Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

On the Black-Box Complexity of Sperner’s Lemma

We present several results on the complexity of various forms of Sperner’s Lemma in the black-box model of computing. We give a deterministic algorithm for Sperner problems over pseudo-manifolds of arbitrary dimension. The query complexity of our algorithm is linear in the separation number of the skeleton graph of the manifold and the size of its boundary. As a corollary we get an deterministic query algorithm for the black-box version of the problem 2D-SPERNER, a well studied member of Papadimitriou’s complexity class PPAD. This upper bound matches the deterministic lower bound of Crescenzi and Silvestri. The tightness of this bound was not known before. In another result we prove for the same problem an lower bound for its probabilistic, and an lower bound for its quantum query complexity, showing that all these measures are polynomially related. Research supported by the European Commission IST Integrated Project Qubit Application (QAP) 015848, the OTKA grants T42559 and T46234, and by the ANR Blanc AlgoQP grant of the French Research Ministry.     

Quality through Managed Improvement and Measurement (QMIM): Towards a Phased Development and Implementation of a Quality Management System for a Software Company

The paper describes results of a longitudinal study of developments in the area of software product and process quality improvement within a Hungarian software company, IQSOFT Ltd. This company has been active in this area since 1993, trying to build, introduce and maintain an efficiently working quality management system which, e.g., fulfils the ISO 9001 requirements, allows steady software process improvement and, at the same time, conforms to company's own needs. Over the last eight years five phases could be distinguished. Each phase is described shortly, following the same structure, namely: basic starting points, key problem areas, literature consulted, activities and design executed, reflections on what happened and why. The lessons resulting from the analysis of this case have been formulated in terms of guidelines. We feel that these are applicable to any low maturity software development organisation embarking on a product or process quality improvement endeavour. These guidelines are developed around a framework containing the basic issues of software production (project management, technical processes and products). The guidelines advocate a careful step-by-step development of definitions, quality characteristics, and metrics related to these objects while at the same time developing and introducing the associated process.     

Model complexity reduction of chemical reaction networks using mixed-integer quadratic programming

The model complexity reduction problem of large chemical reaction networks under isobaric and isothermal conditions is considered. With a given detailed kinetic mechanism and measured data of the key species over a finite time horizon, the complexity reduction is formulated in the form of a mixed-integer quadratic optimization problem where the objective function is derived from the parametric sensitivity matrix. The proposed method sequentially eliminates reactions from the mechanism and simultaneously tunes the remaining parameters until the pre-specified tolerance limit in the species concentration space is reached. The computational efficiency and numerical stability of the optimization are improved by a pre-reduction step followed by suitable scaling and initial conditioning of the Hessian involved. The proposed complexity reduction method is illustrated using three well-known case studies taken from reaction kinetics literature.     

Electrospun poly(aspartic acid) gel scaffolds for artificial extracellular matrix

Biocompatible synthetic polymer gel scaffolds for tissue engineering and regenerative medicine were prepared by reactive electrospinning. Protein‐like nano‐ and microfibres from chemically crosslinked polysuccinimide were obtained. Fibrous poly(aspartic acid) gels with size similar to that of extracellular matrix were obtained by hydrolysis of the polysuccinimide gel fibres. The effects of process parameters on fibre morphology (diameter, swelling degree) and chemical structure were investigated. Sub‐micrometre‐sized biocompatible fibrous scaffolds from a poly(amino acid) is a novel approach with great promise in several biomedical applications due to the tailor‐made synthetic nature, extreme purity and possibility of production on a large scale. © 2014 Society of Chemical Industry     

Electrospray ionization mass spectrometry fingerprinting of Brazilian cacha?as produced in copper alembic and in stainless-steel column stills

Brazilian cacha?a can be produced in two different ways: distilled in stainless steel column or in copper alembic stills. We evaluated 36 samples of commercial non-aged cacha?as: 18 samples of sweetened cacha?as distilled in stainless steel column, and 18 samples distilled in copper alembic stills. Fingerprints were obtained through electrospray ionization mass spectrometry by recording the intensity of the 15 most abundant ions. Principal component analysis was applied to the data and separated the samples in two groups. However, after sample standardization with sugar (20?g?L^?1), it was not possible to group them by type of distillation. The results showed that the technique applied did not allow differentiation of cacha?as based on the distillation system, but for the presence or absence of sugar in them.     

Shape memory crosslinked polyurethanes containing thermoreversible Diels‐Alder couplings

Crosslinked polyurethanes (PUs) containing irreversible (allophanate) and reversible Diels‐Alder chemical bonds were synthesized using various diisocyanates (methylene diphenyl diisocyanate MDI, 1,6‐hexamethylenediisocyanate HDI) and poly(?‐caprolactone) ((PCL) with different molecular weights (M_n = 10 kg/mol, 25 kg/mol, 50 kg/mol) as diol component. The melting/crystallization of PCL and the reversible DA bonds acted as temperature‐activated switches for shape memory performances, while allophanate network provided the permanent crosslinks for these PUs. The reversible DA bonds were obtained by the reaction of diisocyanate‐ended prepolymers with furfurylamine (FA) followed by the addition of bismaleimide (BMI). The permanent crosslinks between the linear chains containing DA bonds were achieved using additional amounts of diisocyanates (MDI or HDI). The above reaction path was supported by infrared spectroscopic results and swelling experiments. Tensile mechanical and shape memory properties in tension of the PUs were determined and discussed as a function of composition and crosslink densities deduced from swelling and dynamic mechanical analysis. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44145.