Acetal formation from formylthiophene-2-carboxylic acids and recalculation of σI and σR substituent constants of the acetal group by 13C NMR chemical shifts

A uv-visible, ¹H and ¹³C nmr study has been carried out to show that 4-, 1, and 5-formylthiophene-2-carboxylic acids, 2, give acetals in methanol. The ms data have confirmed the acetal formation, which has been studied kinetically by the uv technique. The substituent chemical shifts induced on the carboxy carbon atom and on the endocyclic carbon atoms in the acetals formed from 1 and 2 and in the corresponding anions have been used to recalculate σ_I and σ_R values by means of a dual substituent parameter treatment of data.     

Direct regio- and stereoselective synthesis of squalene 2,3;22,23-dioxide using dioxiranes

Dimethyldioxirane (1a) and its trifluoro analog (1b) were employed to achieve selectively the direct transformation of squalene 2,3(S)-oxide and of squalene 2,3(R)-oxide into the corresponding 2,3(S);22(S),23-dioxide and 2,3(R);22(R),23-dioxide, respectively. These transformations were found to occur with convenient regio- and diastereoselectivity, providing easy access to the valuable dioxides metabolites. The powerful methyl(trifluoromethyl)dioxirane (1b) is the reagent of choice to achieve optimum yields of the target compounds.     

Excited state properties of sizable molecules in solution: from structure to reactivity

We review some recent advances in quantum mechanical methods devised specifically for the study of excited electronic state of large size molecules in solution. The adopted theoretical/computational framework is rooted in the density functional theory (DFT) and its time-dependent extension (TD-DFT) for the characterization of ground and excited states, in the polarizable continuum model (PCM) for the treatment of bulk solvent effects, and in time-dependent quantum mechanical methods for chemical dynamics. Selected applications to the simulation of absorption spectra, to the interpretation of time-resolved experiments, and to the computation of dissociative electron transfer rates are presented and discussed.     

Antioxidant and Antiradical Activity of Hydroxy‐Substituted 4‐Thiaflavanes

The antioxidant activities of several hydroxy‐substituted 4‐thiaflavanes, compounds 1 – 3 , were determined by measuring their ability of inhibiting the autoxidation of styrene or cumene. On this basis, the role played by the number and position of OH groups and by the oxidation state of the S‐atom was quantified and rationalized. With these data, it should be possible to optimize the structural features of these ‘double‐faced’ antioxidants for structure? activity‐relationship studies. A comparison between the kinetic data (k_inh) reported in this paper and the previously reported values of the antiradical activities (SC₅₀), measured by the DPPH^. bleaching method, for 1 – 3 is made (Table).     

Building cavities in a fluid of spherical or rod-like particles: a contribution to the solvation free energy in isotropic and anisotropic polarizable continuum model

A general formalism for the calculation of cavitation energies in the framework of the scaled particle theory has been implemented in the Polarizable Continuum Model (PCM), contributing to the nonelectrostatic part of the molecular free energy in solution. The solute cavity and the solvent molecules are described as hard spherocylinders, whose radius and length are related to the actual molecular shape, while the solvent density is estimated from experimental data, or from the solvent molecular volume, suitably scaled. The present model can describe isotropic solutions of spherical and rod-like molecules in spherical or rod-like solvents, and also anisotropic solutions in which the solvent molecules are oriented in space: in this case, the cavitation energy also depends on the relative orientation of solute and solvent molecules. Test calculations have been performed on simple systems to evaluate the accuracy of the present approach, in comparison with other methods and with the available experimental estimates of the cavitation energy, giving encouraging results.     

Cholic acid derivatives containing both 2-naphthylcarbamate and 3,5-dinitrophenylcarbamate groups: a combined circular dichroism-molecular mechanics approach to the definition of their molecular conformation

CD spectra of the chiral auxiliaries for enantioselective HPLC N-allyl-N'-methyl-3,12-bis(2-naphthyl)carbamoyloxy-7-(3,5-dinitrophenyl)carbamoyloxycholan-24-amide (1), N-allyl-N'-methyl-3-(3,5-dinitrophenyl)carbamoyloxy-7,12-bis(2-naphthyl)carbamoyloxycholan-24-amide (2), N-allyl-N'-methyl-3,7-bis(2-naphthyl)carbamoyloxy-12-(3,5-dinitrophenyl)carbamoyloxycholan-24-amide (3), and N-allyl-N'-methyl-3,7,12-tris(2-naphthyl)carbamoyloxycholan-24-amide (4) are presented. To determine the preferred conformations of those chiral auxiliaries, a random search based on the aromatic side-chain conformational degrees of freedom was performed and the energy was minimized using two different molecular mechanics force fields. The low energy structures presenting common features were arranged in groups and selected exploiting appropriate filters. The calculation of theoretical CD spectra according to the De Voe model has allowed a further discrimination among the conformations, specifying which of them gave calculated CD spectra in acceptable agreement with the experimental ones. Finally, taking into account the additivity of the contributions of each 2-naphthylcarbamate chromophore to the CD spectrum of the cholic acid derivatives, and, hence, choosing, for derivatives 1-3, those conformations in which the 2-naphthylcarbamate groups take a similar disposition as in 4, the preferentially assumed conformation of each compound was obtained. A molecular dynamics simulation in the presence of acetonitrile allowed the fluctuations of one of the structures, used as a test case, depending on environmental effects, to be examined.     

