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Marie-Louise Wind Beatrice Braun-Cula Fabian Schax Christian Herwig Prof. Christian Limberg 《Israel journal of chemistry》2020,60(10-11):1057-1060
The isolation and identification of intermediates formed in the course of the activation of dioxygen at transition metal centers reveals important mechanistic insights concerning such processes. We previously reported the reaction of the dinuclear CrII complex [L2Cr2(MeCN)2][Li(MeCN)]2 (L=PhSi(OSiPh2O−)3) ( 5 ) with dioxygen, which resulted in the formation of the CrIV oxo complex [L2Cr2O2][Li(THF)2]2 ( 6 ), as the final room temperature stable product. Here we now report the isolation and characterization of an intermediate en route to 6 , namely the dinuclear CrIII superoxo complex [L2Cr2(O2)2][Li(MeCN)]2 ( 7 ). 7 is the first example of a structurally characterized dinuclear CrIII superoxo complex with two independent side-on bound superoxo ligands. Reactivity studies outline the capability of this superoxo complex to activate weak O−H bonds. 相似文献
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Qingyuan Zhang Xiangming Xiao Ernst Linder Marie-Louise Smith Fred Baret Berrien Moore III 《Remote sensing of environment》2006,105(3):189-203
In this paper, we present an improved procedure for collecting no or little atmosphere- and snow-contaminated observations from the Moderate Resolution Imaging Spectroradiometer (MODIS) sensor. The resultant time series of daily MODIS data of a temperate deciduous broadleaf forest (the Bartlett Experimental Forest) in 2004 show strong seasonal dynamics of surface reflectance of green, near infrared and shortwave infrared bands, and clearly delineate leaf phenology and length of plant growing season. We also estimate the fractions of photosynthetically active radiation (PAR) absorbed by vegetation canopy (FAPARcanopy), leaf (FAPARleaf), and chlorophyll (FAPARchl), respectively, using a coupled leaf-canopy radiative transfer model (PROSAIL-2) and daily MODIS data. The Markov Chain Monte Carlo (MCMC) method (the Metropolis algorithm) is used for model inversion, which provides probability distributions of the retrieved variables. A two-step procedure is used to estimate the fractions of absorbed PAR: (1) to retrieve biophysical and biochemical variables from MODIS images using the PROSAIL-2 model; and (2) to calculate the fractions with the estimated model variables from the first step. Inversion and forward simulations of the PROSAIL-2 model are carried out for the temperate deciduous broadleaf forest during day of year (DOY) 184 to 201 in 2005. The reproduced reflectance values from the PROSAIL-2 model agree well with the observed MODIS reflectance for the five spectral bands (green, red, NIR1, NIR2, and SWIR1). The estimated leaf area index, leaf dry matter, leaf chlorophyll content and FAPARcanopy values are close to field measurements at the site. The results also showed significant differences between FAPARcanopy and FAPARchl at the site. Our results show that MODIS imagery provides important information on biophysical and biochemical variables at both leaf and canopy levels. 相似文献
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This study surveyed the presence of bacterial pathogens in eight Swedish sewage treatment plants (STPs), with four different treatment methods, focusing on detection of zoonotic bacteria in raw and treated sludge. Salmonella spp., Listeria monocytogenes, Campylobacter coli and jejuni, Escherichia coli O157 and indicator bacteria were investigated. Samplings were performed from July 2000 to June 2002, resulting in 64 raw sludge samples and 69 treated sludge samples. The samples from raw sludge (67%) and treated sludge (55%) were positive for Salmonella; 49 different serotypes were detected. Restriction enzyme analysis and pulsed field gel electrophoresis of Salmonella serotypes indicated that Salmonella persists in STPs and that there is a continuous supply of new strains. There are differences in treatment methods concerning the reduction of pathogens and indicator bacteria. If spread on arable land, sludge increases the environmental load of pathogens; this increases the risk for spreading diseases to people and animals. 相似文献
