NMR studies of sulphur heterocycles. II—substituent effects in the thieno[2,3-b] [1]benzothiophene and thieno[3,2-b] [1]benzothiophene systems

Substituent chemical shifts for the title systems have been determined at infinite dilution in CDCl₃ from a study of 40 derivatives. An excellent correlation is found between the ortho effect of substituents in the thiophene ring and the corresponding effects in thiophene itself, indicating negligible perturbation by the fused rings. Long range effects of 2- and 3-substituents on the 5- and 6-protons are electronic in origin, but cannot be interpreted in terms of simple resonance theory. These long range effects correlate linearly with σ_p°. An O, S-cis conformation for the formyl group in 2-formyl-thieno[2,3-6][1]benzothiophene is adduced on the basis of chemical shifts.     

A direct numerical procedure for the Cauchy problem for the heat equation

For the Cauchy problem, u_t = u_xx, 0 < x < 1, 0 < t ? T, u(0, t) = f(t), 0 < t ? T, u_x(0, t) = g(t), 0 < t ? T, a direct numerical procedure involving the elementary solution of υ_t = υ_xx, 0 < x, 0 < t ? T, υ_x(0, t) = g(t), 0 < t ? T, υ(x, 0) = 0, 0 < x and a Taylor's series computed from f(t) ? υ(0, t) is studied. Continuous dependence better than any power of logarithmic is obtained. Some numerical results are presented.     

Celite column chromatography followed by reversed-phase high-performance liquid chromatography: a simple, two-step method for separating 14 testicular steroids

The separation of 14 major testicular steroids has been effected by a simple, two-step procedure involving Celite column chromatography followed by reversed-phase high-performance liquid chromatography. The technique does not alter the resolved steroids, which are then available for subsequent analysis.     

Determination of a source term in a linear parabolic partial differential equation

The determination of a spatially dependent source term in a linear parabolic differential equation whose coefficients depend only on the space variable from the specification of the heat flux at one of the boundaries in addition to the usual boundary-initial conditions is a not wellposed problem in the sense of Hadamard. Continuous dependence upon the data is studied and it is demonstrated that the asymptotic dependence as the norm of the data tends to zero is no worse than logarithmic.

---

Zusammenfassung Wir betrachten eine lineare parabolische Differentialgleichung, deren Koeffizienten zeitunabhängig sind. Die Bestimmung der unbekannten zeitunabhängigen Wärmequelle aus dem seitlichen Wärmefluss, zusätzlich zu den üblichen Randbedingungen ist kein wohlbestimmtes Problem im Sinne von Hadamard. Wir betrachten die stetige Abhängigkeit der Lösungen von diesen Daten und zeigen, dass die asymptotische Abhängigkeit höchstens logarithmisch ist, wenn die Norm der Daten gegen Null strebt.

     

Effect of structure and thermodynamic stability on the response of lanthanide stannate pyrochlores to ion beam irradiation

The lanthanide stannates, Ln2Sn2O7, Ln=La-Lu and Y, have the isometric pyrochlore structure, A2B2O7, and their structural properties have been refined by Rietveld analysis of powder neutron and synchrotron X-ray diffraction data. In this study, the enthalpies of formation of selected stannate pyrochlores, Ln=La, Nd, Sm, Eu, Dy, and Yb, were measured by high-temperature oxide melt solution calorimetry. Their radiation response was determined by 1 MeV Kr2+ ion irradiation combined with in situ TEM observation over the temperature range of 25 to 1000 K. The enthalpy of formation from binary oxides of stannate pyrochlores became more endothermic (from -145 to -40 kJ/mol) as the size of the lanthanide in the A-site decreases. A more exothermic trend of the enthalpy of formation was observed in stannate pyrochlores with larger lanthanide ions, particularly La, possibly as a result of increased covalency in the Sn-O bond. In contrast to lanthanide titanate pyrochlores, Ln2Ti2O7, that are generally susceptible to radiation-induced amorphization and zirconate pyrochlores, Ln2Zr2O7, that are generally resistant to radiation-induced amorphization, the lanthanide stannate pyrochlores show a much greater variation in their response to ion irradiation. La, Nd, and Gd stannates experience the radiation-induced transformation to the aperiodic state, and the critical amorphization temperatures are approximately 960, 700, and 350 K, respectively. Y and Er stannate pyrochlores cannot be amorphized by ion beam irradiation, even at 25 K, and instead disorder to a defect fluorite structure. Comparison of the calorimetric and ion irradiation data for titanate, zirconate, and stannate pyrochlores reveals a strong correlation among subtle changes in crystal structure with changing composition, the energetics of the disordering process, and the temperature above which the material can no longer be amorphized. In summary, as the structure approaches the ideal, ordered pyrochlore structure, radiation-induced amorphization is more easily attained. This is consistent with an increasingly exothermic trend in the enthalpies of formation of pyrochlores from the oxides, that is, the greater the thermochemical stability of the pyrochlore structure, the more likely it will be amorphized upon radiation damage rather than recover to a disordered fluorite structure.     

Altered Lipid Composition of Secretory Cells Following Exposure to Zinc Can Be Correlated to Changes in Exocytosis

A micromolar concentration of zinc has been shown to significantly change the dynamics of exocytosis as well as the vesicle contents in a model cell line, providing direct evidence that zinc regulates neurotransmitter release. To provide insight into how zinc modulates these exocytotic processes, neurotransmitter release and vesicle content were compared with single cell amperometry and intracellular impact vesicle cytometry with a range of zinc concentrations. Additionally, time-of-flight secondary ion mass spectrometry (ToF-SIMS) images of lipid distributions in the cell membrane after zinc treatment correlate to changes in exocytosis. By combining electrochemical techniques and mass spectrometry imaging, we proposed a mechanism by which zinc changes the fusion pore and the rate of neurotransmitter release by changing lipid distributions and results in the modulation of synaptic strength and plasticity.     

Selective C−H Halogenation with a Highly Fluorinated Manganese Porphyrin

The selective C?H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron‐deficient and strained aliphatic molecules is rare. Herein, we report selective C?H chlorination and fluorination reactions promoted by an electron‐deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron‐deficient, and strained substrates with unique regio‐ and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo‐Mn^V species is responsible for hydrogen‐atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step.