Toward robust QSPR models: Synergistic utilization of robust regression and variable elimination

Widely used regression approaches in modeling quantitative structure-property relationships, such as PLS regression, are highly susceptible to outlying observations that will impair the prognostic value of a model. Our aim is to compile homogeneous datasets as the basis for regression modeling by removing outlying compounds and applying variable selection. We investigate different approaches to create robust, outlier-resistant regression models in the field of prediction of drug molecules' permeability. The objective is to join the strength of outlier detection and variable elimination increasing the predictive power of prognostic regression models. In conclusion, outlier detection is employed to identify multiple, homogeneous data subsets for regression modeling.     

Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl‐alkylamine Ligands on Spin Crossover Properties

Iron(II) complexes of the type [Fe(L)(NCS)₂] with tetradentate ligands L are well known to show spin crossover properties. However, this behavior is quite sensitive in regard to small changes of the ligand system. Starting from the thoroughly investigated complex [Fe(tmpa)(NCS)₂] [tmpa = tris(2‐pyridylmethyl)amine, also abbreviated as tpa in the literature] we modified the ligand by increasing systematically the chelate ring sizes from 5 to 6 thus obtaining complexes [Fe(pmea)(NCS)₂], [Fe(pmap)(NCS)₂], and [Fe(tepa)(NCS)₂] [pmea = N,N‐bis[(2‐pyridyl)methyl]‐2‐(2‐pyridyl)ethylamine, pmap = N,N‐bis[2‐(2‐pyridyl)ethyl]‐(2‐pyridyl)methylamine, and tepa = tris[2‐(2‐pyridyl)ethyl]amine]. All complexes were structurally characterized and spin crossover properties were investigated using Mößbauer spectroscopy, magnetic measurements, and IR/Raman analyses. The results demonstrated that only the iron complexes with tmpa and pmea showed spin crossover properties, whereas the complexes with the ligands pmap and tepa only formed high spin complexes. Furthermore, DFT calculations supported these findings demonstrating again the strong influence of ligand environment. Herein the effect of increasing the chelate ring sizes in iron(II) isothiocyanato complexes with tetradentate tripyridyl‐alkylamine ligands is clearly demonstrated.     

New nickel(II) diimine complexes and the control of polyethylene microstructure by catalyst design

Starting from differently substituted boronic acids as versatile building block, new "ortho-aryl" alpha-diimine ligands a-h were synthesized in an easy, high-yielding route. Reaction of the complex precursor diacetylacetonato-nickel(II) with a trityl salt, like [CPh3] [B(C6F5)4] or [CPh3] [SbCl6], in the presence of the diimine ligands afford the monocationic, square planar complexes 2a-g in almost quantitative yields. Suitable crystals (2d',e,f,g) were submitted for X-ray diffraction analysis. A geometry model was developed to describe the orientation of ligand fragments around the nickel(II) center that influence the polymer microstructure. At elevated reaction temperature and pressure, and in the presence of hydrogen, 2a-e catalyze the homopolymerization of ethylene to give branched PE products ranging from HD- to LLD-PE grades. The polymerization results indicate the possibility of precise microstructure control depending on the particular complex substitution. Preliminary investigations on material density and mechanical behavior by uniaxial stretching until failure point toward new material properties that can result from the simple ethylene monomer by catalyst design.     

On a singular boundary value problem arising in the theory of shallow membrane caps

We investigate the following singular boundary value problem which originates from the theory of shallow membrane caps,

     

Strong Cardinals and Sets of Reals in Lω1(ℝ)

We generalize results of [3] and [1] to hyperprojective sets of reals, viz. to more than finitely many strong cardinals being involved. We show, for example, that if every set of reals in L_ω (?) is weakly homogeneously Souslin, then there is an inner model with an inaccessible limit of strong cardinals.     

Bayesian methods for parameter estimation in effective field theories

We demonstrate and explicate Bayesian methods for fitting the parameters that encode the impact of short-distance physics on observables in effective field theories (EFTs). We use Bayes’ theorem together with the principle of maximum entropy to account for the prior information that these parameters should be natural, i.e., O(1) in appropriate units. Marginalization can then be employed to integrate the resulting probability density function (pdf) over the EFT parameters that are not of specific interest in the fit. We also explore marginalization over the order of the EFT calculation, M, and over the variable, R, that encodes the inherent ambiguity in the notion that these parameters are O(1). This results in a very general formula for the pdf of the EFT parameters of interest given a data set, D. We use this formula and the simpler “augmented χ²” in a toy problem for which we generate pseudo-data. These Bayesian methods, when used in combination with the “naturalness prior”, facilitate reliable extractions of EFT parameters in cases where χ² methods are ambiguous at best. We also examine the problem of extracting the nucleon mass in the chiral limit, M₀, and the nucleon sigma term, from pseudo-data on the nucleon mass as a function of the pion mass. We find that Bayesian techniques can provide reliable information on M₀, even if some of the data points used for the extraction lie outside the region of applicability of the EFT.     

Inside Cover: A Spherical Molecule with a Carbon‐Free Ih‐C80 Topological Framework (Angew. Chem. Int. Ed. 27/2009)

Template‐controlled self‐assembly of discrete molecular pentaphosphaferrocene and CuCl units was used to form the first entirely carbon‐free molecule that has C₈₀ topology and encapsulates a carborane unit. In their Communication on page 5046 ff. , M. Scheer and co‐workers report the synthesis and characterization of this impressive supramolecular compound, which displays an electronic interaction between the carborane and the spherical host molecule. C blue, Fe olive, P pink, Cl green, C gray, B/C orange, H white.