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%.     

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.     

Serum estradiol measurement by solid-phase chemiluminescence immunoassay and direct radioimmunoassay

Estradiol017β is determined in serum extracts by solid-phase chemiluminescence immunoassay. The results are compared with those obtained from unextracted serum in routine conditions with a commercial radioimmunoassay (r.i.a.) kit. For the chemiluminescence procedure, a purified monoclonal antibody to estradiol-6-carboxymethyloxime/bovine serum albumin and the homologous chemiluminescent marker conjugate estradiol-6-carboxymethyloxime aminobutylethylisoluminol are used. Bound and free ligand are separated by washing and simple centrifugation. Results obtained by the chemiluminescence assay (y) and by r.i.a. (x) on 170 serum specimens from women during ovulation induction showed good correlation (y = 1.01x ? 16 with r = 0.95). The methods are similar in selectivity, detection limit (ca. 10 ng l^?1) and precision (interassay relative standard deviation, 8–13%).     

19F NMR chemical shifts of n-F-alkyl compounds

The examination of ¹⁹F chemical shifts for ca. 650 F-alkylated compounds of general formula CF₃(CF₂)_nCF₂X led to the following conclusions: the CF₂ groups α to X are very sensitive to the nature of X, and are spread over a range of 85 ppm. The effect of the length of the F-alkyl chain decreases rapidly, so that δCF₂(α) can already be considered as characteristic of X for n = 1 or 2 for most practical purposes. Solvent effects (in 9 different solvents having ε = 1.8 to 52.1) were found to be rather small except for the F-alkyl iodides. A chart which indicates the domain in which the CF₂(α) resonance signal is to be expected is given for 42 different series of F-alkylated compounds; it is expected to provide the synthetic chemist with a useful tool for the identification and characterization of such compounds.     

Classification of the CD. Spectra of carotenoids

The CD. spectra of carotenoids in the 220-500 nm region may by inspection be classified as (a) essentially Conservative, (b) intermediate, or (c) essentially nonconservative. A conservative spectrum shows in that spectral region a sequence of 5-6 relatively sharp Cotton effects of alternating sign, the rotatory strengths of which roughly add to zero. In a non-conservative spectrum Δ? has the same sign over the whole region and its absolute value is in general somewhat smaller. In general, typical conservative spectra invert upon isomerization of the molecule from all-trans to mono-cis. Non-conservative spectra do not invert. The model of a chiral polyene of the length of the conjugated carotene chromophore reproduces well the main features of the conservative spectra. The theoretical predictions and the experimental data are shown to conform to the C₂-rule [43] [44]. The particular nature of the longest-wavelength transition is interpreted. Based on a summary of the chiroptic data on about 50 naturally occurring compounds, the question is discussed of when conservative spectra arise and when not.     

The equilibrium C-H bond length

The equilibrium C-H bond length has been determined up to now for about 40 polyatomic molecules. These data are used to demonstrate the existence of quantitative correlations betweenr _e(C-H), isolated C-H bond stretching frequency and average distancer _g. It is also shown that ab initio calculations are often reliable to calculate the absolute value ofr _e(C-H), if an empirical correction is made. Some other correlations are also discussed. Finally, accurater _e(C-H) values are predicted for simple molecules.     

Introduction to Nambu Jona-Lasinio models of hadrons

These are introductory lectures to the Nambu Jona-Lasinio model with scalar interactions. It is applied to quark models of mesons and baryons. A critical survey is made of regularization methods. The collective rotation of solitons is briefly summarized.Lecture given at the 8th Summer School on Intermediate Energy Physics: Hadron Dynamics at Low and Intermediate Energies, Prague, July 10–14, 1995.     

About SnF2 stannous fluoride. IV. Kinetics of the α → γ and β, γ → α transitions

The kinetics of the reconstructive first order phase transitions α → γ (upon heating) and β, γ → α (upon cooling) of SnF₂ were studied by quantitative X-ray powder diffraction. The main feature of the kinetics is that these transformations are incomplete over a wide temperature range. Consequently it is not possible to fit the experimental data using the usual solid state rate expressions. Although these transitions are not reversible (large hysteresis) the empirical use of a kinetic model of a reversible transformation provides a good fit. The α → γ transformation was also investigated by D.T.A.; this transition was found to be greatly influenced by particle size: the transition temperature increases with grain size, and its enthalpy decreases. The X-ray investigation revealed that the process of the α → γ transformation involves an intermediate noncrystalline phase named the “transition phase.” It is suggested that the transition proceeds through a process of fragmentation-reconstruction.