Synthesis of novel double metal cyanide catalysts and polymerization of PO and CO2

Double metal cyanides (DMC) are a versatile group of complexes that find numerous applications in catalytic conversions, e.g. as catalysts for polycondensation of diols and diacids[1], for the ring-opening polymerization of epoxides[2] and their co- and terpolymerization with CO2[3] and cyclic anhydrides.[4] The DMC catalysts usually have a high selectivity; in case of propylene oxide ring opening polymerizations (and in contrast to e.g. alkali-based catalysts), products with low degrees of unsaturation and narrow molecular weight distributions are obtained. A major challenge in the application of DMC catalysts is that they generally feature an induction period of several minutes up to hours during which no substantial propagation is observed. The length of the induction period is affected for instance by the catalyst preparation itself but also by the presence of impurities.[6,7] Up to this date, no reliable model exists that allows the prediction of the length of this activation step. This does not only result in decreasing overall space-time yield but also is a serious safety issue as the spontaneous initiation at the end of the induction period causes an increase in temperature due to the exothermic polymerization reactions. Please click Additional Files below to see the full abstract

Fast and Rigorous Computation of Gene and Pathway Scores from SNP-Based Summary Statistics.

Integrating single nucleotide polymorphism (SNP) p-values from genome-wide association studies (GWAS) across genes and pathways is a strategy to improve statistical power and gain biological insight. Here, we present Pascal (Pathway scoring algorithm), a powerful tool for computing gene and pathway scores from SNP-phenotype association summary statistics. For gene score computation, we implemented analytic and efficient numerical solutions to calculate test statistics. We examined in particular the sum and the maximum of chi-squared statistics, which measure the strongest and the average association signals per gene, respectively. For pathway scoring, we use a modified Fisher method, which offers not only significant power improvement over more traditional enrichment strategies, but also eliminates the problem of arbitrary threshold selection inherent in any binary membership based pathway enrichment approach. We demonstrate the marked increase in power by analyzing summary statistics from dozens of large meta-studies for various traits. Our extensive testing indicates that our method not only excels in rigorous type I error control, but also results in more biologically meaningful discoveries

Genome-Wide Association between Transcription Factor Expression and Chromatin Accessibility Reveals Regulators of Chromatin Accessibility.

To better understand genome regulation, it is important to uncover the role of transcription factors in the process of chromatin structure establishment and maintenance. Here we present a data-driven approach to systematically characterise transcription factors that are relevant for this process. Our method uses a linear mixed modelling approach to combine datasets of transcription factor binding motif enrichments in open chromatin and gene expression across the same set of cell lines. Applying this approach to the ENCODE dataset, we confirm already known and imply numerous novel transcription factors that play a role in the establishment or maintenance of open chromatin. In particular, our approach rediscovers many factors that have been annotated as pioneer factors

Relationship between ATSR fire counts and CO vertical column densities retrieved from SCIAMACHY onboard ENVISAT

SCIAMACHY (Scanning Imaging Absorption spectroMeter for Atmospheric ChartographY) is the first instrument to allow retrieval of CO by measuring absorption in the near infrared from reflected and scattered sunlight instead of from thermal emission. Thus, in contrast to thermal-infrared satellites (MOPITT), SCIAMACHY is highly sensitive to the lower layers of the troposphere where the sources, such as biomass burning, are located, and where the bulk of the CO is usually found. In many regions of the world, the burning of vegetation has a repeating seasonal pattern, but the amount of CO emitted from biomass burning varies considerably from place to place. Here we present a study on the relationship between fire counts and CO vertical column densities (VCD) in different regions. These results are compared with the CO VCD from MOPITT, aerosol index, and NO_2 tropospheric VCD (TVCD) from SCIAMACHY, and the coupled chemistry climate model (CCM) ECHAM5/MESSY

Boreal forest fires in 1997 and 1998: a seasonal comparison using transport model simulations and measurement data

