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Electrogenerated polymers based on the nickel(II) complex 2,3-dimethyl-N,N'-bis(salicylidene)butane-2,3-diaminatonickel(II), poly[Ni(saltMe)], were characterised by in situ FTIR and UV/Vis spectroscopy and ex-situ EPR spectroscopy in order to gain insights into film structure, electronic states and charge conduction. The role of the nickel ions during film oxidation was probed by using EPR to study naturally abundant Ni and 61Ni-enriched polymers. The data from all the spectroscopic techniques are consistent, and clearly indicate that polymerisation and redox switching are associated with oxidative ligand based processes; coulometry suggests that one positive charge was delocalised through each monomer unit. EPR provided evidence for the non-direct involvement of the metal in polymer oxidation: the polymer is best described as a polyphenylene-type compound (conducting polymer), rather than an aggregation of nickel complexes (redox polymer), and the main charge carriers are identified as polarons. An explanation for the high electrochemical stability and conductivity of poly[Ni(saltMe)] with respect to that of poly[Ni(salen)] is proposed. based on stereochemical repulsion between monomeric units; this can impose a less compact supramolecular structure on polymers with bulkier substituents.

Two copper(II) complexes with five-coordinate Schiff-base ligands derived from acetylacetone and with a N 3 O 2 coordination sphere, namely bis(acetylacetonate)-3-amino-bis(propyldiimine) and bis(acetylacetonate)-3-methylamino-bis(propyldiimine), were entrapped in the interlayers of a pillared layered clay (PILC). A two-step process in the liquid phase was used: (i) adsorption of copper(II) acetylacetonate in the porous structure of the PILC, and (ii) in situ Schiff condensation of the copper(II) precursor complex with the corresponding triamine. The new materials were characterised by

Following oral administration, the bioavailability of progestogens is very low and highly variable, in part due to metabolism by cytochrome P450 enzymes found in the mucosa of the small intestine. Conversely, the mucosa in the colon contains much lower levels of cytochrome P450 enzymes, thus, colonic delivery of progestogens may be beneficial. Microbiota in the colon are known to metabolize a great number of drugs, therefore, it is important to understand the stability of these hormones in the presence of colonic flora before developing formulations. The aim of this study was to investigate the stability of three progestogens: progesterone, and its two synthetic analogues, medroxyprogesterone acetate (MPA) and levonorgestrel (LNG), in the presence of human colonic microbiota. Progesterone, MPA, and LNG were incubated in mixed fecal inoculum (simulated human colonic fluid) under anerobic conditions. Progesterone was completely degraded after 2 h, whereas levels of MPA and LNG were still detectable after 24 h. The half-lives of progesterone, MPA, and LNG in fecal inoculum were 28, 644, and 240 min, respectively. This study describes the kinetics of colonic microbial metabolism of these hormones for the first time. MPA and LNG show promise for delivery to the colon, potentially improving pharmacokinetics over current oral delivery methods.

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In the title complex, trans-(2,2'-[cyclohexane-1,2-diylbis(nitrilomethylidyne)]diphenolato-kappa(4)O,N,N',O')nickel(II)-chloroform (1/1), [Ni(C(20)H(20)N(2)O(2))].CHCl(3), the Ni atom has a square-planar geometry, slightly tetrahedrally distorted. The Ni-N and Ni-O bonding distances are within the expected ranges for Ni-Schiff base derivatives. The diimine bridge has a gauche conformation with the cyclohexyl ring almost coplanar with the NiN(2)O(2) plane. The complex molecules pack in dimers with an Ni.Ni distance of 3.59 (1) A and form a three-dimensional structure displaying a herring-bone configuration. Channels are occupied by solvent molecules, which are involved in C-H.O hydrogen bonds with the ligand O atoms.