Biocatalytic Synthesis of Nitriles through Dehydration of Aldoximes: The Substrate Scope of Aldoxime Dehydratases

Nitriles, which are mostly needed and produced by the chemical industry, play a major role in various industry segments, ranging from high‐volume, low‐price sectors, such as polymers, to low‐volume, high‐price sectors, such as chiral pharma drugs. A common industrial technology for nitrile production is ammoxidation as a gas‐phase reaction at high temperature. Further popular approaches are substitution or addition reactions with hydrogen cyanide or derivatives thereof. A major drawback, however, is the very high toxicity of cyanide. Recently, as a synthetic alternative, a novel enzymatic approach towards nitriles has been developed with aldoxime dehydratases, which are capable of converting an aldoxime in one step through dehydration into nitriles. Because the aldoxime substrates are easily accessible, this route is of high interest for synthetic purposes. However, whenever a novel method is developed for organic synthesis, it raises the question of substrate scope as one of the key criteria for application as a “synthetic platform technology”. Thus, the scope of this review is to give an overview of the current state of the substrate scope of this enzymatic method for synthesizing nitriles with aldoxime dehydratases. As a recently emerging enzyme class, a range of substrates has already been studied so far, comprising nonchiral and chiral aldoximes. This enzyme class of aldoxime dehydratases shows a broad substrate tolerance and accepts aliphatic and aromatic aldoximes, as well as arylaliphatic aldoximes. Furthermore, aldoximes with a stereogenic center are also recognized and high enantioselectivities are found for 2‐arylpropylaldoximes, in particular. It is further noteworthy that the enantiopreference depends on the E and Z isomers. Thus, opposite enantiomers are accessible from the same racemic aldehyde and the same enzyme.     

Thin water films and particle morphology evolution in nanocrystalline MgO

A key question in the field of ceramics and catalysis is how and to what extent residual water in the reactive environment of a metal oxide particle powder affects particle coarsening and morphology. With X‐ray Diffraction (XRD) and Transmission Electron Microscopy (TEM), we investigated annealing‐induced morphology changes on powders of MgO nanocubes in different gaseous H₂O environments. The use of such a model system for particle powders enabled us to describe how adsorbed water that originates from short exposure to air determines the evolution of MgO grain size, morphology, and microstructure. While cubic nanoparticles with a predominant abundance of (100) surface planes retain their shape after annealing to T = 1173 K under continuous pumping with a base pressure of water p(H₂O) = 10^?5 mbar, higher water partial pressures promote mass transport on the surfaces and across interfaces of such particle systems. This leads to substantial growth and intergrowth of particles and simultaneously favors the formation of step edges and shallow protrusions on terraces. The mass transfer is promoted by thin films of water providing a two‐dimensional solvent for Mg²⁺ ion hydration. In addition, we obtained direct evidence for hydroxylation‐induced stabilization of (110) faces and step edges of the grain surfaces.     

On-line monitoring of fuel moisture-content in biomass-fired furnaces by measuring relative humidity of the flue gases

Combustion of biomass for heat and power production is continuously growing in importance, because of incentives for replacing fossil energy resources with renewable ones. In biomass combustion, the moisture content of the fuel is an essential operation parameter, which often fluctuates for biomass fuels. Variation in moisture content complicates the operation of the furnaces and results in an uncertainty in the energy content of the fuel delivered to a plant. The fuel moisture-content in a furnace may be determined either by direct measurement on the entering fuel or by measuring the moisture and oxygen contents of the flue gases deriving the moisture content of the fuel. However, reliable methods of a motivated cost for the small to medium-scale furnaces are today not available. An exception is if the furnace is equipped with flue-gas condenser, which can be used to estimate the moisture content of the flue gases. A limitation of this method is, though, that not all furnaces have flue-gas condensers and that the measured signal has an inherent time delay.In this work, measurement of the relative humidity (RH) of the flue gases from a furnace is investigated as the central component in the on-line monitoring of the moisture content of the fuel in a furnace. The method was analysed with humid air in a laboratory environment and tested for accuracy and dynamical behaviour in two biomass-fired heat-production units, one circulating fluidised-bed boiler (CFB) and one grate furnace. The results show that the method, which is easy to calibrate on site, can be used to predict the moisture content of the biomass fuel in the grate furnace with very good precision (<4% error). Furthermore, the method detects variations in moisture content of the furnace flue gases due to changes in the moisture content of the combusted fuel within the order of seconds. Since the transport time of the flue gases from the furnace to the measurement position is of the same order of magnitude, the total time for detection of a change in the moisture content of the fuel is small enough for the signal to be used to control both the fuel feed and the combustion air in a grate furnace.     

