Molecular Mechanism of the Hydration of Candida antarctica Lipase B in the Gas Phase: Water Adsorption Isotherms and Molecular Dynamics Simulations

Hydration is a major determinant of activity and selectivity of enzymes in organic solvents or in gas phase. The molecular mechanism of the hydration of Candida antarctica lipase B (CALB) and its dependence on the thermodynamic activity of water (a_w) was studied by molecular dynamics simulations and compared to experimentally determined water sorption isotherms. Hydration occurred in two phases. At low water activity, single water molecules bound to specific water binding sites at the protein surface. As the water activity increased, water networks gradually developed. The number of protein‐bound water molecules increased linearly with a_w, until at a_w=0.5 a spanning water network was formed consisting of 311 water molecules, which covered the hydrophilic surface of CALB, with the exception of the hydrophobic substrate‐binding site. At higher water activity, the thickness of the hydration shell increased up to 10 Å close to a_w=1. Above a limit of 1600 protein‐bound water molecules the hydration shell becomes unstable and the formation of pure water droplets occurs in these oversaturated simulation conditions. While the structure and the overall flexibility of CALB was independent of the hydration state, the flexibility of individual loops was sensitive to hydration: some loops, such as those part of the substrate‐binding site, became more flexible, while other parts of the protein became more rigid upon hydration. However, the molecular mechanism of how flexibility is related to activity and selectivity is still elusive.     

Synthesis and characterization of {Fe2CuO} clusters as precursors for nanosized catalytic system for Biginelli reaction

The novel μ₃-oxo-bridged heterotrinuclear iron(III)-copper(II) trichloroacetates of the composition [Fe₂CuO(CCl₃COO)₆(THF)₃] (1a) and [Fe₂CuO(CCl₃COO)₆(4-DMAP)₃] (1b) have been synthesized and characterized by X-ray crystallography, IR and Mossbauer spectroscopy. These clusters were used as precursors for the synthesis of the nanosized catalytic system (～5–6 nm of γ-Fe₂O₃/CuO), which works as an efficient organic phase catalyst (～0.02 mol%) in a one-pot three component Biginelli synthesis.     

Origins of Systems Biology in William Harvey’s Masterpiece on the Movement of the Heart and the Blood in Animals

In this article we continue our exploration of the historical roots of systems biology by considering the work of William Harvey. Central arguments in his work on the movement of the heart and the circulation of the blood can be shown to presage the concepts and methods of integrative systems biology. These include: (a) the analysis of the level of biological organization at which a function (e.g. cardiac rhythm) can be said to occur; (b) the use of quantitative mathematical modelling to generate testable hypotheses and deduce a fundamental physiological principle (the circulation of the blood) and (c) the iterative submission of his predictions to an experimental test. This article is the result of a tri-lingual study: as Harvey’s masterpiece was published in Latin in 1628, we have checked the original edition and compared it with and between the English and French translations, some of which are given as notes to inform the reader of differences in interpretation.     

Temporal Regionalization of 7-Day Low Flows in the St. Lawrence Watershed in Quebec (Canada)

Winter and summer 7-day low flows of eighteen natural rivers in the St. Lawrence River watershed of Quebec were analyzed over the period from 1934 to 2000. The rivers were first subdivided into three modes using principal component analysis. Two of these modes are located on the south shore of the St. Lawrence River, respectively south (Southeast mode) and north (East mode) of the 47°N, and the third (Southwest mode) is located on the north shore. The Southeast mode shows a significant increase in 7-day low flows in winter and summer due to increasing summer and fall precipitation, whereas the Southwest mode shows a significant decrease in summer 7-day low flows due to an increase in evapotranspiration. No significant change in winter and summer 7-day low flows is observed in the East mode. Results show that the variability of 7-day low flows and their link with climate indices are mainly seasonally dependent. The North Atlantic Oscillation (NAO) is the only index which is correlated to 7-day low flows in all three modes. This correlation is positive for north shore rivers and negative for south shore rivers. Furthermore, only north shore rivers are correlated to NAO in both winter and summer.     

The monounsaturated acyl- and alkyl-moieties of wax esters and their distribution in commercial orange roughy (Hoplostethus atlanticus) oil

Wax esters were isolated from commercial orange roughy (Hoplostethus atlanticus) oil by column chromatography and fractionated by argentation thin layer chromatography. Following transesterification, the resultant fatty acid methyl esters and fatty alcohols were analyzed by gas chromatography. both acyl- and alkyl-moieties were mainly of the monoene structure within the 16∶1–22∶1 range. After derivatization, the positions of the double bonds of even numbered fatty acid and fatty alcohol isomers were located by chromatography-mass spectrometry and compared. Results of these positional analyses indicate that the primary desaturation reactions takes place in the Δ9 position of pre-existing (C₁₄ to C₂₄) acyl chains. It is proposed that acyl components from 18∶1 are subjected to chain elongation to form a mixture of 24∶1 isomers as the final product. Apart from the 24∶1 acyl moiety of the wax esters, in which the double bond was almost exclusively in the Δ15 position, de novo biosynthetic reactions on acids and alcohols appear to yield related acyl- and alkyl-moieties of resynthesized wax esters.     

