DANIEL P. ZALESKI, JUSTIN L. NEILL, AND BROOKS H. PATE Department of Chemistry, University of Virginia, McCormick Rd., P.O. Box 400319, Charlottesville,

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DANIEL P. ZALESKI, JUSTIN L. NEILL, AND BROOKS H. PATE Department of Chemistry, University of Virginia, McCormick Rd., P.O. Box , Charlottesville, VA EWA BIALKOWSKA-JAWORSKA AND ZBIGNIEW KISIEL Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, Warszawa, Poland. Structure Study of the Lactide Molecules By Chirped-Pulse FTMW Spectroscopy The Ohio State 66 th International Symposium on Molecular Spectroscopy, June 22 nd, 2011.

Terminology Referring to the chirality of the lactic acid monomers Not the chirality of the lactide unit

3,6-Dimethyl-1,4-Dioxane-2,5-Dione Homo-Chiral Hetero-Chiral G. J. van Hummel, S. Harkema, F. E. Kohn, and J. Feijen. Acta. Cryst., B38, (1982), Hetero lactic acid dimer has a small calculated dipole ~0.3 D (M052X/6-31+G(d,p) Lactide forms from 2 lactic acid molecules, loses 2 water molecules 6-member cyclic diester

Experimental Gordon G. Brown, Brian C. Dian, Kevin O. Douglass, Scott M. Geyer, Steven T. Shipman, and Brooks H. Pate. Rev. Sci. Instrum. 79, , (2008). Originally assigned in a heated racemic lactic acid sample: 100 °C, 45 psi, neon Acquired chirally pure commercial lactide sample: 30 psi, 150 °C x3 24 Gs/s AWG

Heated lactide spectrum

Center of Symmetry – Doubled Isotope Intensities Intensities can determine equivalent positions Simulated isotopes going down are color-coded to left image Isotopes

Lactide-RR M052X/ G(d,p) EXPMP2/6-31G(d,p) A (MHz) (89) B (MHz) (31) C (MHz) (46)822.3 ΔJK (kHz)0.137(28) ΔK (kHz)0.119(25) M052X/ G(d,p): 1027 cm -1 barrier to internal rotation EXPMP2/6-31G(d,p) μ A (D)00 μ B (D)00 μ C (D)1.0*X2.83 Δ i (amu Å 2 ) lines 14 kHz rms

Lactide-RS EXPMP2/6-31G(d,p) A (MHz) (11) B (MHz) (94) C (MHz) (11)901.1 ΔJ (kHz)0.048(14) ΔJK (kHz)-0.038(54) ΔK (kHz)0.192(51) δK (kHz)0.070(68) M052X/ G(d,p): 910 cm -1 (axial) and 1063 cm -1 (equatorial) barriers to internal rotation M052X/ G(d,p) EXPMP2/6-31G(d,p) μ A (D)00.26 μ B (D)0.25*X0.58 μ C (D)1.0*X2.52 Δ i (amu Å 2 ) lines 14 kHz rms

Boat vs Chair Chair is not a minimum Boat is the detected structure M052X/ G(d,p)

O-O- O+O+

Possible Lactide+Water Structures a b EXPab A (MHz) B (MHz) C (MHz) Energy (cm -1 )-5370 M052X/ G(d,p)

Lactide-RR+Water A(O + ) (MHz) A(O - ) (MHz) (40) (56) B(O + ) (MHz) B(O - ) (MHz) (30) (56) C(O + ) (MHz) C(O - ) (MHz) (33) (79) ΔJ(O + ) (kHz)0.3376(29) ΔJK(O + ) (kHz)-0.696(10) ΔK(O + ) (kHz)1.513(12) δJ(O + ) (kHz)0.1233(15) EXPM052X/ G(d,p) μ A (D)1.0*X2.42 μ B (D)1.0*X2.36 μ C (D)1.25*X2.92 Δ i (amu Å 2 ) lines 9 kHz rms

Conclusions  Assigned unambiguously the homo- and hetero-chiral lactides Including a Kraitchman substitution structure for the homo-chiral lactide Electronic structure theory very accurately calculates these structures Autofitting routines, library-free detections  Assigned a potential homo-chiral lactide-water complex Future experiments include isotopically enriched H 2 18 O and D 2 O. A. L. Steber, J. L. Neill, M. T. Muckle, B. H Pate, and D. F. Plusquellic. Strategies for Complex Mixture Analysis in Broadband Microwave Spectroscopy. The Ohio State 65 th International Symposium on Molecular Spectroscopy. June 22, 2010.

Acknowledgments Award Number CHE