Targeting S100A9 Reduces Neutrophil Recruitment,Inflammation and Lung Damage in Abdominal Sepsis

S100A9, a pro-inflammatory alarmin, is up-regulated in inflamed tissues. However, the role of S100A9 in regulating neutrophil activation, inflammation and lung damage in sepsis is not known. Herein, we hypothesized that blocking S100A9 function may attenuate neutrophil recruitment in septic lung injury. Male C57BL/6 mice were pretreated with the S100A9 inhibitor ABR-238901 (10 mg/kg), prior to cercal ligation and puncture (CLP). Bronchoalveolar lavage fluid (BALF) and lung tissue were harvested for analysis of neutrophil infiltration as well as edema and CXC chemokine production. Blood was collected for analysis of membrane-activated complex-1 (Mac-1) expression on neutrophils as well as CXC chemokines and IL-6 in plasma. Induction of CLP markedly increased plasma levels of S100A9. ABR-238901 decreased CLP-induced neutrophil infiltration and edema formation in the lung. In addition, inhibition of S100A9 decreased the CLP-induced up-regulation of Mac-1 on neutrophils. Administration of ABR-238901 also inhibited the CLP-induced increase of CXCL-1, CXCL-2 and IL-6 in plasma and lungs. Our results suggest that S100A9 promotes neutrophil activation and pulmonary accumulation in sepsis. Targeting S100A9 function decreased formation of CXC chemokines in circulation and lungs and attenuated sepsis-induced lung damage. These novel findings suggest that S100A9 plays an important pro-inflammatory role in sepsis and could be a useful target to protect against the excessive inflammation and lung damage associated with the disease.     

Combination of Reaction and Separation in Heterogeneous Catalytic Hydrogenation of Ethylformate

Continuous hydrogenation reaction of ethyl benzoylformate was studied over a (–)‐cinchonidine (CD)‐modified Pt/Al₂O₃ catalyst. The catalyst showed a good stability, and high enantioselectivity was achieved in the fixed‐bed reactor. Chromatographic separation of (R)‐ and (S)‐ethyl mandelate originating from a post‐continuous hydrogenation reaction of ethyl benzoylformate over the (–)‐CD‐modified Pt/Al₂O₃ catalyst was investigated in the same reaction mixture. A commercial column filled with a chiral selector resin was chosen as a perspective preparative‐scale adsorbent. Since adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post‐reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug‐flow model with linear driving force approximation.     

A New Flame Retardant for Wood Materials Tested in Wood‐Plastic Composites

A new flame retardant based on an ammonium phosphonate is studied with respect to its thermal decomposition and its mode of action in wood‐plastic composites (WPCs). The measurements are carried out by means of fire tests (cone calorimeter) and pyrolysis investigations (thermogravimetry, infrared spectroscopy). The flame retardant acts mainly in the condensed phase by increasing the amount of residue formed by the wood part in the WPC. Additional flame dilution is achieved by the release of water, ammonia and carbon dioxide during the decomposition of the flame retardant.

     

Detection of chirality of poly(glycerol methacrylate)s after derivatization by 1H NMR spectroscopy

Chiral poly(glycerol methacrylate)s (PGMAs) are synthesized via ATRP using enantiopure solketal methacrylates followed by acidic hydrolysis. The optical activity of the polymers is confirmed by measurements of the circular dichroism. Furthermore, the chirality of the PGMAs containing repeat units with diol groups is determined via ¹H NMR spectroscopy employing a three-component chiral derivatizing process, involving the treatment of enantiopure polymers with 2-formylphenylboronic acid and enantiopure α-methylbenzylamine (MBA), which yields cyclic boronate diastereoisomers on the pendant groups. The detection of the chirality of the PGMAs is based on the anisotropic shielding/deshielding effect of the phenyl group in (R)- or (S)-MBA. The main advantage of this method is its simplicity as it only involves the mixing of all the components without any further purification steps. This procedure has been applied here for the first time to chiral polymers.     

Erratum to: Fe Oxides on Ag Surfaces: Structure and Reactivity

Topics in Catalysis -