571 research outputs found

    Evaluation of fatigue damage in steel structural components by magnetoelastic Barkhausen signal analysis

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    This paper is concerned with using a magnetic technique for the evaluation of fatigue damage in steel structural components. It is shown that Barkhausen effect measurements can be used to indicate impending failure due to fatigue under certain conditions. The Barkhausen signal amplitude is known to be highly sensitive to changes in density and distribution of dislocations in materials. The sensitivity of Barkhausen signal amplitude to fatigue damage has been studied in the low‐cycle fatigue regime using smooth tensile specimens of a medium strength steel. The Barkhausen measurements were taken at depths of penetration of 0.02, 0.07, and 0.2 mm. It was found that changes in magnetic properties are sensitive to microstructural changes taking place at the surface of the material throughout the fatigue life. The changes in the Barkhausen signals have been attributed to distribution of dislocations in stage I and stage II of fatigue life and the formation of a macrocrack in the final stage of fatigue

    Bitterness suppression with zinc sulfate and na-cyclamate: a model of combined peripheral and central neural approaches to flavor modification

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    Purpose Zinc sulfate is known to inhibit the bitterness of the antimalarial agent quinine [R. S. J. Keast. The effect of zinc on human taste perception. J. Food Sci. 68:1871&ndash;1877 (2003)]. In the present work, we investigated whether zinc sulfate would inhibit other bitter-tasting compounds and pharmaceuticals. The utility of zinc as a general bitterness inhibitor is compromised, however, by the fact that it is also a good sweetness inhibitor [R. S. J. Keast, T. Canty, and P. A. S. Breslin. Oral zinc sulfate solutions inhibit sweet taste perception. Chem. Senses 29:513&ndash;521 (2004)] and would interfere with the taste of complex formulations. Yet, zinc sulfate does not inhibit the sweetener Na-cyclamate. Thus, we determined whether a mixture of zinc sulfate and Na-cyclamate would be a particularly effective combination for bitterness inhibition (Zn) and masking (cyclamate). Method We used human taste psychophysical procedures with chemical solutions to assess bitterness blocking. Results Zinc sulfate significantly inhibited the bitterness of quinine&ndash;HCl, Tetralone, and denatonium benzoate (DB) (p &lt; 0.05), but had no significant effect on the bitterness of sucrose octa-acetate, pseudoephedrine (PSE), and dextromethorphan. A second experiment examined the influence of zinc sulfate on bittersweet mixtures. The bitter compounds were DB and PSE, and the sweeteners were sucrose (inhibited by 25 mM zinc sulfate) and Na-cyclamate (not inhibited by zinc sulfate). The combination of zinc sulfate and Na-cyclamate most effectively inhibited DB bitterness (86%) (p &lt; 0.0016), whereas the mixture\u27s inhibition of PSE bitterness was not different from that of Na-cyclamate alone. Conclusion A combination of Na-cyclamate and zinc sulfate was most effective at inhibiting bitterness. Thus, the combined use of peripheral oral and central cognitive bitterness reduction strategies should be particularly effective for improving the flavor profile of bitter-tasting foods and pharmaceutical formulations. <br /

    Oxygen Tension Is a Determinant of the Matrix-Forming Phenotype of Cultured Human Meniscal Fibrochondrocytes

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    BACKGROUND: Meniscal cartilage displays a poor repair capacity, especially when injury is located in the avascular region of the tissue. Cell-based tissue engineering strategies to generate functional meniscus substitutes is a promising approach to treat meniscus injuries. Meniscus fibrochondrocytes (MFC) can be used in this approach. However, MFC are unable to retain their phenotype when expanded in culture. In this study, we explored the effect of oxygen tension on MFC expansion and on their matrix-forming phenotype. METHODOLOGY/PRINCIPAL FINDINGS: MFC were isolated from human menisci followed by basic fibroblast growth factor (FGF-2) mediated cell expansion in monolayer culture under normoxia (21%O(2)) or hypoxia (3%O(2)). Normoxia and hypoxia expanded MFC were seeded on to a collagen scaffold. The MFC seeded scaffolds (constructs) were cultured in a serum free chondrogenic medium for 3 weeks under normoxia and hypoxia. Constructs containing normoxia-expanded MFC were subsequently cultured under normoxia while those formed from hypoxia-expanded MFC were subsequently cultured under hypoxia. After 3 weeks of in vitro culture, the constructs were assessed biochemically, histologically and for gene expression via real-time reverse transcription-PCR assays. The results showed that constructs under normoxia produced a matrix with enhanced mRNA ratio (3.5-fold higher; p<0.001) of collagen type II to I. This was confirmed by enhanced deposition of collagen II using immuno-histochemistry. Furthermore, the constructs under hypoxia produced a matrix with higher mRNA ratio of aggrecan to versican (3.5-fold, p<0.05). However, both constructs had the same capacity to produce a glycosaminoglycan (GAG) -specific extracellular matrix. CONCLUSIONS: Our data provide evidence that oxygen tension is a key player in determining the matrix phenotype of cultured MFC. These findings suggest that the use of normal and low oxygen tension during MFC expansion and subsequent neo-tissue formation cultures may be important in engineering different regions of the meniscus

