Gravimetric determination of zirconium with a new azopyrazolone derivative

3-Methyl-5-oxo-1-phenyl-2-pyrazolin-4-ylazo-2'-(6',8'-naphthalenedisulfonic acid) (disodium salt) is proposed as a new reagent for the gravimetric determination of zirconium. The precipitate formed at pH 1–1.5 can be weighed directly and there are few interferences.     

Gas chromatography-mass spectrometry of carbonyl compounds in cigarette mainstream smoke after derivatization with 2,4-dinitrophenylhydrazine

An improved gas chromatography-mass spectrometry (GC-MS) method was described for the analysis of carbonyl compounds in cigarette mainstream smoke (CMS) after 2,4-dinitrophenylhydrazine (DNPH) derivatization. Besides formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, methyl ethyl ketone, butyraldehyde, and crotonaldehyde that are routinely analyzed in cigarette smoke, this technique separates and allows the analysis of several C4, C5 and C6 isomeric carbonyl compounds. Differentiation could be made between the linear and branched carbon chain components. In cigarette smoke, the branched chain carbonyls are found at higher level than the linear chain carbonyls. Also, several trace carbonyl compounds such as methoxyacetaldehyde were found for the first time in cigarette smoke. For the analysis, cigarette smoke was collected using DNPH-treated pads, which is a simpler procedure compared to conventional impinger collection. Thermal decomposition of DNPH-carbonyl compounds was minimized by the optimization of the GC conditions. The linear range of the method was significantly improved by using a standard mixture of DNPH-carbonyl compounds instead of individual compounds for calibration. The minimum detectable quantity for the carbonyls ranged from 1.4 to 5.6 microg/cigarette.     

Results from solvophobic theory applied to methylene selectivity in reversed-phase HPLC

A significant amount of work has been previously dedicated to the understanding of methylene selectivity parameter. The conventional theory applied for this understanding was mostly based on the assumption that the difference in the Gibbs free energy of transfer from the mobile phase to the stationary phase is a constant for any two compounds in a homologous series that differ by a CH₂ group. In the present study, it is shown based on solvophobic theory that this assumption is indeed correct, but it provides a theoretical justification for it. Exemplification of the results of theory was obtained using the values for methylene selectivity (α(CH₂)) measured experimentally for seven different C18 chromatographic columns including two core–shell columns and using water and either methanol or acetonitrile as an organic component. Four different homologous series of compounds were used for evaluation. The study proved the theoretical prediction that the values for α(CH₂) obtained using different homologous series of compounds are only slightly different from those obtained using the toluene–butylbenzene series. Even using different homologous series, the same type of information regarding the columns comparison, and the changes in log α(CH₂) with the solvent composition was obtained.     

4‐Methyl‐ and 4‐(Halophenyl)pyrimidinium (4‐Halobenzoyl)methylides. Correlation of Structure,Stability, Reactivity,and Biological Activity

For the first time in the cycloimminium ylide series, we present a theoretical and experimental study concerning the correlation between structure, stability, reactivity, and biological activity of 4‐(R)‐pyrimidinium (4‐halobenzoyl)methylides (R = Me and 4‐chlorophenyl; hal = X = F, Cl, Br, I; see 5 and 6 in Scheme 1). The 4‐methylpyrimidinium (4‐halobenzoyl)methylides 5 are relatively stable compounds, while the (4‐chlorophenyl)pyrimidinium (4‐halobenzoyl)methylides 6 are more unstable. Their stability varies with the nature of the substituents at the ylide carbanion and pyrimidinium cation moieties as confirmed by quantum‐chemical calculations. The latter also disclose the possibility to use pyrimidinium ylides as nucleophilic reagents as well as 1,3‐dipoles in reactions with appropriate reagents. The experimental data obtained confirm the calculations concerning the nucleophilicity and reactivity of the ylides 5 and 6 . Moreover, the influence of microwave irradiation on the synthesis of the pyrimidinium salts 3 and 4 from pyrimidine and an organic halide is studied and reveals a remarkable reaction‐rate increase under microwave irradiation as compared to classical conditions; this allows the general and facile synthesis of the salts 3 and 4 (Scheme 1, Table 1). The in vitro biological activity of the newly obtained 4‐methylpyrimidine compounds is also tested. Some of them exhibit a remarkable activity against different microorganisms (germs and fungi) which allows to establish structure–activity correlations.     