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The rapid, on-site identification of illicit narcotics, such as cocaine, is hindered by the diverse nature of the samples, which can contain a large variety of materials in a wide concentration range. This sample variance has a very strong influence on the analytical methodologies that can be utilized and in general prevents the widespread use of quantitative analysis of illicit narcotics on a routine basis. Raman spectroscopy, coupled with chemometric methods, can be used for in situ qualitative and quantitative analysis of illicit narcotics; however, careful consideration must be given to dealing with the extensive variety of sample types. To assess the efficacy of combining Raman spectroscopy and chemometrics for the identification of a target analyte under real-world conditions, a large-scale model sample system (633 samples) using a target (acetaminophen) mixed with a wide variety of excipients was created. Materials that exhibit problematic factors such as fluorescence, variable Raman scattering intensities, and extensive peak overlap were included to challenge the efficacy of chemometric data preprocessing and classification methods. In contrast to spectral matching analyte identification approaches, we have taken a chemometric classification model-based approach to account for the wide variances in spectral data. The first derivative of the Raman spectra from the fingerprint region (750-1900 cm(-1)) yielded the best classifications. Using a robust segmented cross-validation method, correct classification rates of better than ~90% could be attained with regression-based classification, compared to ~35% for SIMCA. This study demonstrates that even with very high degrees of sample variance, as evidenced by dramatic changes in Raman spectra, it is possible to obtain reasonably reliable identification using a combination of Raman spectroscopy and chemometrics. The model sample set can now be used to validate more advanced chemometric or machine learning algorithms being developed for the identification of analytes such as illicit narcotics. 相似文献
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Thijs W. de Vos Dian Winkelhorst Hans J. Baelde Kyra L. Dijkstra Rianne D. M. van Bergen Lotte E. van der Meeren Peter G. J. Nikkels Leendert Porcelijn C. Ellen van der Schoot Gestur Vidarsson Michael Eikmans Rick Kapur Carin van der Keur Leendert A. Trouw Dick Oepkes Enrico Lopriore Marie-Louise P. van der Hoorn Manon Bos Masja de Haas 《International journal of molecular sciences》2021,22(13)
Fetal and neonatal alloimmune thrombocytopenia (FNAIT) is a disease that causes thrombocytopenia and a risk of bleeding in the (unborn) child that result from maternal alloantibodies directed against fetal, paternally inherited, human platelet antigens (HPA). It is hypothesized that these alloantibodies can also bind to the placenta, causing placental damage. This study aims to explore signs of antibody-mediated placental damage in FNAIT. We performed a retrospective study that included pregnant women, their newborns, and placentas. It comprised 23 FNAIT cases, of which nine were newly diagnosed (14 samples) and 14 were antenatally treated with intravenous immune globulins (IVIg) (21 samples), and 20 controls, of which 10 had anti-HLA-class I antibodies. Clinical information was collected from medical records. Placental samples were stained for complement activation markers (C1q, C4d, SC5b-9, and mannose-binding lectin) using immunohistochemistry. Histopathology was examined according to the Amsterdam criteria. A higher degree of C4d deposition was present in the newly diagnosed FNAIT cases (10/14 samples), as compared to the IVIg-treated FNAIT cases (2/21 samples, p = 0.002) and anti-HLA-negative controls (3/20 samples, p = 0.006). A histopathological examination showed delayed maturation in four (44%) placentas in the newly diagnosed FNAIT cases, five (36%) in the IVIg-treated FNAIT cases, and one in the controls (NS). C4d deposition at the syncytiotrophoblast was present in combination with low-grade villitis of unknown etiology in three newly diagnosed FNAIT cases that were born SGA. We conclude that a higher degree of classical pathway-induced complement activation is present in placentas from pregnancies with untreated FNAIT. This may affect placental function and fetal growth. 相似文献
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The thermal fatigue damage constitutes the major problem of the parts subject to a variation in temperature during their operation. Several materials have been used for such structures in order to limit their damage. The facility of implementation and low cost of cast iron constitute an advantage for its use for the Diesel motors. 相似文献