r. d. suenram, justin lindsay neill, jason j. pajski, gordon g. brown, brooks h. pate department of...
TRANSCRIPT
R. D. Suenram, Justin Lindsay Neill, Jason J. Pajski, Gordon G. Brown, Brooks H. Pate
Department of Chemistry, University of Virginia, McCormick Rd., P.O. Box 400319, Charlottesville, VA 22904
Michael Tubergen
Department of Chemistry, Kent State University, Kent, Ohio 44242
BROADBAND ROTATIONAL SPECTRA OF THE HYDROXY
BUTYRIC ACID SYSTEM
Gamma Hydroxybutyric Acid
• History of abuse since the 1980’s
• Originally thought to have anabolic effects to increase muscle mass
• In 2000 it became a Federally controlled substance and was designated a Schedule I depressant
• Active field of study by Forensic chemists
Gamma Hydroxybutyric Acid
• GC analysis is difficult because of high polarity and thermal instability.
• Thus conversion to derivatives is necessary– Gamma butyrolactone– Silyl derivatives
Hydroxybutyric Acids
Hbapic1.jpg
B-Hydroxybutyric acid
G-butyrolactoneG-Hydroxybutyric acid
A-Hydroxybutyric acid
11 GHz CP-FTMW Spectrometer
Pulse Monitor
12 GHz Oscilloscope (40 Gs/s)
Free Induction Decay
0.5 – 11.5 GHz
Arbitrary Waveform Generator Chirped Pulse
Frequency Sweep
4 GS/sx8
7.5 - 18.5 GHz
TWTAmplifier
FID acquisition and Fourier transform
9.9 GHz PDRO
2 GHz Bandwidth
Nozzle Sample Feed
18.99 GHz PDRO
AHB Conformer I
6.0 10.0 15.0 19.0
Frequency in GHz
AHB Experimental
AHB Conf I sim
*
*
*
* **
*
AHB Conformer II Spectrum
6.0 10.0 15.0 19.0
Frequency in GHz
AHB Experimental minus Conf I
AHB Conf 2 Sim
AHB Structures
Gauche-1Trans-1
Summary of AHB ResultsConformer gauche- 1 gauche- 2 trans- 1 trans- 2
b3lyp/6- 31+g(d,p)
E (hartree) - 382.96 - 382.956325760 - 382.960174762 - 382.956809576Relative E (1/ cm) 89.06 844.7 0.0 738.6
A (MHz) 3382.68 3538.59 4478.06 4423.90B (MHz) 2219.87 2192.30 1808.60 1743.22C (MHz) 1762.97 1682.79 1403.08 1451.30
mua (D) 0.63 1.15 0.47 0.08mub (D) 2.22 0.79 2.33 0.45muc (D) 0.56 0.04 0.03 1.99
gauche fit trans fit
A (MHz) 3371.53 4507.98B (MHz) 2280.10 1832.72C (MHz) 1821.57 1420.03
mua (D)mub (D) mub > mua ~ muc mub > muamuc (D) not observed
BHB Spectrum
Observed Spectrum
6.5 8.5 10.5 12.5 14.5 16.5 18.5
Frequency (GHz)
BHB simulated Spectrum
Lactone Spectrum (Gonzalez, et. al. J. Mol. Struct. 223 (1990))
Gauche and Trans BHB
Summary of BHB ResultsConformer gauche- 1 gauche- 2 trans- 1 trans- 2
b3lyp/6- 31+g(d,p)
E (hartree) - 382.963420487 - 382.960852574 - 382.965594014 - 382.962147811Relative E (1/ cm) 477.0 1040.6 0.0 756.3
A (MHz) 4507.79 4187.88 5402.30 5135.98B (MHz) 1755.73 1877.46 1611.39 1651.17C (MHz) 1623.95 1649.93 1310.67 1316.23
mua (D) 1.7784 0.0439 1.4010 0.0679mub (D) 2.1337 0.0613 2.1916 0.2826muc (D) 0.0555 0.4373 0.5647 0.2590
Experimental
A (MHz) 5422.4B (MHz) 1620.1C (MHz) 1334.3
mua (D)mub (D) mub > mua > mucmuc (D)
GHB and GBL
Gamma Hydroxybutyric Acid Gamma Butyrolactone
GBL Spectrum
6.0 10.0 15.0 19.0
Frequency in GHz
GBL Experimental
GBL Simulated
A = 7279.8 MHzB = 3585.4 MHzC = 2562.5 MHz
GHB Survey
6.0 10.0 15.0 19.0
Frequency in GHz
GHB Experimental
GBL Spectrum
Subtracted spectrum
Subtracted spectra1. GBL + all 13C isotopomers2. EtAc3. Water dimer
Ab Initio Conformers GHB
E = 0 cm-1 E = 3 cm-1
E = 95 cm-1 E = 160 cm-1
GHB ConformersZPE corrected MP2 optimized constants
MP2 / 6-311++G**E / cm-1 A B C
0 4310 1825 16323 4625 1546 147295 4411 1897 1570
160 6428 1216 1090220 4767 1492 1421326 6355 1190 1099348 4983 1709 1349350 4008 1951 1597411 6426 1206 1146429 5946 1283 1195469 6290 1246 1106475 6201 1271 1180481 3990 1922 1730530 6346 1206 1131554 8286 1053 951605 8220 1046 947
Summary
• Hydroxybutyric acids have internal H-bond
• Hydroxyl H to carbonyl oxygen is preferred
• Theory and experiment agree - generally
• For the GHB system, the lactone is preferred for analysis because of stability and intense spectrum
Acknowledgements
Funding:• NSF Chemistry and MRI Program• University of Virginia