Electron backscattered diffraction analysis of friction stir processed nanocomposites produced via spark plasma sintering.

In the present study, Spark Plasma Sintered (SPSed) aluminium matrix composites were severely deformed through Friction stir processing (FSP). Pure aluminium powders and bimodal sized Al2 O3 particles (80 nm and 25 µm) were firstly mixed by ball milling and then consolidated by spark plasma sintering. The effect of the heat input as well the bimodal particle size of the alumina on the materials' microstructure and texture development was evaluated by electron back scattered diffraction (EBSD) analysis. The EBSD analysis clearly showed that the SPSed nanocomposites possessed bimodal aluminium matrix grain structure as well as a crystallography characterised by random texture. In addition, microstructural examination revealed that the partial recrystallisation occurred during SPS for all the nanocomposites. Also, it is revealed that the Zener pinning effect of Al2 O3 nanoparticles retarded recrystallised grain growth following recrystallisation during FSP and then leading to grain refinement of the aluminium. The results revealed that the heat generated during FSP has a remarkable effect on the grain distribution as well as on the crystallographic orientation. Also, a mixture of {112} <110> shear elements and an ideal strong B/B¯ component were observed. The microstructural changes, occurred during FSP in the stir zone region for Al-Al2 O3 nanocomposites, were attributed to both the discontinuous along with the continuous recrystallisation (DDRX/CDRX). It should be pointed out that with increasing the heat input, recrystallised grains portion increased.

Proof-of-concept trial on the efficacy of sodium tungstate in human obesity.

AIM: Considering the poor long-term success of current dietary and pharmacological interventions, we aimed to evaluate the potential effect of sodium tungstate in the treatment of grade I and II obesity (ClinicalTrials.gov identifier: NCT00555074). METHODS: Prospective, randomized, placebo-controlled, double-blind, proof-of-concept study was carried out. Following a 2-week lead-in period, 30 obese (body mass index, BMI 30.0-39.9 kg/m(2)), non-diabetic subjects were randomized to receive either sodium tungstate (100 mg bid) or placebo for 6 weeks. The primary study endpoint was the absolute change in body weight relative to the time of randomization. RESULTS: Treatment with sodium tungstate [-0.135 ± 0.268 kg (95% CI -0.686 to +0.416 kg)] was not associated with a significant weight loss compared to placebo [-0.063 ± 0.277 kg (95% CI -0.632 to +0.507 kg)] (p = 0.854). Likewise, treatment with sodium tungstate was not associated with significant changes in fat mass (DEXA), resting energy expenditure (indirect calorimetry) or caloric consumption (3-day food records). CONCLUSION: Our data do not support sodium tungstate as a pharmacological agent in the treatment of human obesity.

Tribocorrosion behaviour of nanostructured titanium substrates processed by high-pressure torsion.

Aseptic loosening induced by wear particles from artificial bearing materials is one of the main causes of malfunctioning in total hip replacements. With the increase in young and active patients, complications in revision surgeries and immense health care costs, there is considerable interest in wear-resistant materials that can endure longer in the harsh and corrosive body environment. Here, the tribological behaviour of nanostructured titanium substrates processed by high-pressure torsion (HPT) is investigated and compared with the coarse-grained samples. The high resolution transmission electron microscopy reveals that a nanostructured sample has a grain size of 5-10 nm compared to that of ∼ 10 µm and ∼ 50 µm for untreated and annealed substrates, respectively. Dry and wet wear tests were performed using a linear reciprocating ball-on-flat tribometer. Nanostructured samples show the best dry wear resistance and the lowest wear rate in the electrolyte. There was significantly lower plastic deformation and no change in preferred orientation of nanostructured samples attributable to the wear process. Electrochemical impedance spectroscopy (EIS) shows lower corrosion resistance for nanostructured samples. However, under the action of both wear and corrosion the nanostructured samples show superior performance and that makes them an attractive candidate for applications in which wear and corrosion act simultaneously.

