On-line H NMR spectroscopic investigation of hydrogen bonding in supercritical and near critical CO2–methanol up to 35 MPa and 403 K

On-line NMR spectroscopy can beneficially be applied to studies of supercritical and near-critical fluids as an alternative to optical spectroscopy. Up to now high pressure NMR experiments are predominantly accomplished using custom made NMR batch reactors. The authors present a novel high pressure cell with displacement plunger for on-line NMR experiments on compressible fluids which can be used in conjunction with commercially available SCF NMR flow probes. The on-line technique offers advantages compared to stopped flow techniques such as enhanced control of mixture composition and reaction parameters as well as the facility of engagement into the reaction. The new apparatus is used for NMR studies on hydrogen bonding of methanol in near critical and supercritical carbon dioxide up to 403 K and 35 MPa for which data on the chemical shift of the hydroxyl group and methyl group are reported and interpreted.     

In Google We Trust: Users' Decisions on Rank, Position, and Relevance

An eye tracking experiment revealed that college student users have substantial trust in Google's ability to rank results by their true relevance to the query. When the participants selected a link to follow from Google's result pages, their decisions were strongly biased towards links higher in position even if the abstracts themselves were less relevant. While the participants reacted to artificially reduced retrieval quality by greater scrutiny, they failed to achieve the same success rate. This demonstrated trust in Google has implications for the search engine's tremendous potential influence on culture, society, and user traffic on the Web.     

Spatially resolved X-ray diffraction phase mapping and α → β → α transformation kinetics in the heat-affected zone of commercially pure titanium arc welds

Spatially resolved X-ray diffraction (SRXRD) is used to map the α → β → α phase transformation in the heat-affected zone (HAZ) of commercially pure titanium gas tungsten arc welds. In situ SRXRD experiments were conducted using a 180-μm-diameter X-ray beam at the Stanford Synchrotron Radiation Laboratory (SSRL) (Stanford, CA) to probe the phases present in the HAZ of a 1.9 kW weld moving at 1.1 mm/s. Results of sequential linear X-ray diffraction scans made perpendicular to the weld direction were combined to construct a phase transformation map around the liquid weld pool. This map identifies six HAZ microstructural regions between the liquid weld pool and the base metal: (1) α-Ti that is undergoing annealing and recrystallization; (2) completely recrystallized α-Ti; (3) partially transformed α-Ti, where α-Ti and β-Ti coexist; (4) single-phase β-Ti; (5) back-transformed α-Ti; and (6) recrystallized α-Ti plus back-transformed α-Ti. Although the microstructure consisted predominantly of α-Ti, both prior to and after the weld, the crystallographically textured starting material was altered during welding to produce different α-Ti textures within the resulting HAZ. Based on the travel speed of the weld, the α → β transformation was measured to take 1.83 seconds during heating, while the β → α transformation was measured to take 0.91 seconds during cooling. The α → β transformation was characterized to be dominated by long-range diffusional growth on the leading (heating) side of the weld, while the β → α transformation was characterized to be predominantly massive on the trailing (cooling) side of the weld, with a massive growth rate on the order of 100 μm/s.     

Energieinformatik

Due to the increasing importance of producing and consuming energy more sustainably, Energy Informatics (EI) has evolved into a thriving research area within the CS/IS community. The article attempts to characterize this young and highly dynamic field of research by describing current EI research topics and methods and provides an outlook of how the field might evolve in the future. It is shown that two general research questions have received the most attention so far and are likely to dominate the EI research agenda in the coming years: How to leverage information and communication technology (ICT) to (1) improve energy efficiency, and (2) to integrate decentralized renewable energy sources into the power grid. Selected EI streams are reviewed, highlighting how the respective research questions are broken down into specific research projects and how EI researchers have made contributions based on their individual academic background.     

Combination of computational prescreening and experimental library construction can accelerate enzyme optimization by directed evolution

Chiral compounds can be produced efficiently by using biocatalysts. However, wild-type enzymes often do not meet the requirements of a production process, making optimization by rational design or directed evolution necessary. Here, we studied the lipase-catalyzed hydrolysis of the model substrate 1-(2-naphthyl)ethyl acetate both theoretically and experimentally. We found that a computational equivalent of alanine scanning mutagenesis based on QM/MM methodology can be applied to identify amino acid positions important for the activity of the enzyme. The theoretical results are consistent with concomitant experimental work using complete saturation mutagenesis and high-throughput screening of the target biocatalyst, a lipase from Bacillus subtilis. Both QM/MM-based calculations and molecular biology experiments identify histidine 76 as a residue that strongly affects the catalytic activity. The experiments demonstrate its important influence on enantioselectivity.     

Kinetics of Solid-State Reactions in Heterogeneous Catalysis from Time-Resolved X-Ray Absorption Spectroscopy

The potentials of X-ray absorption spectroscopy (XAS) (quantitative phase composition and average valence together with a short-range order structure analysis) combined with a time-resolution in the second range make time-resolved (TR-) XAS a powerful tool for investigating the reactivity of solids in catalysis and solid-state chemistry. General aspects of TR-XAS investigations are discussed (i.e., instrumentation, data analysis). In addition, some experiments illustrate how the kinetics of solid-state reactions in heterogeneous catalysis can be elucidated from TR-XAS studies.     

Engineering of functional supramacromolecular complexes of proteins (enzymes) using reversed micelles as matrix microreactors

The size of the inner water cavity of reversed micelles formedin a triple system ‘water-surfactant-organic solvent’can be widely varied by changing the degree of surfactant hydration.This gives grounds to use reversed micelles as matrix microreactorsfor the design of supramolecular complexes of proteins. Usingultracentrifugation analysis, it has been demonstrated thatthe oligomeric composition of various enzymes (ketoglutaratedehydrogenase, alkaline phosphatase, lactic dehydrogenase, glyceraldehyde-3-phosphatedehydrogenase) solubilized in reversed micelles of Aerosol OT[sodium bis(2-ethylehexyl)sulfosuccinate] in octane changesupon variation of the degree of hydration. An oligomeric complexforms under conditions when the radius of the micelle innercavity is big enough to incorporate this complex as a whole.At lower degrees of hydration the micelles ‘uncouple’such complexes to their components. The catalytic propertiesof various oligomeric complexes have been studied. Possibilitiesof using reversed micelles for the separation of subunits ofoligomeric enzymes under non-denaturating conditions have beendemonstrated. In particular, the isolated subunits of alkalinephosphatase, lactic dehydrogenase and glyceralde-hyde-3-phosphatedehydrogenase have been found to be active in Aerosol OT reversedmicelles. The dependences of the catalytic activity of oligomericenzymes represent saw-like curves. The maxima of the catalyticactivity observed at these curves relate to the functioningof various oligomeric forms of an enzyme. The radii of the micelleinner cavity under conditions when these maxima are observedcorrelate with the linear dimensions of the enzyme oligomericforms. Correlation of the position of a maximum with the shapeof an oligomeric complex is discussed.     

Estimating body shape of dressed humans

The paper presents a method to estimate the detailed 3D body shape of a person even if heavy or loose clothing is worn. The approach is based on a space of human shapes, learned from a large database of registered body scans. Together with this database we use as input a 3D scan or model of the person wearing clothes and apply a fitting method, based on ICP (iterated closest point) registration and Laplacian mesh deformation. The statistical model of human body shapes enforces that the model stays within the space of human shapes. The method therefore allows us to compute the most likely shape and pose of the subject, even if it is heavily occluded or body parts are not visible. Several experiments demonstrate the applicability and accuracy of our approach to recover occluded or missing body parts from 3D laser scans.