A novel PLD configuration for deposition of films of improved quality: a case study of carbon nitride

Pairs of carbon nitride films have simultaneously been deposited by ArF excimer laser ablation of a graphite target in the 2–50 Pa nitrogen pressure window, with one substrate parallel and 48-mm apart from the target in the traditional on-axis geometry, and the other placed in the target plane. The pressure dependence of the apparent growth rate, defined as the measured thickness per number of pulses, is significantly different for the two geometries. In the traditional geometry the growth rate is almost constant at around 0.0035 and 0.023 nm/pulse for 1 and 5 Jcm^-2, respectively, while in the target plane it increases proportionally to the logarithm of the nitrogen pressure for both fluences. Complementary surface characterisation by atomic force microscopy reveals that the films grown in the novel geometry, referred to as inverse pulsed laser deposition, are made up of smaller grains and appear to be more compact. PACS 68.37.Ps; 68.55.-a; 81.15.Fg     

Noncovalent cross-links in context with other structural and functional elements of proteins

Proteins are heteropolymers with evolutionary selected native sequences of residues. These native sequences code for unique and stable 3D structures indispensable for biochemical activity and for proteolysis resistance, the latter which guarantees an appropriate lifetime for the protein in the protease rich cellular environment. Cross-links between residues close in space but far in the primary structure are required to maintain the folded structure of proteins. Some of these cross-links are covalent, most frequently disulfide bonds, but the majority of the cross-links are sets of cooperative noncovalent long-range interactions. In this paper we focus on special clusters of noncovalent long-range interactions: the Stabilization Centers (SCs). The relation between the SCs and secondary structural elements as well as the relation between SCs and functionally important regions of proteins are presented to show a detailed picture of these clusters, which are believed to be primarily responsible for major aspects of protein stability.     

Independent yields of Kr and Xe isotopes in the photofission of heavy nuclei

The yields of Kr (A = 87–93) and Xe (A = 138–143) primary fission fragments produced in ²³²Th, ²³⁸U, and ²⁴⁴Pu photofission upon the scission of a target nucleus and neutron emission were measured in an experiment with bremsstrahlung from electrons accelerated to 25 MeV by a microtron, and the results of these measurements are presented. The experimental procedure used involved the transportation of fragments that escaped from the target by a gas flow through a capillary and the condensation of Kr and Xe inert gases in a cryostat at liquid-nitrogen temperature. The fragments of all other elements were retained with a filter at the capillary inlet. The isotopes of Kr and Xe were identified by the γ spectra of their daughter products. The mass-number distributions of the independent yields of Kr and Xe isotopes are obtained and compared with similar data on fission induced by thermal and fast neutrons; the shifts of the fragment charges with respect to the undistorted charge distribution are determined. Prospects for using photofission fragments in studying the structure of highly neutron-rich nuclei are discussed.     

Finite temperature spectral function of the σ meson from large <Emphasis Type="Italic">N</Emphasis> expansion

The spectral function of the scalar-isoscalar channel of the O(N) symmetric linear σ model is studied in the broken symmetry phase. The investigation is based on the leading order evaluation of the self-energy in the limit of large number of Goldstone bosons. We describe its temperature-dependent variation in the whole low temperature phase. This variation closely reflects the trajectory of the scalar-isoscalar quasi-particle pole. In the model with no explicit chiral symmetry breaking, we studied also the corresponding dynamical exponent near the critical point.     

Three limit cycles for a first‐order exothermic chemical reaction in a continuous stirred‐tank reactor

We study a first‐order exothermic chemical reaction in a continuous stirred‐tank reactor modelled by a 3‐parameter family of vector fields in . We prove that there exist regions in which contain points that depend on parameters such that the chemical reaction has 0, 1, 2, or 3 small amplitude limit cycles that surround the origin. We conclude that this model can reach two stable small amplitude limit cycles. Finally, we show that one of these regions contains the point in the parameter space considered by Gurel and Lapidus [6] who proved numerically the existence of one stable limit cycle. This revised version was published online in July 2006 with corrections to the Cover Date.     

