In vitro and in vivo studies of N,N′-bis[2(2-pyridyl)-methyl]pyridine-2,6-dicarboxamide–copper(II) and rheumatoid arthritis

The thermodynamic equilibria of copper(II), zinc(II) and calcium(II) with N,N′-bis[2(2-pyridyl)-methyl]pyridine-2,6-dicarboxamide (L1) have been studied at 25 °C and an ionic strength of 0.15 mol dm⁻³. Spectroscopic studies suggest metal ion complexation promotes deprotonation and coordination of the amide nitrogens resulting in overall tetragonal coordination of Cu²⁺. Blood–plasma modelling predicts that Cu(II) competes effectively against Zn(II) and Ca(II) for L1 in vivo. Octanol–water partition coefficient studies show that Cu(II)–L1 complexes are reasonably lipophilic. However, the CuL1H₋₂ species which predominates at the physiological pH of 7.4 has poor superoxide dismutase activity. Bio-distribution experiments showed activity accumulation and retention in the body of about 50% of the injected dose for the [⁶⁴Cu]Cu(II)–L1 complex after 24 h.     

Chemical speciation of copper(II) diaminediamide derivative of pentacycloundecane--a potential anti-inflammatory agent

Formation constants of copper(ii), zinc(ii) and calcium(ii) with 3,5-diaminodiamido-4-oxahexacyclododecane (cageL) has been studied by glass electrode potentiometry at 25 degrees C and an ionic strength of 0.15 mol dm(-3). Copper(ii) forms more stable complexes with cageL than zinc(ii) and calcium(ii). Metal ion complexation promotes deprotonation and coordination of the amide nitrogens resulting in overall tetragonal coordination of Cu(2+) suggested by the UV-visible electronic spectra. Speciation calculations using a blood plasma model suggest that zinc(ii) and calcium(ii) are good competitors of copper(ii) in vivo. Bio-distribution experiments using (64)Cu-labelled Cu(ii)-cageL show that about 50% dose of the complex is retained in the body after 24 h.     

A Computational Study of the S2 State in the Oxygen-Evolving Complex of Photosystem II by Electron Paramagnetic Resonance Spectroscopy

The S₂ state produces two basic electron paramagnetic resonance signal types due to the manganese cluster in oxygen-evolving complex, which are influenced by the solvents, and cryoprotectant added to the photosystem II samples. It is presumed that a single manganese center oxidation occurs on S₁ → S₂ state transition. The S₂ state has readily visible multiline and g4.1 electron paramagnetic resonance signals and hence it has been the most studied of all the Kok cycle intermediates due to the ease of experimental preparation and stability. The S₂ state was studied using electron paramagnetic resonance spectroscopy at X-band frequencies. The aim of this study was to determine the spin states of the g4.1 signal. The multiline signal was observed to arise from a ground state spin ½ centre while the g4.1 signal generated at ≈140 K NIR illumination was proposed to arise from a spin 52 center with rhombic distortion. The ‘ground’ state g4.1 signal was generated solely or by conversion from the multiline. The data analysis methods used involved numerical simulations of the experimental spectra on relevant models of the oxygen-evolving complex cluster. A strong focus in this paper was on the ‘ground’ state g4.1 signal, whether it is a rhombic 52 spin state signal or an axial 32 spin state signal. The data supported an X-band CW-EPR-generated g4.1 signal as originating from a near rhombic spin 5/2 of the S₂ state of the PSII manganese cluster.     

Synthesis and Crystal Structure of Pyridin-4-ylmethyl 4-Aminobenzoate,C13H12N2O2

Crystallography Reports - The structure of pyridin-4-ylmethyl 4-aminobenzoate was determined using single crystal X-ray diffraction. The compound was also characterized by elemental analysis, which...