Role of the V=O double bond in the selective oxidation of benzene on V2O5 and V2O5?MoO3 catalysts

Infrared spectra of both fresh and reductively activated V₂O₅ and V₂O₅–MoO₃ catalysts were recorded and compared with the results of catalytic measurements. The results indicate that the presence of V=O double bonds in the catalytically active mass is not essential for the selective oxidation of benzene to maleic anhydride.

---

, V₂O₅ V₂O₅–MoO₃. . , V=O .

     

Correlation between apparent activation energy and selectivity in the oxidation of benzene over vanadia-molybdena catalysts

The existence of a linear correlation between the apparent activation energy of catalytic benzene oxidation and selectivity with respect to maleic anhydride was found in a series of unsupported vanadia-molybdena catalysts. A plausible explanation for such a correlation is given.

---

- . .

     

LC and Principal Component Analysis in the Lipophilicity Study of Seven Angiotensin II-AT1 Receptor Antagonists (Sartans)

Seven sartans have been chromatographed with acetonitrile-buffer and methanol–buffer in different proportions as mobile phases. The retention values, log k or R _M were extrapolated to zero organic modifier content to obtain the log k _w or R _MW values. Calibration equations were obtained for standards of known lipophilicity. A simple method employing a gradient procedure of 10–100% acetonitrile or methanol in 60 min and standards of the extreme lipophilicity was also elaborated. Chromatographic log P values were compared to those calculated by use of different software products. Finally, principal component analysis was performed to explore and visualize similarities and differences among the drugs and among the methods.     

LC and Principal Component Analysis in the Lipophilicity Study of Seven Angiotensin II-AT1 Receptor Antagonists (Sartans)

Seven sartans have been chromatographed with acetonitrile-buffer and methanol–buffer in different proportions as mobile phases. The retention values, log k or R _M were extrapolated to zero organic modifier content to obtain the log k _w or R _MW values. Calibration equations were obtained for standards of known lipophilicity. A simple method employing a gradient procedure of 10–100% acetonitrile or methanol in 60 min and standards of the extreme lipophilicity was also elaborated. Chromatographic log P values were compared to those calculated by use of different software products. Finally, principal component analysis was performed to explore and visualize similarities and differences among the drugs and among the methods.

     

Intermediate Approach to Comparison of Some Goodness-of-Fit Tests

In this paper we present the intermediate approach to investigating asymptotic power and measuring the efficiency of nonparametric goodness-of-fit tests for testing uniformity. Contrary to the classical Pitman approach, the intermediate approach allows the explicit quantitative comparison of powers and calculation of efficiencies. For standard tests, like the Cramér-von Mises test, an intermediate approach gives conclusions consistent with qualitative results obtained using the Pitman approach. For other more complicated cases the Pitman approach does not give the right picture of power behaviour. An example is the data driven Neyman test we present in this paper. In this case the intermediate approach gives results consistent with finite sample results. Moreover, using this setting, we prove that the data driven Neyman test is asymptotically the most powerful and efficient under any smooth departures from uniformity. This result shows that, contrary to classical tests being efficient and the most powerful under one particular type of departure from uniformity, the new test is an adaptive one.     

Characterization of paliperidone photodegradation products by LC‐Q‐TOF multistage mass spectrometry

The photodegradation of paliperidone in aqueous and methanol media under UVA and UVC irradiation was investigated. The identification and structural elucidation of its photodegradation products were performed by the use of the reversed‐phase liquid chromatography coupled with accurate mass hybrid Q‐TOF mass spectrometry and an atmospheric pressure chemical ionization source. Five degradation products were found and their masses were obtained with high accuracy (1.10–5.26 ppm) based on the TOF (MS) spectra. For the structural elucidation of unknown degradation products MS/MS spectra were also registered. However, for the identification of the main photodegradation product (3‐{2‐[4‐(6‐fluoro‐1,3‐benzoxazol‐2‐yl)piperidin‐1‐yl]ethyl}‐9‐hydroxy‐2‐methyl‐6,7,8,9‐tetrahydro‐4H‐pyrido[1,2‐a]pyrimidin‐4‐one) in‐source fragmentation connected with collision‐induced dissociation was used and MS³ spectra were finally performed. The photodegradation of paliperidone yields the first‐order kinetics in all tested conditions. The aqueous medium was in this case much less stable than the methanol solvent regardless of the irradiation source. Additionally, the toxicity of the analyzed photodegradation products was predicted by the use of ECOSAR software and comparable values of LC₅₀ for the main degradants and the parent compound were obtained. Copyright © 2015 John Wiley & Sons, Ltd.     

Molecular organization and aggregation in Langmuir and Langmuir-Blodgett films of azo dye/liquid crystal mixtures

A study of azo dye/liquid crystal mixtures in monolayers formed at air-water (Langmuir films) and air-solid substrate (Langmuir-Blodgett films) interfaces was performed. Three azo dyes with various molecular structure and two liquid crystal materials: 4-octyl-4′-cyanobiphenyl (8CB) and trans-4-octyl(4′-cyanophenyl)-cyclohexane (8PCH) were used. The morphology of Langmuir films was monitored by means of a Brewster angle microscope (BAM). Moreover, a surface pressure and electronic absorption spectra of the monolayer spread on the water surface of dye/liquid crystal mixtures as a function of a mean molecular area were simultaneously recorded. In addition, the absorption for Langmuir-Blodgett films deposited on quartz plates was measured. Information about intermolecular interactions in the mixtures of the nonamphiphilic dye and the liquid crystal with polar terminal group was obtained. Conclusions about the formation of self-aggregates between dye molecules have been drawn. The influence of the dye molecular structure and its concentration on aggregates’ geometry was found.     

The CoO/Co3O4 phase transition studied by PAC

The hyperfine environment of¹¹¹Cd nuclei formed in the radioactive decay of¹¹¹In ions implanted into CoO was studied via the PAC method. The quadrupole coupling constants measured in isochronal and isothermal annealing treatments at various oxygen pressures were related to the initial stages of the CoO→Co₃O₄ phase transition and interpreted as the successive trapping of cation vacancies at the¹¹¹In probe. The phase transition was confirmed by X-ray diffraction, RBS and a PAC measurement on¹¹¹Cd in spinel type Co₃O₄.     

Hyperfine interaction of111Cd in antiferromagnetic cobalt oxide

The temperature dependence of the hyperfine field of substitutional¹¹¹Cd in antiferromagnetic CoO has been measured by means of the perturbed angular correlation technique. The Larmor frequency ω_L is found to obey a power law ω_L(t=ω₀ t ^β) up tot _max=0.4 wheret=1−T/T _N is the reduced temperature withT _N=291.2(3) K and β=0.393 (5) the critical exponent. The results are discussed and compared with PAC experiments on¹¹¹Cd in NiO and Ni and with results obtained by other methods.