendonk, E. Ye, A.D. Bain, "Spin-lattice relaxation in aluminum-doped semiconducting 4H and 6H polytypes of silicon carbide." Solid State Nucl.Magn.Reson. 45-46 45-50 (2012).
9. L.J.M. Davis, B. Ellis, T.N. Ramesh, L.F. Nazar, A.D. Bain, G.R. Goward, "Li-6 1D EXSY NMR spectroscopy: a new tool for studying lithium dynamics in paramagnetic materials applied to monoclinic Li2VPO4F" J.Phys.Chem. C 115 22603-22608 (2011).
10. A.D. Bain, M. Baron, S.K. Burger, V.J. Kowalewski, M.B. Rodriguez, "Interconversion study in 1,4 substituted six-membered cyclohexane-type rings. Structure and dynamics of trans-1,4-dibromo-1,4-dicyanocyclohexane" J.Phys.Chem. A 115 6207-9216 (2011).
11. M. Ababneh-Khasawneh, B.E. Fortier-McGill, M.E. Occhionorelli, A.D. Bain, "Solvent effects on chemical exchange in a push-pull ethylene as studied by NMR: the importance of entropy" J.Phys.Chem. A 115 7531-7537 (2011).
12. C.M. Widdifield, A.D. Bain, D.L. Bryce, "Definitive solid-state 185/187Re NMR spectral evidence for and analysis of the origin of high-order quadrupole-induced effects for I = 5/2" Phys.Chem.Chem.Phys. 13 12413-12420 (2011).
13. C.K. Anand, A.D. Bain, S.C. Watson, "Use of continuous optimization methods to find carbon links in 2D INADEQUATE spectra" J.Magn.Reson. 210 146-150 (2011).
14. A.D. Bain, C.K. Anand, Z. Nie, "Exact solution of the CPMG pulse sequence with phase variation down the echo train: application to R2 measurements" J.Magn.Reson. 209 183-194 (2011).
15. T.L. Spencer, G.R. Goward, A.D. Bain, "Exact calculation of the response of a quadrupolar nucleus to radiofrequency irradiation" Can.J.Chem. 89 764-769 (2011).
16. A.D. Bain, B. Berno, "Liouvillians in NMR: the direct method revisited" Prog.Nucl.Magn.Reson.Spectrosc. 59 223-244(2011).
17. R.J. Kalbasi, A.R. Massah, F. Zamani, A.D. Bain, B. Berno, "Metal (Co, Mn)-amine-functionalized mesoporous silica SBA-15: synthesis, characterization and catalytic properties in hydroxylation of benzene" Journal of Porous Materials 18 475-482 (2011).
18. N. Vasdev, M.D. Moran, H.M. Tuononen, R. Chirakal, R.J. Suontamo, A.D. Bain, G.J. Schrobilgen, "NMR spectroscopic evidence for the intermediacy of XeF3 in XeF2/F-. Exchange, attempted synthesis and thermochemistry of XeF3- salts and theoretical studies of the XeF3- anion" Inorg.Chem. 49 8997-9004 (2010).
19. A.D. Bain, C.K. Anand, Z. Nie, "Exact solution to the Bloch equations and application to the Hahn echo" J.Magn.Reson. 206 227-240 (2010) .
20. A.D. Bain, D.W. Hughes, C.K. Anand, Z. Nie, V. Robertson, "Problems, artifacts and solutions in the INADEQUATE NMR experiment" Magn.Reson.Chem. 48 630-641 (2010).
21. S.K. Amini, H. Shaghaghi, A.D. Bain, A. Chabok, and M. Tafazzoli "Magnetic resonance tensors in uracil: Calculation of C-13, N-15, O-17 NMR chemical shifts, O-17 and N-14 electric field gradients and measurement of C-13 and N-15 chemical shifts" Solid State Nuclear Magnetic Resonance 37 13-20 (2010).
