An integrated qualitative and quantitative modeling framework for computer‐assisted HAZOP studies

The article proposes a novel practical framework for computer‐assisted hazard and operability (HAZOP) that integrates qualitative reasoning about system function with quantitative dynamic simulation in order to facilitate detailed specific HAZOP analysis. The practical framework is demonstrated and validated on a case study concerning a three‐phase separation process. The multilevel flow modeling (MFM) methodology is used to represent the plant goals and functions. First, means‐end analysis is used to identify and formulate the intention of the process design in terms of components, functions, objectives, and goals on different abstraction levels. Based on this abstraction, qualitative functional models are constructed for the process. Next MFM‐specified causal rules are extended with systems specific features to enable proper reasoning. Finally, systematic HAZOP analysis is performed to identify safety critical operations, its causes and consequences. The outcome is a qualitative hazard analysis of selected process deviations from normal operations and their consequences as input to a traditional HAZOP table. The list of unacceptable high risk deviations identified by the qualitative HAZOP analysis is used as input for rigorous analysis and evaluation by the quantitative analysis part of the framework. To this end, dynamic first‐principles modeling is used to simulate the system behavior and thereby complement the results of the qualitative analysis part. The practical framework for computer‐assisted HAZOP studies introduced in this article allows the HAZOP team to devote more attention to high consequence hazards. © 2014 American Institute of Chemical Engineers AIChE J 60: 4150–4173, 2014     

Facets of visual aesthetics

Visual aesthetics has been shown to critically affect a variety of constructs such as perceived usability, satisfaction, and pleasure. Given the importance of visual aesthetics in human–computer interaction, it is vital that it is adequately assessed. The present research aimed at providing a precise operational definition and to develop a new measure of perceived visual aesthetics of websites. Construction of the Visual Aesthetics of Website Inventory (VisAWI) was based on a comprehensive and broad definition of visual aesthetics so that the resulting instrument would completely describe the domain of interest. Four interrelated facets of perceived visual aesthetics of websites were identified and validated in a series of seven studies. Simplicity and Diversity have repeatedly been treated as formal parameters of aesthetic objects throughout the history of empirical aesthetics, Colors are a critical property of aesthetic objects, and Craftsmanship addresses the skillful and coherent integration of the relevant design dimensions. These four facets jointly represent perceived visual aesthetics, but are still distinguishable from each other and carry unique meaning. The subscales contained in the VisAWI demonstrate good internal consistencies. Evidence for the convergent, divergent, discriminative, and concurrent validity of the VisAWI is provided. Overall, the present research suggests that the VisAWI appears to be a sound measure of visual aesthetics of websites comprising facets of both practical and theoretical interest.     

Serendipitous Identification of a Covalent Activator of Liver Pyruvate Kinase

Enzymes are effective biological catalysts that accelerate almost all metabolic reactions in living organisms. Synthetic modulators of enzymes are useful tools for the study of enzymatic reactions and can provide starting points for the design of new drugs. Here, we report on the discovery of a class of biologically active compounds that covalently modifies lysine residues in human liver pyruvate kinase (PKL), leading to allosteric activation of the enzyme (EC₅₀=0.29 μM). Surprisingly, the allosteric activation control point resides on the lysine residue K282 present in the catalytic site of PKL. These findings were confirmed by structural data, MS/MS experiments, and molecular modelling studies. Altogether, our study provides a molecular basis for the activation mechanism and establishes a framework for further development of human liver pyruvate kinase covalent activators.     

The Effect of Alkali Ions on the Incorporation of Aluminum in the Calcium Silicate Hydrate (C–S–H) Phase Resulting from Portland Cement Hydration Studied by 29Si MAS NMR

The incorporation of aluminum in the calcium–silicate–hydrate (C–S–H) phases formed by hydration of three different white Portland cements has been investigated by ²⁹Si MAS NMR. The principal difference between the three cements is their bulk Al₂O₃ contents and quantities of alkali (Na⁺ and K⁺) ions. ²⁹Si MAS NMR allows indirect detection of tetrahedral Al incorporated in the silicate chains of the C–S–H structure by the resonance from Q²(1Al) sites. Analysis of the relative ²⁹Si NMR intensities for this site, following the hydration for the three cements from 0.5 d to 30 weeks, clearly reveals that the alkali ions promote the incorporation of Al in the bridging sites of the dreierketten structure of SiO₄ tetrahedra in the C–S–H phase. The increased incorporation of Al in the C–S–H phase with increasing alkali content in the anhydrous cement is in accord with a proposed substitution mechanism where the charge deficit, obtained by the replacement of Si⁴⁺ by Al³⁺ ions in the bridging sites, is balanced by adsorption/binding of alkali ions in the interlayer region most likely in the near vicinity of the AlO₄ tetrahedra. This result is further supported by similar ²⁹Si MAS NMR experiments performed for the white Portland cements hydrated in 0.30M NaOH and NaAlO₂ solutions.     

