S‐Adenosyl Methionine Cofactor Modifications Enhance the Biocatalytic Repertoire of Small Molecule C‐Alkylation

A tandem enzymatic strategy to enhance the scope of C‐alkylation of small molecules via the in situ formation of S‐adenosyl methionine (SAM) cofactor analogues is described. A solvent‐exposed channel present in the SAM‐forming enzyme SalL tolerates 5′‐chloro‐5′‐deoxyadenosine (ClDA) analogues modified at the 2‐position of the adenine nucleobase. Coupling SalL‐catalyzed cofactor production with C‐(m)ethyl transfer to coumarin substrates catalyzed by the methyltransferase (MTase) NovO forms C‐(m)ethylated coumarins in superior yield and greater substrate scope relative to that obtained using cofactors lacking nucleobase modifications. Establishing the molecular determinants that influence C‐alkylation provides the basis to develop a late‐stage enzymatic platform for the preparation of high value small molecules.     

A Study of Ammonium Mono-, Di- and Triphosphate Heterogeneous Systems in View of their Use as Liquid Fertilizers

Abstract

Ammonium phosphates belong among principal compounds of multicomponent liquid fertilizers and thus this study has been directed toward agrochemical application. For this reason, in the system of NH⁺ ₄, H⁺ PO³ ₄, P₂O⁴ ₇, P₃O^5- ₁₀ - H₂O, the subsystem, NH₄H₂PO₄ - (NH₄)₂H₂P₂O₇ - (NH₄)₃H₂P₃O₁₀?(NH₄)₃PO₄ - (NH₄)₄P₂O₇ - (NH₄)₅P₃O₁₀ - H₂O, was studied in which the pH of saturated solutions varies from 5 to 8. The solubility was studied in the partial pseudoternary systems. The experimental temperatures were selected immediately above the corresponding cryohydratic points, from 0 to -8°C. The sum of the results obtained can be schematically represented as a set of the curves of simultaneous crystallization of two solids on the mantle of a trigonal prism which represents the salt composition of the studied system.     

Bioluminescence in Dinoflagellates: Evidence that the Adaptive Value of Bioluminescence in Dinoflagellates is Concentration Dependent

Three major hypotheses have been proposed to explain why dinoflagellate bioluminescence deters copepod grazing: startle response, aposematic warning, and burglar alarm. These hypotheses propose dinoflagellate bioluminescence (A) startles predatory copepods, (B) warns potential predators of toxicity, and (C) draws the attention of higher order visual predators to the copepod's location. While the burglar alarm is the most commonly accepted hypothesis, it requires a high concentration of bioluminescent dinoflagellates to be effective, meaning the bioluminescence selective advantage at lower, more commonly observed, dinoflagellate concentrations may result from another function (e.g. startle response or aposematic warning). Therefore, a series of experiments was conducted to evaluate copepod grazing (Acartia tonsa) on bioluminescent dinoflagellates (during bioluminescent and nonbioluminescent phases, corresponding to night and day, respectively) at different concentrations (10, 1000, and 3000 cells mL^?1), on toxic (Pyrodinium bahamense var. bahamense) and nontoxic (Lingulodinium polyedrum) bioluminescent dinoflagellates, and in the presence of nonluminescent diatoms (Thalassiosira eccentrica). Changes in copepod ingestion rates, clearance rates, and feeding preferences as a result of these experimental factors, particularly during the mixed trails with nonluminescent diatoms, indicate there is a concentration threshold at which the burglar alarm becomes effective and below which dinoflagellate bioluminescence functions as an aposematic warning.     

