We use high-resolution rotational spectroscopy to investigate the structural intricacies of the lactone form of mevalonic acid, precursor of the mevalonate pathway. By combining microwave spectroscopy with supersonic expansions and quantum-chemical calculations, we determine the two most stable conformations of the precursor. Complementary micro-solvation studies reveal that aggregation of the first water molecule induces a substantial structural rearrangement comprising a hydroxy rotation and an endocyclic core torsion to create a favourable geometry to accommodate the water molecule. We discuss the conformational aspects of the precursor in isolation and under micro-hydrated conditions.
REFERENCES
1.
I.
Buhaescu
and H.
Izzedine
, “Mevalonate pathway: A review of clinical and therapeutical implications
,” Clin. Biochem.
40
, 575
–584
(2007
).2.
P. J.
Mullen
, R.
Yu
, J.
Longo
, M. C.
Archer
, and L. Z.
Penn
, “The interplay between cell signalling and the mevalonate pathway in cancer
,” Nat. Rev. Cancer
16
, 718
–731
(2016
).3.
W.
Caminati
, P.
Moreschini
, and P. G.
Favero
, “The hydrogen bond between water and aromatic bases of biological interest: Rotational spectrum of pyridazine–water
,” J. Phys. Chem. A
102
, 8097
–8100
(1998
).4.
L. B.
Favero
and W.
Caminati
, “Hydrated complexes of atmospheric interest: Rotational spectrum of diacetyl–water
,” J. Phys. Chem. A
113
, 14308
–14311
(2009
).5.
C.
Pérez
, J. L.
Neill
, M. T.
Muckle
, D. P.
Zaleski
, I.
Peña
, J. C.
López
, J. L.
Alonso
, and B. H.
Pate
, “Water-water and water-solute interactions in microsolvated organic complexes
,” Angew. Chem., Int. Ed.
54
, 979
–982
(2015
).6.
E. G.
Schnitzler
, C.
Badran
, and W.
Jäger
, “Contrasting effects of water on the barriers to decarboxylation of two oxalic acid monohydrates: A combined rotational spectroscopic and ab initio study
,” J. Phys. Chem. Lett.
7
, 1143
–1147
(2016
).7.
C.
Pérez
, A.
Krin
, A. L.
Steber
, J. C.
López
, Z.
Kisiel
, and M.
Schnell
, “Wetting camphor: Multi-isotopic substitution identifies the complementary roles of hydrogen bonding and dispersive forces
,” J. Phys. Chem. Lett.
7
, 154
–160
(2016
).8.
S.
Blanco
, P.
Pinacho
, and J. C.
López
, “Hydrogen-bond cooperativity in formamide2-water: A model for water-mediated interactions
,” Angew. Chem., Int. Ed.
55
, 9331
–9335
(2016
).9.
S. R.
Domingos
, C.
Pérez
, and M.
Schnell
, “Communication: Structural locking mediated by a water wire: A high-resolution rotational spectroscopy study on hydrated forms of a chiral biphenyl derivative
,” J. Chem. Phys.
145
, 161103
(2016
).10.
E. G.
Schnitzler
, N. A.
Seifert
, S.
Ghosh
, J.
Thomas
, Y.
Xu
, and W.
Jäger
, “Hydration of the simplest α-keto acid: A rotational spectroscopic and ab initio study of the pyruvic acid-water complex
,” Phys. Chem. Chem. Phys.
19
, 4440
–4446
(2017
).11.
G. G.
Brown
, B. C.
Dian
, K. O.
Douglass
, S. M.
Geyer
, S. T.
Shipman
, and B. H.
Pate
, “A broadband Fourier transform microwave spectrometer based on chirped pulse excitation
,” Rev. Sci. Instrum.
79
, 053103
(2008
).12.
B. G.
Park
and R. W.
Field
, “Perspective: The first ten years of broadband chirped pulse Fourier transform microwave spectroscopy
,” J. Chem. Phys.
144
, 200901
(2016
).13.
D.
Schmitz
, V.
Alvin Shubert
, T.
Betz
, and M.
Schnell
, “Multi-resonance effects within a single chirp in broadband rotational spectroscopy: The rapid adiabatic passage regime for benzonitrile
,” J. Mol. Spectrosc.
280
, 77
–84
(2012
).14.
C.
Pérez
, S.
Lobsiger
, N. A.
Seifert
, D. P.
Zaleski
, B.
Temelso
, G. C.
Shields
, Z.
Kisiel
, and B. H.
Pate
, “Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer
,” Chem. Phys. Lett.
571
, 1
–15
(2013
).15.
M.
Frisch
, G.
Trucks
, H.
Schlegel
, G.
Scuseria
, M.
Robb
, J.
Cheeseman
, G.
Scalmani
, V.
Barone
, B.
Mennucci
, G.
Petersson
, H.
Nakatsuji
, M.
Caricato
, X.
Li
, H.
Hratchian
, A.
Izmaylov
, J.
Bloino
, G.
Zheng
, J.
Sonnenberg
, M.
Hada
, M.
Ehara
, K.
Toyota
, R.
Fukuda
, J.
Hasegawa
, M.
Ishida
, T.
Nakajima
, Y.
Honda
, O.
Kitao
, H.
Nakai
, T.
Vreven
, J.
Montgomery
, J.
Peralta
, F.
Ogliaro
, M.
Bearpark
, J.
Heyd
, E.
Brothers
, K.
Kudin
, V.
Staroverov
, R.
Kobayashi
, J.
Normand
, K.
Raghavachari
, A.
Rendell
, J.
Burant
, S.
