Metabolic composition and authenticity evaluation of bergamot essential oil assessed by nuclear magnetic resonance spectroscopy.

In this work, a sample of pure and certified bergamot essential oil (BEO) was extensively studied for the first time directly by NMR spectroscopy with the aim of investigating its metabolic composition, quantifying the main components of this complex natural matrix and simultaneously assessing whether the NMR technique is able to highlight possible frauds to which this high-cost product may be subjected. Eleven low molecular weight compounds have been identified by using 1D H and C-{H} NMR experiments, 2D homo- and heteronuclear correlation NMR spectra, and 2D H DOSY experiments; the most abundant of them, i.e.

Phase behavior of hard C_{2h}-symmetric particle systems.

Using Monte Carlo numerical simulation, this work sketches the phase diagram of systems of certain hard C_{2h}-symmetric particles, formed by gluing two aligned and displaced hard spherocylinders with a cylindrical-length-to-diameter ratio realistically, if viewed not only from the lyotropic colloidal liquid-crystal side but also from the thermotropic low-molecular-mass liquid-crystal side, equal to 5, as a function of the displacement. Several distinctive phases are observed, such as a nonperiodic smectic-B-like phase, a nonperiodic smectic-H-like phase, a smectic-C phase, and a short-layer-spacing uniaxial smectic-A phase but no biaxial nematic phase.

Assessing the stable conformations of ibuprofen in solution by means of Residual Dipolar Couplings.

Detailing the conformational equilibria between global and local minimum energy structures of anti-inflammatory α-arylpropionic acids directly in solution is of the utmost importance for a better understanding of the structure-activity relationships, hence providing valuable clues for rational structure-based drug design studies. Here the conformational preferences of the widely used pharmaceutical ibuprofen were investigated in solution by NMR spectroscopy in weakly ordering phases. A thorough theoretical treatment of the anisotropic interactions that are relevant for NMR spectra led to a conformational model characterized by six pairs of symmetry-related conformers, in particular four couples of gauche structures, with a total probability of 93%, and 2 couples of trans structures, counting for the remaining 7%.

Doped ionic liquid crystals as effective weakly alignment media for polar solutes.

The ionic liquid crystal 1-dodecyl-3-methylimidazolium tetrafluoroborate slightly doped with water is presented as a promising NMR alignment medium for the measurement of residual dipolar couplings for polar molecules dissolved therein.

Detection of Significant Aprotic Solvent Effects on the Conformational Distribution of Methyl 4-Nitrophenyl Sulfoxide: From Gas-Phase Rotational to Liquid-Crystal NMR Spectroscopy.

The conformational equilibrium of methyl 4-nitrophenyl sulfoxide (MNPSO) was experimentally investigated in the gas phase by using microwave spectroscopy and in isotropic and nematic liquid-crystal solutions, in which the solvents are nonaqueous and aprotic, by using NMR spectroscopy; moreover, it was theoretically studied in vacuo and in solution at different levels of theory. The overall set of results indicates a significant dependence of the solute conformational distribution on the solvent dielectric permittivity constant: when dissolved in low-polarity media, the most stable conformation of MNPSO proved to be strongly twisted with respect to that in more polar solvents, in which the conformational distribution maximum essentially coincides with that obtained in the gas phase. We discuss a possible explanation of this behavior, which rests on electrostatic solute-solvent interactions and is supported by calculations of the solute electric dipole moment as a function of the torsional angle.

Conformational investigation in solution of a fluorinated anti-inflammatory drug by NMR spectroscopy in weakly ordering media.

The structural and conformational elucidation of flexible bioactive molecules in solution is currently a crucial goal for the scientific community, but it is rarely achievable by available techniques. The anti-inflammatory drug diflunisal is presented here as a model case for supporting the efficiency of NMR spectroscopy combined with the use of weakly ordering media as a promising methodology for the conformational investigation of small bioactive molecules. Starting from NMR anisotropic data (40 independent dipolar couplings), a quite accurate description of its torsional distribution around the inter-ring C-C bond was found, characterized by a pair of two couples of conformers.

Smectic order parameters via liquid crystal NMR spectroscopy: Application to a partial bilayer smectic A phase.

Solute molecules were dissolved in the liquid crystal 4-cyano-4'-n-octyloxybiphenyl (8OCB), known to form a partial bilayer smectic-A phase. Through measurement of solutes' and solvent's orientational order parameters via nuclear magnetic resonance spectroscopy, and their analysis via a statistical thermodynamic density functional theory, values of the solvent's positional order parameters and solutes' positional-orientational distribution functions were obtained. Near to the transition to the nematic phase, the main positional order parameter of the smectic liquid crystal turned out to be comprised in the interval 0.

