Showing papers on "Conformational isomerism published in 2005"

Spectroscopic characterization of the conformational states of the bis(trifluoromethanesulfonyl)imide anion (TFSI

Abstract: Ab initio calculations were combined with infrared and Raman studies to distinguish spectroscopically the two conformers of the bis(trifluoromethanesulfonyl)imide anion, (TFSI−). Spectra of crystalline LiTFSI complexes with organic ligands, where the anion adopts a known conformational state, are presented to confirm the calculated spectra. Several regions are identified where either the infrared or the Raman spectra contain separate bands for the two conformers. The conformational equilibrium between the transoid and cisoid rotamers is then illustrated from the infrared spectra of solutions of LiTFSI in aprotic solvents. The transoid form is found to be more stable than the cisoid form by about 2.2 kJ mol−1, in good agreement with the present and earlier theoretical predictions. It is also shown that the IR and Raman spectral changes coming from conformational isomerism have to be carefully distinguished from those due to ionic interactions. Copyright © 2005 John Wiley & Sons, Ltd.

Evidence of Conformational Equilibrium of 1-Ethyl-3-methylimidazolium in Its Ionic Liquid Salts: Raman Spectroscopic Study and Quantum Chemical Calculations

Abstract: Raman spectra of liquid 1-ethyl-3-methylimidazolium (EMI+) salts, EMI+BF4-, EMI+PF6-, EMI+CF3SO3-, and EMI+N(CF3SO2)2-, were measured over the frequency range 200−1600 cm-1. In the range 200−500 cm-1, we found five bands originating from the EMI+ ion at 241, 297, 387, 430, and 448 cm-1. However, the 448 cm-1 band could hardly be reproduced by theoretical calculations in terms of a given EMI+ conformer, implying that the band originates from another conformer. This is expected because the EMI+ involves an ethyl group bound to the N atom of the imidazolium ring, and the ethyl group can rotate along the C−N bond to yield conformers. The torsion energy for the rotation was then theoretically calculated. Two local minima with an energy difference of ca. 2 kJ mol-1 were found, suggesting that two conformers are present in equilibrium. Full geometry optimizations followed by normal frequency analyses indicate that the two conformers are those with planar and nonplanar ethyl groups against the imidazolium ring pl...

Stereoselective C-Glycosylation Reactions of Ribose Derivatives: Electronic Effects of Five-Membered Ring Oxocarbenium Ions

Abstract: The factors controlling the highly α-selective C-glycosylation of ribose derivatives were determined by examining the stereoselective reactions of 18 ribose analogues differing in substitution at C-2, C-3, and C-4. The lowest energy conformers of the intermediate oxocarbenium ions display the C-3 alkoxy group in a pseudoaxial orientation to maximize electrostatic effects. To a lesser extent, the C-2 substituent prefers a pseudoequatorial position, and the alkyl group at C-4 has little influence on conformational preferences. In all cases, the product was formed by stereoelectronically preferred inside attack on the lowest energy conformer.

Chain Conformations and Photoluminescence of Poly(di-n-octylfluorene)

Abstract: The diverse steady-state spectroscopic properties of poly(di-n-octylfluorene) are addressed from a molecular-level perspective. Modeling of representative oligomers support the experimental observation of at least three distinguishable classes of conformational isomers with differing chain torsion angles. One class appears to be populated by a single compact structural isomer, and this conforms to the so-called beta phase. A rigorous Franck-Condon analysis of the photoluminescence in conjunction with Frenkel-type exciton band structure calculations is performed. These results accurately reproduce all major spectral features of the photoabsorption and those of singlet exciton emission.

