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Computer-assisted Fitting of Dynamic 1H-NMR spectra coupled

to Platinum

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Kinetic Rates that can be measured by NMR

k < 10-3 s-1

Classic Kinetic Study, integration (non equilibrium)

0.01 s-1 < k < 1 s-1

Saturation Transfer, EXSY, Difference Spectroscopy (equilibrium)

1 s-1 < k < 100 s-1

Lineshape AnalysisLineshape Analysis (equilibrium)

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Lineshape Analysis

Calibrate the Temperature of the Probe Acquire the Variable Temperature Spectra Simulate and Fit the SpectraSimulate and Fit the Spectra Plot the Eyring Equation Compare ∆H‡ and ∆S‡ of Different Compounds Elaborate a Theory

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Measuring the Temperature inside the Tube

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Rectified Plot

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DNMR: the program

Journal of the American Chemical Society | 91:6 | March 12, 1969

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2 nuclei are not enough

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DNMR3: Time Requirements in 1969

“... the computation of a typical exchange-broadened spectrum arising from a general 4-spin

system exchanging between 2 configurations takes about 14 minutes of CPU time...”

“The time for computing the coordinates of the plot from the complex vectors usually ranges from

1 to 4 minutes...”

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From Hilbert space to Liouville Space

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How large is this Liouville Space ?

n = number of nuclei m = number of

chemical states d = number of

dimensions d = m 22n

“n” “d” “m”1 8 22 32 23 128 24 512 25 2048 26 8192 2

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How can you fit a spectrum with DNMR?

Trial and Error ? Systematic Search ? Least Square Fitting ? Computer-assisted fitting !Computer-assisted fitting !

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Which application for Windows?

DNMR5 (VAX, $145-290) + Fortran77 Compiler http://www.qcpe.indiana.edu/cgi-bin/view_catalog.pl

WinDNMR http://www.chem.wisc.edu/areas/reich/plt/windnmr.htm

gNMR http://home.cc.umanitoba.ca/~budzelaa/gNMR/gNMR.html

MEXICO + C Compiler http://www.chemistry.mcmaster.ca/bain/exchange.html

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It takes a Lot of Ingredients to Make an Interactive DNMR...

Fast Executable Code

Overlays

Relations, Equalities, Symmetry

State of the Art Graphics

Full-featured Processing Application

Generalization in the Liouville Space

iNMR / Mac OS XiNMR / Mac OS X

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Table of Definitions

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Interactive Interface

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Experimental Spectrum Overlaid over the Simulation

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Processing the Spectrum

This is a great

algorithm, but not for this task

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The smoother effectively flattens the baseline under the narrow peaks

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Local (from 7 to10 ppm) Phase and Baseline Correction

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Industrial Software Can't Be Fast

Generic Math Libraries ?

Legacy: Arcane Fortran Algorithm

Glue Code

Graphic User Interface

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How iNMR works: 2 User Interfaces

G.U.I.

Translation

Translation

DNMR

Dialog

EssentialParameters

Tables,Definitions

LiteratureParameters Hamiltonian

Plot

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Coalescence of the Methyls

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Mono-coordinated Naphthyridine

N N N N

PtI2CO PtI

2CO

A

B

C

N N N N

195PtI2CO

A

BC

195PtI2CO

A

BC

1 2

3 4

StrategyStrategy

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First Step: Let's Fill in the Tables

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Fitting the Static Spectrum

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Fitting the Static Spectrum

Set the Parameters from the Most Evident to the Least Evident one

Start from well defined Multiplets Set Chemical Shifts and Large Js in the first

two systems Set small couplings Set Line Widths Set the coupling with Pt

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Going Dynamic

(1) only exchanges with (2) (3) only exchanges with (4)

k12

= k34

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Going Dynamic

Peaks near the coalescence let you fit the exchange rate with accuracy

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Heating changes all the parameters, not just the Exchange Rates

Chemical Shifts change with temperatureInterlock the shifts above coalescence

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229 K:we can't change some Js anymore

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235 Kthe H-Pt Coupling is still there

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240 K

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245 K : second coalescence

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256 K : third coalescence

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269 K : we can only change pairs of chemical shifts

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280 K => k = 1200 s-1

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295 K => k = 6000 s-1

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Eyring Equation (draft)

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Eyring Equation (draft)

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295 K => k = 5000 s-1

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The End (for now)