Electroreductive polymerization of trans-[RuCl 2(vpy) 4] on Nd-Fe-B magnets: electrochemical impedance spectroscopy interpretation, Raman spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy analysis

The electropolymerization of trans-[RuCl₂(vpy)₄] (vpy=4-vinylpyridine) monomer on Nd-Fe-B magnets was studied by electrochemical impedance spectroscopy (EIS). Impedance diagrams obtained during the polymerization process were used to monitor film formation. The EIS results gave insight into the electrochemical phenomena occurring at the magnet surface as the polymerization process progressed. The film structure and morphology were also studied by X-ray photoelectron spectroscopy, scanning electron microscopy and Raman spectroscopy. The Raman spectroscopy results showed that the polymerization takes place at the vinyl groups of the monomer and also that the redox polymer structure is very similar to that of the monomer. The ratio of the intensity of the XPS peaks for fluorine (from the electrolyte PF₆ ^–) and ruthenium present in the film showed that the polymer on Nd-Fe-B contained an equal proportion of Ru²⁺ and Ru³⁺, indicating that part of the film is positively charged, i.e. {[RuCl₂(vpy)₄]⁺} _n .     

Nickel speciation via voltammetric quantification of nickel metal,oxides and salts

A practical speciation method for a solid mixture of nickel species applicable to atmospheric monitoring of Ni⁰, Ni²⁺ and NiO_x is reported. This involves magnetic extraction of Ni⁰ to separate it from the water-soluble nickel salts and the insoluble oxides, followed by adsorptive stripping voltammetry to quantify the nickel in each fraction. The separation scheme was validated by using calibration standards and by simulating air-filter samples prepared with authentic nickel products. The recoveries of nickel were Ni⁰ 94–105% and total nickel 95–102%.     

The efficacy and progress in using radiation as a quarantine treatment of tropical fruits—a case study in Hawaii

Most tropical fruits for export must be treated with an approved quarantine treatment. Three and a half decades of research have demonstrated the efficacy of irradiation as a quarantine treatment in terms of efficiency, effectiveness, and product quality retention. The USFDA and the USDA-APHIS approved irradiation to disinfest fresh foods/fresh papayas in 1986 and 1989, respectively. In early 1995, the Hawaii Department of Agriculture was granted a special permit from USDA-APHIS allowing untreated Hawaiian fruits to be irradiated on the US mainland. The objectives were to gain experience in commercial irradiation as a quarantine treatment and to gather data on shipping and handling procedures, and on product quality. In April 1995, the first shipment of Hawaiian fruit was irradiated at a minimum quarantine dose of 0.25 kGy in an Isomedix plant near Chicago, and then distributed to supermarkets in Illinois and Ohio. Continuous shipments, irradiation, and marketing of various tropical fruits in the US have shown commercial efficacy, quality retention, and excellent consumer acceptance. A commercial e-beam/converted X-ray facility was installed by Titan Corp. on the Island of Hawaii and was operational by late July 2000. Hawaii has become the first place in the world to use irradiation as a quarantine treatment of fruits.     

Mixed-Metal Clusters of Palladium

The importance of palladium complexes in catalytic processes is well-demonstrated by its applications in hydrogenation processes in industry. Mixed metal clusters of palladium are of interest as the palladium ion can attain either a 16- or 18-electron configuration which is an important feature for catalytic processes. Recent developments in the preparation, characterization, chemical and physical properties of these clusters are discussed in this review.     

Synthesis of 1,1-linked galactosyl mannosides carrying a thiazine ring as mimetics of sialyl Lewis X antigen: investigation of the effect of carboxyl group orientation on P-selectin inhibition

This paper describes the synthesis of 1,1-linked galactosyl mannosides as sialyl Lewis X mimetics that contain a spiro-ring to position the carboxylate group in a well-defined orientation. It was found that compound 4 is more active as a P-selectin inhibitor (IC50 = 19 microM) than the parent disaccharide 2, which contains a flexible carboxyl group (IC50 = 193 microM). This result is consistent with that observed in the previous NMR study of sialyl Lewis X bound to P-selectin. The chemistry described here should be useful for the development of selective inhibitors of E-, P-, and L-selectins.     

Trace level analysis of volatile and semi-volatile organic compounds in water using a membrane/jet separator interfaced to an ion trap mass spectrometer

An ion trap mass spectrometer, equipped with a membrane/jet separator interface, is used for the direct detection of volatile and semi-volatile organic compounds in aqueous solutions. Aqueous sample is passed through a capillary membrane, the outside surface of which is continuously purged by helium. The permeate is pneumatically transported to the mass spectrometer via a jet separator which acts as an additional enrichment device. The performance and response characteristics of non-porous silicone and microporous polytetrafluoroethylene (PTFE) membranes are studied. The microporous membrane allows sufficient water to pass for it to be used as a reagent gas for chemical ionization. Both types of membranes provide detection limits in the parts per trillion (pptr) to parts per billion (ppb) range with a linear dynamic range of 3 orders of magnitude for some volatile organic compounds. Results show that there is no detectable matrix effect on response in the selected cases examined. The use of microporous membranes to analyze more polar compounds, such as 5-hydroxymethyl furfuraldehyde and lactic acid, is also demonstrated. The effects of other experimental parameters, such as membrane temperature and length, on sensitivity are also investigated.     

PHEOPHORBIDE a-INDUCED PHOTO-OXIDATION OF CYTOCHROME c: IMPLICATION FOR PHOTODYNAMIC THERAPY

Pheophorbide a-induced photo-oxidation, in vitro, of cytochrome c oxidase and cytochrome c results in irreversible modifications to both protein components. Photo-oxidation of cytochrome c, as exhibited by change in its heme oxidation state, displays exponential kinetics and is detected with a lag period. Both the photo-induced inactivation of the enzyme, and destruction of the substrate ability of cytochrome c occur as complex multi-process events. Under similar experimental conditions, the loss of the substrate capability of cytochrome c develops approximately three times faster than inactivation of the enzyme. The slight lag in the photo-oxidation of cytochrome c is due to pheophorbide a-induced superoxide production. However, the relative amount of photo-oxidant produced is considerably more effective than the cytochrome c reducing capacity of the superoxide. Neither hydroxyl radical nor hydrogen peroxide are involved in the photo-oxidation of the heme function. The possibilities of heme oxidation by a singlet oxygen mediated pathway or direct electron abstraction involving the heme or apoprotein are not excluded. It is proposed that a multi-site oxidation of numerous reduced energy cofactors within cells may augment collateral enzyme inactivation in maximizing photosensitizer-induced cytotoxicity. Accordingly, amphipathic photosensitizers, capable of accessing both lipid and aqueous compartments containing reduced cofactors, may be more effective agents for photodynamic therapy than those which exhibit a high specificity of subcellular localization.     

Relationship between tetrahedron shape measures

Tetrahedron shape measures are used for evaluating the quality of tetrahedra in finite element meshes. Three shape measures, theminimum solid angle _min theradius ratio , and themean ratio , are discussed in this paper. A new formula for the computation of a solid angle of tetrahedron is derived. For different shape measures andv (with values 1), we establish a relationship between andv of the form wherec ₀,c ₁,e ₀, ande ₁ are positive constants. This means that if one measure approaches zero for a poorly-shaped tetrahedron, so does the other. Combined with the property that each measure attains a maximum value only for the regular tetrahedron, this means that the shape measures are equivalent.This work was partially supported by a grant from the Natural Sciences and Engineering Research Council of Canada.