Solvent-deficient synthesis of cerium oxide: Characterization and kinetics

The reaction mechanism and kinetics of CeO₂ synthesis using a solvent-deficient method are investigated by simultaneous thermogravimetric analysis (TGA)/differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The decomposition process of the cerium(III) nitrate hexahydrate and ammonium bicarbonate precursor mixture with four observed stages is monitored using TGA/DSC measurements in a nonisothermal regime with heating rates of 5, 10, 15 and 20?°C min^?1. The proposed mechanism indicates a complex synthesis with several parallel reactions, some of which occur at room temperature. A detailed kinetic analysis is performed using isoconversional (expanded Friedman, modified Coats-Redfern and Kissinger) and model fitting (N^th order and nucleation and growth models) methods. The first three stages are best described by the N^th order model with activation energy values of 21, 53 and 90?kJ?mol^?1. The last stage, during which ammonium nitrate decomposition occurs, is best fit by the nucleation and growth model and has an activation energy of 129?kJ?mol^?1. The proposed mechanism, supported by the kinetic analysis in our study, indicates that CeO₂ has already formed before the reaction reaches 200?°C. The average crystallite size of CeO₂ synthesized at 300?°C, which was calculated from the XRD measurements and observed in the SEM and TEM data, is between 10 and 20?nm.     

Borcalein: a Carborane-Based Analogue of Baicalein with 12-Lipoxygenase-Independent Toxicity

12-Lipoxygenase is crucial for tumour angiogenesis. 5,6,7-Trihydroxy-2-phenyl-4H-1-benzopyran-4-one (baicalein) is a suitable inhibitor for this enzyme but is rapidly metabolised in vivo. Thus, an improvement of the metabolic stability is necessary to enhance the therapeutic efficiency. An emerging approach to enhance metabolic stability of carbon-based pharmaceuticals is the use of metabolically stable, non-toxic boron clusters, such as dicarba-closo-dodecaborane(12)s (carboranes) as phenyl mimetics. Therefore, the unsubstituted phenyl ring of baicalein was replaced by meta-carborane, resulting in borcalein, the carborane analogue of baicalein. This substitution resulted in a decreased inhibitory activity toward 12-lipoxygenase, but led to increased toxicity in melanoma (A375, B16, B16F10) and colon cancer cell lines (SW480, HCT116, CT26CL25) with decreased tumour selectivity in comparison to baicalein. Surprisingly, borcalein displays a different mechanism of cytotoxicity with increased intracellular production of reactive oxygen species (ROS), reactive nitrogen species (RNS) and nitric oxide (NO).     

Some results on the Drazin inverse of a modified matrix

We give new conditions under which the Drazin inverse of a modified matrix $A-CD^DB$ can be expressed in terms of the Drazin inverse of $A$ and its generalized Schur complement $Z=D-BA^DC$ , generalizing some recent results in the literature.     

Quinoline-Conjugated Ruthenacarboranes: Toward Hybrid Drugs with a Dual Mode of Action

The role of autophagy in cancer is often complex, ranging from tumor-promoting to -suppressing effects. In this study, two novel hybrid molecules were designed, containing a ruthenacarborane fragment conjugated with a known modulator of autophagy, namely a quinoline derivative. The complex closo-[3-(η⁶-p-cymene)-1-(quinolin-8-yl-acetate)-3,1,2-RuC₂B₉H₁₀] ( 4 ) showed a dual mode of action against the LN229 (human glioblastoma) cell line, where it inhibited tumor-promoting autophagy, and strongly inhibited cell proliferation, de facto blocking cellular division. These results, together with the tendency to spontaneously form nanoparticles in aqueous solution, make complex 4 a very promising drug candidate for further studies in vivo, for the treatment of autophagy-prone glioblastomas.     

Perinatal lead and mercury exposure in Austria

Objective

The heavy metals lead (Pb) and mercury (Hg) are ubiquitous environmental pollutants with high neurotoxic potential. We aimed to compare perinatal Pb and Hg concentrations and to explore the potential association between Pb and Hg exposure and newborn anthropometry.