22. T.R. Field and A.D. Bain "Origins of spin noise" Applied Magnetic Resonance 38 167-178 (2010).
23. S.K. Amini, M. Tafazzoli, H.A. Jenkins, G.R. Goward and A.D. Bain "Measurement and density functional calculations of C-13 and N-15 NMR chemical shift tensors of a push-pull ethylene" Can. J. Chem. 87 563-570 (2009).
24. C.K. Anand, A. Sharma, and A.D. Bain "Optimal sampling patterns for multi-dimensional T2 experiments" J. Magn. Reson. 197 63-70 (2009).
25. A.F. Cozzolino, A.D. Bain, S. Hanhan and I.R.M. Vargas-Baca "N-triphenylboryl- and N,N'-bis(triphenylboryl)-benzo-2,1,3-telluradiazole" J. Chem. Soc, Chem Commun 4043-4045 (2009).
26. R.M. Gregory and A.D. Bain "The effects of finite pulses in NMR: phase and intensity distortions" Concepts in Magnetic Resonance 34 A, 305-314 (2009).
27. J.S. Hartman, B. Berno, P. Hazendonk, C.W. Kirby, E. Ye, J.W. Zwanziger and A.D. Bain "NMR studies of nitrogen doping in the 4H polytype of silicon carbide: Site assignments and spin-lattice relaxation" J. Phys. Chem. C 113, 15024-15036 (2009).
28. M.Vijaykumar,A.D. Bain and G.R. Goward "Investigations of proton conduction mechanism in the high temperature phase of RbH2PO4 using multinuclear NMR analysis" J. Phys. Chem. C 113, 17950-17957 (2009).
29. H.Amarne,A.D. Bain, K. Neumann and P.M. Zelisko "Extensions of a basic laboratory experiment: 4+2 and 2+2 cycloadditions" J Chem. Ed. 85 104-106, (2008).
30. A.D. Bain. "Chemical Exchange" Annu. Rep. NMR Spectrosc 63 23-48 (2008).
31. W.Wang,A.D. Bain, L.Q. Wang,G.J. Exharos and A.D.Q. Li "Frustration of molecular assembly leads to a basket-shaped cyclophane with observable chiral dynamics" J Phys. Chem A 112 3094 -3103, (2008).
32. C.K. Anand, A.D. Bain and Z. Nie "Simulations of steady-state NMR of coupled systems using Liouville space and computer algebra methods" J. Magn. Reson. 189 200-208 (2007).
33. J.S. Hartman, A.Narayanan, S.Rigby, D.R. Sliwinski, N.Halden and A.D. Bain "Stretched-exponential spin-lattice relaxation in Si-29 MAS NMR of heterogeneous systems: synthetic paramagnetics-doped forsterites and willemites" Can. J Chem 85 56-65, (2007).
34. D.M. Pawar,D.Cain,G.Gill,A.D. Bain, R.H. Sullivan and E.A. Noe "Interconversion of carbon sites in boat-chair-boat cyclodecane; Conformations of chlorocyclodecane and cyclodecyl acetate" J Org. Chem 72 25-29, (2007).
35. A.D. Bain. H. Chen and P.M.H. Harrison "Studies of structure and dynamics in a nominally-symmetric twisted amide by NMR and electronic structure calculations" Can. J Chem 84 412-428, (2006).
36. A.D. Bain. "Chemical Exchange" "Modern Magentic Resonance (Ed. G.A Webb), Springer 1-7, (2006).
37. A.D. Bain. "A simple proof that third-order quadrupole perturbations of the NMR central transition of half-integral nuclei are zero." J Magn Reson 179 308-310, (2006).
38. A.D. Bain, "Operator formalisms - an overview." Concepts Magn Reson 28 A 369-383, (2006).
39. A.D. Bain, H. Chen, P.H.M. Harrison "Studies of structure and dynamics in a nominally-symmetric twisted amide by NMR and electronic structure calculations." Can J Chem 84, 421-428, (2006).
