1. FOUR STRUCTURES OF TARTARIC ACID REVEALED IN THE GAS PHASE
V. CORTIJO, V. DIEZ, E.R. ALONSO, S. MATA, JOSE L. ALONSO
Lab. Espectroscopia y Bioespectroscopia
Edificio de Investigación QUIFIMA
Area de Química-Física. Parque Científico.
Unidad Asociada CSIC.
Universidad de Valladolid
Valladolid, Spain
International Symposium on Molecular Spectroscopy
72nd MEETING - JUNE 19-23, CHAMPAIGN-URBANA, ILLINOIS

2. Research in our group is devoted to :
*Rotational Spectra of Molecules of Astrophysical Interest
The combination of Lab. Data and Radioastronomy provides a power capability for the detection and conclusive identification of molecular
species in the ISM
Frequency Domain
Stark Modulation MW + MMW: 8  110 GHz
Frequency Modulation MMW and Sub-MMW : 50  1000 GHz
*Conformation and Structure of Biomolecules
Rotational studies of solid biomolecules by FTMW spectroscopy in a supersonic expansion combined with laser ablation techniques of vaporization
Time Domain
MB-FTMW: 2  26 GHz
LA-MB-FTMW: 2  10 GHz
LA-MB-FTMW: 4  26 GHz
CP-FTMW: 2  40 GHz

3. Cork of Ribera de Duero WINE
TARTARIC ACID
MOTIVATION OF THE WORK
The stereoisomer (R,R) is obtained exclusively from the natural residues in winemaking.
Cork of Ribera de Duero WINE
The enantiomerism phenomenon discovered by Louis Pasteur (1857) through enantioselective tartrate fermentations placed to tartaric acid as one of the most important organic compound.
Properties: Natural Antioxidant, Preservative and acidifying.
Relevant Industrial applications:
Organic and pharmaceutical chemistry
Cosmetics
Food and beverage industries
(R,R) Tartaric acid
m.p. 174C

4. The naturally occuring form of tartaric acid
Their properties are the result of the great hability of tartaric acid to create varios types of hydrogen bonds, closely related to its structure and the presence of multiple OH within it. 
Two chirality centers
Pair of enantiomers
Meso compound
(R,R) Tartaric acid
(S,S) Tartaric acid
The naturally occuring form of tartaric acid

5. STRUCTURAL INFORMATION AVAILABLE FOR (R,R) TARTARIC ACID
Condensed phases :
X-Ray
F. Stern and C. A. Beevers. The crystal structure of tartaric acid. Acta Crystallogr. 1950, 3, 341.
Y. Okaya, N. R. Stemple and M.I. Kay. Refinement of the structure of D-Tartaric acid by X-Ray and neutron diffraction. Acta Cryst. (1966). 21, 237.
THz-vibrational spectroscopy
Elewina M. Witko and Timothy M. Korter. Investigation of the low-frequency vibrations of the crystalline Tartaric acid using terahertz spectroscopy and solid-state density functional-theory. J. Phys. Chem. A. 2011, 115,
P.L. Polavarapu, C. S. Ewig and T. Chandramouly. Conformations of tartaric acid and its esters. J. Am. Chem. Soc., 1987, 109,
Jacek Gawronski, Krystyna Gawronska, Pawel Skowronek, Urzsula Rychlewska, Beata Warzajtis, Jacek Rychlewski, Marcin Hoffmann and Agnieszka Szarecka. Factors affecting conformation of (R,R) Tartaric acid ester, amide and nitrile derivates. X-Ray diffraction, Circular dichroism, nuclear magnetic resonance and ab initio studies Tetrahedrom, Vol. 53, Nº 17, , 1997.
Vibrational circular dichroism
H-NMR C-NMR
José Ascenso and Victor M. S. Gil. The conformations of tartaric acids in aqueous solution studied by 1H and 13C nuclear magnetic resonance. Can. J. Chem., 58, 1376 (1980).
Vibrational Raman Optical Activity
L. D. Barron. Raman optical activity of tartaric acid and related molecules. Tetrahedron, Vol 34, (1978).
L. D. Barron, A. R. Gargaro and L. Hecht. Experimental and ab initio theoretical vibrational Raman optical activity of tartaric acid. Spectrochimica Acta, Vol. 48A, Nº 8, , 1992.

6. BECAUSE IT IS A SOLID WITH HIGH MELTING POINT (174C)
TARTARIC ACID
Condensed phases results are only consistent with the existence of a trans configuration
Gauche
Trans G- T G+
DESPITE THE IMPORTANT ROLE OF TARTARIC ACID, THERE EXISTS NO DETAILED EXPERIMENTAL INFORMATION ABOUT ITS CONFORMATIONAL BEHAVIOR.
WHY?
BECAUSE IT IS A SOLID WITH HIGH MELTING POINT (174C)

7. Narrowband LA-MB-FTMW
Experimental Approach
Laser Ablation
Vaporization
Spectroscopic
Characterization
FT-MW
Supersonic Expansion
Gas Phase Isolation
Narrowband LA-MB-FTMW
Broadband LA-CP-FTMW

8. Our group and sugars, dipeptides, nucleosides….etc:
D-xylose. Phys.Chem. Chem. Phys., 2013, 15, 18243
Erythrose. Chem. Commun., 2013, 49, 10826
2-Deoxy-D-ribose. Angew. Chem. 2013, 125, 1 – 7
D-fructopyranose. ChemPhysChem., 2013, 14, 893 – 895
D-glucose. Chem. Sci., 2014, 5, 515
D-glucosamine. Phys. Chem. Chem. Phys., 2014,16,
α-D-galactose. Chem. Commun., 2015, 51,
Ketohexoses . Chem.E.J. 22, (2016)
Uridine. Angew.Chem.Int.Ed. 54, (2015)
Exoanomeric effect. J. Phys.Chem.Lett., 7, 845−850 (2016)
Gycine-Glycine. Angew.Chem.Int. Ed. 2017, 56,6420 – between others.....