Hydrogen bonding and cooperativity in isolated and hydrated sugars: mannose, galactose, glucose, and lactose

Abstract: The conformation of phenyl-substituted monosaccharides (mannose, galactose, and glucose) and their singly hydrated complexes has been investigated in the gas phase by means of a combination of mass selected, conformer specific ultraviolet and infrared double resonance hole burning spectroscopy experiments, and ab initio quantum chemistry calculations. In each case, the water molecule inserts into the carbohydrate at a position where it can replace a weak intramolecular interaction by two stronger intermolecular hydrogen bonds. The insertion can produce significant changes in the conformational preferences of the carbohydrates, and there is a clear preference for structures where cooperative effects enhance the stability of the monosaccharide conformers to which the water molecule chooses to bind. The conclusions drawn from the study of monosaccharide−water complexes are extended to the disaccharide lactose and discussed in the light of the underlying mechanisms that may be involved in the binding of carbo...

Gauche effect in 1,2-difluoroethane. Hyperconjugation, bent bonds, steric repulsion.

Abstract: Natural bond orbital deletion calculations show that whereas the gauche preference arises from vicinal hyperconjugative interaction between anti C-H bonds and C-F* antibonds, the cis C-H/C-F* interactions are substantial (approximately 25% of the anti interaction). The established significantly >60 degrees FCCF dihedral angle for the equilibrium conformer can then be rationalized in terms of the hyperconjugation model alone by taking into account both anti interactions that maximize near 60 degrees and the smaller cis interactions that maximize at a much larger dihedral angle. This explanation does not invoke repulsive forces to rationalize the 72 degrees equilibrium conformer angle. The relative minimum energy for the trans conformer is the consequence of a balance between decreasing hyperconjugative stabilization and decreasing steric destabilization as the FCCF torsional angle approaches 180 degrees . The torsional coordinate is predicted to be strongly contaminated by CCF bending, with the result that approximately half of the trans --> gauche stabilization energy stems from mode coupling.

Comparative analysis of protein-bound ligand conformations with respect to catalyst's conformational space subsampling algorithms.

Abstract: We examined the quality of Catalyst's conformational model generation algorithm via a large scale study based on the crystal structures of a sample of 510 pharmaceutically relevant protein−ligand complexes extracted from the Protein Data Bank (PDB). Our results show that the tested algorithms implemented within Catalyst are able to produce high quality conformers, which in most of the cases are well suited for in silico drug research. Catalyst-specific settings were analyzed, such as the method used for the conformational model generation (FAST vs BEST) and the maximum number of generated conformers. By setting these options for higher fitting quality, the average RMS values describing the similarity of experimental and simulated conformers were improved from an RMS of 1.06 with max. 50 FAST generated conformers to an RMS of 0.93 with max. 255 BEST generated conformers, which represents an improvement by 12%. Each method provides best fitting conformers with an RMS value < 1.50 in more than 80% of all cas...

Folding structures of isolated peptides as revealed by gas-phase mid-infrared spectroscopy.

Abstract: To understand the intrinsic properties of peptides, which are determined by factors such as intramolecular hydrogen bonding, van der Waals bonding and electrostatic interactions, the conformational landscape of isolated protein building blocks in the gas phase was investigated. Here, we present IR-UV double-resonance spectra of jet-cooled, uncapped peptides containing a tryptophan (Trp) UV chromophore in the 1000-2000 cm(-1) spectral range. In the series Trp, Trp-Gly and Trp-Gly-Gly (where Gly stands for glycine), the number of detected conformers was found to decrease from six (Snoek et al., PCCP, 2001, 3, 1819) to four and two, respectively, which indicates a trend to relaxation to a global minimum. Density functional theory calculations reveal that the O-H in-plane bending vibration, together with the N-H in-plane bend ing and the peptide C=O stretching vibrations, is a sensitive probe to hydrogen bonding and, thus, to the folding of the peptide backbone in these structures. This enables the identification of spectroscopic fingerprints for the various conformational structures. By comparing the experimentally observed IR spectra with the calculated spectra, a unique conformational assignment can be made in most cases. The IR-UV spectrum of a Trp-containing nonapeptide (Trp-Ala-Gly-Gly-Asp-Ala-Ser-Gly-Glu) was recorded as well and, although the IR spectrum is less well-resolved (and it probably results from different isomers), groups of amide I (peptide C=O stretching) and amide II (N-H in-plane bending) bands can still be recognised, in agreement with predictions at the AM1 level.