40. A.D.Bain, M. Khasawneh. "From NQR to NMR: the complete range of quadrupole interactions." Concepts Magn Reson 22A, 69-78, (2004).
41. R.M. Epand, R.F. Epand, A.D. Bain, B.G. Sayer, D.W. Hughes. "Properties of polyunsaturated phosphatidylcholine membranes in the presence and absence of cholesterol". Magn Reson Chem 42, 139-147, (2004).
42. Y. Fu, Z. Zhou, P. Hazendonk, A.D. Bain, F.R. Fronczek, J. Escobedo, M.L. McLaughlin, R.P. Hammer. "NMR studies of a piperidine spin system from a Boc-protected piperidine-spiro-hydantoin." J Molec Struct 687 , 65-72, (2004).
43. M. Khasawneh, J.S. Hartman, A.D. Bain. "Direct detection of chlorine-35 multiple-quantum NMR transitions in a single crystal of sodium chlorate" Mol Phys 102, 975-983, (2004).
44. J.K. Lee, A.D. Bain, P. Berti. "Probing the transition states of four glucoside hydrolyses with C-13 kinetic isotope effects measured at natural abundance by NMR spectroscopy" J Am Chem Soc 126, 3769-3776, (2004).
45. A.D. Bain, "Exact calculation, using angular momentum, of combined Zeeman and quadrupolar interactions in NMR" Molec. Phys. 101 3163-3175 (2003).
46. A.D. Bain, "Chemical exchange in NMR" Prog. Nucl. Magn. Reson. Spectrosc. 43, 63-103, (2003).
47. H. Kampermann, A.D. Bain, and R.S. Dumont. "Residual dipolar coupling in the CP/MAS NMR spectra of spin-1/2 nuclei coupled to quadrupolar nuclei. Application of Floquet theory" J. Chem. Phys. 116 2464-2471 (2002). Abstract
48. A.D. Bain, and R.S. Dumont. "Introduction to Floquet theory. The calculation of spinning sideband intensities in MAS NMR" Concepts Magn. Reson. 13 159-170 (2001).Abstract
49. A.D. Bain, D.M. Rex and R.N. Smith. "Fitting dynamic NMR lineshapes" Magn. Reson. Chem. 39 122-126 (2001). Abstract
50. P. Hazendonk, A.D. Bain, H. Grondey,  P.H.M. Harrison  and R.S. Dumont . "Simulations of chemical exchange lineshapes in CP/MAS spectra using Floquet theory and sparse matrix methods" Journal of Magnetic Resonance146 33-42 (2000). Abstract
51. R.S. Dumont, P. Hazendonk and A.D. Bain "Dual Lanczos simulation of dynamic NMR spectra for systems with many spins or exchange sites" J. Chem. Phys. 113 3270-3281 (2000).
52. A.D. Bain, M.A. Brook, P.Hazendonk, D. Reid and R. Stan. "Analysis of the NMR spectra of some dimethylsilanes" Magn. Reson. Chem. 38 894-895 (2000).
53. Magnetic Resonance: Chemical Exchange Effects in NMR" Encylopedia of Spectroscopy and Spectrometry, J. Lindon, G. Tranter and J. Homes, eds. Academic Press, London (2000).
54. M. Stradiotto, P. Hazendonk, A.D. Bain,A.D. M.A. Brook and M.J. McGlinchey. "Probing the effect of organic and organometallic functionalization on [1,5] silicon shifts in indenylsilanes" Organometallics 19 590-601 (2000).