    Landmarking the brain for geometric morphometric analysis: An error study

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    Neuroanatomic phenotypes are often assessed using volumetric analysis. Although powerful and versatile, this approach is limited in that it is unable to quantify changes in shape, to describe how regions are interrelated, or to determine whether changes in size are global or local. Statistical shape analysis using coordinate data from biologically relevant landmarks is the preferred method for testing these aspects of phenotype. To date, approximately fifty landmarks have been used to study brain shape. Of the studies that have used landmark-based statistical shape analysis of the brain, most have not published protocols for landmark identification or the results of reliability studies on these landmarks. The primary aims of this study were two-fold: (1) to collaboratively develop detailed data collection protocols for a set of brain landmarks, and (2) to complete an intra- and inter-observer validation study of the set of landmarks. Detailed protocols were developed for 29 cortical and subcortical landmarks using a sample of 10 boys aged 12 years old. Average intra-observer error for the final set of landmarks was 1.9 mm with a range of 0.72 mm-5.6 mm. Average inter-observer error was 1.1 mm with a range of 0.40 mm-3.4 mm. This study successfully establishes landmark protocols with a minimal level of error that can be used by other researchers in the assessment of neuroanatomic phenotypes. © 2014 Chollet et al

    Rh-POP Pincer Xantphos Complexes for C-S and C-H Activation. Implications for Carbothiolation Catalysis