Global search for minimum energy (H2O)n clusters, n = 3-5.

Abstract: The Gaussian-3 (G3) model chemistry method has been used to calculate the relative deltaG(o) values for all possible conformers of neutral clusters of water, (H2O)n, where n = 3-5. A complete 12-fold conformational search around each hydrogen bond produced 144, 1728, and 20,736 initial starting structures of the water trimer, tetramer, and pentamer. These structures were optimized with PM3, followed by HF/6-31G* optimization, and then with the G3 model chemistry. Only two trimers are present on the G3 potential energy hypersurface. We identified 5 tetramers and 10 pentamers on the potential energy and free-energy hypersurfaces at 298 K. None of these 17 structures were linear; all linear starting models folded into cyclic or three-dimensional structures. The cyclic pentamer is the most stable isomer at 298 K. On the basis of this and previous studies, we expect the cyclic tetramers and pentamers to be the most significant cyclic water clusters in the atmosphere.

The Strength of Parallel-Displaced Arene-Arene Interactions in Chloroform

Abstract: Triptycene-derived compounds have been prepared to serve as conformational equilibrium reporters for direct measurements of arene−arene interactions in the parallel-displaced orientation. A series of such compounds bearing arenes with different substituents were synthesized, and the ratios of the syn and anti conformers were determined by variable-temperature NMR spectroscopy. The syn conformer allows attached arenes to interact with each other while the anti conformer does not. The free energies derived from the syn/anti ratios in chloroform range from slightly positive (0.2 kcal/mol) to considerably negative (−0.98 kcal mol) values. The interactions between the arenes bearing electron-donating groups (EDG) are either negligible or slightly repulsive, while the interactions between arenes bearing electron-withdrawing groups (EWG) are attractive. Intermediate free energy values are obtained for those compounds bearing arenes with one EDG and one EWG.

Coded amino acids in gas phase: the shape of isoleucine.

Abstract: The solid α-amino acid isoleucine has been vaporized by laser ablation and expanded in a supersonic jet, where the molecular conformations of the isolated molecule were probed using Fourier transform microwave spectroscopy. Two conformers of neutral isoleucine have been detected in gas phase, the most stable being stabilized by an intramolecular hydrogen bond N−H···OC and a cis-COOH arrangement. The higher energy form is stabilized by an intramolecular hydrogen bond N···H−O. The sec-butyl side chain of the amino acid adopts the same configuration in the two observed conformers, with a staggered configuration at Cβ similar to that observed in valine and a trans arrangement of Cα and Cδ. Ab initio calculations at MP2/6-311++G(d,p) level reproduce satisfactorily the experimental results.

The presentation of an approach for estimating the intramolecular hydrogen bond strength in conformational study of β-Aminoacrolein

Abstract: All the plausible conformations of β-aminoacrolein (AMAC) have been investigated by the Bekes-Lee-Yang-Parr (B3LYP) nonlocal density functional with extended 6-311++G** basis set for studying the stability order of conformers and the various possibilities of intramolecular hydrogen bonding formation. In general the ketoamine (KA) conformers of AMAC, by mean average, are more stable than the corresponding enolimine (EI) and ketoimine (KI) analogues and this stability is mainly due to the π-electron resonance in these conformers that established by NH2 functional group. The contribution of resonance to the stability of chelated KA conformers is about 75.6 kJ/mol, which is greater than that of the hydrogen bond energy ( E HB =35.0 kJ/mol). The relative decreasing order of the various hydrogen bond energies was found to be: O–H⋯N imine (strong)>N amine -H⋯O keto (normal)>N imine -H⋯O hydroxyl (weak) > N imine -H⋯O keto (weak). Hydrogen bond energies for all systems were obtained from the method that we called related rotamers method (RRM). The topological properties of the electron density contributions for various type of intramolecular hydrogen bond have been analyzed in term of the Bader theory of atoms in molecules (AIM). The results of these calculations support the previous calculations, which obtained by the related rotamer methods.

