Structurally Simple Osmium(II) Polypyridyl Complexes as Photosensitizers for Photodynamic Therapy in the Near Infrared.

Five osmium(II) polypyridyl complexes of the general formula [Os(4,7-diphenyl-1,10-phenanthroline)2 L]2+ were synthesized as photosensitizers for photodynamic therapy by varying the nature of the ligand L. Thanks to the pronounced π-extended structure of the ligands and the heavy atom effect provided by the osmium center, these complexes exhibit a high absorption in the near-infrared (NIR) region (up to 740 nm), unlike related ruthenium complexes. This led to a promising phototoxicity in vitro against cancer cells cultured as 2D cell layers but also in multicellular tumor spheroids upon irradiation at 740 nm. The complex [Os(4,7-diphenyl-1,10-phenanthroline)2 (2,2'-bipyridine)]2+ was found to be the most efficient against various cancer cell lines, with high phototoxicity indexes. Experiments on CT26 tumor-bearing BALB/c mice also indicate that the OsII complexes could significantly reduce tumor growth following 740 nm laser irradiation. The high phototoxicity in the biological window of this structurally simple complex makes it a promising photosensitizer for cancer treatment.

Removal of ofloxacin antibiotic using heterogeneous Fenton process over modified alginate beads.

The aim of this work is to study the heterogeneous oxidative degradation of ofloxacin antibiotic using a composite material prepared from sodium alginate and cyclohexane dinitrilo tetraacetic acid (CDTA). The characterization tests indicated the successful incorporation of metal chelator and iron. It was also demonstrated that the synthesized beads are mesoporous. The influence of several experimental parameters (i.e.: H2O2 dose, working temperature, beads loading and initial drug concentration) on the process performances was evaluated. The reaction temperature significantly affects the drug conversion efficiency. It was also observed that the synthesized material was efficient toward the target antibiotic degradation in the presence of small quantities of hydrogen peroxide. Under optimum conditions (0.05 g of granules, initial drug concentration=10mg/L, 25µL of 10mmol/L H2O2), conducted in a batch reaction, 94% degradation of ofloxacin was reached. The results also indicate that the composite material showed a reasonable stability; a relatively low decrease of activity after four successive runs (only 9%) and a negligible iron leaching (0.8%) have been observed. The synthesized composite material offered interesting advantages in terms of simplicity, good stability, ease of recovery from the liquid medium after use and its efficiency in the presence of low quantities of oxidant. It constitutes a good candidate in the water treatment area.

Crystal structure of tris-(4,7-diphenyl-1,10-phenanthroline-κ2 N,N')cobalt(III) tris-(hexa-fluoro-phosphate) monohydrate.

The title compound, [Co(C72H48N6)](PF6)3·H2O, crystallizes with one tripositive complex mol-ecule, three hexa-fluoro-phosphate anions and one solvent mol-ecule of water in the asymmetric unit. The N6 coordination set around the central CoIII atom defines a distorted octa-hedral environment. Four fluorine atoms of one hexa-fluoro-phosphate anion are disordered over two sets of positions with site-occupancy factors of 0.697 (5) and 0.303 (5). In the crystal, inter-molecular π-π stacking inter-actions, C-H⋯π, C-H⋯F and O-H⋯F and inter-actions are present.

New insight into suction and dilution effects in CE coupled to MS via an ESI interface. II--dilution effect.

