Effects of delayed linear electrical perturbation of the Belousov-Zhabotinsky reaction: a case of complex mixed mode oscillations in a batch reactor

Delayed feedbacks are quite common in many physical and biological systems and in particular many physiological systems. Delay can cause a stable system to become unstable and vice versa. One of the well-studied non-biological chemical oscillators is the Belousov-Zhabotinskii (BZ) reaction. This gives relaxation oscillations for a considerable period of time under batch conditions. This paper deals with the effect of perturbing the limit cycle oscillation of BZ reaction by employing a delayed electrical feedback to the system under batch conditions. The parameters chosen to study are external resistance and delay. For various resistances and delays the system was electrically perturbed and found to exhibit various complex mixed mode oscillations. The dynamic features are accounted for by the Oregonator model, with time delay incorporated in one of the variables. This revised version was published online in June 2006 with corrections to the Cover Date.     

The thermal properties of complex, nanophase-separated macromolecules as revealed by temperature-modulated calorimetry

Linear, flexible macromolecules are long recognized as phase structures limited to micrometer and nanometer dimensions with covalent bonds crossing the interfaces. This special, usually non-equilibrium structure leads to unique properties and a multitude of changes for different thermal and mechanical histories. Analyses that enable the study of these properties are temperature-modulated calorimetry and related techniques which allow the separation of equilibrium and non-equilibrium responses. Research on these topics is reviewed and combined to a model for the nanophases. The new approach to the complex nanophase systems yields a better understanding of the relationship between structure and thermodynamic properties. Special emphasis is placed on the size and surface effects on the glass and melting transitions, the development of rigid-amorphous phases, and the reversible melting within the globally metastable structure.     

M~＋＋BrCN─→MCN~＋＋Br气相反应的从头算研究

Ｍ~＋＋ＢｒＣＮ─→ＭＣＮ~＋＋Ｂｒ气相反应的从头算研究朱荣顺，戴树珊（云南大学化学系，昆明，６５００９１）关键词气相反应，过渡金属阳离子，溴化氰，从头算，相对论赝势对过渡金属离子与一些小分子的气相反应已有大量的实验和理论研究［１～５］，ＭｉｃｈｅｌＳ...     

Synthesis and characterization of a new isocyanato carborane anion [7-OCN-7-CB10H12]; study on its reactivity toward amino containing compounds

The new isocyanato carborane anion, [7-OCN-7-CB₁₀H₁₂]⁻ was prepared by the reaction of 7-H₃N-7-CB₁₀H₁₂ with triphosgene in the presence of triethylamine. The structure of this compound was established by ¹H, ¹¹B and ¹³C NMR as well as IR spectroscopy. The reactivigty of this compound with a series of organic amines was investigated. The resulting ureas were obtained in good to excellent yields. This approach is suitable for development of compounds for use in tumor selective Boron Neutron Capture Therapy (BNCT).     

Small-angle neutron-scattering study of concentrated nonionic-amphiphile solutions

The structure of aqueous solutions of two polyoxyethylene non-ionic amphiphiles, C₁₀E₅ and C₈E₄, is studied by small-angle neutron-scattering along isothermal paths crossing the isotropic single-phase region from 0% to 100% amphiphile volume fractions. The scattered intensityI(k) shows a peak at a valuek _m , which grows monotonically as the amphiphile volume fraction increases. The interpretation of the scattering data lead to the following conclusion: as increases the micellar structure becomes less and less sharp, but some orientational correlations between neighboring amphiphile molecules are preserved even in the pure amphiphile phase.     

Study of the Crystallization of an Aromatic Poly-ether-ketone (PK99) by Calorimetric and X-ray Analysis

An analysis of the crystallization behaviour of a new poly(aryl-ether-ether-ketone-ketone), PK99, by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) is presented. Isothermal crystallization TG were obtained in the whole range between the glass transition temperature (T _g) and the melting temperature (T _m) as a consequence of the slow crystallization kinetics stemming from the closeness of these transitions. The calorimetric results, compared with WAXD data, were applied to determine the theoretical melting temperature and crystallization enthalpy. The DSC and WAXD data were combined in order to calculate the total amount of the crystallizable fraction of the polymer, and a model was proposed to explain the difference between the fractions of crystallinity observed with these techniques. The thermal and X-ray data were also correlated with different lamellar morphologies arising from the crystallization conditions. Finally, DSC experiments on the crystallized sample were used to detect the presence of a rigid amorphous phase which does not relax at T _g. This revised version was published online in July 2006 with corrections to the Cover Date.     

