Conformation-specific spectroscopy and populations of diastereomers of a model monolignol derivative: chiral effects in a triol chain.
ABSTRACT Single-conformation spectroscopy of two diastereomers of 1-(4-hydroxy-3-methoxyphenyl)propane-1,2,3-triol (HMPPT) has been carried out under isolated, jet-cooled conditions. HMPPT is a close analog of coniferyl alcohol, one of the three monomers that make up lignin, the aromatic biopolymer that gives structural integrity to plants. In HMPPT, the double bond of coniferyl alcohol has been oxidized to produce an alkyl triol chain with chiral centers at C(α) and C(β), thereby incorporating key aspects of the β-O-4 linkage between monomer subunits that occurs commonly in lignin. Both (R,S)- and (R,R)-HMPPT diastereomers have been synthesized in pure form for study. Resonant two-photon ionization (R2PI), UV hole-burning (UVHB)/IR-UV hole-burning (IR-UV HB), and resonant ion-dip infrared (RIDIR) spectroscopy have been carried out, providing single-conformation UV spectra in the S(0)-S(1) region (35200-35800 cm(-1)) and IR spectra in the hydride stretch region. Five conformers of (R,S)- and four conformers of (R,R)-HMPPT are observed and characterized, leading to assignments for all nine conformers. Spectroscopic signatures for α-β-γ, γ-β-α, and α-γ-β-π chains and two cyclic forms [(αβγ) and (αγβ)] of the glycerol side chain are determined. Infrared ion-gain (IRIG) spectroscopy is used to determine fractional abundances for the (R,S) diastereomer and constrain the populations present in (R,R). The two diastereomers have very different conformational preferences. More than 95% of the population of (R,R) configures the glycerol side chain in a γ-β-α triol chain, while in (R,S)-HMPPT, 51% of the population is in α-β-γ chains that point in the opposite direction, with an additional 21% of the population in H-bonded cycles. The experimental results are compared with calculations to provide a consistent explanation of the diastereomer-specific effects observed.
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ABSTRACT: The spectroscopy of two flexible hydrocarbons, 1,2-diphenylethane (DPE) and 2,2,2-paracyclophane (TCP) is presented, and a predictive theoretical model for describing the alkyl CH stretch region of these hydrocarbons is developed. Ultraviolet hole-burning spectroscopy identified two isomers of DPE and a single conformation of TCP present in the supersonic jet expansion. Through the analysis of the ground state low-frequency vibronic spectroscopy obtained by dispersed fluorescence, conformational assignments were made for both DPE and TCP. The two isomers of DPE were found to retain the low energy structures of butane, being present in both the gauche and anti structures. TCP forms a C(2) symmetric structure, differing from the predicted lower energy C(3) conformation by the symmetry of the ethano bridges (-CH(2)CH(2)-) linking the phenyl substituents. Resonant ion-dip infrared spectroscopy is used to record single-conformation IR spectra of the two conformers of DPE and the single conformer of TCP in the alkyl CH stretch region and in the mid-IR that covers the CH bend fundamentals. A local mode Hamiltonian that incorporates cubic stretch-bend coupling is developed. Its parameters are obtained from density functional theory methods. Full dimensional calculations are compared to those that use reduced dimensional Hamiltonians in which anharmonic CH stretches and scissor modes are Fermi coupled. Excellent agreement is found. Scale factors of select terms in the reduced dimensional Hamiltonian are determined by fitting the theoretical Hamiltonian to the anti-DPE spectrum. The scaled Hamiltonian is then used to predict successfully structures for the remaining lower symmetry experimentally determined spectra in the alkyl CH stretch region.The Journal of Chemical Physics 02/2013; 138(6):064308. · 3.12 Impact Factor
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ABSTRACT: The dynamics of structure evolution of nanodiamonds ranging from 22 to 318 atoms of various shapes is studied by density functional tight-binding molecular dynamics. The spherical and cubic nanodiamonds can be transformed into fullerene-like structures upon heating. A number of the transformed fullerenes consist of pentagons and hexagons only. Others contain squares, heptagons, and octagons. One simulated fullerene is an isomer of C(60). The temperature of the transformation depends on the size, shape, and orientation of initial cluster. To be transformed into onion-like fullerenes, the spherical nanodiamonds should have 200 atoms or more, while the cubic ones require 302 atoms or more. The time-resolved energy profiles of all the transformations clearly reveal three-stage transformation character. During the first stage, the energy reduces quickly due to converting sp(3) carbon with dangling bond at the surface into sp(2) one, and the formation of partial sp(2) envelope wrapping the cluster. For the second stage, energy decreases slowly. The remaining interior carbon atoms come to the surface through the hole in the sp(2) envelope, and similar amount of sp(3) and sp(2) atoms coexist. The third stage involves the closure of holes, accompanied by the detachment of C(2) molecules and carbon chains from the edges. The energy decreases relatively fast in this stage. The proposed three-stage transformation pathway holds for all the simulations performed in this work, including those with the instant heating.The Journal of Physical Chemistry A 06/2011; 115(30):8327-34. · 2.77 Impact Factor
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ABSTRACT: Ultraviolet spectroscopy of the G- and S-type lignin subunits, guaiacol (G) and syringol (S), along with their para-methylated derivatives 4-methylguaiacol (4-MG) and 4-methylsyringol (4-MS), has been carried out in the cold, isolated environment of a supersonic jet. The excitation spectra and dispersed fluorescence (DFL) spectra of G and 4-MG show strong S0-S1 origins and Franck-Condon activity involving both the ring modes typical of aromatic derivatives, and the four lowest frequency out-of-plane modes (a") and lowest in-plane mode (a') involving the OH and OCH3 groups. The four low-frequency out-of-plane modes undergo extensive Duschinsky mixing between the ground and excited state. In 4-MG, combination bands involving methyl rotor levels with out-of-plane modes appeared with surprisingly high intensity, indicating a high degree of hindered rotor-vibration coupling in both S0 and S1. These mixing effects accompany the change in geometry upon π-π∗ electronic excitation going from a planar ground state to a non-planar excited state. Time-dependent density functional theory (TDDFT M05-2X∕6-311++G(d,p)) calculations predict a geometric distortion along the out-of-plane oxygen flapping coordinate, yielding a double minimum potential in S1 with a barrier to planarity of 195 cm(-1) in G. The excitation spectrum of S and 4-MS showed a much higher degree of spectral congestion and a larger geometry change evident by a shifted intensity distribution peaking ∼300 cm(-1) above the electronic origin. TDDFT calculations predict a larger geometry change in S compared with G, with the OH and H-bonded methoxy groups displaced in opposite directions above∕below the ring plane. Dispersed fluorescence from all S1 excited state levels in S∕4-MS yield only broad emission peaking far to the red of the excitation wavelength (-4500 cm(-1)). Several hypotheses regarding the source of this broad, redshifted emission were tested, but the cause remains unclear. p-Methylation was found to significantly redshift the UV absorption in both 4-MG and 4-MS, and methyl rotor transitions were assigned in both allowing for the determination of the shape and barrier heights of their respective potentials. These results provide a foundation for the discrimination of G- and S-chromophores in lignin oligomers, and demonstrate the potential for site-selective absorption.The Journal of Chemical Physics 10/2013; 139(14):144313. · 3.12 Impact Factor