Forest fire emissions have a strong impact on the concentrations of trace gases and aerosols in the atmosphere. In order to quantify the influence of boreal forest fire emissions on the atmospheric composition, the fire seasons of 1997 and 1998 are compared in this paper. Fire activity in 1998 was very strong, especially over Canada and Eastern Siberia, whereas it was much weaker in 1997. According to burned area estimates the burning in 1998 was more than six times as intense as in 1997. Based on hot spot locations derived from ATSR (Along Track Scanning Radiometer) data and official burned area data, fire emissions were estimated and their transport was simulated with a Lagrangian tracer transport model. Siberian and Canadian forest fire tracers were distinguished to investigate the transport of both separately. The fire emissions were transported even over intercontinental distances. Due to the El Niño induced meteorological situation, transport from Siberia to Canada was enhanced in 1998. Siberian fire emissions were transported towards Canada and contributed concentrations more than twice as high as those due to Canada's own CO emissions by fires. In 1998 both tracers arrive at higher latitudes over Europe, which is due to a higher North Atlantic Oscillation (NAO) index in 1998. The simulated emission plumes are compared to CMDL (Climate Monitoring and Diagnostics Laboratory) CO₂ and CO data, Total Ozone Mapping Spectrometer (TOMS) aerosol index (AI) data and Global Ozone Monitoring Experiment (GOME) tropospheric NO₂ and HCHO columns. All the data show clearly enhanced signals during the burning season of 1998 compared to 1997. The results of the model simulation are in good agreement with ground-based as well as satellite-based measurements

A machine learning pipeline for discriminant pathways identification

Motivation: Identifying the molecular pathways more prone to disruption during a pathological process is a key task in network medicine and, more in general, in systems biology. Results: In this work we propose a pipeline that couples a machine learning solution for molecular profiling with a recent network comparison method. The pipeline can identify changes occurring between specific sub-modules of networks built in a case-control biomarker study, discriminating key groups of genes whose interactions are modified by an underlying condition. The proposal is independent from the classification algorithm used. Three applications on genomewide data are presented regarding children susceptibility to air pollution and two neurodegenerative diseases: Parkinson's and Alzheimer's. Availability: Details about the software used for the experiments discussed in this paper are provided in the Appendix

Satellite measurements of formaldehyde linked to shipping emissions

International shipping is recognized as a pollution source of growing importance, in particular in the remote marine boundary layer. Nitrogen dioxide originating from ship emissions has previously been detected in satellite measurements. This study presents the first satellite measurements of formaldehyde (HCHO) linked to shipping emissions as derived from observations made by the Global Ozone Monitoring Experiment (GOME) instrument. <br><br> We analyzed enhanced HCHO tropospheric columns from shipping emissions over the Indian Ocean between Sri Lanka and Sumatra. This region offers good conditions in term of plume detection with the GOME instrument as all ship tracks follow a single narrow track in the same east-west direction as used for the GOME pixel scanning. The HCHO signal alone is weak but could be clearly seen in the high-pass filtered data. The line of enhanced HCHO in the Indian Ocean as seen in the 7-year composite of cloud free GOME observations clearly coincides with the distinct ship track corridor from Sri Lanka to Indonesia. The observed mean HCHO column enhancement over this shipping route is about 2.0×10<sup>15</sup> molec/cm<sup>2</sup>. <br><br> Compared to the simultaneously observed NO<sub>2</sub> values over the shipping route, those of HCHO are substantially higher; also the HCHO peaks are found at larger distance from the ship routes. These findings indicate that direct emissions of HCHO or degradation of emitted NMHC cannot explain the observed enhanced HCHO values. One possible reason might be increased CH<sub>4</sub> degradation due to enhanced OH concentrations related to the ship emissions, but this source is probably too weak to fully explain the observed values. <br><br> The observed HCHO pattern also agrees qualitatively well with results from the coupled earth system model ECHAM5/MESSy applied to atmospheric chemistry (EMAC). However, the modelled HCHO values over the ship corridor are two times lower than in the GOME high-pass filtered data. This might indicate uncertainties in the satellite data and used emission inventories and/or that the in-plume chemistry taking place in the narrow path of the shipping lanes are not well represented at the rather coarse model resolution

Managing affect in learners' questions in undergraduate science

This is the author's accepted manuscript. The final published article is available from the link below. Copyright @ 2012 Society for Research into Higher Education.This article aims to position students' classroom questioning within the literature surrounding affect and its impact on learning. The article consists of two main sections. First, the act of questioning is discussed in order to highlight how affect shapes the process of questioning, and a four-part genesis to question-asking that we call CARE is described: the construction, asking, reception and evaluation of a learner's question. This work is contextualised through studies in science education and through our work with university students in undergraduate chemistry, although conducted in the firm belief that it has more general application. The second section focuses on teaching strategies to encourage and manage learners' questions, based here upon the conviction that university students in this case learn through questioning, and that an inquiry-based environment promotes better learning than a simple ‘transmission’ setting. Seven teaching strategies developed from the authors' work are described, where university teachers ‘scaffold’ learning through supporting learners' questions, and working with these to structure and organise the content and the shape of their teaching. The article concludes with a summary of the main issues, highlighting the impact of the affective dimension of learning through questioning, and a discussion of the implications for future research