Chemical synthesis of a dual branched malto-decaose: a potential substrate for alpha-amylases

A convergent block strategy for general use in efficient synthesis of complex alpha-(1-->4)- and alpha-(1-->6)-malto-oligosaccharides is demonstrated with the first chemical synthesis of a malto-oligosaccharide, the decasaccharide 6,6'-bis(alpha-maltosyl)-maltohexaose, with two branch points. Using this chemically defined branched oligosaccharide as a substrate, the cleavage pattern of seven different alpha-amylases were investigated. Alpha-amylases from human saliva, porcine pancreas, barley alpha-amylase 2 and recombinant barley alpha-amylase 1 all hydrolysed the decasaccharide selectively. This resulted in a branched hexasaccharide and a branched tetrasaccharide. Alpha-amylases from Asperagillus oryzae, Bacillus licheniformis and Bacillus sp. cleaved the decasaccharide at two distinct sites, either producing two branched pentasaccharides, or a branched hexasaccharide and a branched tetrasaccharide. In addition, the enzymes were tested on the single-branched octasaccharide 6-alpha-maltosyl-maltohexaose, which was prepared from 6,6'-bis(alpha-maltosyl)-maltohexaose by treatment with malt limit dextrinase. A similar cleavage pattern to that found for the corresponding linear malto-oligosaccharide substrate was observed.     

Rational design, synthesis and pharmacological evaluation of the (2R)- and (2S)-stereoisomers of 3-(2-carboxypyrrolidinyl)-2-methyl acetic acid as ligands for the ionotropic glutamate receptors

In this paper we describe the rational design, synthesis and pharmacological evaluation of two new stereoisomeric (S)‐glutamate (Glu) analogues. The rational design was based on hybrid structures of the natural product kainic acid, a synthetic analogue CPAA and the high‐affinity Glu analogue SYM2081. Pharmacological evaluation of the two stereoisomers revealed that one stereoisomer showed a subtype selectivity profile with low micromolar affinity for GluK1 and GluK3 and a 10‐ to 15‐fold lower affinity for GluK2. The other stereoisomer displayed full selectivity for the KA over AMPA and NMDA receptors (GluK1–3: 0.39, 0.51 and 0.099 µM , respectively).     

Combined TPS, XPS, EXAFS, and NO-TPD study of the sulfiding of Mo/Al2O3

The sulfiding of Mo/Al₂O₃ in H₂S/Ar versus in H₂S/H₂ has been studied by temperature-programmed sulfiding (TPS), X-ray photon electron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS), and temperature-programmed desorption of NO (NO-TPD). All the applied techniques agree on the sulfur content in the sulfided catalysts and the findings are in accord with a model for the H₂S production reaction. The nucleation and growth of well-ordered MoS₂ clusters are probed by XPS during sulfiding with and without the presence of hydrogen. The resulting dispersion of the MoS₂ phase is evaluated on the basis of XPS, EXAFS, and NO-TPD, and is found to be highest when the sulfiding occurs in the presence of hydrogen.     

Investigation and simulation of a cross-flow air classifier

Extensive experimental tests and a computational study of the performance in a cross-flow air classifier have been carried out. A computational fluid dynamics (CFD) package—Fluent—is used to first understand and explain why the cuts or the sharpness of cut of this classifier are not as sharp as they ought to be, and then to optimize the geometry and operational conditions.

Flow fields of the classifier under various set-up conditions and geometry were measured by using laser Doppler anemometry (LDA). Using sieve analyses and the HELOS-laser method, the patterns of behaviour of separation parameters such as cut size and sharpness of cut have been investigated at different boundary conditions.

Using the Fluent package, a two-dimensional computational fluid dynamics model has been developed. The model is based on the Euler–Lagrangian approach. Different turbulence models have been tested. Both Fluent 4.5, with a structured grid, and Fluent 5.1, with structured and unstructured grids, have been used.

Discussions and analyses of the experimental, as well as the computational results, are presented. The simulation with a structured grid shows good agreement with experimental data, except for the sharpness of cut. The reasons of poor performance of the classifier have been found. The geometry is optimized and other conditions were also improved. The performance of the classifier is improved. The experimental observations together with the computed results should increase the depth of understanding of the underlying mechanisms.