Iyengar
, J.
Tomasi
, M.
Cossi
, N.
Rega
, J.
Millam
, M.
Klene
, J.
Knox
, J.
Cross
, V.
Bakken
, C.
Adamo
, J.
Jaramillo
, R.
Gomperts
, R.
Stratmann
, O.
Yazyev
, A.
Austin
, R.
Cammi
, C.
Pomelli
, J.
Ochterski
, R.
Martin
, K.
Morokuma
, V.
Zakrzewski
, G.
Voth
, P.
Salvador
, J.
Dannenberg
, S.
Dapprich
, A.
Daniels
, O.
Farkas
, J.
Foresman
, J.
Ortiz
, J.
Cioslowski
, and D.
Fox
, gaussian 09, Revision 2, Gaussian, Inc.
, 2009
.16.
K.
Chruszcz-Lipska
, A.
Jaworska
, E.
Szczurek
, and M.
Baranska
, “(-)-R-Mevalonolactone studied by ROA and SERS spectroscopy
,” Chirality
26
, 453
–461
(2014
).17.
Y.
Zhao
and D. G.
Truhlar
, “The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other functionals
,” Theor. Chem. Acc.
120
, 215
–241
(2008
).18.
S.
Grimme
, J.
Antony
, S.
Ehrlich
, and H.
Krieg
, “A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu
,” J. Chem. Phys.
132
, 154104
(2010
).19.
S.
Grimme
, S.
Ehrlich
, and L.
Goerigk
, “Effect of the damping function in dispersion corrected density functional theory
,” J. Comput. Chem.
32
, 1456
–1465
(2011
).20.
J.
Zhang
and M.
Dolg
, “ABCluster: The artificial bee colony algorithm for cluster global optimization
,” Phys. Chem. Chem. Phys.
17
, 24173
–24181
(2015
).21.
C. M.
Western
, “PGOPHER: A program for simulating rotational, vibrational and electronic spectra
,” J. Quant. Spectrosc. Radiat. Transfer
186
, 221
(2017
).22.
J.
Kraitchman
, “Determination of molecular structure from microwave spectroscopic data
,” Am. J. Phys.
21
, 17
–24
(1953
).23.
Z.
Kisiel
, “Least-squares mass-dependence molecular structures for selected weakly bound intermolecular clusters
,” J. Mol. Spectrosc.
218
, 58
–67
(2003
).24.
M. J.
Tubergen
, C. R.
Torok
, and R. J.
Lavrich
, “Effect of solvent on molecular conformation: Microwave spectra and structures of 2-aminoethanol van der Waals complexes
,” J. Chem. Phys.
119
, 8397
–8403
(2003
).25.
B. M.
Giuliano
and W.
Caminati
, “Isotopomeric conformational change in anisole-water
,” Angew. Chem., Int. Ed.
44
, 603
–606
(2005
).26.
H.
Fricke
, K.
Schwing
, A.
Gerlach
, C.
Unterberg
, and M.
Gerhards
, “Investigations of the water clusters of the protected amino acid Ac-Phe-OMe by applying IR/UV double resonance spectroscopy: Microsolvation of the backbone
,” Phys. Chem. Chem. Phys.
12
, 3511
–3521
(2010
).27.
A. R.
Conrad
, N. H.
Teumelsan
, P. E.
Wang
, and M. J.
Tubergen
, “A spectroscopic and computational investigation of the conformational structural changes induced by hydrogen bonding networks in the glycidol-water complex
,” J. Phys. Chem. A
114
, 336
–342
(2010
).28.
H.
Zhu
, M.
Blom
, I.
Compagnon
, A. M.
Rijs
, S.
Roy
, G.
von Helden
, and B.
Schmidt
, “Conformations and vibrational spectra of a model tripeptide: Change of secondary structure upon micro-solvation
,” Phys. Chem. Chem. Phys.
12
, 3415
–3425
(2010
).29.
J.
Thomas
, O.
Sukhorukov
, W.
Jäger
, and Y.
Xu
, “Direct spectroscopic detection of the orientation of free OH groups in methyl lactate-(water)1,2 clusters: Hydration of a chiral hydroxy ester
,” Angew. Chem., Int. Ed.
53
, 1156
–1159
(2014
).30.
B.
Jeziorski
, R.
Moszynski
, and K.
Szalewicz
, “Perturbation theory approach to intermolecular potential energy surfaces of van der Waals complexes
,” Chem. Rev.
94
, 1887
–1930
(1994
).31.
T. M.
Parker
, L. A.
Burns
, R. M.
Parrish
, A. G.
Ryno
, and C. D.
Sherrill
, “Levels of symmetry adapted perturbation theory (SAPT). I. Efficiency and performance for interaction energies
,” J. Chem. Phys.
140
, 094106
(2014
).32.
J. M.
Turney
, A. C.
Simmonett
, R. M.
Parrish
, E. G.
Hohenstein
, F. A.
Evangelista
, J. T.
Fermann
, B. J.
Mintz
, L. A.
Burns
, J. J.
Wilke
, M. L.
Abrams
, N. J.
Russ
, M. L.
Leininger
, C. L.
Janssen
, E. T.
Seidl
, W. D.
Allen
, H. F.
Schaefer
, R. A.
King
, E. F.
Valeev
, C. D.
Sherrill
, and T. D.
Crawford
, “Psi4: An open-source ab initio electronic structure program
,” Wiley Interdiscip. Rev.: Comput. Mol. Sci.
2
, 556
–565
(2012
).© 2017 Author(s).
2017
Author(s)
You do not currently have access to this content.
