györgy tarczay, gábor magyarfalvi
DESCRIPTION
Photoelastic modulator (PEM) Vibrational circular dichroism (VCD) spectroscopy FT-IR Polarization filter Photoelastic modulator (PEM) MCT detector Sample Multiplexer Lock-in amplifier Optical filterTRANSCRIPT
Gyrgy Tarczay, Gbor Magyarfalvi
ON THE ADVANTAGES OF MATRIX-ISOLATION VIBRATIONAL CIRCULAR
DICHROISM SPECTROSCOPY Gyrgy Tarczay, Gbor Magyarfalvi Laboratory
of Molecular Spectroscopy Elemr Vass Laboratory for Chiroptical
Structure Analysis Institute of Chemistry, Etvs University,
Budapest, Hungary 61st International Symposium on Molecular
Spectroscopy, Columbus, 2006 Photoelastic modulator (PEM)
Vibrational circular dichroism (VCD) spectroscopy FT-IR
Polarization filter Photoelastic modulator (PEM) MCT detector
Sample Multiplexer Lock-in amplifier Optical filter Advantages of
VCD spectroscopy
Unlike in electronic CD spectroscopy (ECD) the investigated chiral
molecule does not need to have any chromophoric groups VCD spectra
have richer structural content than ECD spectra the absolute
configuration determination can be based on more assigned bands ab
initio calculation of VCD spectra can be carried out much more
accurately the probability of an incorrect assignment is much
smaller than in the case of ECD spectroscopy Commercially available
spectrometers from the late 90s (BioTools, Bruker, Jasco)
Matrix-isolation VCD spectroscopy Previous Studies I.
a-pinene Matrix VCD VCD in CCl4 Matrix IR IR in CCl4 D. W.
Schlosser, F. Devlin, K. Jalkamen, and P. J. Stephens, Chem. Phys.
Lett. 88, 286 (1982) Matrix-isolation VCD spectroscopy Previous
Studies II.
a-pinene Matrix VCD Matrix IR Neat liquid VCD Neat liquid IR D. O.
Henderson and P. L. Polavarapu, J. Am. Chem. Soc. 108, 7110 (1986)
Conclusions of previous matrix-isolation VCD studies
Well resolved features Intensity gain compared to spectra of neat
liquids or solutions Better correspondence between experiment and
computations BUT No work has been published after these two studies
It seems that the more labor-intensive matrix VCD measurements are
not worth the candle in the case of single-conformer and/or weakly
interacting molecules WHAT IS THE CASE WITH MORE COMPLEX SYSTEMS?
molecules with multiple conformers and/or H-bonding capability
chiralchiral and chiralachiral molecular complexes chiral radicals
Conformers of 2-amino-1-propanol
3 torsional angles 25 conformers 10-15 conformers are predicted to
be present over 1% at room temperature 5 conformers have been
identified in the matrix isolation IR spectra R. Fausto, C. Cacela,
M. L. Duarte, J. Mol. Struct , 365 (2000) IR and VCD spectra of
R-2-amino-1-propanol
Matrix-isolation VCD 10 Matrix-isolation IR Neat liquid VCD Neat
liquid IR Wavenumber/ cm-1 G. Tarczay, E. Vass, G. Magyarfalvi,
Angew. Chem. Int. Ed. 45, 1775 (2006) Calculated and
matrix-isolation IR and VCD spectra of R-2-amino-1-propanol
(BPW91/TZ2P) IR (BPW91/TZ2P) G. Tarczay, E. Vass, G. Magyarfalvi,
Angew. Chem. Int. Ed. 45, 1775 (2006) Conformers of
Ac-Ala-NHMe
j B3LYP/6-31++G** gD dD aL eD bL(D) eL aD dL gL bL ~40% gL ~54% 0 f
dD ~5% 0 j eD ~0.1% IR spectrum of Ac-Ala-NHMe
bL gL dD Amide A vibrational mode Amide I and II vibrational modes
MI-IR Calculated Wavenumber / cm-1 Wavenumber / cm-1 G. Pohl, G.
Magyarfalvi, E. Vass, A. Perczel, G. Tarczay, to be submitted.
Experimental and calculated VCD spectra of Ac-Ala-NHMe
Wavenumber / cm-1 Ar matrix Solution (CH2Cl2) Calculated bL gL dD
DA - + G. Pohl, G. Magyarfalvi, E. Vass, A. Perczel, G. Tarczay to
be submitted. Rotatory strength surfaces of amide I vibrational
modes of the bL conformer of Ac-Ala-NHMe
j f j j-je j-je f-fe f-fe G. Pohl, G. Magyarfalvi, E. Vass, A.
Perczel, G. Tarczay, to be submitted. Potential energy surface
(PES) and rotatory strength surfaces (RSSs) of bL Ac-Ala-NHMe
(Amide I modes) PES DE /cm-1 r0 r0 j-je j-je re re f-fe f-fe G.
Pohl, G. Magyarfalvi, E. Vass, A. Perczel, G. Tarczay, to be
submitted. Calculated VCD and IR spectra of theg'Gg'
R-2-amino-1-propanolwater complex
4000 3500 3000 2500 2000 1500 1000 500 Wavenumber/cm-1 IR VCD G.
Tarczay, E. Vass, G. Magyarfalvi, Angew. Chem. Int. Ed. 45, 1775
(2006) Complexation of Ac-Ala-NHMe and water
8 K 15 K 8 K bL gL A 8 K H2O Wavenumber / cm-1 Matrix-isolation VCD
spectroscopy
ADVANTAGES Investigation of complex systems (multiple conformers,
complexes, radicals) Simultaneous determination of configuration
and conformation It can help the assignment of matrix isolation IR
spectra Neither aggregates nor complexes with solvents have to be
considered for theoretical calculations LIMITATIONS Maximum size of
the molecule that can be evaporated (Knudsen cell) Maximum size of
the molecule that can be calculated (parallel codes) DIFFICULTIES
thick and homogenous matrices are required (long deposition times)
light scattering on thick layers (long measurements) possible
artifacts due to non-parallel alignment, strength in window
material (CsI BaF2), interference, background (dual modulation)
Matrix 2006 Etvs University
Gyrgy Tarczay Gbor Magyarfalvi Elemr Vass Matrix isolation remains
an activity involving anti-social hours of work. Cradock and
Hinchliffe: Matrix Isolation, Cambridge University Press Gbor Bazs
Edit Mtyus Gbor Pohl