Conformational distribution of trans-stilbene in solution investigated by liquid crystal NMR spectroscopy and compared with in vacuo theoretical predictions.

The basic question about the structure and the conformational distribution of a π-conjugated, flexible organic molecule (interesting in itself, in relation to the balance of forces determining its torsional equilibrium) becomes a really intriguing problem in the case of trans-stilbene (t-St), a "fundamental" molecule from a chemical point of view, as well as the prototype fragment of a series of derivatives endowed with several important biological and technological properties. As a matter of fact, the problem of t-St planarity when the molecule is isolated or in solution is a particularly debated question. In the present paper we studied the conformational distribution of t-St in solution, by resorting to the powerful technique of liquid crystal NMR spectroscopy (LXNMR), and we compared the obtained experimental results with accurate theoretical calculations carried out in vacuo, by using the MP2/6-31G** method (allowing for bond lengths and angles relaxation every 3° torsional steps).

Rigid probe solutes in a smectic-A liquid crystal: an unconventional route to the latter's positional order parameters.

Biphenylene and pyrene were dissolved in the nematic and smectic-A phases of the liquid crystal 4,4'-di-n-heptyl-azoxybenzene and the orientational order parameters of both solutes and solvent measured via proton and deuteron nuclear-magnetic-resonance spectroscopy. This new data set was then merged with the one previously obtained, formed by 4,4'-di-chloro-benzene and naphthalene as solutes in the same solvent, and the resulting overall data set analyzed with a statistical thermodynamic density-functional theory to provide positional-orientational distribution functions of the various solutes along with the smectic solvent's positional order parameters.

Experimental assessment of the vibration-reorientation contribution to liquid crystal NMR dipolar couplings: the case of tetramethylallene dissolved in a nematic mesophase.

In the present paper, the peculiar orientational behavior, studied by liquid crystal NMR (LXNMR) spectroscopy, of the D(2d) symmetry quasi-spherical molecule of tetramethylallene (TMA) dissolved in the nematic solvent I52 is exploited to attempt a quantitative experimental assessment of the correlation between molecular vibrations and overall rotations in weakly oriented molecules. The analysis of the very small D(HH) and (1)D((13)C-H) dipolar couplings, available from the natural abundance LXNMR spectra of TMA at different temperatures, allows for a derivation leading (by making a few approximations) to the quantification of the vibration-reorientation (also called nonrigid) contribution affecting the observed direct (1)D((13)C-H) dipolar coupling. The obtained results show that, under the particular conditions of the studied system (very weak orientational ordering of a highly symmetric molecule), this contribution is particularly important, in order to reproduce the whole value of the "observed" dipolar coupling.

Orientational mechanisms in liquid crystalline systems. 1. A reaction field analytical description of the interaction between the electric quadrupole moment of a probe solute and the electric field gradient of a nematic solvent.

In the present paper, the fundamental problem of calculating the electric field gradient (EFG) experienced by a highly idealized solute, represented by a general point quadrupole immersed in an anisotropic uniaxial medium, has been tackled. Following a generalized reaction field approach (based upon the original ideas and the "mean-field philosophy" due to Kirkwood and Onsager) in the linear response approximation, a closed analytical expression of the EFG has been derived (to the best of our knowledge, for the first time). The obtained expression is particularly simple and elegant, also thanks to the oversimplifying approximation that the virtual cavity containing the solute is assumed to be perfectly spherical.

Orientational mechanisms in liquid crystalline systems. 2. The contribution to solute ordering from the reaction field interaction between the solute electric quadrupole moment and the solvent electric field gradient.

In the previous paper of this issue, [Celebre, G.; Ionescu, A. J.

Solvent smectic order parameters from solute nematic order parameters.

In liquid crystals, while the second and fourth rank orientational order parameters characterizing a nematic phase can be experimentally determined via several techniques, there is no straightforward experiment rendering the positional order parameters characterizing a smectic A phase. This work illustrates a novel method to estimate the positional order parameters of a smectogenic liquid crystal solvent from knowledge of the orientational order parameters of a number of solutes dissolved therein. The latter order parameters can be experimentally determined via liquid crystal NMR spectroscopy.

Multitechnique investigation of conformational features of small molecules: the case of methyl phenyl sulfoxide.