Online ice crystal size measurements during sorbet freezing by means of the focused beam reflectance measurement (FBRM) technology. Influence of operating conditions

In ice cream and sorbet manufacturing small ice crystals are desired to deliver a product with a smooth texture and good palatability. This research studied the influence of the operating conditions on the ice crystal size and the draw temperature of the sorbet during the freezing process. The evolution of ice crystal size was tracked with the focused beam reflectance measurement (FBRM) technique, which uses an in situ sensor that makes it possible to monitor online the chord length distribution (CLD) of ice crystals in sorbets containing up to 40% of ice. The refrigerant fluid temperature had the most significant influence on the mean ice crystal chord length, followed by the dasher speed, whereas the mix flow rate had no significant influence. A decrease in the refrigerant fluid temperature led to a reduction in ice crystal size, due to the growth of more small ice crystals left behind on the scraped wall from previous scrapings. Increasing the dasher speed slightly reduced the mean ice crystal chord length, due to the production of new small ice nuclei by secondary nucleation. For a given refrigerant fluid temperature and dasher speed, low mix flow rates resulted in lower draw temperatures, due to the fact that the product remains in contact with the freezer wall longer. High dasher speeds warmed the product slightly, due to the dissipation of frictional energy in the product, the effect of which was in part moderated by the improvement in the heat transfer coefficient between the product and the freezer wall.     

Long-term natural attenuation of carbon and nitrogen within a groundwater plume after removal of the treated wastewater source

Disposal of treated wastewater for more than 60 years onto infiltration beds on Cape Cod, Massachusetts produced a groundwater contaminant plume greater than 6 km long in a surficial sand and gravel aquifer. In December 1995 the wastewater disposal ceased. A long-term, continuous study was conducted to characterize the post-cessation attenuation of the plume from the source to 0.6 km downgradient. Concentrations and total pools of mobile constituents, such as boron and nitrate, steadily decreased within 1-4 years along the transect. Dissolved organic carbon loads also decreased, but to a lesser extent, particularly downgradient of the infiltration beds. After 4 years, concentrations and pools of carbon and nitrogen in groundwater were relatively constant with time and distance, but substantially elevated above background. The contaminant plume core remained anoxic for the entire 10-year study period; temporal patterns of integrated oxygen deficit decreased slowly at all sites. In 2004, substantial amounts of total dissolved carbon (7 mol C m(-2)) and fixed (dissolved plus sorbed) inorganic nitrogen (0.5 mol N m(-2)) were still present in a 28-m vertical interval at the disposal site. Sorbed constituents have contributed substantially to the dissolved carbon and nitrogen pools and are responsible for the long-term persistence of the contaminant plume. Natural aquifer restoration at the discharge location will take at least several decades, even though groundwater flow rates and the potential for contaminant flushing are relatively high.     

Towards trust management standardization

Recent research in the field of security has evolved into trust issues, which are now one of the interesting research topics. A majority of current approaches proposes techniques that support users' trust processes, while a minority of them addresses the essence of trust. The latter approaches form the basis for the work presented in this paper. Outer manifestations of trust phenomenon are formalized in order to facilitate the development in this field. The main goal is to provide means for computable trust that can be used in a standardized way for contemporary internet-based applications, independently of its cognitive principles.     

Intrinsic properties of the optical coupling between axisymmetric Gaussian beams

On the basis of the overlap integral method, an approximate analytical model is derived to estimate the coupled optical power between axisymmetric Gaussian beams when transverse, axial, and angular misalignments simultaneously exist in three dimensions. Seven optical properties are derived from a detailed analysis of the model. Because the model is an approximate analytical solution to the overlap integral method, the existence of each property is also investigated by a numerical solution. Results show that all seven properties are intrinsic to the optical coupling phenomenon between Gaussian beams. Because numerous single-mode device-to-fiber coupling systems can be well described by use of Gaussian beams, the seven properties provide a solid basis to develop model-based algorithms for single-mode device-to-fiber alignment automation.     

A model to describe the interaction between UO2 and zircaloy in the temperature range 1000–1700°C

During high temperature transients the Zircaloy claddings in a nuclear power reactor may chemically interact with their environment, either on the internal or on the external surfaces. The external oxidation due to the interaction with the coolant has been extensively studied and described in models. However, the internal oxide-metal interaction is less well known and has not yet been satisfactorily described in models. In this paper the internal oxidation, which results from the reduction of the UO₂ pellets by the Zircaloy cladding material is analyzed. A model is developed which solves only the oxygen diffusion problem in the five phases which are formed due to the UO₂/Zircaloy interaction, without taking into account zirconium and uranium diffusion. The oxygen diffusion coefficients of four of the phases are determined and the oxygen concentrations at some of the interfaces are adjusted in order that the interface movements be in accordance with the experimental data published in the literature for the temperature range 1000 to 1700°C. The model attempts only to simulate the kinetics of the system during the first stages of the process when all the interface movements obey parabolic rate laws.