Synthesis, characterization, and biomedical evaluation of ethylene-bridged tetra-NHC Pd(ii), Pt(ii) and Au(iii) complexes, with apoptosis-inducing properties in cisplatin-resistant neuroblastoma cells.

Synthesis and characterization of the first two cyclic ethylene-bridged tetradentate NHC ligands, with an unsaturated (imidazole) and saturated backbone (2-imidazoline), are described. Complexes of both ligands containing palladium(ii) have been obtained. For platinum(ii) and gold(iii), only the unsaturated tetracarbene complexes could be isolated. The attempts to synthesize a methylene-bridged 2-imidazoline macrocycle are also described. Furthermore, a novel bisimidazolinium ligand precursor and its open-chain PdII and PtII tetracarbene complexes are obtained. Finally, it is shown that the unsaturated gold(iii) tetracarbene is able to induce apoptosis in malignant SK-N-AS neuroblastoma cells via the mitochondrial and ROS pathway and overcomes resistance to cisplatin in vitro.

The first macrocyclic abnormally coordinating tetra-1,2,3-triazole-5-ylidene iron complex: a promising candidate for olefin epoxidation.

The first macrocyclic and abnormally coordinating, mesoionic N-heterocyclic carbene iron complex has been synthesised and characterised via ESI-MS, EA, SC-XRD, CV, NMR and UV/Vis spectroscopy. 13C-NMR spectroscopy and CV measurements indicate a strong σ-donor ability of the carbene moieties, suggesting an efficient catalytic activity of the iron complex in oxidation reactions. Initial tests in the epoxidation of cis-cyclooctene as a model substrate confirm this assumption.

Under the hood of satellite empirical chlorophyll a algorithms: revealing the dependencies of maximum band ratio algorithms on inherent optical properties.

Empirically-based satellite estimates of chlorophyll a [Chl] (e.g. OC3) are an important indicator of phytoplankton biomass. To correctly interpret [Chl] variability, estimates must be accurate and sources of algorithm errors known. While the underlying assumptions of band ratio algorithms such as OC3 have been tacitly hypothesized (i.e. CDOM and phytoplankton absorption covary), the influence of component absorption and scattering on the shape of the algorithm and estimated [Chl] error has yet to be explicitly revealed. We utilized the NOMAD bio-optical data set to examine variations between satellite estimated [Chl] and in situ values. We partitioned the variability into (a) signal contamination and (b) natural phytoplankton variability (variability in chlorophyll-specific phytoplankton absorption). Not surprisingly, the OC3 best-fit curve resulted from a balance between these two different sources of variation confirming the bias by detrital absorption on global scale. Unlike previous descriptions of empirical [Chl] algorithms, our study (a) quantified the mean detrital:phytoplankton absorption as ~1:1in the global NOMAD data set, and (b) removed detrital (CDOM + non-algal particle) absorption in radiative transfer models directly showing that the scale of the remaining variability in the band ratio algorithm was dominated by phytoplankton absorption cross section.