Study of nitrogen containing compounds in the polar troposphere

Atmospheric nitrogen compounds play a critical role in tropospheric photochemistry and are crucial to understand the chemical and physical evolution of atmospheric pollutants in polar areas. Measurements of these species in remote areas are rare, although their relevance is well established. Sampling campaigns of gaseous and particulate atmospheric trace species were performed in Arctic and in Antarctica during three consecutive years (1997-1999), using a proper combination of annular denuders and filter pack. After sampling, the ionic species were extracted with aqueous solutions and analysed by means of ion chromatography. Quality assurance on the sampling and analytical steps allowed accurate and precise measurements of all relevant compounds, which are thought to be important to nitrogen chemistry, at very low concentration levels. In addition, the measurements also included a multistage low-pressure impactor for the collection of particulate matter in different size regions (0.035-15.9 mm). Results obtained from these campaigns demonstrate that the minor components may be measured at levels as low as a few nanograms per cubic meter. The reported concentrations are to be considered among the first observations of nitrogen containing compounds in polar sites.     

A combined theoretical and experimental approach to determining order parameters of solutes in liquid crystals from 13C NMR data

The ordering properties of an anisotropic liquid crystal can be studied by recording 13C NMR spectra at different temperatures for a number of rigid solutes. The traditional difficulty in analyzing 13C data comes from the scarcity of experimental information about the carbon shielding tensors and from their limited transferability among different solutes. We show that these obstacles can be overcome by computing high-level ab initio shielding tensors, also including the solvent effects by the polarizable continuum model. The reliability of this combined approach is carefully verified, and the order parameters of several solutes are obtained by reanalyzing previously published spectra. The quality of the results is shown to be comparable to deuterium NMR without the need of isotopic substitution.     

Acrylonitrile-acrylic acid copolymer membrane imprinted with uric acid for clinical uses

The preparation of new polymeric membranes using molecular imprinting technology for application in blood filtration devices is described. Membranes, based on an acrylic acid-acrylonitrile copolymer, produced through phase inversion, were modified by introducing specific binding sites for uric acid into their structure. The materials prepared are intended for use to selectively remove uric acid from the blood in the case of increased serum uric acid values associated with different pathologies. The interactions at a molecular level between the membrane forming copolymer and the template were investigated by means of calorimetry, infrared spectroscopy and morphological analysis. The presence of interactions between the template and the copolymer, and a good thermal stability of the imprinted membranes were observed. In addition, the results of rebinding tests on the imprinted membranes indicated a good capacity of molecular recognition for the template and satisfactory selectivity properties towards compounds of similar structure such as theophylline. Membrane permeability values suggest their application as (ultra) haemofiltration devices. Poly(acrylonitrile-co-acrylic acid) membrane.     

Theoretical studies on the effects of methods and parameterization on the calculated free energy of hydration for small molecules

Free energies of hydration (FEH) have been computed for 13 neutral and nine ionic species as a difference of theoretically calculated Gibbs free energies in solution and in the gas phase. In‐solution calculations have been performed using both SCIPCM and PCM polarizable continuum models at the density functional theory (DFT)/B3LYP and ab initio Hartree–Fock levels with two basis sets (6‐31G* and 6‐311++G**). Good linear correlation has been obtained for calculated and experimental gas‐phase dipole moments, with an increase by ～30% upon solvation due to solute polarization. The geometry distortion in solution turns out to be small, whereas solute polarization energies are up to 3 kcal/mol for neutral molecules. Calculation of free energies of hydration with PCM provides a balanced set of values with 6‐31G* and 6‐311++G** basis sets for neutral molecules and ionic species, respectively. Explicit solvent calculations within Monte Carlo simulations applying free energy perturbation methods have been considered for 12 neutral molecules. Four different partial atomic charge sets have been studied, obtained by a fit to the gas‐phase and in‐solution molecular electrostatic potentials at in‐solution optimized geometries. Calculated FEH values depend on the charge set and the atom model used. Results indicate a preference for the all‐atom model and partial charges obtained by a fit to the molecular electrostatic potential of the solute computed at the SCIPCM/B3LYP/6‐31G* level. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004