Corrosion behavior of metastable AISI 321 austenitic stainless steel: Investigating the effect of grain size and prior plastic deformation on its degradation pattern in saline media.

The role of grain size and strain rate on the corrosion behavior of plastically-deformed Ti-stabilized austenitic stainless steel (AISI 321) in saline media was investigated. The as-received coarse-grained alloy (CG: ~37 µm) was subjected to thermomechanical processing to develop fine (FG: ~3 µm) and ultrafine (UFG: ~0.24 µm) grained structures. These samples were deformed under high (dynamic) and low (quasi-static) strain-rate conditions to a similar true strain of ~0.86. Microstructural analyses on specimens after deformation prior to corrosion study suggests a shift from the estimated stacking fault energy value of the steel. Electrochemical tests confirm the highest corrosion resistance for UFG specimens due to the formation of the most stable adsorbed passive film. This is followed by FG and CG specimens in that order. For the three grain sizes, the corrosion resistance of specimen deformed under quasi-static loading condition is higher than that subjected to dynamic impact loading while the corrosion resistance of undeformed samples is the least. This work also confirms the non-detrimental effect of TiCs in AISI 321 austenitic stainless steel on its corrosion resistance. However, TiNs were observed to be detrimental by promoting pitting corrosion due to galvanic coupling of TiNs with their surrounding continuous phase. The mechanism of pitting in AISI 321 in chloride solution is proposed.

Total selenium and selenomethionine in pharmaceutical yeast tablets: assessment of the state of the art of measurement capabilities through international intercomparison CCQM-P86.

Results of an international intercomparison study (CCQM-P86) to assess the analytical capabilities of national metrology institutes (NMIs) and selected expert laboratories worldwide to accurately quantitate the mass fraction of selenomethionine (SeMet) and total Se in pharmaceutical tablets of selenised-yeast supplements (produced by Pharma Nord, Denmark) are presented. The study, jointly coordinated by LGC Ltd., UK, and the Institute for National Measurement Standards, National Research Council of Canada (NRCC), was conducted under the auspices of the Comité Consultatif pour la Quantité de Matière (CCQM) Inorganic Analysis Working Group and involved 15 laboratories (from 12 countries), of which ten were NMIs. Apart from a protocol for determination of moisture content and the provision of the certified reference material (CRM) SELM-1 to be used as the quality control sample, no sample preparation/extraction method was prescribed. A variety of approaches was thus used, including single-step and multiple-step enzymatic hydrolysis, enzymatic probe sonication and hydrolysis with methanesulfonic acid for SeMet, as well as microwave-assisted acid digestion and enzymatic probe sonication for total Se. For total Se, detection techniques included inductively coupled plasma (ICP) mass spectrometry (MS) with external calibration, standard additions or isotope dilution MS (IDMS), inductively coupled plasma optical emission spectrometry , flame atomic absorption spectrometry and instrumental neutron activation analysis. For determination of SeMet in the tablets, five NMIs and three academic/institute laboratories (of a total of five) relied upon measurements using IDMS. For species-specific IDMS measurements, an isotopically enriched standard of SeMet (76Se-enriched SeMet) was made available. A novel aspect of this study relies on the approach used to distinguish any errors which arise during analysis of a SeMet calibration solution from those which occur during analysis of the matrix. To help those participants undertaking SeMet analysis to do this, a blind sample in the form of a standard solution of natural abundance SeMet in 0.1 M HCl (with an expected value of 956 mg kg(-1) SeMet) was provided. Both high-performance liquid chromatography (HPLC)-ICP-MS or gas chromatography (GC)-ICP-MS and GC-MS techniques were used for quantitation of SeMet. Several advances in analytical methods for determination of SeMet were identified, including the combined use of double IDMS with HPLC-ICP-MS following extraction with methanesulfonic acid and simplified two-step enzymatic hydrolysis with protease/lipase/driselase followed by HPLC-ICP-IDMS, both using a species-specific IDMS approach. Overall, satisfactory agreement amongst participants was achieved; results averaged 337.6 mg kg(-1) (n = 13, with a standard deviation of 9.7 mg kg(-1)) and 561.5 mg kg(-1) (n = 11, with a standard deviation of 44.3 mg kg(-1)) with median values of 337.6 and 575.0 mg kg(-1) for total Se and SeMet, respectively. Recovery of SeMet from SELM-1 averaged 95.0% (n = 9). The ability of NMIs and expert laboratories worldwide to deliver accurate results for total Se and SeMet in such materials (selensied-yeast tablets containing approximately 300 mg kg(-1) Se) with 10% expanded uncertainty was demonstrated. The problems addressed in achieving accurate quantitation of SeMet in this product are representative of those encountered with a wide range of organometallic species in a number of common matrices.

