A Raman spectroscopic study of the antimonite mineral peretaite Ca(SbO)4(OH)2(SO4)2•2H2O

Raman spectra of mineral peretaite Ca(SbO)4(OH)2(SO4)2•2H2O were studied, and related to the structure of the mineral. Raman bands observed at 978 and 980 cm-1 and a series of overlapping bands observed at 1060, 1092, 1115, 1142 and 1152 cm-1 are assigned to the SO42- ν1 symmetric and ν3 antisymmetric stretching modes. Raman bands at 589 and 595 cm-1 are attributed to the SbO symmetric stretching vibrations. The low intensity Raman bands at 650 and 710 cm-1 may be attributed to SbO antisymmetric stretching modes. Raman bands at 610 cm-1 and at 417, 434 and 482 cm-1 are assigned to the SO42- 4 and 2 bending modes, respectively. Raman bands at 337 and 373 cm-1 are assigned to O-Sb-O bending modes. Multiple Raman bands for both SO42- and SbO stretching vibrations support the concept of the non-equivalence of these units in the coquandite structure.

Factores de riesgo asociados en la aparición del SBO en nuevas instituciones

El Síndrome de Burnout (SBO) es definido por Thomaé, Ayala, Sphan y Stortti como una respuesta al stress laboral crónico que se caracteriza por tres síntomas principales: agotamiento emocional, despersonalización y baja realización personal. Suele darse con más frecuencia en aquellos trabajadores que interactúan constantemente con los usuarios directos: servicios de salud, atención, asistencia social. Se trata de una experiencia subjetiva interna que agrupa sentimientos y actitudes y que tiene un cáliz negativo para el sujeto, dado que implica alteraciones, problemas y disfunciones psicofisiológicas. El actual informe se enmarca dentro del proyecto acreditado 'Identificación de factores asociados a la re - intervención en problemáticas asistenciales de jóvenes II', que se está realizando en el Grupo de Investigación GIPJURI de Psicología Jurídica de la Facultad de Psicología de la Universidad Nacional de Mar del Plata. Para la consecución de sus objetivos acudimos a los Centros de Protección de los Derechos del Niño (CPDeN) que son unidades técnico operativas con una o más sedes, creadas por la ley nacional 26.061 de Protección Integral de los Derechos de las niñas, niños y adolescentes; y la ley provincial 13.298 de la Promoción y Protección de los Derechos de los Niños, que desempeñan las funciones de facilitar que el niño que tenga amenazados o violados sus derechos, pueda acceder a los programas y planes disponibles en su comunidad . El trabajo que dimos en llamar 'Factores de riesgo asociados en la aparición del SBO en nuevas instituciones', además de enmarcarse en dicho proyecto, se presenta a continuación y en base a los datos recolectados para un informe previo denominado 'El Síndrome de Burnout (SBO) en nuevas instituciones'. Este último se realizó durante el año 2010 a modo de sondeo de situación en relación al SBO en los Centros de Protección de los Derechos de los Niños del partido de General Pueyrredón. Se evaluaron tres escalas de manera anónima mediante el inventario de Maslach, éstas fueron 'agotamiento emocional' (EE), 'despersonalización' (D) y 'realización personal' (PA). De una población total de 30 profesionales se tomó una muestra de 25 que accedieron a responder al cuestionario de manera voluntaria. Los datos obtenidos revelan en general un alto nivel de EE, así como también de PA. Por otro lado contamos con una serie de entrevistas semiestructuradas administradas a 28 de los 30 profesionales a través de las cuales obtuvimos información de tipo cualitativa; con la cual nos proponemos arribar a hipótesis acerca de las variables que puedan estar interviniendo en relación al síndrome con el fin de, en un futuro proyecto, pensar en medidas o acciones institucionales para prevenir su aparición o detener su proliferación

