Fieller Stability Measure: a novel model-dependent backtesting approach

Dataset shift is present in almost all real-world applications, since most of them are constantly dealing with changing environments. Detecting fractures in datasets on time allows recalibrating the models before a significant decrease in the model’s performance is observed. Since small changes are normal in most applications and do not justify the efforts that a model recalibration requires, we are only interested in identifying those changes that are critical for the correct functioning of the model. In this work we propose a model-dependent backtesting strategy designed to identify significant changes in the covariates, relating a confidence zone of the change to a maximal deviance measure obtained from the coefficients of the model. Using logistic regression as a predictive approach, we performed experiments on simulated data, and on a real-world credit scoring dataset. The results show that the proposed method has better performance than traditional approaches, consistently identifying major changes in variables while taking into account important characteristics of the problem, such as sample sizes and variances, and uncertainty in the coefficients.     

Diffusion of linear paraffins in silicalite studied by the ZLC method in the presence of CO2

The diffusion behavior of C₄–C₁₀ n-alkanes in silicalite-1 has been investigated by using the Zero Length Column method. The diffusivities derived from measurements at different purge rates with different purge gases confirming intracrystalline diffusion control. Data are compared with results reported in the literature for MFI zeolites. The diffusivities were found to be consistent and agree well with data previous obtained by ZLC. However, these data showed a remarkable disagreement with other reported techniques (PFG-NMR, QENS and Permeation). The eventual influence of carbon dioxide (CO₂) adsorption on diffusion properties of n-alkanes in silicalite was also investigated. For this purpose, a series of experiments was performed involving hydrocarbons mixed with CO₂. Data were obtained at 303 K and flow rates between 20 and 80 mL/min. The presence of CO₂ does not seem to influence the intracrystalline transport rate of the investigated light hydrocarbons (n-C₄ and n-C₆). On the other hand, the situation for n-C₈ and n-C₁₀ is more complex. The diffusivity values are higher compared to the previously reported values.     

Dramatic pressure-dependent quenching effects in supercritical CO2 assessed by the fluorescence of 4'-dimethylamino-3-hydroxyflavone. Thermodynamic versus kinetics control of excited-state intramolecular proton transfer

Steady-state fluorescence of 4'-dimethylamino-3-hydroxyflavone (DMA3HF) was observed in supercritical carbon dioxide (scCO(2)). Excited-state intramolecular proton transfer (ESIPT) occurs resulting in two well-separated emission bands corresponding to the normal and tautomer forms. As the scCO(2) density exceeds 0.7 g/mL, the relative intensity of the two bands tends to a constant value, comparable to that observed for organic solvents with ET(30) = 33.0 +/- 0.5 kcal/mol, such as toluene and di-n-butyl ether. At lower densities, the substantial decrease of the total fluorescence intensity (a 600-fold decrease as the pressure decreases from 100 to 80 bar) is accompanied by an even more accentuated decrease of the tautomer fluorescence. This can be explained by a shift in the equilibrium between normal and tautomer forms, concomitant with a more efficient quenching of the less solvated fluorophore, that may change the thermodynamic control of the relative population of the two emissive species to a kinetic control.     

Experimental and theoretical study of lanthanide complexes based on linear and macrocyclic polyaminopolycarboxylic acids containing pyrazolylethyl arms

We report the synthesis of two novel Gd(III)-complexes derived from linear and macrocyclic polyaminopolycarboxylic acids 1 and 2, which contain a 3,5- dimethylpyrazolyl-ethyl arm, and a study of their relaxivity properties. The relationships between the experimental and theoretical results have provided interesting information about the kinetic and thermodynamic stability of these complexes.     

Thermally induced phase transition in helical comblike poly(beta-peptide)s: an atomistic simulation

Atomistic Monte Carlo (MC) simulations have been used to study a thermally induced phase transition in poly(alpha-octadecyl-beta,L-aspartate). Simulations were performed by using the parallelized version of Configurational Bias MC algorithm adapted to study comblike polymers. A total of 1.15. 10(6) steps were carried out for a molecular system constituted by 6240 atoms/pseudoatoms. Results were consistent with available experimental observations. The limitations of atomistic simulations to study large length-scale phenomena are discussed.     

