Synthesis and inversion barriers of undeca- and dodeca-substituted saddle shaped porphyrin complexes

Synthesis and barriers to inversion of a series of highly saddle shaped complexes are reported. The ΔG^≠ has decreased by 8 kJ mol⁻¹ at 243 K when the meso phenyl groups are replaced by bulkier 2,6-dichlorophenyl groups, and by 17 kJ mol⁻¹ when one of the peripheral ethyl groups is removed.     

NMR studies of phosphinenickel(0) complexes of ethyl methacrylate Ni(PR3)2(CH2=C(CH3)COOC2H5)

¹³C NMR data are given for a series of phosphinenickel(0) complexes of ethyl methacrylate (ema), Ni(PR₃)₂(CH₂=C(CH₃)COOC₂H₅) (PR₃ = PPh₃ (Ia), PEtPh₂ (Ib), PEt₂Ph (Ic), PMe₂Ph (Id), PEt₃ (Ie)). The olefinic carbon signals of ema shift upfield by 71.5–86.5 ppm on coordination, the magnitude of the upfield shift increasing with increase in the bacisity of the phosphine ligand. The effect of the basicity of PR₃ is discussed on the basis of the back-bonding from Ni to ema. Variable temperature¹H NMR studies reveal that the ema of Id, the complex having the least sterically demanding phosphine ligands, exchanges with free ema in toluene on the NMR time scale. The dependence of the rate of exchange on the concentration of ema shows that the exchange proceeds through anS_N2 mechanism. The activation parameters are: ΔH₂₇₃^≠ 2.75 kcal/mol, ΔG₂₇₃^≠ 12.7 kcal/mol, ΔS₂₇₃^≠ ?37 e.u. The³¹P NMR spectra of the complexes show two doublets when the exchange is frozen out, indicating the inequivalence of the two phosphine ligands in the ema-coordinated complex. The difference in the³¹P chemical shifts of the two coordinated tertiary phosphines increases with increase in the basicity of the PR₃ ligand.     

Linearized method: A new approach for kinetic analysis of central dopamine D(2) receptor specific binding

We proposed a new method (;linearized method') to analyze neuroleptic ligand-receptor specific binding in a human brain using positron emission tomography (PET). We derived the linear equation to solve four rate constants, k(3), k(4), k(5), k(6) from PET data. This method does not demand a radioactivity curve in plasma as an input function to the brain, and can perform fast calculations in order to determine rate constants. We also tested the nonlinearized method including nonlinear equations which is a conventional analysis using plasma radioactivity corrected for ligand metabolites as an input function. We applied these methods to evaluate dopamine D(2) receptor specific binding of [(11)C] YM-09151-2. The value of B(max)/K(d)=k(3)/k (4) obtained by the linearized method was 5.72+/-3.1 which was consistent with the value of 5.78+/-3.4 obtained by the nonlinearized method.     

Low energy asymptotics for Schrödinger operators with slowly decreasing potentials

Low energy behavior of Schrödinger operators with potentials which decay slowly at infinity is studied. It is shown that if the potential is positive then the zero energy is very regular and the resolvent is smooth near 0. This implies rapid local decay for the solutions of the Schrödinger equation. On the other hand, if the potential is negative then the resolvent has discontinuity at zero energy. Thus one cannot expect local decay faster than ordert ^–1 ast.     

Flow injection analysis of potassium using an all-solid-state potassium-selective electrode as a detector

The concentration of potassium was determined by a combination of flow injection analysis (FIA) with an all-solid-state potassium sensor detection. The all-solid-state potassium-selective electrode possessing long-term potential stability was fabricated by coating an electroactive polypyrrole/poly(4-styrenesulfonate) film electrode with a plasticized poly(vinyl chloride) membrane containing valinomycin. The simple FIA system developed in this laboratory demonstrated sensitivity identical to that in the batch system and achieved considerably rapid assay (150 samples h⁻¹). Analyses of soy sauce and control serum samples by this FIA system yielded results in good agreement with those obtained by conventional measurements.