The hyphenation of CE with MS is nowadays accepted as a powerful analytical approach. As far as ESI, the most common interface, is concerned, one challenge is to provide the most sensitive as well as quantitative information, which is quite a difficult task, as it is linked, among other factors, to suction and dilution effects. In the coaxial ESI configuration, it has been previously demonstrated that suction effect depends on many parameters inherent to the ESI interface geometry, the prevailing ones being the CE capillary protrusion from the interface needle, the sheath liquid (SL) and the overall BGE flow rates and velocity profile. In this paper, dilution effect is studied, as the CE electrolyte is mixed with SL at the interface. Considering peak intensity and efficiency, this effect was studied as a function of the various parameters of the interface (capillary protrusion from the SL tube, nebulizing gas, SL and CE electrolyte flow rates) or of the source (skimmer and ESI voltages, drying gas flow rate and temperature). It appears that the dilution effect seems slightly lower than what can be anticipated from the proportions of the liquid flow rates. This study also indicates that suction effect has to be considered first to better understand the dilution phenomenon, as suction effect leads to an increase in peak intensity, before a dilution effect appears.

Heterogeneous Fenton oxidation of ofloxacin drug by iron alginate support.

A new catalytic wet peroxide oxidation of ofloxacin antibiotic is presented in this work. The removal was achieved using a biodegradable sodium alginate-iron material. Several parameters were studied such as iron content, drying duration of the catalytic support, temperature, solid amount and initial drug concentration. The process showed a strong oxidative ability; at optimum conditions, a nearly complete removal of the drug (around 98%) has been reached after three h of treatment. A relatively low decrease of support activity (around 10%) has been observed after three successive oxidation runs and a low iron leaching has been detected (1.2% of the incorporated quantity). The removal of the substrate has been also examined in the absence of hydrogen peroxide in order to discriminate between the contributions of simple adsorption and oxidation processes in the drug disappearance. We also discussed the influence of the studied experimental parameters on the removal kinetic.

Treatment of electroplating wastewater containing Cu2+, Zn2+ and Cr(VI) by electrocoagulation.

The performance of electrocoagulation, with aluminium sacrificial anode, in the treatment of metal ions (Cu2+, Zn2+ and Cr(VI)) containing wastewater, has been investigated. Several working parameters, such as pH, current density and metal ion concentrations were studied in an attempt to achieve a higher removal capacity. Results obtained with synthetic wastewater revealed that the most effective removal capacities of studied metals could be achieved when the pH was kept between 4 and 8. In addition, the increase of current density, in the range 0.8-4.8 A dm(-2), enhanced the treatment rate without affecting the charge loading, required to reduce metal ion concentrations under the admissible legal levels. The removal rates of copper and zinc were found to be five times quicker than chromium because of a difference in the removal mechanisms. The process was successfully applied to the treatment of an electroplating wastewater where an effective reduction of (Cu2+, Zn2+ and Cr(VI)) concentrations under legal limits was obtained, just after 20 min. The electrode and electricity consumptions were found to be 1 g l(-1) and 32 A h l(-1), respectively. The method was found to be highly efficient and relatively fast compared to conventional existing techniques.

A novel coated platinum electrode for oseltamivir determination in pharmaceuticals.

New coated platinum selective electrodes have been prepared and used for the determination of oseltamivir phosphate (OSL) in bulk drug solutions and in pharmaceutical preparations. Electrodes were using plasticized PVC membranes doped with ion-pair complexes based on drug-phosphomolybdate and drug-tetraphenylborate as electroactive materials. The influence of membrane composition (plasticizers and ion-pair complexes) has been investigated. Optimum performance was obtained for two polymeric membranes: PVC:o-NPPE:OSL-TPB in the ratio of 30:68:2 (%, w:w:w) and PVC:DPP:OSL-PMA in the ratio of 30:68:2 (%, w:w:w). The electrodes exhibited linear responses over large concentration ranges (1.0×10(-5)-1.0×10(-2) and 5.0×10(-5)-5.0×10(-2)M, respectively) with near-Nernstian responses (58.9 and 57.3mV/decade, respectively). The selectivity coefficients indicated good selectivity for OSL drug over a large number of organic compounds and some inorganic cations. The proposed electrodes were successfully applied to the determination of OSL in raw material and in pharmaceutical formulations. The results were validated by comparison with a capillary electrophoresis method.

Evaluation of radiological impacts of tenorm in the Tunisian petroleum industry.

