Photoinduced formation of a cryptand from a coronand: an unexpected switch in cation binding affinity

Aza-crown ethers 2 and 3 with anthracene-containing pendant arms have been synthesised and characterised. Both compounds bind Group 1 metal cations in solution, forming complexes of 1:1 stoichiometry. The properties of compound 2 and its complexes have been studied by a range of techniques, including NMR, UV and fluorescence spectroscopy and X-ray crystallography. The pendant arms can adopt either a cis or a trans geometry, the cis geometry favoured with larger cations. The geometry of the complex affects the fluorescence properties of the system, with larger cations giving higher excimer/monomer ratios. Upon irradiation at lambda>300 nm, coronand 2 forms the cryptand 5 through a reversible intramolecular [4pi+4pi] cycloaddition reaction. The rates of the forward and reverse reactions of this photochromic process are cation dependent; in particular the rate of the thermal reverse reaction is decreased by smaller cations and increased by larger cations, especially Rb(+). The metal binding constants in methanol for 2 and 5 have been determined, revealing that the cryptand 5 binds Na(+) and Rb(+) more weakly than crown ether 2 by over two orders of magnitude.     

Characteristics and design procedure of hyperbolic dies

Nozzle profiles capable of generating constant extensional strain rates are termed hyperbolic dies. When used in polymer extrusion, they exhibit greater potential in inducing and retaining polymer molecular orientation than conventional capillary dies. Most mathematical expressions found in the literature involve several processing variables in describing and designing such nozzle profiles. This report reveals that a hyperbolic die profile, although rather complicated, can be expressed with equations in terms of two ordinary geometrical parameters—the exit diameter and the hyperbolic length. This finding greatly simplifies the design procedure of hyperbolic dies. The extensional strain rate of a hyperbolic die can be related to the length-to-diameter ratio for any given exit diameter. Examples of various types of die profiles are presented and their constant extensional strain-rate characteristics are discussed.     

电荷密度波状态下的TaS_3的某些动态特性及其可能的电子学应用

本文对处在电荷密度波(CDW''S)状态下的TaS₃的直流及交流导电特性进行了仔细的观测,揭示出准一维导体TaS₃的交流响应中滞后现象及相移的存在,演示了准一维导体TaS₃在其转换温度以下所具有的强烈非线性导电特性的各种可能的电子学应用(包括频率转换、调制、外差等),展示了一类新的体效应CDW''S电子器件的可能性。文中还提出了一个电路模型,唯象地描述了所观察到的实验现现象。     

Fluorescence of fly ash samples: Implications for in situ and remote detection

A study of the fluorescence spectra of fly ash samples from different sources has shown that each samples has a characteristic fluorescence and excitation spectrum which could be used to identify and monitor its presence. Fluorescence lifetime studies of samples from different sources have demonstrated characteristic features which can be used for identification. The fluorescence method should be useful for in situ and remote monitoring applications.     

Coupled nuclear and electronic spin-wave modes

The dispersion relation for the coupled nuclear and electronic spin-wave modes that exist in magnetically ordered materials due to the hyperfine interaction is derived by means of a diagrammatic method employing the drone-fermion representation.     

Electrophilic substitution in phenanthroline coordinated to transition metal ions. Rates of nitration of some rhodium(III) and cobalt(III) complexes

Summary The rates of nitration in sulphuric acid of 1,10-phenanthroline coordinated to rhodium(III) and cobalt(Ill) in a number of complexes have been measured and found to be much greater in these complexes than in free phenanthroline under the same conditions. Relative rates are generally higher in those complexes which bear the smaller overall positive charges, but these charges may be modified by protonation of the other ligands in the complexes.Contrary to earlier reports, some other electrophilic substitutions do not occur in a variety of phenanthroline complexes.     

Negative thermal expansion in ZrW2O8: mechanisms, rigid unit modes, and neutron total scattering

The local structure of the low-temperature ordered phase of the negative thermal expansion (NTE) material has been investigated by reverse Monte Carlo (RMC) modeling of neutron total scattering data. We obtain, for the first time, quantitative measurements of the extent to which the and polyhedra move as rigid units, and we show that these values are consistent with the predictions of rigid unit mode theory. We suggest that rigid unit modes are associated with the NTE. Our results do not support a recent interpretation of x-ray-absorption fine structure spectroscopy data in terms of a larger rigid structural component involving the Zr-O-W linkage.