9. FABRY-PEROT RESONATOR
Broadband Laser Ablation CP-FTMW
CP-FT-MW
Vaccum Chamber
FABRY-PEROT RESONATOR
Picosecond Laser
Picosecond LASER
CP-FTMW Spectrometer
Valladolid 2016
Valladolid 2012

10. EXPERIMENT :
LA-CP-FTMW
THE EXPERIMENT
Diffusion
pump
Jet
Laser

11. Broadband Fourier Transform: Operation
Gas pulse
Jet Ne
Laser pulse
Solid
sample
Rotary
Diffusion
pump
Laser
Nd:YAG laser

12. Broadband Fourier Transform: Operation
CP-FTMW
spectrometer
Gas pulse
Molecular emission Ne
Laser pulse
Chirped MW pulse
Rotary
Diffusion
pump
Detection

13. Broadband Fourier Transform: Operation
CP-FTMW
spectrometer
Gas pulse
Molecular emission Ne
Laser pulse
Chirped MW pulse
Rotary
Diffusion
pump
Detection
Detection
Frequency-domain
Time-domain FT

14. LA-CP-FTMW
Laser
Jet

15. Chirped MW pulse Detection
Gas pulse
Laser pulse
Jet
Chirped MW pulse
Detection
Time-domain
Frequency-domain FT

16. BROADBAND ROTATIONAL SPECTRA OF (R,R) TARTARIC ACID
Strong progressions of c-type R branch transitions were easily identified in the spectrum .
3 2,1 ← 2 1,1
2 2,0 ← 1 1,0
2 2,1 ← 1 1,1
3 2,2 ← 2 1,2 
J+12,J ← J1,J J+12,J-1 ← J1,J-1
3 1,2 ← 2 0,2
4 1,3 ← 3 0,3
5 1,4 ← 4 0,4 
 J+11,J ← J0,J
C2 symmetry conformer?
Selection rules

17. C2 C2 C2
A = T, G- o G+
C3 = s or a
C2 = s or a C2 C3

18. Searching for C2 symmetry conformers  G+a,a and G+s,s
Selection rules
Much weaker new c-type R-branch progressions were identified .
2 2,0 ← 1 1,0 
2 2,1 ← 1 1,1 
3 2,1 ← 2 1,1
3 2,2 ← 2 1,2

19. C2 C2
G+s,s was not found

20. After remove all lines corresponding to the conformers Ts,s and G+a,a an exhaustive inspection of the broadband spectrum allow us to find new b-type R-branch lines attributable to a third rotamer III. 
2 2,1 ← 1 1,0
2 2,0 ← 1 1,1
3 2,2 ← 2 1,1
3 2,1 ← 2 1,2
By an iterative process of fitting and prediction also a type R-branch rotational transitions were identified. 
5 1,5 ← 4 1,4
5 0,5 ← 4 0,4
4 1,3 ← 3 1,2
5 1,4 ← 4 1,3

21. v
Rotamer I  T s,s C2 C2
Rotamer II  G+a,a
Rotamer III  G-a,s

22. After remove all lines corresponding to Ts,s G+a,a and G-a,s conformers a set of a type R-branch rotational transitions were assigned to rotamer IV
By an iterative process of fitting and prediction also c-type R-branch transitions were measured. 
6 1,6 ← 5 1,5
6 0,6 ← 5 0,5
6 1,5 ← 5 1,4
5 1,5 ← 4 1,4
5 0,5 ← 4 0,4 
5 1,4 ← 4 1,3

23. Rotamer I  T s,s Rotamer II  G+a,a Rotamer III  G-a,sC2 C2
Rotamer II  G+a,a
Rotamer III  G-a,s
Rotamer IV  T s,a

24. Experimental Populations
THE CONFORMATIONAL PANORAMA OF NATURAL OCCURING TARTARIC ACID
Experimental Populations
NTs,s : NG-a,s : NG+a,a : NTs,a = 1 : 0.4 : 0.3 : 0.2.
T s,a
(649 cm-1)
OH…OH…OH…O
cis-carboxylic 2 3 E
G+ a,a
(318 cm-1) 3 2 C2
OH…OH…O
Close a six member ring 3 2
G- a,s
(317 cm-1)
OH…OH…OH…O
OH…O
close a seven member ring C2 3 2
T s,s
(0 cm-1)
Two OH…O
Two cis-carboxylic
Searching for more conformers ……
THANKS FOR YOUR ATTENTION
The most abundant species

25. Universidad de Valladolid Molecular Astrophysics
Research Funded by:
Contact :
Pr. José L. Alonso
GEM , Edificio Quifima, Unidad Asociada CSIC,
Universidad de Valladolid
Valladolid, Spain
POSTDOCTORAL POSITION AVAILABLE September 2017
Four years grant PhD thesis
September 2017
(FP/ ) / ERC-2013-SyG
Grant No
Grants CTQ P
CTQ P
CSD
Molecular Astrophysics
Grants: VA175U13
VA077U16