The health impacts associated with uncontrolled release of TENORM in products and wastes released in the petroleum industry are of great concern. In this study, evaluation of TENORM in the Tunisian petroleum products and wastes is presented. Fourteen products samples, twelve waste samples and three samples from the surrounding environment were collected from the Tunisian Refinery STIR site and from two onshore production oilfields. The activity concentrations of (232)Th, (226)Ra and (40)K for all samples were determined using gamma-ray spectrometry with High Purity Germanium (HPGe) detector. The activity concentrations of (224)Ra were calculated only for scale samples. The radium equivalent activity, external and internal hazard indices, absorbed doses rates in air and annual effective dose were also estimated. It was noticed that maximum value of Ra(eq) activity was found to be 398 Bq/kg in scale (w8) collected from an onshore production oilfield which exceeds the maximum Ra(eq) value of 370 Bq/kg recommended for safe use. All hazard indices indicated that scale samples (w6, w7, w8 and w11) could be a significant waste problem especially sample (w8). In this study, the radium isotopic data were used to provide an estimate of scale samples ages by the use of the (224)Ra/(228)Ra activity ratio dating method. Ages of collected scales were found to be in the range 0.91-2.4 years. In this work, radioactivity (NORM contamination) in samples collected from the refinery STIR are showed to be insignificant if compared to those from onshore oilfield production sites.

A new insight into suction and dilution effects in capillary electrophoresis coupled to mass spectrometry via an electrospray ionization interface. Part I-Suction effect.

The hyphenation of CE with MS is nowadays accepted as a powerful analytical approach. Employing ESI, the most common interface, one challenge is to provide quantitative information, which is quite a difficult task, as it is linked, among other factors, to suction and dilution effects. In the coaxial ESI configuration, the suction effect has been presented in literature as stemming from nebulizing gas (NG) flow rate and drying gas temperature. But as this interface consists in three concentric capillaries, allowing for BGE, sheath liquid (SL) and NG mixing, it is demonstrated herein that other parameters are also involved in this suction effect: the CE capillary protrusion from the interface needle, SL flow rate, and overall BGE flow rate and velocity profile. Whereas NG flow rate is the parameter affecting suction to a greater extent, separation capillary protruding length, SL, and overall BGE flow rate have a significant additional impact on this phenomenon. It is shown that SL flow rate can affect suction differently according to the NG velocity, which may be explained by modification of the Taylor cone geometry. Furthermore, it appears that suction effect is noticeably favored by a parabolic velocity profile of the BGE, again probably due to the Taylor cone shape modification. Finally, the temperature gradient created by the contact between the heated NG and the separation capillary enhances this effect.

Single-run separation of cationic, anionic, and polyanionic compounds by CE-ESI-MS.

A method for a single-run separation of cationic, anionic, and polyanionic compounds by CE hyphenated to ESI MS (CE-ESI-MS) is described. One of the main issues for coupling CE to MS with an ESI source consists in maintaining an electric contact for the electrophoretic separation. This condition is only performed if a liquid flow arising from the separation capillary is directed to the needle, making it coupling-compatible. This latter situation is incompatible with the separations of polyanionic compounds of higher electrophoretic mobility (in absolute value) than the electroosmotic mobility, performed in bare fused-silica capillaries under a negative polarity. In this study, several alternative approaches were evaluated to circumvent this difficulty, and applied to the setup of the CE-MS separation of a mixture containing both cationic and polyanionic compounds, which are synthesis intermediates of contrast agents for medical imaging. Eventually, the detection of the cationic and anionic compounds in a single run could be obtained by either using neutrally coated polymethylsiloxane (DB-1) capillaries and simultaneously applying a negative voltage polarity and a pressure allowing to compensate for the residual cathodic EOF or by dynamically modifying the inner wall of a bare fused-silica capillary with a polycationic polymer (hexadimethrine bromide) and using it afterwards under negative voltage polarity.