Structural Selection by Microsolvation: Conformational Locking of Tryptamine

Abstract: The conformational space of tryptamine has been thoroughly investigated using rotationally resolved laser-induced fluorescence spectroscopy. Six conformers could be identified on the basis of the inertial parameters of several deuterated isotopomers. Upon attaching a single water molecule, the conformational space collapses into a single conformer. For the hydrogen-bonded water cluster, this conformer is identified unambiguously as tryptamine A. In the complex, the water molecule acts as proton donor with respect to the amino group. An additional interaction with one of the aromatic C-H bonds selectively stabilizes the observed conformer more than all other conformers. Ab initio calculations confirm much larger energy differences between the conformers of the water complex than between those of the monomers.

Gas Phase Formation of a 310-Helix in a Three-Residue Peptide Chain: Role of Side Chain-Backbone Interactions as Evidenced by IR−UV Double Resonance Experiments

Abstract: The first spectroscopic evidence for the gas-phase formation of helical structures in short peptide chains is reported, using the IR−UV double resonance technique and DFT quantum chemistry calculations. The study involves three chemically protected peptides, all based on the same Ac-(Ala)3-NH2, (Ac = acetyl, Ala = alanine) tripeptide, in which one of the Ala residues is substituted by the aromatic phenylalanine residue. For the three molecules, only one main conformer is observed in the supersonic expansion. IR analysis shows that the structure of this conformer is strongly dependent upon the substitution site: the helical 310-type structure is observed only when Phe occupies the central residue of the chain. The present work also emphasizes that the 310-helix formation does compete with other archetypal H-bonding patterns, such as 27-ribbon or mixed structures, whose relative energetics can be greatly influenced by a modest NH-aromatic interaction.

Detailed ab initio studies of the conformers and conformational distributions of gaseous tryptophan.

Abstract: A systematic and extensive conformational search has been performed to characterize the gas-phase tryptophan structures. A total of 648 unique trial structures were generated by allowing for all combinations of internal single-bond rotamers and were optimized at the DFT/B3LYP/6-311G* level of theory. A total of 45 local minima conformers were found. Further optimization of the 45 conformers with B3LYP and MP2/6-311++G** did not produce meaningful structural change, and accurate geometries, dipole moments, rotational constants, harmonic frequencies, and relative energies were then determined. Combined with statistical mechanics principles, the conformational distributions of gas-phase tryptophan at different temperatures are shown. The results clearly support the conclusion drawn by Compagnon et al. that only one dominant isomer existed in the molecular beam at 85 K and add further evidence that the supersonic jet expansion or embedding helium droplets did not produce an equilibrium distribution.

Three-Membered Ring or Open Chain Molecule − (F3C)F2SiONMe2 a Model for the α-Effect in Silicon Chemistry

Abstract: (F3C)F2SiONMe2 was prepared from LiONMe2 and F3CSiF3. It was characterized by gas IR and multinuclear solution NMR spectroscopy and by mass spectrometry. Its structure was elucidated by single crystal X-ray crystallography and by gas electron diffraction. (It exists as a conformer mixture.) Important findings were extremely acute SiON angles [solid 74.1(1)°, gas anti 84.4(32)° and gauche 87.8(20)°] and short Si···N distances [solid 1.904(2) A]. The bending potential of the SiON unit was calculated at the MP2/6-311++G(3df,2dp) level of theory and appears very flat and highly asymmetric. The calculated atomic charges (NPA) are counterintuitive to the expected behavior for a classical Si−N dative bond, as upon formation of the Si···N bond electron density is transferred mainly from oxygen to nitrogen, while the silicon charge is almost unaffected. Despite the molecular topology of a three-membered ring, the topology of the electron density shows neither a bond critical point between Si and N atoms nor a ring...