The conformational distribution of methyl phenyl sulfoxide (a molecule representative of a very important class of reagents widely used in asymmetric synthesis) has been studied in two different phases of matter (gas phase and solution) by a comprehensive approach including theoretical calculations, microwave spectroscopy, liquid crystal NMR experiments, and atomistic molecular dynamics computer simulations. The aim was to investigate the combined action of intra- and intermolecular interactions in determining the molecule's conformational equilibrium, upon which important physicochemical properties (inter alia, the chemoselectivity) significantly depend. Basically, the results converge in describing the tendency of the molecule to favor stable conformations governed by intramolecular interactions (in particular, the expected optimization between steric repulsion and conjugation of pi systems).

An explicit relationship between the dielectric anisotropy and the average electric field gradient in nematic solvents.

Nowadays, the interaction between the electric quadrupole moment of a probe-solute and the so-called average electric field gradient (EFG) of the nematic medium is commonly suggested as an important long-range mechanism contributing to the ordering of small molecules dissolved in nematic solvents. Anyway, an explicit relationship between the solvent's EFG and some macroscopic property of the medium has never been established explicitly. In this work, a derivation is carried out leading to a simple formula that shows that the EFG of a nematic solvent is directly related to the dielectric permittivity of the medium (in particular, to its dielectric anisotropy, Deltaepsilon) and to the quadrupole moment of the solute.

Intrinsic information content of NMR dipolar couplings: a conformational investigation of 1,3-butadiene in a nematic phase.

The conformational equilibrium of 1,3-butadiene in a condensed fluid phase is investigated by liquid-crystal NMR spectroscopy. The full set of D(HH) and D(CH) dipolar couplings is determined from the analysis of the (1)H spectra of the three 1,3-butadiene most-abundant isotopomers (i.e.

On the analysis of Liquid Crystal NMR dipolar coupling data via mixed a priori-maximum entropy methods.

In this Letter, a general expression is derived for the conformational distribution function of a molecule dissolved in an anisotropic condensed fluid medium by combining an a priori model with the maximum entropy principle applied to treatment of liquid crystalline-NMR data. The recently proposed additive potential maximum entropy (APME) method is recovered as a special case, when the AP is chosen as the a priori model and the orientational order is low.

Orientational ordering of solutes in confined nematic solvents: a possible way to probe director distributions.

We propose a method to study the director distribution in a nematic liquid crystal confined in a slab geometry. It is based on the measurement, by NMR spectroscopy, of the Saupe ordering matrices of a collection of biaxial solute molecules dissolved in the confined nematic liquid crystal of interest. Due to the combined action of the surface anchoring and magnetic field interactions, the director is generally not uniformly aligned within the cell.

Solute-solvent interactions and chiral induction in liquid crystals.

The induction of a cholesteric phase by doping an achiral nematic liquid crystal with an enantiopure solute is a phenomenon that, as in all general supramolecular phenomena of chiral amplification, depends in a subtle way on intermolecular interactions. The micrometric helical deformation of the phase director in the cholesteric phase is generated by the interplay of anisotropy and chirality of probe-medium interactions. In the case of a flexible chiral dopant, the solvent can influence the twisting power in two ways, difficult to disentangle: it is responsible for the solute orientational order, an essential ingredient for the emergence of phase chirality; but also it can affect the dopant conformational distribution and then the chirality of the structures present in the solution.

The structure of acrolein in a liquid crystal phase.

The (1)H NMR spectrum of a sample of acrolein dissolved in the nematic liquid crystal phase I52 has been analysed to yield 18 dipolar couplings between all the magnetic nuclei in the molecule; moreover, the (13)C and (13)C{(1)H} NMR spectra of a sample of acrolein in CDCl(3) were recorded and analysed to determine the indirect J(ij) couplings. The data were used to obtain the relative positions of the carbon and hydrogen atoms, assuming that these are independent of the conformations generated by rotation around the C--C bond through an angle phi, and to obtain a probability distribution P(phi). It has been found that in the liquid phase, the distribution is a maximum at the trans form whereas the abundance of the cis form is significantly smaller compared with that found by microwave spectroscopy or high level quantum mechanical calculations.

Is styrene planar in liquid phases?

The proton NMR spectra of two (13)C-labeled isotopomers of styrene dissolved in two liquid crystalline solvents have been obtained and analyzed to yield four sets each of 24 dipolar couplings. These couplings were then used to investigate the structure of the ring and the ene fragments of the molecule, and the position of the maximum, phi(0), in the ring-ene bond rotational probability distribution. To do this, the effect on the dipolar couplings of small-amplitude vibrational motion was taken into account using vibrational wave functions calculated by molecular orbital and density functional methods.