Tribo-electrochemical technique for studying tribocorrosion behavior of biomaterials.

Tribocorrosion is the term which describes the synergy between tribological and electrochemical processes. An apparatus was designed and built to study the tribocorrosion behavior of biomaterials. Electrochemical set-up with three electrodes is used for controlling the potential of the surface of a conducting material subjected to classical wear testing. Using this equipment, it is possible to carry out friction and wear tests in electrolytic solution under well-defined electrochemical conditions determined by the applied electrode potential. In this paper, this apparatus was described and the tests of deposited TiN on pure Ti for corrosion and tribocorrosion behavior under simulated body fluid were conducted. The presence of TiN layer on the surface of Ti has increased the open circuit potential. The charge transfer resistance (R(ct)) determined using electrochemical impedance spectroscopy (EIS) was higher for the nitrided surfaces than for the Ti substrates. However after wear test, R(ct) was significantly reduced because the protective layer was damaged.

Analysis for metallothioneins using coupled techniques.

Analytical chemistry of metallothioneins based on the coupling of a high resolution separation technique with an element or species selective detection technique is discussed. The role of size-exclusion chromatography (SEC) with on-line atomic spectrometric detection for the quantification of metallothionein fraction in cell cytosols is evaluated. Particular attention is given to the conditions for the separation of metallated metallothionein isoforms (MT-1, MT-2, MT-3) and sub-isoforms within these classes by anion-exchange and reversed-phase HPLC. Techniques for interfacing chromatography with atomic absorption spectrometry (AAS), inductively coupled plasma atomic emission spectrometry (ICP AES) and ICP mass spectrometry (MS) are assessed. The potential of electrospray (tandem) mass spectrometry for the characterization of metallothionein isoforms with respect to molecular mass and aminoacid sequence is highlighted. Perspectives for capillary zone electrophoresis (CZE), microbore and capillary HPLC with ICP MS and electrospray MS(/MS) detection for the probing of metallothioneins are discussed. Applications of hyphenated techniques to the analysis of real-world samples are reviewed.

Validation of the determination of copper and zinc in blood plasma and urine by ICP MS with cross-flow and direct injection nebulization.

The simultaneous determination of copper and zinc in human plasma and urine by inductively coupled plasma mass spectrometry (ICP MS) is discussed. The performances of a cross-flow nebulizer and a direct-injection nebulizer (DIN) were compared. Flow-injection-DIN-ICP MS analysis of clinical samples using 1-2 mul samples was optimized. Isobaric interferences were discussed and were demonstrated to be eliminated for the (65)Cu and most of the Zn nuclides. The need for standard addition to compensate for signal suppression in the case of some serum samples was indicated. Results obtained by ICP MS using calibration with aqueous standard solutions were found to be in good agreement with those obtained by flame AAS for a batch of real blood plasma and urine samples. The methods developed were validated by analysis of several standard reference materials.