Internal rotation in propionic acid: near-infrared-induced isomerization in solid argon.

Abstract: The conformational system of propionic acid (CH3CH2COOH) is studied in solid argon. It is predicted by the ab initio calculations that this molecule has four stable conformers. These four structures are denoted Tt, Tg±, Ct, and Cg±, and they differ by the arrangement around the C−O and Cα−C bonds. The ground-state Tt conformer is the only form present at 8 K after deposition of an argon matrix containing propionic acid. For the CH3CH2COOH and CH3CH2COOD isotopologues, narrow-band excitation of the first hydroxyl stretching overtone of the conformational ground state promotes the Cα−C and C−O internal rotations producing the Tg± and Ct conformers, respectively. A subsequent vibrational excitation of the produced Tg± form induces its conversion to the Cg± conformer by rotation around the C−O bond. In the dark, all of the produced conformers decay to the conformational ground state at different rates. The decay kinetics and its temperature dependence allow the identification of the conformers by IR absorptio...

Secondary structures of short peptide chains in the gas phase: double resonance spectroscopy of protected dipeptides.

Abstract: The conformational structure of short peptide chains in the gas phase is studied by laser spectroscopy of a series of protected dipeptides, Ac-Xxx-Phe-NH(2), Xxx=Gly, Ala, and Val. The combination of laser desorption with supersonic expansion enables us to vaporize the peptide molecules and cool them internally; IR/UV double resonance spectroscopy in comparison to density functional theory calculations on Ac-Gly-Phe-NH(2) permits us to identify and characterize the conformers populated in the supersonic expansion. Two main conformations, corresponding to secondary structures of proteins, are found to compete in the present experiments. One is composed of a doubly gamma-fold corresponding to the 2(7) ribbon structure. Topologically, this motif is very close to a beta-strand backbone conformation. The second conformation observed is the beta-turn, responsible for the chain reversal in proteins. It is characterized by a relatively weak hydrogen bond linking remote NH and CO groups of the molecule and leading to a ten-membered ring. The present gas phase experiment illustrates the intrinsic folding properties of the peptide chain and the robustness of the beta-turn structure, even in the absence of a solvent. The beta-turn population is found to vary significantly with the residues within the sequence; the Ac-Val-Phe-NH(2) peptide, with its two bulky side chains, exhibits the largest beta-turn population. This suggests that the intrinsic stabilities of the 2(7) ribbon and the beta-turn are very similar and that weakly polar interactions occurring between side chains can be a decisive factor capable of controlling the secondary structure.

A Computational Study of [2.2]Cyclophanes

Abstract: A computational study of isomeric [2.2]cyclophanes, namely [2.2]paracyclophane 1, [2.2]metacyclophane 2, and [2.2]metaparacyclophane 3, has been carried out. For 1, geometry optimizations performed by various methods at different basis sets showed that MP2/6-31+G(d,p) and B3PW91/6-31+G(d,p) provide the best results in comparison to the X-ray data. Compound 1 has D(2) symmetry with distorted bridges. A conformational search was performed for [2.2]cyclophanes 2 and 3. Each cyclophane exists in two conformations which have different energies in the case of 3 but are degenerate in the case of 2. Relative energies and strain energies at the bridges follow the same order, indicating that the relief of bridge tension and repulsion between pi clouds are determining factors for the stability of [2.2]cyclophanes. Through a decomposition of strain energy, it can be concluded that both the rings or the bridges can absorb strain, but it depends on the conformer of butane that is considered in the calculation of SE(br). Changes in aromaticity of these compounds were evaluated by NICS and HOMA and were compared with benzene and xylenes dimers as models. Despite distortions from planarity and shortening and lengthening of the C-C bonds relative to the mean, the phenyl rings are aromatic. NICS suggests a concentration of electronic density between the rings as a result of bridging process. Computed MK, NPA, and GAPT charges were compared for the isomeric cyclophanes. The GIAO chemical shifts were calculated and indicate that 1 has a larger diamagnetic anisotropy than the other isomers.