Factores de riesgo asociados en la aparición del SBO en nuevas instituciones

El Síndrome de Burnout (SBO) es definido por Thomaé, Ayala, Sphan y Stortti como una respuesta al stress laboral crónico que se caracteriza por tres síntomas principales: agotamiento emocional, despersonalización y baja realización personal. Suele darse con más frecuencia en aquellos trabajadores que interactúan constantemente con los usuarios directos: servicios de salud, atención, asistencia social. Se trata de una experiencia subjetiva interna que agrupa sentimientos y actitudes y que tiene un cáliz negativo para el sujeto, dado que implica alteraciones, problemas y disfunciones psicofisiológicas. El actual informe se enmarca dentro del proyecto acreditado 'Identificación de factores asociados a la re - intervención en problemáticas asistenciales de jóvenes II', que se está realizando en el Grupo de Investigación GIPJURI de Psicología Jurídica de la Facultad de Psicología de la Universidad Nacional de Mar del Plata. Para la consecución de sus objetivos acudimos a los Centros de Protección de los Derechos del Niño (CPDeN) que son unidades técnico operativas con una o más sedes, creadas por la ley nacional 26.061 de Protección Integral de los Derechos de las niñas, niños y adolescentes; y la ley provincial 13.298 de la Promoción y Protección de los Derechos de los Niños, que desempeñan las funciones de facilitar que el niño que tenga amenazados o violados sus derechos, pueda acceder a los programas y planes disponibles en su comunidad . El trabajo que dimos en llamar 'Factores de riesgo asociados en la aparición del SBO en nuevas instituciones', además de enmarcarse en dicho proyecto, se presenta a continuación y en base a los datos recolectados para un informe previo denominado 'El Síndrome de Burnout (SBO) en nuevas instituciones'. Este último se realizó durante el año 2010 a modo de sondeo de situación en relación al SBO en los Centros de Protección de los Derechos de los Niños del partido de General Pueyrredón. Se evaluaron tres escalas de manera anónima mediante el inventario de Maslach, éstas fueron 'agotamiento emocional' (EE), 'despersonalización' (D) y 'realización personal' (PA). De una población total de 30 profesionales se tomó una muestra de 25 que accedieron a responder al cuestionario de manera voluntaria. Los datos obtenidos revelan en general un alto nivel de EE, así como también de PA. Por otro lado contamos con una serie de entrevistas semiestructuradas administradas a 28 de los 30 profesionales a través de las cuales obtuvimos información de tipo cualitativa; con la cual nos proponemos arribar a hipótesis acerca de las variables que puedan estar interviniendo en relación al síndrome con el fin de, en un futuro proyecto, pensar en medidas o acciones institucionales para prevenir su aparición o detener su proliferación

Factores de riesgo asociados en la aparición del SBO en nuevas instituciones

El Síndrome de Burnout (SBO) es definido por Thomaé, Ayala, Sphan y Stortti como una respuesta al stress laboral crónico que se caracteriza por tres síntomas principales: agotamiento emocional, despersonalización y baja realización personal. Suele darse con más frecuencia en aquellos trabajadores que interactúan constantemente con los usuarios directos: servicios de salud, atención, asistencia social. Se trata de una experiencia subjetiva interna que agrupa sentimientos y actitudes y que tiene un cáliz negativo para el sujeto, dado que implica alteraciones, problemas y disfunciones psicofisiológicas. El actual informe se enmarca dentro del proyecto acreditado 'Identificación de factores asociados a la re - intervención en problemáticas asistenciales de jóvenes II', que se está realizando en el Grupo de Investigación GIPJURI de Psicología Jurídica de la Facultad de Psicología de la Universidad Nacional de Mar del Plata. Para la consecución de sus objetivos acudimos a los Centros de Protección de los Derechos del Niño (CPDeN) que son unidades técnico operativas con una o más sedes, creadas por la ley nacional 26.061 de Protección Integral de los Derechos de las niñas, niños y adolescentes; y la ley provincial 13.298 de la Promoción y Protección de los Derechos de los Niños, que desempeñan las funciones de facilitar que el niño que tenga amenazados o violados sus derechos, pueda acceder a los programas y planes disponibles en su comunidad . El trabajo que dimos en llamar 'Factores de riesgo asociados en la aparición del SBO en nuevas instituciones', además de enmarcarse en dicho proyecto, se presenta a continuación y en base a los datos recolectados para un informe previo denominado 'El Síndrome de Burnout (SBO) en nuevas instituciones'. Este último se realizó durante el año 2010 a modo de sondeo de situación en relación al SBO en los Centros de Protección de los Derechos de los Niños del partido de General Pueyrredón. Se evaluaron tres escalas de manera anónima mediante el inventario de Maslach, éstas fueron 'agotamiento emocional' (EE), 'despersonalización' (D) y 'realización personal' (PA). De una población total de 30 profesionales se tomó una muestra de 25 que accedieron a responder al cuestionario de manera voluntaria. Los datos obtenidos revelan en general un alto nivel de EE, así como también de PA. Por otro lado contamos con una serie de entrevistas semiestructuradas administradas a 28 de los 30 profesionales a través de las cuales obtuvimos información de tipo cualitativa; con la cual nos proponemos arribar a hipótesis acerca de las variables que puedan estar interviniendo en relación al síndrome con el fin de, en un futuro proyecto, pensar en medidas o acciones institucionales para prevenir su aparición o detener su proliferación

Analysis of the damage domains of sbo sequences with rcp passive thermal shutdown

The integrated Safety Assessment (ISA) methodology, developed by the Spanish Nuclear Safety Council (CSN), has been applied to a thermal-hydraulic analysis of PWR Station Blackout (SBO) sequences in the context of the IDPSA (Integrated Deterministic-Probabilistic Safety Assessment) network objectives. The ISA methodology allows obtaining the damage domain (the region of the uncertain parameters space where the damage limit is exceeded) for each sequence of interest as a function of the operator actuations times. Given a particular safety limit or damage limit, several data of every sequence are necessary in order to obtain the exceedance frequency of that limit. In this application these data are obtained from the results of the simulations performed with MAAP code transients inside each damage domain and the time-density probability distributions of the manual actions. Damage limits that have been taken into account within this analysis are: local cladding damage (PCT>1477 K); local fuel melting (T>2499 K); fuel relocation in lower plenum and vessel failure. Therefore, to every one of these damage variables corresponds a different damage domain. The operation of the new passive thermal shutdown seals developed by several companies since Fukushima accident is considered in the paper. The results show the capability and necessity of the ISA methodology, or similar, in order to obtain accurate results that take into account time uncertainties.

Raman spectroscopic study of the antimonate mineral brandholzite Mg[Sb(OH)12].6H2O

Raman spectra of brandholzite Mg[Sb(OH)6].6H2O were studied, complemented with infrared spectra, and related to the structure of the mineral. An intense Raman sharp band at 618 cm-1 is attributed to the SbO symmetric stretching mode. The low intensity band at 730 cm-1 is ascribed to the SbO antisymmetric stretching vibration. Low intensity Raman bands were found at 503, 526 and 578 cm-1. Corresponding infrared bands were observed at 527, 600, 637, 693, 741 and 788 cm-1. Four Raman bands observed at 1043, 1092, 1160 and 1189 cm-1 and eight infrared bands at 963, 1027, 1055, 1075, 1108, 1128, 1156 and 1196 cm-1 are assigned to δ SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and hydroxyl units is observed. Raman bands are observed at 3240, 3383, 3466, 3483 and 3552 cm-1, infrared bands at 3248, 3434 and 3565 cm-1. The first two Raman bands and the first infrared band are assigned to water stretching vibrations. The two higher wavenumber Raman bands observed at 3466 and 3552 cm-1 and two infrared bands at 3434 and 3565 cm-1 are assigned to the stretching vibrations of the hydroxyl units. Observed Raman and infrared bands are connected with O-H…O hydrogen bonds and their lengths 2.72, 2.79, 2.86, 2.88 and 3.0 Å (Raman) and 2.73, 2.83 and 3.07 Å (infrared).

Raman spectroscopic study of the antimonate mineral bahianite Al5Sb35+O14(OH)2

Raman spectroscopy has been used to characterise the antimonate mineral bahianite Al5Sb35+O14(OH)2 , a semi-precious gem stone. The mineral is characterised by an intense Raman band at 818 cm-1 assigned to Sb3O1413- stretching vibrations. Other lower intensity bands at 843 and 856 cm-1 are also assigned to this vibration and this concept suggests the non-equivalence of SbO units in the structure. Low intensity Raman bands at 669 and 682 cm-1 are probably assignable to the OSbO antisymmetric stretching vibrations. Raman bands at 1756, 1808 and 1929 cm-1 may be assigned to δ SbOH deformation modes, whilst Raman bands at 3462 and 3495 cm-1 are assigned to AlOH stretching vibrations. Complexity in the low wave number region is attributed to the composition of the mineral.

Raman spectroscopic study of the antimonate mineral lewisite (Ca,Fe,Na)2(Sb,Ti)2O6(O,OH)7

The mineral lewisite, (Ca,Fe,Na)2(Sb,Ti)2O6(O,OH)7 an antimony bearing mineral has been studied by Raman spectroscopy. A comparison is made with the Raman spectra of other minerals including bindheimite, stibiconite and roméite. The mineral lewisite is characterised by an intense sharp band at 517 cm-1 with a shoulder at 507 cm-1 assigned to SbO stretching modes. Raman bands of medium intensity for lewisite are observed at 300, 356 and 400 cm-1. These bands are attributed to OSbO bending vibrations. Raman bands in the OH stretching region are observed at 3200, 3328, 3471 cm-1 with a distinct shoulder at 3542 cm-1. The latter is assigned to the stretching vibration of OH units. The first three bands are attributed to water stretching vibrations. The observation of bands in the 3200 to 3500 cm-1 region suggests that water is involved in the lewisite structure. If this is the case then the formula may be better written as Ca, Fe2+, Na)2(Sb, Ti)2(O,OH)7 •xH2O.

Raman spectroscopic study of the antimonate mineral brizziite NaSbO3

Raman spectra of antimonate mineral brizziite NaSbO3 were studied and related to the structure of the mineral. Two sharp bands at 617 and 660 cm-1 are attributed to the SbO3- symmetric stretching mode. The reason for two symmetric stretching vibrations depends upon the bonding of the SbO3- units. The band at 617 cm-1 is assigned to bonding through the Sb and the 660 cm-1 to bonding through the oxygen. The low intensity band at 508 cm-1 is ascribed to the SbO antisymmetric stretching vibration. Low intensity bands were found at 503, 526 and 578 cm-1. Sharp Raman bands observed at 204, 230, 307 and 315 cm-1are assigned to OSbO bending modes. Raman spectroscopy enables a better understanding of the molecular structure of the mineral brizziite.

Vibrational spectroscopic study of the antimonate mineral stibiconite Sb3+Sb5+2O6(OH)

The Raman and infrared spectrum of the antimonate mineral stibiconite Sb3+Sb5+2O6(OH) were used to define aspects of the molecular structure of the mineral. Bands attributable to water, OH stretching and bending and SbO stretching and bending were assigned. The mineral has been shown to contain both calcium and water and the formula is probably best written (Sb3+,Ca)ySb5+2-x(O,OH,H2O)6-7 where y approaches 1 and x varies from 0 to 1. Infrared spectroscopy complimented with thermogravimetric analysis proves the presence of water in the stibiconite structure. The mineral stibiconite is formed through replacement of the sulphur in stibnite. No Raman or infrared bands attributable to stibnite were identified in the spectra.

Raman spectroscopic study of the antimonate mineral bottinoite Ni[Sb2(OH)12].6H2O and in comparison with brandholzite Mg[Sb5+2(OH)12]•6H2O

Raman spectra of bottinoite Ni[Sb(OH)6].6H2O were studied, and related to the molecular structure of the mineral. An intense sharp Raman band at 618 cm-1 is attributed to the SbO symmetric stretching mode. The low intensity band at 735 cm-1 is ascribed to the SbO antisymmetric stretching vibration. Low intensity Raman bands were found at 501, 516 and 578 cm-1. Four Raman bands observed at 1045, 1080, 1111 and 1163 cm-1 are assigned to δ SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and hydroxyl units is observed. Raman bands are observed at 3223, 3228, 3368, 3291, 3458 and 3510 cm-1. The first two Raman bands are assigned to water stretching vibrations. The two higher wavenumber Raman bands observed at 3466 and 3552 cm-1 and two infrared bands at 3434 and 3565 cm-1 are assigned to the stretching vibrations of the hydroxyl units. Observed Raman and infrared bands are connected with O-H…O hydrogen bonds and their lengths 2.72, 2.79, 2.86, 2.88 and 3.0 Å (Raman) and 2.73, 2.83 and 3.07 Å (infrared).

Cross-talk of subchondral bone osteoblasts and articular cartilage chondrocytes : a new insight in understanding osteoarthritis pathogenesis

Osteoarthritis (OA) is the most common musculoskeletal disorder and represents a major health burden to society. In the course of the pathological development of OA, articular cartilage chondrocytes (ACCs) undergo atypical phenotype changes characterized by the expression of hypertrophic differentiation markers. Also, the adjacent subchondral bone shows signs of abnormal mineral density and enhanced production of bone turnover markers, indicative of osteoblast dysfunction. Collectively these findings indicate that the pathological changes typical of OA, involve alterations of the phenotypic properties of cells in both the subchondral bone and articular cartilage. However, the mechanism(s) by which these changes occur during OA development are not completely understood. The purpose of this project was to address the question of how subchondral bone osteoblasts (SBOs) and ACCs interact with each other with respect to regulation of respective cells’ phenotypic properties and in particular the involvement of mitogen activated protein kinase (MAPK) signalling pathways under normal and OA joint condition. We also endeavoured to test the influence of cross-talk between SBOs and ACCs isolated from normal and OA joint on matrix metalloproteinase (MMP) expression. For this purpose tissues from the knees of OA patients and normal controls were collected to isolate SBOs and ACCs. The cellular cross-talk of SBOs and ACCs were studied by means of both direct and indirect co-culture systems, which made it possible to identify the role of both membrane bound and soluble factors. Histology, immunohistochemistry, qRT-PCR, zymography, ELISA and western blotting were some of the techniques applied to distinguish the changes in the co-cultured vs. non co-cultured cells. The MAPK signalling pathways were probed by using targeted MAPK inhibitors, and their activity monitored by western blot analysis using phospho MAPK specific antibodies. Our co-culture studies demonstrated that OA ACCs enhanced the SBOs differentiation compared to normal ACCs. We demonstrated that OA ACCs induced these phenotypic changes in the SBOs via activating an ERK1/2 signalling pathway. The findings from this study thus provided clear evidence that OA ACCs play an integral role in altering the SBO phenotype. In the second study, we tested the influence of normal SBOs and OA SBOs on ACCs phenotype changes. The results showed that OA SBOs increased the hypertrophic gene expression in co-cultured ACCs compared to normal SBOs, a phenotype which is considered as pathological to the health and integrity of articular cartilage. It was demonstrated that these phenotype changes occurred via de-activation of p38 and activation of ERK1/2 signaling pathways. These findings suggest that the pathological interaction of OA SBOs with ACCs is mediated by cross-talking between ERK1/2 and p38 pathways, resulting in ACCs undergoing hypertrophic differentiation. Subsequent experiments to determine the effect on MMP regulation, of SBOs and ACCs cross-talk, revealed that co-culturing OA SBOs with ACCs significantly enhanced the proteolytic activity and expression of MMP-2 and MMP-9. In turn, co-culture of OA ACCs with SBOs led to abundant MMP-2 expression in SBOs. Furthermore, we showed that the addition of ERK1/2 and JNK inhibitors reversed the elevated MMP-2 and MMP-9 production which otherwise resulted from the interactions of OA SBOs-ACCs. Thus, this study has demonstrated that the altered interactions between OA SBOs-ACCs are capable of triggering the pathological pathways leading to degenerative changes seen in the osteoarthritic joint. In conclusion, the body of work presented in this dissertation has given clear in vitro evidence that the altered bi-directional communication of SBOs and ACCs may play a role in OA development and that this process was mediated by MAPK signalling pathways. Targeting these altered interactions by the use of MAPK inhibitors may provide the scientific rationale for the development of novel therapeutic strategies in the treatment and management of OA.

A Raman spectroscopic study of the antimony mineral klebelsbergite Sb4O4(OH)2(SO4)

Many minerals based upon antimonite and antimonate anions remain to be studied. Most of the bands occur in the low wavenumber region, making infrared spectroscopy difficult to use. This problem can be overcome by using Raman spectroscopy. Raman spectra of the mineral klebelsbergite Sb4O4(OH)2(SO4) were studied, and related to the structure of the mineral. Raman bands observed at 971 cm-1 and a series of overlapping bands are observed at 1029, 1074, 1089, 1139 and 1142 cm-1 are assigned to the SO42- ν1 symmetric and ν3 antisymmetric stretching modes. Two Raman bands are observed at 662 and 723 cm-1 and assigned to the SbO ν3 antisymmetric and ν1 symmetric stretching modes. The intense Raman bands at 581, 604 and 611 cm-1 are assigned to the ν4 SO42- bending modes. Two overlapping bands at 481 and 489 cm-1 are assigned to the ν2 SO42- bending mode. Low intensity bands at 410, 435 and 446 cm-1 may be attributed to OSbO bending modes. The Raman band at 3435 cm-1 is attributed to the OH stretching vibration of the OH units. Multiple Raman bands for both SO42- and SbO stretching vibrations support the concept of the non-equivalence of these units in the klebelsbergite structure. It is proposed that two sulphate anions are distorted to different extents in the klebelsbergite structure.

Vibrational spectroscopic study of the antimonate mineral bindheimite Pb2Sb2O6(O,OH)

Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the antimonate mineral bindheimite Pb2Sb2O6(O,OH). The mineral is characterised by an intense Raman band at 656 cm-1 assigned to SbO stretching vibrations. Other lower intensity bands at 664, 749 and 814 cm-1 are also assigned to stretching vibrations. This observation suggests the non-equivalence of SbO units in the structure. Low intensity Raman bands at 293, 312 and 328 cm-1 are assigned to the OSbO bending vibrations. Infrared bands at 979, 1008, 1037 and 1058 cm-1 may be assigned to δ OH deformation modes of SbOH units. Infrared bands at 1603 and 1640 cm-1 are assigned to water bending vibrations, suggesting that water is involved in the bindheimite structure. Broad infrared bands centred upon 3250 cm-1 supports this concept. Thus the true formula of bindheimite is questioned and probably should be written as Pb2Sb2O6(O,OH,H2O)

The effectiveness of workshops as managerial learning opportunities

Purpose The purpose of this paper is to examine the effectiveness of workshops as a learning tool for small business owner‐managers (SBO‐Ms). It aims to concentrate on workshops delivered over 18 months from January 2007 to July 2008 as part of several publicly‐funded small business development programmes in two Australian local government areas (LGAs). Design/methodology/approach Effectiveness is measured in terms of meeting the overarching learning needs and expectations of participants in the context of the programme goals. The paper analyses data gathered from workshop participants either post‐workshop, in later focus groups or through a questionnaire as well as additional feedback from participants and the organisers' reflections. The thematic analysis is organised through an analogy of “going shopping”, where the SBO‐M shopper is buying “learning” when they attend a workshop. Findings Understanding motivation to participate or the “what's in it for me” is important as SBO‐Ms tend to be reluctant, resist or fail to engage with externally sponsored business support initiatives. Workshops were valued for the “space” they create to reflect on practice. For many SBO‐Ms, content “comes alive” with discussion while networking helps reduce the isolation SBO‐Ms can feel. Practical implications The shopping analogy suggests workshops must cater for purposeful shoppers as well as browsers, while interaction with others in the workshop is critical to realising the value of workshops. Originality/value Knowing whether, and how, workshops deliver learning can help to better target and refine these types of support initiatives to ensure they provide positive outcomes for individuals, organisations and economies.