AB initio study of the regular polyhedral molecules N4, P4, As4, N8, P8 and As8

Ab initio pseudopotential SCF calculations were performed on tetrahedral X₄ molecules using double-zeta basis sets with and without d functions. The inclusion of d orbitals shortens the bond lengths, stabilizes the X₄ structures and intensifies the electron density inside the tetrahedron. The cubic X₈ molecules, calculated without d AOs, are not predicted to be more stable than 2X₄. Repulsions between parallel bonds in X₈ may compensate the lack of ring strain.     

Numerical computation of the electrostatic interaction energy between methanol and the dyad water-imidazole

Summary The electrostatic interaction energy between methanol and the dyad water-imidazole has been computed numerically at three levels of approximation from 3D grids of the charge density of one partner and the electrostatic potential of the other. The minimum positions and energy values thus obtained compare well with those calculated analytically. The numerical procedure is especially interesting for the prediction of the stable conformers.     

Synthese de N-(tetrazol-5-yl) azetidin-2-ones

The title compounds were obtained by addition of a glycine enolate to a N-(tetrazol-5-yl) imine followed by cyclisation. This route provided both the $\text{cis}$ and the $\text{trans}$ substituted azetidinones. The $\text{cis}$ compounds possessed improved antibiotic activity as compared to the $\text{trans}$ counterparts.     

Solvation of uranyl(II), europium(III) and europium(II) cations in "basic" room-temperature ionic liquids: a theoretical study

We report a molecular dynamics study of the solvation of UO2(2+), Eu3+ and Eu2+ ions in two "basic" (Lewis acidity) room-temperature ionic liquids (IL) composed of the 1-ethyl-3-methylimidazolium cation (EMI+) and a mixture of AlCl4- and Cl- anions, in which the Cl-/AlCl4- ratio is about 1 and 3, respectively. The study reveals the importance of the [UO2Cl4]2- species, which spontaneously form during most simulations, and that the first solvation shell of europium is filled with Cl- and AlCl4- ions embedded in a cationic EMI+ shell. The stability of the [UO2Cl4]2- and [Eu(III)Cl6]3- complexes is supported by quantum mechanical calculations, according to which the uranyl and europium cations intrinsically prefer Cl- to the AlCl4- ion. In the gas phase, however, [Eu(III)Cl6]3- and [Eu(II)Cl6]4- complexes are predicted to be metastable and to lose two to three Cl- ions. This contrasts with the results of simulations of complexes in ILs, in which the "solvation" of the europium complexes increases with the number of coordinated chlorides, leading to an equilibrium between different chloro species. The behavior of the hydrated [Eu(OH2)8]3+ complex is considered in the basic liquids; the complex exchanges H2O molecules with Cl- ions to form mixed [EuCl3(OH2)4] and [EuCl4(OH2)3]- complexes. The results of the simulations allow us to better understand the microscopic nature and solvation of lanthanide and actinide complexes in "basic" ionic liquids.     

Separation mechanism of nortriptyline and amytriptyline in RPLC

The single and the competitive equilibrium isotherms of nortriptyline and amytriptyline were acquired by frontal analysis (FA) on the C18- bonded discovery column, using a 28/72 (v/v) mixture of acetonitrile and water buffered with phosphate (20 mM, pH 2.70). The adsorption energy distributions (AED) of each compound were calculated from the raw adsorption data. Both the fitting of the adsorption data using multi-linear regression analysis and the AEDs are consistent with a trimodal isotherm model. The single-component isotherm data fit well to the tri-Langmuir isotherm model. The extension to a competitive two-component tri-Langmuir isotherm model based on the best parameters of the single-component isotherms does not account well for the breakthrough curves nor for the overloaded band profiles measured for mixtures of nortriptyline and amytriptyline. However, it was possible to derive adjusted parameters of a competitive tri-Langmuir model based on the fitting of the adsorption data obtained for these mixtures. A very good agreement was then found between the calculated and the experimental overloaded band profiles of all the mixtures injected.     

Synthèse des (R)- et (S)-O-isopropylidène-1,2-glycérols. Détermination de la pureté optique

Synthesis of the (R)- and (S)-Glycerol Acetonides. Determination of the Optical Purity The optical purity of (R)-glycerol acetonide ( 1 ) and (S)-glycerol acetonide ( 1 ′) has been determined with great accuracy by gas chromatography after derivatization. The optical purity of (S)-glycerol actonide prepared from D -mannitol was > 99.4% while for (R)-glycerol acetonide obtained from L -serine it was 95%.     