Study design

Pregnant women were recruited in 2005 at the General Hospital Vienna for participation in this longitudinal study. Pb and Hg concentrations were measured in maternal blood and hair, placenta, cord blood, meconium, and breast milk of 53 mother-child pairs by CV-AAS, GF-AAS, and HPLC-CV-ICPMS. We conducted bivariate analyses and categorical regression analysis (CATREG) to evaluate the determinants of Pb and Hg exposure, and of infant anthropometry.

Results

Median Pb and total Hg contents were low, i.e., 25 μg/L (maternal blood-Pb), 13 μg/L (cord blood-Pb), 0.7 μg/L (maternal blood-Hg), and 1.1 μg/L (cord blood-Hg). Hg levels in maternal and fetal tissues were frequently correlated (r > 0.3, P < 0.05, respectively). Regarding Pb, only maternal blood and cord blood concentrations correlated (P = 0.043). Cord blood levels indicated higher Hg exposure but lower Pb exposure relative to maternal blood contents. Adjusted CATREG models indicated the significant predictors of birth length (placenta-Pb, gestational length, meconium-Pb), birth weight (placenta-Pb, gestational length, maternal blood-Pb), and head circumference (maternal education, maternal height). Besides one significant correlation between maternal hair Hg and birth length, the mercury levels were not associated with newborn anthropometry.

Conclusions

Our data implicate that different modes of action may exist for placentar transfer of Pb and Hg as well as that low Pb exposure levels can result in lower birth weight. The findings related to newborn anthropometry need to be confirmed by the examination of larger study groups. Further research is needed to clarify the mechanisms of Pb and Hg transfer via the placenta, and to explore how prenatal Pb exposure is related to intrauterine growth.     

Cytotoxicity and fibroblast properties during in vitro test of biphasic calcium phosphate/poly-dl-lactide-co-glycolide biocomposites and different phosphate materials

Reconstruction of bone defects is one of the major therapeutic goals in various clinical fields. Bone replacement materials must satisfy a number of criteria. Biological criteria are biocompatibility, controlled biodegradability, and osteoconductive or even osteogenic potential. The material should have a three-dimensional structure with an interconnected pore system so as to permit cell growth and transport of substances. The surface must permit cell adhesion and proliferation. Composite biomaterials have enormous potential for natural bone tissue reparation, filling and augmentation. Calcium hydroxyapatite/polymer composite biomaterials belong to this group of composites and, because of their osteoconductive and biocompatible properties, can be successfully implemented within bone tissue reparations. In this study, possible differences between BCP/DLPLG, pure BCP, and Bio-Oss materials were examined in vitro. During overnight incubations, fibroblast and fibroblast-like cells (L929, MRC5) were able to adhere, spread, and remain viable on BCP, BCP/PLGA, and Bio-Oss discs, as was evidenced by using light- and LVSEM-microscopy. Inhibiting influence over the cell growth is more pronounced in the cases of BCP usage on both cell lines--41.29% for L929 and 43.08% for MRC-5 cells. MRC-5 cells are, within the given experimental conditions, less sensitive on inhibiting effects for the materials BCP/PLGA and Bio-Oss (10.13% and 10.76%, respectively) than for the L929 cell lines (23.02% and 15.44%, respectively).     

Hematite Core Nanoparticles with Carbon Shell: Potential for Environmentally Friendly Production from Iron Mining Sludge

Hematite nanoparticles with amorphous, yet relatively uniform carbon shell, were produced based exclusively on the waste sludge from the iron mine as the raw material. The procedure for acid digestion-based purification of the sludge with the full recovery of acid vapors and the remaining non-toxic rubble is described. Synthesis of the hematite nanoparticles was performed by the arrested precipitation method with cationic surfactant. The particles were thoroughly characterized and the potential of their economical production for the battery industry is indicated.