CNDO/S-CI calculation of Hubbard parameters for doubly charged TCNQ tetramer

Using the CNDO/S-CI method the energies of the low-lying singlets and triplets of a doubly charged tetramer of TCNQ in the eclipsed geometry were calculated. The exact solution of the nearest-neighbour-version of the EHH for the case of two electrons and four sites was found. Fitting the EHH energy levels on the CNDO/S-CI spectra, the Hubbard parameters were estimated:U ₀=2.50 eV,V ₁=0.71 eV, ¦t¦=0.32 eV. The effect of strong correlation of the unpaired electrons on the electronic distribution in the ground and optically excited states of the tetramer is discussed.Dedicated to Professor Miroslav Trlifaj on the occasion of his sixtieth birthday.     

Diterpenoid Alkaloids of Delphinium buschianum Grossh.

From the aerial parts of Delphinium buschianum Grossh ., collected in Turkey, a new diterpenoid alkaloid 1 , named budelphine, was isolated along with the known diterpenoid alkaloids karakoline ( 2 ), 18‐hydroxy‐14‐O‐methylgadesine ( 3 ), delsoline ( 4 ), lapaconidine ( 5 ), columbianine ( 6 ), 14‐benzoylneoline ( 7 ), and hetisine ( 9 ). The structure of 1 was established on the basis of ¹H‐, ¹³C‐, DEPT, ¹H,¹H‐COSY, NOESY, HSQC, and HMBC NMR studies.     

Anomalous NMR behavior of meso compounds with remote stereogenic centers on addition of chiral shift reagent or chiral solvating agent

A problem has arisen in using chiral shift reagents (CSR) and chiral solvating agents (CSA) to determine meso and racemic forms of diastereoisomers in which the stereogenic centers of the molecules are separated by achiral spacers. It is found that NMR signals of both meso and racemic forms of diastereoisomers may exhibit doubling on addition of CSR/CSA, which means that unequivocal assignments cannot be made without characterizing the effects for separate meso and racemic forms; this is particularly important for additions of CSR/CSA at relatively low concentrations, which always result in the splitting of some NMR signals of diastereoisomers. The phenomenon is demonstrated in the (31)P NMR spectra of meso and racemic forms of three spermine-bridged gem-disubstituted cyclotriphosphazatrienes, 1a-c, and compared with analogous achiral molecules, the per-substituted spermine-bridged cyclotriphosphazatrienes 2a-d. As expected, only one set of (31)P NMR signals was observed for the achiral compounds 2a-d, even on addition of CSA. Two sets of (31)P NMR ABX multiplets corresponding to meso and racemic diastereoisomers were observed for compounds 1a-c; on addition of CSA, the signals of at least one of the multiplets for each compound separated into more than the expected groups of three lines with an intensity distribution of 2:1:1. To understand this phenomenon, the meso and racemic forms of 1a and 1b and the meso form of 1c have been separated and characterized by X-ray crystallography. On addition of CSA to the racemic forms of 1a and 1b, the (31)P NMR spectrum shows the expected doubling of signals, but, unexpectedly, the same is observed for each of the meso forms of 1a-c. Analogous results using both CSA and CSR have been obtained for the meso and racemic forms of the diastereoisomeric piperazine-bridged macrocyclic-phosphazene compound, 3, whereas no effect was observed for the two meso forms of the doubly bridged macrocyclic-phosphazene compound 4. The phenomenon of doubling of the (31)P NMR signals of the meso form of singly bridged cyclotriphosphazatrienes, 1a-c and 3, is explained by consideration of the equilibrium in solution of independent complexation of a chiral ligand with molecules that have two chiral cyclophosphazene moieties separated by an achiral spacer group. The results show that the stereogenicity of such diastereoisomeric molecules in solution cannot be characterized unequivocally by NMR measurements on addition of either CSR or CSA.     

Construction of a thermoanalyzer for DTA-TD-TMAG-T measurements on metals up to 1100 °C

A thermoanalyzer is described for the simultaneous testing of metals and alloys by three methods: differential thermal analysis (DTA), thermal dilatometry (TD) and thermomagnetometry (TMAG). One reference specimen is used as a standard for each of the above kinds of analysis. Measurements can be performed in vacuum or in a static or dynamic atmosphere of gases at any pressure between normal and 5× 10^–5 Torr. The temperature of the sample can be changed linearly in the range 20–1100 °C. DTA and TD are performed classically, whereas TMAG is based on the temperature and magnetic field-dependences of the reversible magnetic susceptibility of the sample. Some analysis results are presented.

