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.     

MODIS Collection 5 global land cover: Algorithm refinements and characterization of new datasets

Information related to land cover is immensely important to global change science. In the past decade, data sources and methodologies for creating global land cover maps from remote sensing have evolved rapidly. Here we describe the datasets and algorithms used to create the Collection 5 MODIS Global Land Cover Type product, which is substantially changed relative to Collection 4. In addition to using updated input data, the algorithm and ancillary datasets used to produce the product have been refined. Most importantly, the Collection 5 product is generated at 500-m spatial resolution, providing a four-fold increase in spatial resolution relative to the previous version. In addition, many components of the classification algorithm have been changed. The training site database has been revised, land surface temperature is now included as an input feature, and ancillary datasets used in post-processing of ensemble decision tree results have been updated. Further, methods used to correct classifier results for bias imposed by training data properties have been refined, techniques used to fuse ancillary data based on spatially varying prior probabilities have been revised, and a variety of methods have been developed to address limitations of the algorithm for the urban, wetland, and deciduous needleleaf classes. Finally, techniques used to stabilize classification results across years have been developed and implemented to reduce year-to-year variation in land cover labels not associated with land cover change. Results from a cross-validation analysis indicate that the overall accuracy of the product is about 75% correctly classified, but that the range in class-specific accuracies is large. Comparison of Collection 5 maps with Collection 4 results show substantial differences arising from increased spatial resolution and changes in the input data and classification algorithm.     

Hierarchical mapping of Northern Eurasian land cover using MODIS data

The Northern Eurasian land mass encompasses a diverse array of land cover types including tundra, boreal forest, wetlands, semi-arid steppe, and agricultural land use. Despite the well-established importance of Northern Eurasia in the global carbon and climate system, the distribution and properties of land cover in this region are not well characterized. To address this knowledge and data gap, a hierarchical mapping approach was developed that encompasses the study area for the Northern Eurasia Earth System Partnership Initiative (NEESPI). The Northern Eurasia Land Cover (NELC) database developed in this study follows the FAO-Land Cover Classification System and provides nested groupings of land cover characteristics, with separate layers for land use, wetlands, and tundra. The database implementation is substantially different from other large-scale land cover datasets that provide maps based on a single set of discrete classes. By providing a database consisting of nested maps and complementary layers, the NELC database provides a flexible framework that allows users to tailor maps to suit their needs. The methods used to create the database combine empirically derived climate–vegetation relationships with results from supervised classifications based on Moderate Resolution Imaging Spectroradiometer (MODIS) data. The hierarchical approach provides an effective framework for integrating climate–vegetation relationships with remote sensing-based classifications, and also allows sources of error to be characterized and attributed to specific levels in the hierarchy. The cross-validated accuracy was 73% for the land cover map and 73% and 91% for the agriculture and wetland classifications, respectively. These results support the use of hierarchical classification and climate–vegetation relationships for mapping land cover at continental scales.     

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.     

A Study on the Buckling Behaviour of Strips and Plates with Residual Stresses

During and after rolling or flattening of metal strips and plates the permissible deviations from flatness are described by the permissible absolute wave height and the flatness index. Both values can be determined on a measuring table while the material is not subjected to global tension. Because this procedure is expensive, time‐consuming and allows measurement only at discrete positions along the strip length, on‐line flatness measuring systems are used which can detect the distribution of longitudinal tensile stresses distributed across the strip width allowing for the calculation of the flatness index. This value does not always agree with the value obtained directly by measuring on the table even when the measurement of the longitudinal tensile stress distribution operates perfectly. It can be shown that the measurement of the tensile stress distribution does not give a direct indication on the wave height in the tension‐free state determined on the measuring table. To explain the relationship between tensile stress distribution in the strip and the flatness measurement on the measuring table, the buckling behavior is analysed both with and without dead load for simple symmetrical residual stress distributions resulting, e.g., from the rolling process. Based on the knowledge of the distribution of the longitudinal residual stresses across the strip width, the flatness index and the wave height can be determined by using a specialized finite element model. If the direct measurement is performed under action of dead load, large differences between the directly and indirectly obtained flatness index are observed. Below a certain limit of the intensity of the residual stress distribution the strips and plates lie flat on the measuring table. Above this limit the strip lying on the table exhibits post‐bucking deformations. In the latter case, the wave height increases with strip thickness and intensity of residual stresses.     

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.