A New Laboratory Experiment Based on a Chemical Transformation of Santonin: Synthesis of Santonic Acid

In this paper we describe a new comprehensive laboratory experiment based on a chemical transformation of santonin. The experiment is designed as a puzzle-solving exercise for advanced undergraduate organic chemistry courses and consists of the structure elucidation of santonic acid, the product obtained by the action of strong alkalis on santonin. An enquiry-based approach helps the students achieve this goal by combining their knowledge of organic chemistry and spectroscopy together with mechanistic thinking.     

Synthesis and structural characterization of cadmium(II) complexes with chelating keto-hydroxy compounds: The X-ray molecular structure of [Cd2(nq)4(H2O)4]·3H2O (nqH = 2-hydroxynaphthoquinone)

The reaction of cadmium(II) acetate dehydrate with the complexing agents tropolone (tropH), 2-hydroxynaphthoquinone (nqH), 1,2-dihydroxyanthraquinone (alizH₂), and 1,8-dihydroxyanthraquinone (chryzH₂), afforded the complexes [Cd(trop)₂] 1, [Cd₂(nq)₄(H₂O)₄]·3H₂O 2·3H₂O, [Cd(alizH)₂(H₂O)₃] 3, and [Cd(chryzH)₂(H₂O)₂] 4, respectively. The X-ray molecular structure of the dinuclear complex 2·3H₂O reveals that each cadmium(II) atom is seven-coordinated. The nature of water molecules (lattice or coordinated) was discerned by thermogravimetric studies. The ¹¹³Cd NMR spectra were discussed in light of the chemical exchange.     

Poly(ethylene‐co‐1,4‐cyclohexylenedimethylene terephthalate) copolyesters obtained by ring opening polymerization

Cyclic oligomer fractions of ethylene terephthalate c(ET)_n and 1,4‐cyclohexylenedimethylene terephthalate c(CT)_n were obtained by cyclodepolymerization of their respective polyesters, the former containing around 80 mol % of trimer and the latter with around 70 mol % of trimer to pentamer. Mixtures of these fractions at selected compositions were subjected to ring opening copolymerization to give a series of poly(ethylene‐co‐cyclohexylenedimethylene terephthalate) copolyesters with ET/CT comonomer ratios ranging from 90/10 to 10/90. The copolyesters were characterized by GPC and NMR, and their thermal properties were evaluated by DSC and TGA. They had essentially the same composition as the feed from which they were produced and had an average‐weight molecular weights between 30,000 and 40,000 g/mol with polydispersities between 2 and 2.7. The distribution of the monomeric units in these copolyesters was essentially at random although it evolved to be a blocky microstructure as the contents in the two comonomers became more dissimilar. Their thermal behavior was the expected one for these types of copolyesters with crystallinity and heating stability decreasing with the content in CT units. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5954–5966, 2009     

Linear polyurethanes made from naturally occurring tartaric acid

Naturally occurring tartaric acid was used as raw material for the synthesis of novel linear polyurethanes (PURs) bearing two carboxylate side‐groups in the repeating unit. Aliphatic and aromatic PURs were obtained by reaction in solution of alkyl and benzyl tartrates with hexamethylene diisocyanate and 4,4′‐methylene‐bis(phenyl isocyanate), respectively. All the novel PURs were thermally stable and optically active. The aliphatic carboxylate‐containing PURs had M_w in the 40–70 kDa range, with PD between 2.1 and 2.5; all were semicrystalline polymers with melting temperatures between 100 and 150 °C and T_g in the 50–80 °C range. The aromatic PURs were amorphous materials with molecular weights between 18 kDa and 25 kDa and T_g above 130 °C. Hydrogenolysis of the PUR made from hexamethylene diisocyanate and benzyl tartrate yielded PURs containing up to 40% of free carboxylic side‐groups. The tartrate‐derived PURs displayed enhanced sensitivity to hydrolysis compared with their unsubstituted 2,6‐PUR homologs. The PURs bearing free carboxylic groups were unique in being degraded by water upon incubation under physiological conditions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2391–2407, 2009     

On assigning drivers for a home-delivery system on a performance basis

Consider a firm providing home-delivery of small parcels within a short period of time. The paper proposes a method to estimate the productivity of each driver on any fictitious route using linear regressions. The method separates the trip time in terms of the time spent: with customers, driving, and all other activities. Our tests show that productivity, measured in terms of number of customers visited per hour, vary across drivers. Even more, the same driver’s productivity vary for peak and off-peak demand periods considerably. This methodology should enhance the reliability of the driver scheduling programs, since it reduces the error and bias of the productivity offered by the assigned set of drivers. It shall also improve the reliability of the delivery time promised to the customer.