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    The neutral Rh­(I)–Xantphos complex [Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos)­Cl]<sub><i>n</i></sub>, <b>4</b>, and cationic Rh­(III) [Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos)­(H)<sub>2</sub>]­[BAr<sup>F</sup><sub>4</sub>], <b>2a</b>, and [Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos-3,5-C<sub>6</sub>H<sub>3</sub>(CF<sub>3</sub>)<sub>2</sub>)­(H)<sub>2</sub>]­[BAr<sup>F</sup><sub>4</sub>], <b>2b</b>, are described [Ar<sup>F</sup> = 3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>; Xantphos = 4,5-bis­(diphenylphosphino)-9,9-dimethylxanthene; Xantphos-3,5-C<sub>6</sub>H<sub>3</sub>(CF<sub>3</sub>)<sub>2</sub> = 9,9-dimethylxanthene-4,5-bis­(bis­(3,5-bis­(trifluoromethyl)­phenyl)­phosphine]. A solid-state structure of <b>2b</b> isolated from C<sub>6</sub>H<sub>5</sub>Cl solution shows a κ<sup>1</sup>-chlorobenzene adduct, [Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos-3,5-C<sub>6</sub>H<sub>3</sub>(CF<sub>3</sub>)<sub>2</sub>)­(H)<sub>2</sub>(κ<sup>1</sup>-ClC<sub>6</sub>H<sub>5</sub>)]­[BAr<sup>F</sup><sub>4</sub>], <b>3</b>. Addition of H<sub>2</sub> to <b>4</b> affords, crystallographically characterized, [Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos)­(H)<sub>2</sub>Cl], <b>5</b>. Addition of diphenyl acetylene to <b>2a</b> results in the formation of the C–H activated metallacyclopentadiene [Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos)­(ClCH<sub>2</sub>Cl)­(σ,σ-(C<sub>6</sub>H<sub>4</sub>)­C­(H)CPh)]­[BAr<sup>F</sup><sub>4</sub>], <b>7</b>, a rare example of a crystallographically characterized Rh–dichloromethane complex, alongside the Rh­(I) complex <i>mer</i>-[Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos)­(η<sup>2</sup>-PhCCPh)]­[BAr<sup>F</sup><sub>4</sub>], <b>6</b>. Halide abstraction from [Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos)­Cl]<sub><i>n</i></sub> in the presence of diphenylacetylene affords <b>6</b> as the only product, which in the solid state shows that the alkyne binds perpendicular to the κ<sup>3</sup>-POP Xantphos ligand plane. This complex acts as a latent source of the [Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos)]<sup>+</sup> fragment and facilitates <i>ortho</i>-directed C–S activation in a number of 2-arylsulfides to give <i>mer</i>-[Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos)­(σ,κ<sup>1</sup>-Ar)­(SMe)]­[BAr<sup>F</sup><sub>4</sub>] (Ar = C<sub>6</sub>H<sub>4</sub>COMe, <b>8</b>; C<sub>6</sub>H<sub>4</sub>(CO)­OMe, <b>9</b>; C<sub>6</sub>H<sub>4</sub>NO<sub>2</sub>, <b>10</b>; C<sub>6</sub>H<sub>4</sub>CNCH<sub>2</sub>CH<sub>2</sub>O, <b>11</b>; C<sub>6</sub>H<sub>4</sub>C<sub>5</sub>H<sub>4</sub>N, <b>12</b>). Similar C–S bond cleavage is observed with allyl sulfide, to give <i>fac</i>-[Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos)­(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)­(SPh)]­[BAr<sup>F</sup><sub>4</sub>], <b>13</b>. These products of C–S activation have been crystallographically characterized. For <b>8</b> in situ monitoring of the reaction by NMR spectroscopy reveals the initial formation of <i>fac</i>-κ<sup>3</sup>-<b>8</b>, which then proceeds to isomerize to the <i>mer</i>-isomer. With the <i>para</i>-ketone aryl sulfide, 4-SMeC <sub>6</sub>H<sub>4</sub>COMe, C–H activation <i>ortho</i> to the ketone occurs to give <i>mer</i>-[Rh­(κ<sup>3</sup>-<sub>P,O,P</sub>-Xantphos)­(σ,κ<sup>1</sup>-4-(COMe)­C<sub>6</sub>H<sub>3</sub>SMe)­(H)]­[BAr<sup>F</sup><sub>4</sub>], <b>14</b>. The temporal evolution of carbothiolation catalysis using <i>mer</i>-κ<sup>3</sup>-<b>8</b>, and phenyl acetylene and 2-(methylthio)­acetophenone substrates shows initial fast catalysis and then a considerably slower evolution of the product. We suggest that the initially formed <i>fac</i>-isomer of the C–S activation product is considerably more active than the <i>mer</i>-isomer (i.e., <i>mer</i>-<b>8</b>), the latter of which is formed rapidly by isomerization, and this accounts for the observed difference in rates. A likely mechanism is proposed based upon these data

    Tension-Compression Loading with Chemical Stimulation Results in Additive Increases to Functional Properties of Anatomic Meniscal Constructs

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    Objective: This study aimed to improve the functional properties of anatomically-shaped meniscus constructs through simultaneous tension and compression mechanical stimulation in conjunction with chemical stimulation. Methods: Scaffoldless meniscal constructs were subjected to simultaneous tension and compressive stimulation and chemical stimulation. The temporal aspect of mechanical loadingwas studied by employing two separate five day stimulation periods. Chemical stimulation consisted of the application of a catabolic GAG-depleting enzyme, chondroitinase ABC (C-ABC), and an anabolic growth factor, TGF-b1. Mechanical and chemical stimulation combinations were studied through a full-factorial experimental design and assessed for histological, biochemical, and biomechanical properties following 4 wks of culture. Results: Mechanical loading applied from days 10–14 resulted in significant increases in compressive, tensile, and biochemical properties of meniscal constructs. When mechanical and chemical stimuliwere combined significant additive increases in collagen per wet weight (4-fold), compressive instantaneous (3-fold) and relaxation (2-fold) moduli, and tensile moduli in the circumferential (4-fold) and radial (6-fold) directions were obtained. Conclusions: This study demonstrates that a stimulation regimen of simultaneous tension and compression mechanical stimulation, C-ABC, and TGF-b1 is able to create anatomic meniscus constructs replicating the compressive mechanica
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