Laser desorption VUV postionization MS imaging of a cocultured biofilm

Laser desorption postionization mass spectrometry (LDPI-MS) imaging is demonstrated with a 10.5 eV photon energy source for analysis and imaging of small endogenous molecules within intact biofilms. Biofilm consortia comprised of a synthetic Escherichia coli K12 coculture engineered for syntrophic metabolite exchange are grown on membranes and then used to test LDPI-MS analysis and imaging. Both E. coli strains displayed many similar peaks in LDPI-MS up to m/z 650, although some observed differences in peak intensities were consistent with the appearance of byproducts preferentially expressed by one strain. The relatively low mass resolution and accuracy of this specific LDPI-MS instrument prevented definitive assignment of species to peaks, but strategies are discussed to overcome this shortcoming. The results are also discussed in terms of desorption and ionization issues related to the use of 10.5 eV single-photon ionization, with control experiments providing additional mechanistic information. Finally, 10.5 eV LDPI-MS was able to collect ion images from intact, electrically insulating biofilms at ～100 μm spatial resolution. Spatial resolution of ～20 μm was possible, although a relatively long acquisition time resulted from the 10 Hz repetition rate of the single-photon ionization source.

Prediction of extraction efficiency in supported liquid membrane with a stagnant acceptor phase by means of artificial neural network

An artificial neural network model of supported liquid membrane extraction process with a stagnant acceptor phase is proposed. Triazine herbicides and phenolic compounds were used as model compounds. The model is able to predict the compound extraction efficiency within the same family based on the octanol–water partition coefficient, water solubility, molecular mass and ionisation constant of the compound. The network uses the back‐propagation algorithm for evaluating the connection strengths representing the correlations between inputs (octanol–water partition coefficients logP, acid dissociation constant pK_a, water solubility and molecular weight) and outputs (extraction efficiency in dihexyl ether and undecane as organic solvents). The model predicted results in good agreement with the experimental data and the average deviations for all the cases are found to be smaller than ±3%. Moreover, standard statistical methods were applied for exploration of relationships between studied parameters.     

Toward efficient catalysts for electrochemical CO2 conversion to C2 products

With impressive progress in carbon capture and renewable energy, carbon dioxide (CO₂) conversion into useful chemicals has become a potential tool against climate change. Electrochemical CO₂ conversion into C₂ products (ethylene and ethanol) is an especially economically promising approach and an active research area. Nonetheless, catalyst layer design for CO₂ conversion is challenging because of the complex CO₂-to-C₂ reaction pathways. In this review, we highlight key ideas in catalyst layer design for CO₂ conversion to C₂ in the past few years. We identify three fundamental principles to control catalyst selectivity—local CO₂ and CO concentration, local pH, and intermediate–catalyst interaction. To achieve these goals, we introduce design strategies for both catalytic materials and overall catalyst layer morphology.     

Sulfur doping of AlN and AlGaN for improved n‐type conductivity

Achieving high levels of n‐type conductivity in AlN and high Al‐content nitride alloys is a long standing problem; significant decreases in conductivity are observed as the Al content is increased, a phenomenon that has been attributed to donors such as oxygen or silicon forming DX centers. We address this problem through a comprehensive first‐principles hybrid density functional study of potential n‐type dopants, identifying S_N and Se_N as two elements which are potential shallow donors because they do not undergo a DX transition. In particular, S_N is highly promising as an n‐type dopant because it also has a low formation energy and hence a high solubility. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Mixed‐Metal MIL‐100(Sc,M) (M=Al,Cr, Fe) for Lewis Acid Catalysis and Tandem CC Bond Formation and Alcohol Oxidation

The trivalent metal cations Al³⁺, Cr³⁺, and Fe³⁺ were each introduced, together with Sc³⁺, into MIL‐100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X‐ray diffraction (PXRD) and solid‐state NMR, UV/Vis, and X‐ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL‐100 samples were prepared in which part of the Fe is present as α‐Fe₂O₃ nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed‐metal catalysts in Lewis acid catalysed Friedel–Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed‐metal Sc,Fe materials give acceptable activity: 40 % Fe incorporation only results in a 20 % decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported α‐Fe₂O₃ nanoparticles were also active Lewis acid species, although less active than Sc³⁺ in trimer sites. The incorporation of Fe³⁺ into MIL‐100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc³⁺ and Fe³⁺. A procedure for using these mixed‐metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal.