The co-ordination chemistry of tellurium and related selenium ligands

2-(2-pyridyl)phenyl(p-ethoxyphenyl)tellurium(II), (RR1Te) reacts with HgC12 at room temperature to give white HgCl2.RR1Te. On setting aside, or on warming the reaction mixture a yellow material, [R1HgCl.(RTeCl)2] is formed. Multinuclear NMR(125Te, 199Hg, 1H) and mass spectroscopy confirm the formulation, and confirm the ease of transfer of the p-ethoxyphenyl group (R1) between the metal centres. The crystal structure of the yellow material consists of two discrete RTeCl molecules together with a R1HgCl molecule. There is no dative bond formation between these species, hence the preferred description of the formation of an inclusion complex. The reaction of RR1Te with Copper(I) chloride in the cold gives an air sensitive yellow product Cu3Cl3(RR1Te)2(0.5CH3CN); under reflux in air changes to the green Cu2Cl(RR1Te)(0.5 EtOH). By contrast, the reaction of RR1Te with acetonitrile solution of Copper(II) salts under mild conditions affords the white materials CuCl(RR1Te) and CuBr(RR1Te)H2O. RR1Te reacts with PdCl2 and PtCl2 to give materials albeit not well defined, can be seen as intermediates to the synthesis of inorganic phase of the type M3XTe2XCl2X. Paramagnetism is associated with some of the palladium and platinum products. The 195Pt NMR measurement in DMSO establishes the presence of six platinum species, which are assigned to Pt(IV), Pt(III) or Pt(II). The reactions show that in the presence of PdCl2 or PtCl2 both R and R1 are very labile. The reaction of RHgCl(R= 2-(2-pyridyl)phenyl) with SeX4(X= Cl, Br) gives compounds which suggest that both Trans-metallation and redox processes are involved. By varying reaction conditions materials which appear to be intermediates in the trans-metallation process are isolated. Potentially bidentate tellurium ligands having molecular formula RTe(CH2)nTeR,Ln, (R= Ph,(t-Bu). C6H4, n = 5,10) are prepared. Palladium and Platinum complexes containing these ligands are prepared. Also complex Ph3SnC1L(L = p-EtO.C6H4) is prepared.

Skeletal muscle atrophy, a link between depression of protein synthesis and increase in degradation

Both proteolysis-inducing factor (PIF) and angiotensin II have been shown to produce a depression in protein synthesis in murine myotubes concomitant with an increased phosphorylation of eukaryotic initiation factor 2 (eIF2α). Both PIF and angiotensin II were shown to induce autophosphorylation of the RNA-dependent protein kinase (PKR), and an inhibitor of this enzyme completely attenuated the depression in protein synthesis and prevented the induction of eIF2α phosphorylation. The PKR inhibitor also completely attenuated the increase in protein degradation induced by PIF and angiotensin II and prevented the increase in proteasome expression and activity. To confirm these results myotubes were transfected with plasmids that express either wild-type PKR, or a catalytically inactive PKR variant, PKRΔ6. Myotubes expressing PKRΔ6 showed no increase in eIF2α phosphorylation in response to PIF or angiotensin II, no depression in protein synthesis, and no increase in protein degradation or increase in proteasome expression. Induction of the ubiquitin-proteasome pathway by PIF and angiotensin II has been linked to activation of the transcription factor nuclear factor-κB (NF-κB). Inhibition of PKR prevented nuclear migration of NF-κB in response to both PIF and angiotensin II, by preventing degradation of the inhibitor protein I-κB. Phosphorylation of PKR and eIF2α was also significantly increased in the gastrocnemius muscle of weight losing mice bearing the MAC16 tumor, suggesting that a similar process may be operative in cancer cachexia. These results provide a link between the depression of protein synthesis in skeletal muscle and the increase in protein degradation. © 2007 by The American Society for Biochemistry and Molecular Biology, Inc.

Ag alloyed Pd single-atom catalysts for efficient selective hydrogenation of acetylene to ethylene in excess ethylene

Semihydrogenation of acetylene in an ethylene-rich stream is an industrially important process. Conventional supported monometallic Pd catalysts offer high acetylene conversion, but they suffer from very low selectivity to ethylene due to overhydrogenation and the formation of carbonaceous deposits. Herein, a series of Ag alloyed Pd single-atom catalysts, possessing only ppm levels of Pd, supported on silica gel were prepared by a simple incipient wetness coimpregnation method and applied to the selective hydrogenation of acetylene in an ethylene-rich stream under conditions close to the front-end employed by industry. High acetylene conversion and simultaneous selectivity to ethylene was attained over a wide temperature window, surpassing an analogous Au alloyed Pd single-atom system we previously reported. Restructuring of AgPd nanoparticles and electron transfer from Ag to Pd were evidenced by in situ FTIR and in situ XPS as a function of increasing reduction temperature. Microcalorimetry and XANES measurements support both geometric and electronic synergetic effects between the alloyed Pd and Ag. Kinetic studies provide valuable insight into the nature of the active sites within these AgPd/SiO2 catalysts, and hence, they provide evidence for the key factors underpinning the excellent performance of these bimetallic catalysts toward the selective hydrogenation of acetylene under ethylene-rich conditions while minimizing precious metal usage.

The spectral distribution of biologically active solar radiation at Miami, Florida, USA

The spectral distribution of solar radiation was studied under different sky conditions during a 15- month period in Miami, Florida (USA), and over a latitudinal gradient at solar maximum. Spectroradiometric scans were characterized for total irradiance (300- 3000 nm) and the relative energetic and photon contributions of the following wavelength regions: UV-B (300-320nm); UV-A (320-400nm); B (400-500rim); PAR (400-700 nm); R (600-700 nm); and FR (728- 732 rim). Notable results include: (i) significantly higher UV-A energy fluxes than currently in use for laboratory experiments involving the biological effects of this bandwidth (values ranged from 33.6 to 55.4 W/m 2 in Miami over the year); (ii) marked diurnal shifts in B:R and R:FR, with elevated R:FR values in early morning: (iii) a strong correlation between R: FR and atmospheric water content; and (iv) unusually high PAR values under direct sunlight with cloudy skies (2484 ~tmot/2 per s).

An integrated flow and transport model to study the impact of mercury remediation strategies for East Fork Poplar Creek watershed, Oak Ridge, Tennessee

An integrated flow and transport model using MIKE SHE/MIKE 11 software was developed to predict the flow and transport of mercury, Hg(II), under varying environmental conditions. The model analyzed the impact of remediation scenarios within the East Fork Poplar Creek watershed of the Oak Ridge Reservation with respect to downstream concentration of mercury. The numerical simulations included the entire hydrological cycle: flow in rivers, overland flow, groundwater flow in the saturated and unsaturated zones, and evapotranspiration and precipitation time series. Stochastic parameters and hydrologic conditions over a five year period of historical hydrological data were used to analyze the hydrological cycle and to determine the prevailing mercury transport mechanism within the watershed. Simulations of remediation scenarios revealed that reduction of the highly contaminated point sources, rather than general remediation of the contaminant plume, has a more direct impact on downstream mercury concentrations.

An Integrated Flow and Transport Model to Study the Impact of Mercury Remediation Strategies for East Fork Poplar Creek Watershed, Oak Ridge, Tennessee

An integrated flow and transport model using MIKE SHE/MIKE 11 software was developed to predict the flow and transport of mercury, Hg(II), under varying environmental conditions. The model analyzed the impact of remediation scenarios within the East Fork Poplar Creek watershed of the Oak Ridge Reservation with respect to downstream concentration of mercury. The numerical simulations included the entire hydrological cycle: flow in rivers, overland flow, groundwater flow in the saturated and unsaturated zones, and evapotranspiration and precipitation time series. Stochastic parameters and hydrologic conditions over a five year period of historical hydrological data were used to analyze the hydrological cycle and to determine the prevailing mercury transport mechanism within the watershed. Simulations of remediation scenarios revealed that reduction of the highly contaminated point sources, rather than general remediation of the contaminant plume, has a more direct impact on downstream mercury concentrations.

Last Interglacial synthesis of high-latitude temperature: temperature anomalies and associated errors for 4 time slices

The Last Interglacial (LIG, 129-116 thousand of years BP, ka) represents a test bed for climate model feedbacks in warmer-than-present high latitude regions. However, mainly because aligning different palaeoclimatic archives and from different parts of the world is not trivial, a spatio-temporal picture of LIG temperature changes is difficult to obtain. Here, we have selected 47 polar ice core and sub-polar marine sediment records and developed a strategy to align them onto the recent AICC2012 ice core chronology. We provide the first compilation of high-latitude temperature changes across the LIG associated with a coherent temporal framework built between ice core and marine sediment records. Our new data synthesis highlights non-synchronous maximum temperature changes between the two hemispheres with the Southern Ocean and Antarctica records showing an early warming compared to North Atlantic records. We also observe warmer than present-day conditions that occur for a longer time period in southern high latitudes than in northern high latitudes. Finally, the amplitude of temperature changes at high northern latitudes is larger compared to high southern latitude temperature changes recorded at the onset and the demise of the LIG. We have also compiled four data-based time slices with temperature anomalies (compared to present-day conditions) at 115 ka, 120 ka, 125 ka and 130 ka and quantitatively estimated temperature uncertainties that include relative dating errors. This provides an improved benchmark for performing more robust model-data comparison. The surface temperature simulated by two General Circulation Models (CCSM3 and HadCM3) for 130 ka and 125 ka is compared to the corresponding time slice data synthesis. This comparison shows that the models predict warmer than present conditions earlier than documented in the North Atlantic, while neither model is able to produce the reconstructed early Southern Ocean and Antarctic warming. Our results highlight the importance of producing a sequence of time slices rather than one single time slice averaging the LIG climate conditions.

Topographischer Ueberblick der Stadt Frankfurt am Main nach ihren Quartieren, Gegenden, Gebäulichkeiten und Feldgütern : nebst Angabe derjenigen Häuser, auf welchen gegenwärtig die Gast- ... und sonstige Feuer-Gerechtigkeiten ruhen

von Carl Ludwig Franck, Hypothekenbuchführer

Estudo fitoquímico de Waltheria ferruginea

The Waltheria genus belonging to the Sterculiaceae family, it is reported as a prolific source of flavonoids and quinolone alkaloids, substances of great interest due to several associated biological activities. This work describes a novel phytochemical study from Waltheria ferruginea, aiming to contribute to the chemical knowledge of this specie and the isolation of substances with biological potential. For the phytochemical study were used chromatography techniques on silica gel and molecular exclusion in Sephadex LH-20.The structural elucidation of the isolated compounds was performed through spectrometric techniques 1H and 13C NMR, including uni and bidimensional pulse sequences, and comparison with data from literature. Five substances were isolated, namely: the flavonids kaempferol-3-O-β-(6''-cumaroil)-glucopyranoside (F1) and kaempferol -3 -O- β - glucopyranoside (F2), both analyzes with pharmacological properties, the flavonol quercetin-3-O-β-glucopyranoside (F3 ) pure and in the epimeric mixture α (F3') and (F3), the terpenegeranyl - geranyl (G1) and the 12-hydroxi-octadecanoic acid, all no previous reported in the literature.

Sedimentology on cores off Filchner Shelf Ice, Weddell Sea, Antarctica

The sediments of 14 box cores and 7 gravity cores, mainly taken directly in front of the Filchner(-Ronne) ice shelf northwest of Berkner Island (Weddell Sea), allowed to distinguish six sediment types. On the one hand,the retreat of the at first grounded and then floated ice from the last glacial maximum is documented. On the other hand,the sediments give an insight into extensive Holocene sediment deposition and remobilization northwest of Berkner Island. The ortho till was deposited directly by the grounded ice sheet and is lacking any marine influence. After floating of the ice shelf, partly very weIl stratified, partly unstratified, non-bioturbated paratill is deposited beneath the ice shelf. Lack of IRD-content in the paratill immediately above the orthotill indicates freezing at the bottom of the ice, at least for a short period after the ice became afloat. The orthotill and paratill contain small amounts of fragmented Tertiary diatoms, which allow the conclusion, that glacial-marine sediments in the accumulation area of the Ronne ice shelf will be eroded and later deposited by ice in the investigation area. Starting of bioturbation and therefore change in sedimentation from paratill to bioturbated paratill,is caused by the retreat of the ice shelf to its actual position. Isostatic uplift of the sea-bed after the Ice Age causes minor water depths with higher current velocities. The fine-fraction is eroding and mean particle-size will increase. Maybe, also isostatic uplift is responsible for repeated great advances of the floated ice shelf as shown in an erosional horizon in some cores containing bioturbated paratill. Postglacial sediment-thicknesses exceed 3 m. Assuming floating of the ice 15.000 YBP, accumulation rates reach nearly 20cm/lOOO years. Following the theories about sediment input in front of wide ice shelves, this was not expected. In the shallower water depths of Berkner Bank, the oscillations of the ice shelf are recorded in the sediments. Sorting and redistribution by high current velocities from beneath the ice up to the calving line, lead to the deposition of the weIl to very weIl sorted sandy till. In front of the calving line the finer fraction will settle down. Remobilization is possible by bioturbation and increasing current-velocity. According to the intensity of mixing of the sandy till with the fine fraction, modified till or muddy till results.

Tab. 1. Listing of BGR seismic refraction results off West Spitsbergen

Three main depositional sequences have been determined in the seismic records taken off West Spitsbergen (1) a Plio-Pleistocene sequence SPI-I with velocities of 1.7 to 2.8 km/sec; (2) a Pliocene allochthonous sequence SPI-II with velocities of 2.4 to 2.8 km/sec underlying unconformity U1; (3) a pre-Middle Oligocene sequence SPI-III with velocities of 2.9 to 4.8 km/sec underlying a distinct unconformity (U2) and deposited in front of the downfaulted Spitsbergen Platform indicating some opening of the Greenland Sea already before tbe time of magnetic anomaly 13 (36 m.y.b.p.). A marked change in the seismic configuration of the oceanic basement has been observed about 30 to 40 km east of the central Knipovich graben. The transition from the oceanic crust of the Knipovich Ridge to the strongly faulted, continental substratum of the Spitsbergen Platform occurs over a narrow zone and is associated with a pre-Middle Oligocene depocenter.

Geochemistry of tetrapyrrole, carotenoid, and perylene pigments in sediments at DSDP Holes 63-467 and 63-471

Twenty-one core samples from DSDP/IPOD Leg 63 were analyzed for products of chlorophyll diagenesis. In addition to the tetrapyrrole pigments, perylene and carotenoid pigments were isolated and identified. The 16 core samples from the San Miguel Gap site (467) and the five from the Baja California borderland location (471) afforded the unique opportunity of examining tetrapyrrole diagenesis in clay-rich marine sediments that are very high in total organic matter. The chelation reaction, whereby free-base porphyrins give rise to metalloporphyrins (viz., nickel), is well documented within the downhole sequence of sediments from the San Miguel Gap (Site 467). Recognition of unique arrays of highly dealkylated copper and nickel ETIO-porphyrins, exhibiting nearly identical carbonnumber homologies (viz., C-23 to C-30; mode = C-26), enabled subtraction of this component (thought to be derived from an allochthonous source) and thus permitted description of the actual in situ diagenesis of autochthonous chlorophyll derivatives.

"Per aurem intrat Christus in Mariam". Aproximación iconográfica a la "conceptio per aurem" en la pintura italiana del Trecento desde fuentes patrísticas y teológicas

La tesis mariológica de la conceptio per aurem, según la cual la Virgen María habría concebido a Jesucristo por el oído en el momento de escuchar del ángel el mensaje celestial anunciándole que, sin perder su virginidad, sería madre del Hijo de Dios encarnado, ha merecido hasta ahora muy pocos estudios académicos rigurosamente fundados en fuentes primarias. De hecho, en la literatura especializada son muy escasas las referencias a tal teoría y, cuando algún estudioso la evoca, casi siempre se contenta con aludir a ella, sin aportar pruebas documentales. Sin embargo, tal como lo revelan las nueve pinturas italianas aquí analizadas, esa teoría fue ilustrada mediante sutiles metáforas visuales en muchas obras pictóricas medievales, las cuales se inspiraron en una sólida tradición literaria. Además una pléyade de Padres de la Iglesia y teólogos medievales testimonia, mediante afirmaciones explícitas, que semejante teoría gozó de notable aceptación entre los maestros del pensamiento cristiano. Basándose en numerosos textos patrísticos y teológicos, este artículo intenta dos objetivos esenciales: exponer, ante todo, las distintas formulaciones teóricas propuestas por esos pensadores; y además, tratar de poner en luz los significados dogmáticos que subyacen bajo esa sorprendente tesis.

Welke 'acteur' neemt de controllerrol als extraverte business partner?

Which 'actor' takes the management accountant role as an extravert business partner? Does a relation between the personal trait Extraversion and fulfilling a management accountant role as a business partner exist? Open Universiteit Nederland End thesis MSc Management, Accounting & Finance Support 1: Prof. dr. A.C.N. van de Ven RA Support 2: dr. P.C.M. Claes Examinator: dr. P. Kamminga Date of approval: September 3, 2014 student: P.R. van der Wal (studentnumber 839104017 email petervanderwal2003@yahoo.com The main question of this research is: Does a relation between the personal trait Extraversion and fulfilling a management accountant role as a business partner exist? This research is based on the dataset obtained by the controller survey 2013, executed in commission of the 'Open Universiteit' (Bork & van der Wal, 2014). From the literature review it is clear: among other management accountant roles we need business partners. And there is a relation between the personal trait Extraversion and fulfilling the role as business partner. At the same time a lack of necessary personal traits for this role has been noticed, among which is Extraversion. The factor- and cluster analyses reported by Bork & van der Wal (2014) resulted in the identification of two types of management accountant roles. In this extended research TYPE II is identified as a business partner because (s)he practices activity-combinations which are related to strategy, analyzing, supporting management in decision making, advisory, change-agency and representing the organization. 36% of the population of Dutch management accountants with a master degree (or similar) meet with the role of the business partner. Although the fulfillment of the role (TYPE II) is not purely business partnering. E.g. reporting and scorekeeping are still activities executed by TYPE II and it is not clear to what extent. Apart from that, role TYPE I executes change management and risk-management activities, which are (according to the definition) activities that belong to the business partner. The role as business partner is practiced but not that optimal as defined in theory. The logistic regression analyses on the survey-data show that Extraversion among three other triggers is significant for the prediction of the fulfillment of the management accountant role (Bork & van der Wal, 2014). A more extravert personal trait predicts a preference for TYPE II, which relates to the business partner. This 'in depth research' concentrated on the relation between the Big Five personal traits and the six activity-combinations (factors) instead of on the two clusters (I and II). The statistic analyses confirm the predicting influence of Extraversion on the business partner role. Although, except for one factor, no extra significance has been found in this additional research. The essential question can be confirmed positively: the management accountant role business partner exists in practice, some management accountants are more extravert then others, and there is a positive relation between extraversion and fulfilling the business partner role. Some formulated research limitations are related to the statistical weakness of some prediction outcomes and to interpretation differences that might occur. Further research can e.g. concentrate on the other personal traits and the significance for role-differentiation in education programs. The management accountant survey 2013 Management accountant roles in 2013 in the Netherlands Open Universiteit Nederland End thesis MSc Management, Accounting & Finance Support 1: Prof. dr. A.C.N. van de Ven RA Support 2: dr. P.C.M. Claes Examinator: dr. P. Kamminga Date of approval: September 3, 2014 student: P.R. van der Wal and H.J. Bork studentnumber: 839104017 and 838532340) email: petervanderwal2003@yahoo.com and hjbork@hotmail.com This paper describes the conceptual model and results of the 'management accountants survey 2013'. The survey is part of a longitudinal survey, earlier executed in 2004, 2007 and 2010 under responsibility of the 'Open Universiteit Nederland'. Secondly the dataset of this survey will be used by us to do our own analyses on the predicting value of the triggers 'personality factor: extraversion' and 'lever of control: interactive controls' on the management accounting role that comes close to a role defined as 'Business Partner'. Scientific research shows that there are different management accounting roles, and that these roles change and that preferences exist for certain roles (Verstegen B. , Loo, Mol, Slagter, & Geerkens, 2007). The main question that will be answered in this paper is which coherent combinations of activities are being executed by management accountants in 2013 in the Netherlands by master-graduates? And secondly which triggers of management accountants' activities predict to which cluster a management accountant belongs? The conceptual model of this research has been developed in 2004 (Verstegen B. , Loo, Mol, Slagter, & Geerkens, 2007). For this research the same 37 activities as in the former researches are included (appendix 1). In the trigger-set (appendix 1) some adaptations have been made for reasons of restricting the length of the survey and to pinpoint on particular research goals (e.g. personality and levers of control). The coherent combinations of activities were found by a factor-analysis and the groups of controllers by a cluster analysis. A regression analysis shows which trigger-items are most significant. The survey has been sent to 2.353 students that finished a controller-study on a Dutch University. There was a 9% (211) response with a completely filled survey. 137 of which indicated to work in a controller-function at the moment. These controllers have been included in the results. The factor-analysis results in six different coherent combinations of activities (factors). Shortly these factors are: advising top management on strategic level with result-effecting information (1), organizing internal reporting (2) organizing and representing the organization on external reporting (3), advising and managing changes by shortcomings in processes and control systems (4), maintaining and managing administrative organization- , information- and control systems (5) and organizing/executing risk management and internal audit (6). Factors 4, 5 and 6 are clustered in cluster TYPE I (125 controllers) and factors 1, 2 and 3 in cluster TYPE II (69 controllers). TYPE II can be associated with the management accountant role 'Business Partner', although the accountant keeps partly active in a scorekeeper role. The four most significant triggers for predicting being a TYPE II controller are 'Executing a risk-management task in order to meet compliance standards' (1), extraversion (2), company size in terms of fte (3) and gender (4).