Computational Study of Structures and Properties of Metallaboranes: Cobalt Bis(dicarbollide)

Abstract: A density functional study at the BP86/AE1 level is presented for the cobalt bis(dicarbollide) ion [3-Co-(1,2-C2B9H11)2]- (1) and selected isomers and rotamers thereof. Rotation of the two dicarbollide moieties with respect to each other is facile, as judged by the small energetic separation of the three rotamers located (within 11 kJ mol(-1)) and by the low barriers for their interconversion (at most 41 kJ mol(-1)). Among the isomers differing in carbon atom positions that contain two equivalent dicarbollide ligands, the 1,7 ("carbon apart") form [2-Co-(1,7-C2B9H11)2]- is the most stable, 121 kJ mol(-1) below 1. The electronic structure of 1 is characterized in terms of molecular orbitals, population analysis, and excitation energies from time-dependent density functional theory, relevant to UV/Vis spectroscopy. Experimental 11B NMR chemical shifts of 1 are reproduced to better than 5 ppm at the GIAO-B3LYP/II' level, and the computed delta(11B) values are only little affected by rotational averaging or the presence of a polarizable continuum. Larger such effects are found for the as-yet unknown 59Co chemical shift, for which a value in the range between -1800 and -2400 ppm is predicted. Even though the accuracy achieved for the theoretical delta(11B) values is somewhat lower than that for heteroboranes at conventional ab initio levels, the level of density functional employed can afford qualitatively reliable chemical shifts, which can be useful in assignments and structural refinements of heteroboranes containing transition metal.

Systematic ab initio studies of the conformers and conformational distribution of gas-phase tyrosine.

Abstract: A full structural assignment of the conformers of gaseous tyrosine is presented. A total of 1296 unique trial structures were generated by allowing for all combinations of internal single-bond rotamers and optimized at the B3LYP∕6-311G* level of theory and then subjected to further optimization at the B3LYP∕6-311++G** level. A total of 76 conformers are found and their dipole moments, rotational constants, and harmonic frequencies are determined. Accurate relative energies are given at the MP2∕6-311G(2df,p)∕∕B3LYP∕6-311++G** level of theory. Characteristic H-bonding types are classified and listed for all the conformers. The four most stable conformers display an intramolecular H bond, COOH⋯NH2, and an additional H-bonding interaction between the amino group and π electron of the aromatic ring. The results further confirm that the global minimum conformations of the aromatic amino acids have the same H-bonding type. Combined with statistical mechanics principles, conformational distributions at various te...

Spectroscopic Evidence for Gas-Phase Formation of Successive β-Turns in a Three-Residue Peptide Chain

Abstract: We report the first gas-phase spectroscopic study of a three-residue model of a peptide chain, Ac-Phe-Gly-Gly-NH2 (Ac = acetyl), using the IR/UV double resonance technique. The existence of at least five different conformers under supersonic expansion conditions is established, most of them exhibiting rather strong intramolecular H-bonds. One of the most populated conformers, however, exhibits a different H-bonding network characterized by two weak H-bonds. Comparison of the amide A and I/II experimental data with density functional theory calculations carried out on a series of selected conformations enables us to assign this conformer to two successive beta-turns along the peptide chain, the two H-bonds being of C10 type, i.e., each of them closing a 10-atom ring in the molecule. The corresponding form is found to be more stable than the 310 helix secondary structure (not observed), presumably because of specific effects due to the glycine residues.

