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

Characterizing catalyst performance of DMCs on PO homopolymerization

Double metal cyanide (DMC) complexes are known effective catalysts for the ring-opening polymerization of propylene oxide to generate polyether polyols (Scheme 1).1,2 The high activity of DMC catalysts relative to basic alkaline catalysts eliminates the need for expensive removal of residual catalyst from the product. Furthermore, the poly(propylene glycol) (PPG) products prepared by DMC catalysts have - contrary to products from alkaline catalysis - a low degree of unsaturation and narrow molecular weight distributions. Latter is advantageous with respect to the resulting low viscosities. A common challenge when applying DMC catalysts is the need for an activation procedure, leading to an induction period of unknown length (Figure 1).2,3 In a larger, usually semibatch process, PO monomer can only be added after the activation has been secured; the concentration of PO must not reach certain limits as its ring-opening is highly exothermal. Please click Additional Files below to see the full abstract

Nonparametric Bayesian inference for perturbed and orthologous gene regulatory networks

Motivation: The generation of time series transcriptomic datasets collected under multiple experimental conditions has proven to be a powerful approach for disentangling complex biological processes, allowing for the reverse engineering of gene regulatory networks (GRNs). Most methods for reverse engineering GRNs from multiple datasets assume that each of the time series were generated from networks with identical topology. In this study, we outline a hierarchical, non-parametric Bayesian approach for reverse engineering GRNs using multiple time series that can be applied in a number of novel situations including: (i) where different, but overlapping sets of transcription factors are expected to bind in the different experimental conditions; that is, where switching events could potentially arise under the different treatments and (ii) for inference in evolutionary related species in which orthologous GRNs exist. More generally, the method can be used to identify context-specific regulation by leveraging time series gene expression data alongside methods that can identify putative lists of transcription factors or transcription factor targets. Results: The hierarchical inference outperforms related (but non-hierarchical) approaches when the networks used to generate the data were identical, and performs comparably even when the networks used to generate data were independent. The method was subsequently used alongside yeast one hybrid and microarray time series data to infer potential transcriptional switches in Arabidopsis thaliana response to stress. The results confirm previous biological studies and allow for additional insights into gene regulation under various abiotic stresses. Availability: The methods outlined in this article have been implemented in Matlab and are available on request

Auger de-excitation of metastable molecules at metallic surfaces

We study secondary electron emission from metallic surfaces due to Auger de-excitation of diatomic metastable molecules. Our approach is based on an effective model for the two active electrons involved in the process -- a molecular electron described by a linear combination of atomic orbitals when it is bound and a two-center Coulomb wave when it is not and a metal electron described by the eigenfunctions of a step potential -- and employs Keldysh Green's functions. Solving the Dyson equation for the retarded Green's function by exponential resummation we are able to treat time-nonlocal self-energies and to avoid the wide-band approximation.Results are presented for the de-excitation of \NitrogenDominantMetastableState\ on aluminum and tungsten and discussed in view of previous experimental and theoretical investigations. We find quantitative agreement with experimental data for tungsten indicating that the effective model captures the physics of the process quite well. For aluminum we predict secondary electron emission due to Auger de-excitation to be one to two orders of magnitude smaller than the one found for resonant charge-transfer and subsequent auto-detachment.Comment: 15 pages, 9 figures, revised version using an improved single-electron basi

Ego-Splitting and the Transcendental Subject. Kant’s Original Insight and Husserl’s Reappraisal

In this paper, I contend that there are at least two essential traits that commonly define being an I: self-identity and self-consciousness. I argue that they bear quite an odd relation to each other in the sense that self-consciousness seems to jeopardize self-identity. My main concern is to elucidate this issue within the range of the transcendental philosophies of Immanuel Kant and Edmund Husserl. In the first section, I shall briefly consider Kant’s own rendition of the problem of the Egosplitting. My reading of the Kantian texts reveals that Kant himself was aware of this phenomenon but eventually deems it an unexplainable fact. The second part of the paper tackles the same problematic from the standpoint of Husserlian phenomenology. What Husserl’s extensive analyses on this topic bring to light is that the phenomenon of the Ego-splitting constitutes the bedrock not only of his thought but also of every philosophy that works within the framework of transcendental thinking