The dependence of the conduction band edge of the alkali earth metal bismuthates on their composition

We present a comparative analysis of the conduction band edge of the alkali earth metal bismuthates containing Mg, Ca, Sr, and Ba. The conduction band edges were computed using the method suggested by Butler and Ginley. The calculations reveal that they depend on the bismuthate’s composition and vary over a wide range. We demonstrate that the energy of the conduction band increases in the series Ca?→?Sr?→?Ba. It also increases with an increase of the alkali earth metal content. The performed calculations help to determine the potential alkali earth metal bismuthate photocatalysts. The most promising compositions found in this study include strontium and barium bismuthates in which the number of the alkali earth metal atoms in the cationic sublattice exceeds the number of the bismuth atoms.     

Multiply Nitrated High‐Energy Dense Oxidizers Derived from the Simple Amino Acid Glycine

Various energetic polynitro esters, carbamates, and nitrocarbamates that were derived from the amino acid glycine were fully characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Owing to their positive oxygen balance, the suitability of these compounds as potential oxidizers in energetic formulations was investigated and discussed. In addition, the heats of formation of the products were calculated by using the Gaussian 09 program package at the CBS‐4M level of theory. From these values and the calculated densities (from the X‐ray data), several detonation parameters, such as detonation pressure, velocity, energy, and temperature, were computed by using the EXPLO5 code. Furthermore, their sensitivities towards impact, friction, and electrostatic discharge were tested by using a drop hammer, a friction tester (both BAM certified), and a small‐scale electrical‐discharge device, respectively.     

Aliphatic hydroxylation and epoxidation of capsaicin by cytochrome P450 CYP505X

Microbial cytochrome P450 enzymes (CYPs) are able to mimic the metabolism of human CYPs. One challenge is to identify the respective drug metabolites and to compare substrate specificities to those of the human enzymes. In this study, a class VIII self-sufficient CYP from Aspergillus fumigatus (CYP505X) and variants of this enzyme were heterologously expressed in E. coli. The substrate scope of the variants was determined using active pharmaceutical ingredients (APIs) and (hetero)cyclic compounds. Capsaicin – the active compound in chili peppers – was oxidized most efficiently (4.36?μM/min) in a whole cell mediated biotransformation. The products were isolated, purified and their structures elucidated by 1D and 2D NMR. The two major metabolites showed modifications on the lipophilic side chain. Specifically, capsaicin was hydroxylated at position 8 to give (E)-8-hydroxy-N-(4-hydroxy-3-methoxybenzyl)-8-methylnon-6-enamide and epoxidized at the double bond to give N-(4-hydroxy-3-methoxybenzyl)-5-(3-isopropyloxiran-2-yl)-pentanamide.     

Natural-based plasticizers and biopolymer films: A review

In recent years, much attention has been focused on research to replace petroleum-based commodity plastics, in a cost-effective manner, with biodegradable materials offering competitive mechanical properties. Biopolymers have been considered as the most promising materials for this purpose. However, they generally present poor mechanical properties regarding processability and end-use application, since the fragility and brittleness exhibited during thermoformation can limit their potential for application. In order to overcome this problem, plasticizers are added to provide the necessary workability to biopolymers. This class of products became more visible when biodegradable additives and plasticizers also became the focus of material scientists. The use of natural and/or biodegradable plasticizers, with low toxicity and good compatibility with several plastics, resins, rubber and elastomers in substitution of conventional plasticizers, such as phthalates and other synthetic conventional plasticizers attracted the market along with the increasing worldwide trend towards use of biopolymers. Here we discuss the main results and developments in natural plasticizer/synthetic and biopolymer-based films during the last decades.     

Assembly of ethylzincate compounds into supramolecular structures

Sodium and potassium triethylzincate were isolated by Wanklyn in 1858, and are corner stones in the history of organometallic chemistry. Crystallisation of organozincates from neat dialkylzinc, in the absence of a coordinating solvent, can be expected to result in assembly of supramolecular structures, rather than formation of discrete molecules in the crystalline state. This inspired us to reinvestigate Wanklyn’s classical compounds. Crystallisation of sodium triethylzincate from benzene led to metallation of benzene and the formation of diethylphenylzincate anions. The compound is a two-dimensional network where Na⁺ ions link the zincate anions by coordination to both ethyl- and phenyl groups. We have also, accidently, isolated crystals of the two-dimensional coordination network [K₂(ZnEt₂)₄O]_n, displaying a rare oxo-centred core with an octahedral oxide ion surrounded by four zinc atoms and two potassium atoms.     

Synthesis of porphyrin‐end‐functionalized polycyclohexane with well‐controlled and defined polymer chain structure

Tetraphenylporphyrin‐end‐functionalized polycyclohexane (H₂TPP‐PCHE) and its metal complexes (MTPP‐PCHE) were synthesized as the first successful example of porphyrin‐end‐functionalized transparent and stable polymers with a well‐controlled and defined polymer chain structure. Chloromethyl‐end‐functionalized poly(1,3‐cyclohexadiene) (CM‐PCHD) was synthesized as prerequisite prepolymer by the postpolymerization reaction of poly(1,3‐cyclohexadienyl)lithium and chloro(chloromethyl)dimethylsilane. CM‐end‐functionalized PCHE (CM‐PCHE) was prepared by the complete hydrogenation of CM‐PCHD with p‐toluenesulfonyl hydrazide. H₂TPP was incorporated onto the polymer chain end by the addition of 5‐(4‐hydroxyphenyl)‐10,15,20‐triphenylporphyrin to CM‐PCHE. The complexation of H₂TPP‐PCHE and Zn(OAc)₂ (or PtCl₂) yielded a zinc (or platinum) complex of H₂TPP‐PCHE. H₂TPP‐PCHE and MTPP‐PCHE were readily soluble in common organic solvents, and PCHE did not inhibit the optical properties of the H₂TPP, ZnTPP, and PtTPP end groups. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Stochastic Control Methods: Hedging in a Market Described by Pure Jump Processes

This paper considers the asset price movements in a financial market with a risky asset and a bond. The dynamics of the risky asset, modeled by a marked point process, depend on a stochastic factor, modeled also by a marked point process. The possibility of common jump times with the price is allowed. The problem studied is to determine a strategy maximizing the expected value of a utility function of the hedging error. Two different approaches are considered: an Hamilton Jacobi Bellmann equation is studied for a simplified model and a contraction technique is introduced for a more general model.     

Seismic strengthening of stone masonry walls with glass fiber reinforced polymer strips and mechanical anchorages

Experimental Techniques - This paper presents a strengthening technique for traditional load-bearing stone masonry walls. The technique consists in the application of GFRP strips on masonry wall...