Slow interconversion of enantiomeric conformers or atropisomers of anilide and urea derivatives of 2-substituted anilines

Abstract: N-Acylated 2-substituted anilines undergo slow Ar–N bond rotation, allowing in some cases isolation of enantiomeric or diastereoisomeric atropisomers and in others the determination of the rate of Ar–N bond rotation by NMR. 2-Iodoanilides bearing a branched N-substituent demonstrate sufficient enantiomeric stability to be resolvable, either by HPLC or by formation of diastereoisomeric lactanilide derivatives. For the first time, the rates of Ar–N rotation in 2-substituted N,N′-diarylureas have been established: they mainly fall in the region of 50–70 kJ mol−1 with a relatively weak dependence on substituent size.

Shape of 4(S)- and 4(R)-Hydroxyproline in Gas Phase

Abstract: The α-amino acids 4(S)-hydroxyproline and 4(R)-hydroxyproline have been studied under isolation conditions in gas phase using laser-ablation molecular-beam Fourier transform microwave spectroscopy. Two conformers of each molecule have been detected in the jet-cooled rotational spectrum. The most stable conformer in both molecules exhibits an intramolecular N···H−O hydrogen bond (configuration 1) between the hydrogen atom of the carboxylic group and the nitrogen atom. The second conformer is characterized by an intramolecular N−H···OC hydrogen bond (configuration 2). The conformers of 4(R)-hydroxyproline adopt a Cγ-exo puckering, while those of 4(S)-hydroxyproline present a Cγ-endo ring conformation. These ring conformations, which show the same propensity observed in collagen-like peptides, are stabilized by additional intramolecular hydrogen bonds involving the 4-hydroxyl group, with the exception of the most stable form of 4(S)-hydroxyproline for which a n−π* interaction between the oxygen atom of the 4...

Gas-phase models of γ turns: Effect of side-chain/backbone interactions investigated by IR/UV spectroscopy and quantum chemistry

Abstract: The conformations of laser-desorbed jet-cooled short peptide chains Ac–Phe–Xxx–NH2 (Xxx=Gly, Ala, Val, and Pro) have been investigated by IR/UV double resonance spectroscopy and density-functional-theory (DFT) quantum chemistry calculations. Singly γ-folded backbone conformations (βL-γ) are systematically observed as the most stable conformers, showing that in these two-residue peptide chains, the local conformational preference of each residue is retained (βL for Phe and γ turn for Xxx). Besides, β turns are also spontaneously formed but appear as minor conformers. The theoretical analysis suggests negligible inter-residue interactions of the main conformers, which enables us to consider these species as good models of γ turns. In the case of valine, two similar types of γ turns, differing by the strength of their hydrogen bond, have been found both experimentally and theoretically. This observation provides evidence for a strong flexibility of the peptide chain, whose minimum-energy structures are contr...

A Microwave and Quantum Chemical Study of the Conformational Properties and Intramolecular Hydrogen Bonding of 1-Fluorocyclopropanecarboxylic Acid

Abstract: The structural and conformational properties of 1-fluorocyclopropanecarboxylic acid have been explored by microwave spectroscopy and a series of ab initio (MP2/6-311++G(d,p) level), density functional theory (B3LYP/aug-cc-pVTZ level), and G3 quantum chemical calculations. Four “stable” conformers, denoted conformers I−IV, were found in the quantum chemical calculations, three of which (conformers I −III) were predicted to be low-energy forms. Conformer I was in all the quantum chemical calculations predicted to have the lowest energy, conformer III to have the second lowest energy, and conformer II to have the third lowest energy. Conformers II and III were calculated to have relatively large dipole moments, while conformer I was predicted to have a small dipole moment. The microwave spectrum was investigated in the 18−62 GHz spectral range. The microwave spectra of conformers II and III were assigned. Conformer I was not assigned presumably because its dipole moment is comparatively small. Conformer II i...