A Versatile Long‐Wavelength‐Absorbing Scaffold for Eu‐Based Responsive Probes

Coumarin‐sensitized, long‐wavelength‐absorbing luminescent Eu^III‐complexes have been synthesized and characterized. The lanthanide binding site consists of a cyclen‐based chelating framework that is attached through a short linker to a 7‐hydroxycoumarin, a 7‐B(OH)₂‐coumarin, a 7‐O‐(4‐pinacolatoboronbenzyl)‐coumarin or a 7‐O‐(4‐methoxybenzyl)‐coumarin. The syntheses are straightforward, use readily available building blocks, and proceed through a small number of high‐yielding steps. The sensitivity of coumarin photophysics to the 7‐substituent enables modulation of the antenna‐absorption properties, and thus the lanthanide excitation spectrum. Reactions of the boronate‐based functionalities (cages) with H₂O₂ yielded the corresponding 7‐hydroxycoumarin species. The same species was produced with peroxynitrite in a ×10⁶–10⁷‐fold faster reaction. Both reactions resulted in the emergence of a strong ≈407 nm excitation band, with concomitant decrease of the 366 nm band of the caged probe. In aqueous solution the methoxybenzyl caged Eu‐complex was quenched by ONOO^?. We have shown that preliminary screening of simple coumarin‐based antennae through UV/Vis absorption spectroscopy is possible as the changes in absorption profile translate with good fidelity to changes in Eu^III‐excitation profile in the fully elaborated complex. Taken together, our results show that the 7‐hydroxycoumarin antenna is a viable scaffold for the construction of turn‐on and ratiometric luminescent probes.     

Determination of drug-cyclodextrin binding constants by capillary zone electrophoresis

Binding constants of the optical isomers of Deprenyl® (selegiline) and its potential metabolites with (2,6-di-O-methyl)--cyclodextrin were determined using electrophoretic mobility data gained from separations performed by capillary electrophoresis, and absorbancies obtained from spectrophotometric experiments. To calculate equilibrium constants l: l complex formation have been assumed. The comparison of the equilibrium constants calculated from different methods shows similar values in their order of magnitude. Their difference may probably be explained by the different media of the measurements. The effect of the structure of compounds on chiral discrimination were also elucidated.     

Isomerization of substituted tricyclic 4,5-dihydropyrazoles

Summary The acid and base catalyzed isomerization of some tricyclic 2-pyrazolines with N-Carbamoyl-,N-thiocarbamoyl-and N-phenyl substituents was investigated. Starting fromcis ortrans 3-H, 3a-H diastereomers, equilibrium mixtures ofcis andtrans diastereomers were prepared which were separated and subsequently studied by¹H NMR and¹³C NMR spectroscopy. A mechanism for the isomerization of the pyrazolines is suggested, supported by a deuterium exchange at C-3a.

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Isomerisierung von einigen substituierten 4,5-Dihydropyrazolen

Zusammenfassung Die Isomerisierung einiger tricyclischer 2-Pyrazoline mit N-Carbamoyl-, N-Thiocarbamoyl-und N-Phenyl-substituenten unter saurer und basischer Katalyse wurde untersucht. Ausgehend von dencis odertrans 3-H,3a-H-Diastereomeren wurdencis- undtrans Gleichgewichtsgemische gewonnen, die getrennt und durch¹H- und¹³C-NMR-Spektroskopie untersucht wurden. Ein Mechanismus für die Isomerisierung von Pyrazolinen wird vorgeschlagen, der durch den Deuteriumaustausch in Position 3a-C unterstützt wird.

     

Thermal behavior of furosemide

Data from theoretical, thermal, and spectroscopic methods were compared in order to map a possible mechanism for the thermal decomposition of furosemide, a diuretic compound, in solid state. TG/DTG curves suggested a two-stage decomposition process. The first product of decomposition is water (m/z = 18), released due to a dimerization resulting in the formation of an amide. Then carbon dioxide (m/z = 44), nitroxide (m/z = 30), and 2-methyl-furanyl ion (m/z = 81) are released in the second stage. The chlorine substituted benzene ring, due to the double bond conjugated system, being the last fraction to decompose. Theoretical calculations presented are in agreement with experimental results.     

The role of the solvation shell decomposition of alkali metal ions in their selective complexation by resorcinarene and its cavitand

2-Methylresorcinarene and its methylene-bridged cavitand derivative as host compounds were investigated in selective complexation of alkali metal ions as guests in methanol media by photoluminescence measurements. These host molecules possess either flexible (2-methylresorcinarene) or rigid (cavitand) molecular skeleton. The Benesi–Hildebrand method and the van't Hoff theory have been applied to determine the stability constants and the thermodynamic parameters, respectively. Considerable interactions between 2-methylresorcinarene and Li⁺ or Na⁺ ions have been observed while the rigid cavitand derivative can interact only with K⁺ or Cs⁺ ions. Neither the complexes of 2-methylresorcinarene with K⁺ or Cs⁺ nor those of the cavitand derivative with Li⁺ or Na⁺ ions are stable at room temperature in methanol media. Quantum-chemical investigations justified that only solvated Li⁺ and Na⁺ ions can form stable complexes with 2-methylresorcinarene while unsolvated K⁺ and Cs⁺ ions form stable complexes with the methylene-bridged cavitand. These results highlight that the stability of the guest solvation shell and its size could play a key role in the selectivity behaviour of host molecules.