Occurrence and effects of organotins on adult common whelk (Buccinum undatum) (Mollusca, Gastropoda) in harbours and in a simulated dredging situation.

Transplanted common whelk (Buccinum undatum) (Mollusca, Gastropoda) accumulated fairly high levels of organotins (tributyltin (TBT) and triphenyltin (TPT)) during exposure in three harbours with different TBT contamination. This did not though lead to an increase in imposex frequency in the adult females studied. Simulating harbour dredging in an experiment using suspended sediment from one of the harbours only resulted in a low concentration of TBT in the tissues of the common whelk and subsequently no changes in the occurrence and degree of imposex. The common whelk seemed to receive the main part of TBT from the water column and the limited bioaccumulation in the experiment indicates that desorption of TBT from the suspended sediment was slow. After TBT has been totally banned, dredging of contaminated sediments will cause increased exposure of the biota to TBT. Due to slow desorption the increase may however, be slight and temporary to pelagic and epibenthic species unless the settled particles are resuspended.

Early diagnosis of maxillary carcinoma.

Problems of early diagnosis of maxillary carcinoma are discussed and symptomatology of early and relatively early cases is fully presented. In cases which might be suspected of being malignant thoughtful attention to all details of examination and careful evaluation of seemingly insignificant symptoms and signs are of greatest importance. All methods of early detection of antral cancer are evaluated. The most valuable from among them are: tomography, including panoramic tomography, and sinoscopy. Measures which should be taken to shorten the interval between symptoms onset and the definite diagnosis of maxillary carcinoma are specified.

Speciation of iodine-containing proteins in Nori seaweed by gel electrophoresis laser ablation ICP-MS.

An analytical approach providing an insight into speciation of iodine in water insoluble fraction of edible seaweed (Nori) was developed. The seaweed, harvested in the Galician coast (Northwestern Spain), contained 67.7±1.3 µg g(-1) iodine of which 25% was water soluble and could be identifies as iodide. Extraction conditions of water insoluble residue using urea, NaOH, SDS and Triton X-100 were investigated. The protein pellets obtained in optimized conditions (after precipitation of urea extracts with acetone), were digested with trypsin and protease XIV. Size exclusion chromatography-ICP-MS of both enzymatic digests demonstrated the occurrence of iodoaminoacids putatively present in proteins. Intact proteins could be separated by gel electrophoresis after an additional extraction of the protein extract with phenol. Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS PAGE) with laser ablation ICP-MS detection of (127)I indicated the presence of iodine in protein bands corresponding to molecular masses of 110 kDa, 40 kDa, 27 kDa, 20 kDa and 10 kDa. 2D IEF-SDS PAGE with laser ablation ICP-MS (127)I imaging allowed the detection of 5 iodine containing protein spots in the alkaline pI range.

Morphological Characterization of the Polyflux 210H Hemodialysis Filter Pores.

Background. Morphological characterization of hemodialysis membranes is necessary to improve pore design. Aim. To delineate membrane pore structure of a high flux filter, Polyflux 210H. Methods. We used a Joel JSM-6010LV scanning electron microscope (SEM) and a SU6600 Hitachi field emission scanning electron microscope (FESEM) to characterize the pore and fiber morphology. The maximal diameters of selected uremic toxins were calculated using the macromolecular modeling Crystallographic Object-Oriented Toolkit (COOT) software. Results. The mean pore densities on the outermost and innermost surfaces of the membrane were 36.81% and 5.45%, respectively. The membrane exhibited a tortuous structure with poor connection between the inner and outer pores. The aperture's width in the inner surface ranged between 34 and 45 nm, which is 8.76-11.60 times larger than the estimated maximum diameter of ß2-microglobulin (3.88 nm). Conclusion. The results suggest that the diameter size of inner pore apertures is not a limiting factor to middle molecules clearance, the extremely diminished density is. Increasing inner pore density and improving channel structure are strategies to improve clearance of middle molecules.