Stability-indicating high-performance liquid chromatographic assay of buspirone HCl

The United States Pharmacopoeia high-performance liquid chromatographic (HPLC) assay method of buspirone is not able to discriminate buspirone from its degradation products. The purpose of this work is to develop a sensitive, selective, and validated stability-indicating HPLC assay for the analysis of a buspirone hydrochloride in a bulk drug. Buspirone HCI and its potential impurities and degradation products are analyzed on an Ultrasphere C18 column heated to 40 degrees C using a gradient program that contains monobasic potassium phosphate buffer solution (pH 6.9) and acetonitrile-methanol mixture (13:17) of 35% for 5 minutes, then increased to 54% in 5.5 minutes. The samples are monitored using a photo-diode array detector and integrated at 244 and 210 nm. The stress testing of buspirone HCI shows that buspirone acid hydrochloride is the major degradation product. The developed method shows a separation of buspirone degradation product and its potential impurities in one run. The stability of buspirone HCI is studied under accelerated conditions in order to provide a rapid indication of differences that might result from a change in the manufacturing process or source of the sample. The forced degradation conditions include the effect of heat, moisture, light, acid-base hydrolysis, sonication, and oxidation. The compatibility of buspirone HCI with some pharmaceutical excipients is studied under stress conditions. The linear range of buspirone HCI is between 5 and 200 ng/microL with a limit of quantitation of 2.5 ng/microL. The intraassay percentage deviation is not more than 0.38%, and the day-to-day variation was not more than 0.80%. The selectivity, repeatability, linearity, range, accuracy, sample solution stability, ruggedness, and robustness show acceptable values.     

Synthesis of functionalized analogs of pyochelin, a siderophore of Pseudomonas aeruginosa and Burkholderia cepacia

Using an improved synthesis of pyochelin, a siderophore common to several pathogenic Pseudomonas species, three functionalized pyochelin analogs were efficiently synthesized starting from appropriate 2-hydroxybenzonitriles.     

Jet cooled NO2 intra cavity laser absorption spectroscopy (ICLAS) between 11200 and 16150 cm

We have combined the high sensitivity of the ICLAS technique with the rotational cooling effect of a slit jet expansion in order to observe and to understand the visible and near infrared NO₂ spectrum. By this way, an equivalent absorption pathlength of several kilometers through rotationally cooled molecules has been achieved. Due to the vibronic interaction between the two lowest electronic states, ²A₁ and à ²B₂, this spectrum is vibronically dense and complex. Moreover, the dense room temperature rotational structure is perturbed by additional rovibronic interactions. In contrast, the rotational analysis of our jet cooled spectrum is straightforward. The NO₂ absorption spectrum is vanishing to the IR but, owing to the high sensitivity of the ICLAS technique, we have been able to record the NO₂ spectrum down to 11200 cm⁻¹ with a new Ti:sapphire ICLAS spectrometer. As a result 249 ²B₂ vibronic bands have been observed (175 cold bands and 74 hot bands) in the 11200–16150 cm⁻¹ energy range. Due to the cooling effect of the slit jet we have reduced the rotational temperature down to about 12 K and at this temperature the K = 0 subbands are dominant. Consequently, we have analysed only the K = 0 manifold for N 7 of each vibronic band. The dynamical range of the band intensities is about one thousand. Due to the strong vibronic interaction between the ²A₁ and à ²B₂ electronic states, we observed not only the a₁ vibrational levels of the à ²B₂ state but also the b₂ vibrational levels of the ²A₁ state interacting with the previous ones. By comparison with the calculated density of states, we conclude that we have observed about 65% of the total number of ²B₂ vibronic levels located in the studied range. However, there are more missing levels in the IR because of the weakness of the spectrum in this range. The correlation properties of this set of vibronic levels have been analysed calculating the power spectrum of the absorption stick spectrum which displays periodic motions: the dominant period, at 714 ± 20 cm⁻¹, corresponds to the bending motion of the à ²B₂ state. The other observed periods remain unassigned. In contrast the next neighbor spacing distribution (NNSD) shows a strong level repulsion, i.e. a manifestation of quantum chaos. These two observations, apparently contradictory, can be rationalized as follows: the short time dynamics, for t < 10⁻¹² s, is “regular” while for longer times the dynamics becomes “chaotic”. We suggest that this behavior may be observed directly with a pump and probe fs laser experiment.