55. A.D. Bain, P. Hazendonk and P. Couture. "A reinterpretation of the substituent effect on the amide barrier. An experimental and theoretical study" Can. J. Chem. 77 1340-1348 (1999). Abstract
56. A.D. Bain. "On combination lines in the NMR spectra of strongly coupled spin systems" Can. J. Chem. 77 1810-1812 (1999). Abstract
57. P.J. Heard, A.D. Bain, P.Hazendonk and D.A. Tocher. "A detailed NMR study of the solution stereodynamics in tricarbonylrhenium(I) halide complexes of the non-racemic chiral ligand 2,6-bis[(4R,5R)-dimethyl-1,3-dioxan-2-yl]pyridine (L1) and the molecular structure of fac-[ReBr(CO)3L1]" J. Chem. Soc. Dalton Trans. 4495-4501 (1999).
58. A.D. Bain, R.A. Bell, D.A. Fletcher, P. Hazendonk, R.A. Maharajh, S. Rigby and J.F. Valliant. "NMR studies of chemical exchange amongst five conformers of a ten-membered ring compound containing two amide bonds and a disulfide" J. Chem. Soc., Perkin Transactions II 1447-1453 (1999). Abstract
59. A.D. Bain, D.A. Fletcher and P. Hazendonk. "What is a transition?" Concepts in Magnetic Resonance 10 85- 98 (1998). Abstract
60. A.D. Bain. "Blurring the distinction between slow and intermediate chemical exchange" Biochem.Cell Biol 76 171-176 (1998). Abstract
61. E. Vallazza, A.D. Bain and T.W. Swaddle. "Dynamics of silicate exchange in highly alkaline potassium silicate solutions" Can. J. Chem. 76 183-193 (1998).
62. A.D. Bain, E.P. Mazzola and S.W. Page. "A proposed standard sample for Nuclear Overhauser Effect Measurements " Magn. Reson. Chem. 36 403-406 (1998).
63. A.D. Bain and P. Hazendonk. "Solvent effects on internal rotation barriers in furfural. NMR measurements and ab initio molecular orbital methods using continuum models" J. Phys. Chem. A 101 7182-7188 (1997).
64. A.D. Bain and E.W. Randall. "Hahn spin echoes in large static gradients following a series of 90 degree pulses." J. Magn. Reson. 123 A 49-55 (1997).
65. R.S. Dumont, S. Jain and A.D. Bain. "Simulation of many-spin system dynamics via sparse matrix methods." J. Chem . Phys. 106 5928-5936 (1997).
66. A.D. Bain and I.W. Burton. "Quadrature detection in one or more dimensions" Concepts in Magnetic Resonance 8 191-204 (1996).
67. A.D. Bain and G.J. Duns. "A unified approach to dynamic NMR based on a physical interpretation of the transition probability" Can. J. Chem. 74, 819-824, (1996). Abstract
68. A.D. Bain, G.J. Duns, F. Rathgeb and J. Vanderkloet. "A study of chemical exchange in unequally populated system by novel NMR methodologies. Application to the cis-trans isomerization in furfural." J. Phys. Chem. 99, 17338-17343, (1995).
69. S. Rigby, L. Girard, A.D. Bain and M.J. McGlinchey. "Molecular dynamics of dl and meso bis(indenyl)dimethylsilane: re-examination of the mechanism of interconversion by using single selective inversion NMR." Organometallics 14,3798-3801, (1995).
70. A.D. Bain and G.J. Duns. "A new method for calculating NMR chemical exchange lineshapes." J. Magn. Reson. 112 A, 258-260 (1995).
71. A.D. Bain, G.J. Duns, S. Ternieden, J. Ma and N.H. Werstiuk. "The barrier to internal rotation and chemical exchange in N-acetylpyrrole. A study based on NMR methods and molecular modelling." J. Phys. Chem. 98, 7458-7463, (1994).
72. A.D. Bain, I.W. Burton and W.F. Reynolds. "Artifacts in two-dimensional NMR." Prog. Nucl. Magn. Reson. Spectrosc. 26, 59-89, (1994).
73. A.D. Bain and J.A. Cramer. "Optimal nmr measurements for slow exchange in two-site and three-site systems." J. Phys. Chem.97, 2884-2887, (1993).

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