Phase transition and mixed oxide-proton conductivity in germanium oxy-apatites

La_9.75□_0.25(Ge₆O₂₄)O_2.62 oxy-apatite shows a phase transition from triclinic to hexagonal symmetry at approximately 1020 K that has been characterised by high-temperature synchrotron X-ray and neutron powder diffraction, and ionic conductivity measurements. The crystal structure at 1073 K has been determined from joint Rietveld refinements of synchrotron X-ray and neutron powder diffraction data. The study shows that hexagonal-La_9.75□_0.25(Ge₆O₂₄)O_2.62 contains interstitial oxygen at the position previously reported for other oxy-germanates. Changes in the oxide conductivity associated with this structural transition are discussed. The thermal analyses showed a weight loss on heating close to 600 K very likely due to water release. The synchrotron thermodiffractometric study shows an anomaly in the cell parameters evolution at that temperature, which indicates that this residual water is located into the apatite channels. The electrical characterisation under different atmospheres (dry and wet synthetic air) indicates that there is a significant proton contribution to the overall conductivity below 600 K, mainly under wet atmosphere.     

分子诱导效应指数与链烷烃的沸点

利用基团的诱导效应指数，首次提出了分子的诱导效应指数的概念，并定义了 链烷烃的有效碳链长度NC＝（MIs,N/MIb,N)·N，式中MIs,N,MIb,N分别为直链和支 链异构体的分子诱导效应指数。研究结果表明，链烷烃的沸点Tb(℃）与NC关系是 ：1n(806.5-Tb)=6.9824-0.11431NC^2/3     

Boson peak and fast relaxation process near the glass transition in polystyrene

Atactic polystyrene, both side group and main chain deuterated, was investigated by inelastic neutron scattering in a wide temperature range around the glass transition from 2 to 450 K. In the glass the Boson peak position is only very weakly influenced by the deuteration of the phenyl group. In the neighborhood of the glass transition temperatureT _g we find a fast relaxation process similar to other glasses. The onset of the fast relaxation in polystyrene, however, is observed already at temperaturesT _g — 200 K. Results from partially deuterated polystyrene suggest a change of the phenyl ring dynamics already far belowT _g.     

The Role of Chemistry in the Development of Boron Neutron Capture Therapy of Cancer

A therapeutic method that selectively destroys malignant cells in the presence of normal cells is a highly valued goal of oncologists and the possible salvation of cancer patients afflicted with some incurable forms of the disease. Selective cell destruction is, in principle, possible with a binary therapeutic strategy based upon the neutron capture reaction observed with the ¹⁰B nucleus and a neutron of low kinetic energy (thermal neutron). This nuclear fission reaction produces both ⁴He and ⁷Li⁺ nuclei along with about 2.4 MeV of kinetic energy and weak γ-radiation. Since the energetic and cytotoxic product ions travel only about one cell diameter in tissue one may specify the cell type to be destroyed by placing innocent ¹⁰B nuclei on or within only the doomed cells. This article describes the current status of chemical research aimed at the eventual adoption of this therapeutic method (boron neutron capture therapy or BNCT). The multidisciplinary nature of this research effort involves chemistry, biology, nuclear physics, medicine, and related specialties. Methods devised for bringing ¹⁰B nuclei to tumor cells in therapeutic amounts are correlated with the structure of a generalized cell and the various cellular compartments available for boron localization. The synthesis methods employed for the creation of boron-containing biomolecules and drugs are presented along with representative data concerning their efficacy in tumor localization. The outlook for BNCT is especially bright at this time because of rapid developments in the fields of bioorganometallic chemistry, microbiology, immunology, and nuclear science, to name but a few. Very effective boron delivery vehicles have been demonstrated, and through the interaction of chemistry and biology these species are undergoing further improvement and evaluation of their suitability for BNCT.