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Zusammenfassung Es wird ein Thermoanalysator zur simultanen Untersuchung von Metallen und Legierungen durch drei Methoden beschrieben: Differentialthermoanalyse (DTA), Thermodilatometrie (TD) und Thermomagnetometrie (TMAG). Für alle drei Verfahren wurde die gleiche Referenzsubstanz als Standard benutzt. Messungen können im Vakuum oder is statischer bzw. bewegter Atmosphäre von Gasen beliebigen Druckes zwischen Normaldruck und 5·10^–5 Torr durchgeführt werden. Die Temperatur der Probe kann zwischen 20 und 1100 °C linear variiert werden. Während DTA und TG die herkömmlichen Verfahren zu Grunde liegen, basiert TMAG auf der Temperatur- und Magnetfeldabhängigkeit der reversiblen magnetischen Suszeptibilität der Probe. Einige Analysenergebnisse wurden dargestellt.

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: (), () (). . , 5·10^–5 . 20–1100°. , . .

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Presented at the 4th European Symposium on Thermal Analysis and Calorimetry, Jena, GDR, August 1987.     

Serum pharmacochemistry combined with multiple data processing approach to screen the bioactive components and their metabolites in Mutan Cortex by ultra‐performance liquid chromatography tandem mass spectrometry

Root cortex of Paeonia suffruticosa Andrews (Paeoniaceae), known as Moutan Cortex (MC), is known to have anti‐allergic and anti‐inflammatory properties. However, the constituents absorbed into blood after oral administration of MC remain unknown. A sensitive and rapid method by ultra‐high‐pressure liquid chromatography–electrospray ionization–quadrupole‐time‐of‐flight mass spectrometry (UPLC‐ESI‐Q‐TOF‐MS) technology and the MetaboLynx^TM software combined with multiple data processing approach (Mdpa) was established to investigate the absorbed constituents in rats after oral administration of MC, providing unique high‐throughput capabilities for drug metabolism study. A hyphenated electrospray ionization and quadrupole‐time‐of‐flight analyzer was used for the determination of accurate mass of the fragment ion in negative mode, with excellent MS mass accuracy and enhanced data acquisition. This rapid automated analysis method was successfully applied for screening and identification of the constituents absorbed and metabolized studies of MC after oral administration to rats. A total of 46 peaks were obtained from MC, 41 of which were tentatively characterized. In the VIP‐plot of orthogonal partial least‐squares discriminant analysis, 23 interesting ions in serum samples were extracted, and 16 parent components and seven metabolites were detected in vivo. The integrative serum pharmacochemistry technique, UPLC‐ESI‐Q‐TOF‐MS, and Mdpa method were successfully applied for rapid discovery of multiple components from MC. Copyright © 2013 John Wiley & Sons, Ltd.     

Photochemical Processes Involved in a Biopolymer Doped by Chromium(VI) during Hologram Recording

This paper is devoted to the study of the photochemical processes occurring during hologram formation in a biopolymer, agar doped by chromium(VI). The evolution of both the absorbing chromium species and the polymer allowed elucidating the reactions taking place during irradiation in conditions representative of hologram formation. As previously observed with dichromated poly(vinyl alcohol) (PVA), polymer containing hydroxyl groups as agar, irradiation of dichromated agar provoked a two step reduction of chromium species and the crosslinking of the host polymer. But agar has a rather complex chemical structure and the photoproducts formed along the polymeric chains throughout the photoredox process were different in agar and in PVA. The photostability of the matrix, that has been proven, coupled with the possibility to record good quality holograms, allowed us to propose dichromated agar as a new natural photosensitive biomaterial.     

Facile Method for 1,3‐Dipolar Cycloaddition Reaction of Azomethine Ylides: Highly Stereoselective Synthesis of Substituted Pyrrolidine Derivatives

The substituted pyrolidine derivatives with high stereoselectivity were obtained through cycloaddition reaction in the presence of a Lewis acid namely diethylzinc by solvent‐free grinding method.