Spiroheterocyclic compounds: old stories with new outcomes

An efficient and straightforward method for the preparation of spirodiazine derivatives is reported which involves mild reaction conditions and easily accessible reactants. A new class of spiroazaheterocycles, spiro[pyrrolidine-pyrrolo[3,4-c]pyrroles], is obtained. A feasible explanation is given for the unexpected results obtained at high energy (high temperatures, MW and ultrasound irradiation).     

Self-injection length in La0.7Ca0.3MnO3-YBa2Cu3O7-δ ferromagnet-superconductor multilayer thin films

We have carried out extensive studies on the self-injection problem in barrierless heterojunctions between La_0.7Ca_0.3MnO₃ (LCMO) and YBa₂Cu₃O_7-δ (YBCO) thin films. The heterojunctions were formed in situ by sequentially growing LCMO and YBCO films on 〈100〉 LaAlO₃ (LAO) substrate using a pulsed laser deposition (PLD) system. YBCO micro-bridges with 64 μm width were patterned both on the LAO (control) and LCMO side of the substrate. Critical current, I _c, was measured at 77 K on both the control side as well as the LCMO side for different YBCO film thickness. It was observed that while the control side showed a J _c of ∼ 2 × 10⁶ A/cm², the LCMO side showed about half the value for the same thickness (1800 ?). The difference in J _c indicates that a certain thickness of YBCO has become ‘effectively’ normal due to self-injection. From the measurement of J _c at two different thicknesses (1800 ? and 1500 ?) of YBCO films both on the LAO as well as the LCMO side, the value of self-injection length (at 77 K) was estimated to be ∼ 900 ?. To the authors’ best knowledge, this is the first time that self-injection length has been quantified. A control experiment carried out with LaNiO₃ deposited by PLD on YBCO did not show any evidence of self-injection.     

Contributions to the degenerated branching mechanism of the thermal decomposition of ammonia

By continuing our studies on the reaction kinetics and mechanism of ammonia thermal decomposition, new evidences are brought about supporting the indirectly branched chain mechanism advanced previously. The dependence of the induction period of the hydrogen formation as a reaction final product on the maximum concentration of hydrazine as the reaction molecular intermediate evidences indirectly branched chain mechanism affording preponderantly the hydrogen formation from hydrazine. The branching factor value of 0.00136 s⁻¹ was found by means of three laws specific to the reaction developing according to three rules specific to the degenerated branching. This value indicates degenerated branching occurring rather as a scarce event according to literature data where this factor is shown to be between 0.00016 and 0.01666 s⁻¹.     

Nicolae Teclu (1839-1916) A pioneer of flame spectroscopy

A brief account is given of Teclu's career and his contributions as a pioneer of the study of flames.     

Gas chromatography/mass spectrometry versus liquid chromatography/fluorescence detection in the analysis of phenols in mainstream cigarette smoke

A new gas chromatographic/mass spectrometric (GC/MS) technique for the analysis of hydroxybenzenes (phenols) in mainstream cigarette smoke has been developed. The technique allows the measurement of 24 individual compounds, and the sum of a few other alkyl-dihydroxybenzenes. A critical evaluation is done for the new technique and for an established high-performance liquid chromatographic (HPLC) technique reported in the literature for the analysis of hydroxybenzenes in cigarette smoke, which uses fluorescence detection. Compared with the HPLC procedure, the new technique has similar accuracy, precision, and robustness. However, the GC/MS procedure allows for a larger number of phenols to be analyzed simultaneously, and eliminates any potential interference that may appear in the HPLC method. Using the GC/MS analysis, it was found that besides the main phenols typically measured in mainstream cigarette smoke such as phenol, catechol, hydroquinone, and cresols, many other phenols that are present at lower levels can be quantitated in mainstream cigarette smoke.