Polyurethanes based on 2,2‐Dinitropropane‐1,3‐diol and 2,2‐bis(azidomethyl)propane‐1,3‐diol as potential energetic binders

On the base of 2,2‐bis(azidomethyl)propane‐1,3‐diol (BAMP) and 2,2‐dinitropropane‐1,3‐diol (DNPD) four different polyurethanes were synthesized in a polyaddition reaction using hexamethylene diisocyanate (HMDI) and diisocyanato ethane (DIE). The obtained prepolymers were mainly characterized using vibrational spectroscopy (IR) and elemental analysis. For determination of low and high temperature behavior, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used. Investigations concerning friction and impact sensitivities were carried out using a BAM drop hammer and friction tester. The energetic properties of the polymers were determined using bomb calorimetric measurements and calculated with the EXPLO5 V6.02 computer code. The obtained values were compared with the glycidyl azide polymer (GAP). The compounds turned out to be insensitive toward friction (>360 N) and less sensitive toward impact (40 J). The good physical stabilities, along with their sufficient thermal stability (170–210 °C) and moderate energetic properties renders these polymers into potential compounds for applications as binders in energetic formul;ations. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43991.     

High‐Temperature Neutron Diffraction,Raman Spectroscopy,and First‐Principles Calculations of Ti3SnC2 and Ti2SnC

Herein, we report—for the first time—on the additive‐free bulk synthesis of Ti₃SnC₂. A detailed experimental study of the structure of the latter together with a secondary phase, Ti₂SnC, is presented through the use of X‐ray diffraction (XRD), and high‐resolution transmission microscopy (HRTEM). A previous sample of Ti₃SnC₂, made using Fe as an additive and Ti₂SnC as a secondary phase, was studied by high‐temperature neutron diffraction (HTND) and XRD. The room‐temperature crystallographic parameters of the two MAX phases in the two samples are quite similar. Based on Rietveld analysis of the HTND data, the average linear thermal expansion coefficients of Ti₃SnC₂ in the a and c directions were found to be 8.5 (2)·10^?6 K^?1 and 8.9 (1)·10^?6 K^?1, respectively. The respective values for the Ti₂SnC phase are 10.1 (3)·10^?6 K^?1 and 10.8 (6)·10^?6 K^?1. Unlike other MAX phases, the atomic displacement parameters of the Sn atoms in Ti₃SnC₂ are comparable to those of the Ti and C atoms. When the predictions of the atomic displacement parameters obtained from density functional theory are compared to the experimental results, good quantitative agreement is found for the Sn atoms. In the case of the Ti and C atoms, the agreement is more qualitative. We also used first principles to calculate the elastic properties of both Ti₂SnC and Ti₃SnC₂ and their Raman active modes. The latter are compared to experiment and the agreement was found to be good.     

Borcalein: a Carborane-Based Analogue of Baicalein with 12-Lipoxygenase-Independent Toxicity

12-Lipoxygenase is crucial for tumour angiogenesis. 5,6,7-Trihydroxy-2-phenyl-4H-1-benzopyran-4-one (baicalein) is a suitable inhibitor for this enzyme but is rapidly metabolised in vivo. Thus, an improvement of the metabolic stability is necessary to enhance the therapeutic efficiency. An emerging approach to enhance metabolic stability of carbon-based pharmaceuticals is the use of metabolically stable, non-toxic boron clusters, such as dicarba-closo-dodecaborane(12)s (carboranes) as phenyl mimetics. Therefore, the unsubstituted phenyl ring of baicalein was replaced by meta-carborane, resulting in borcalein, the carborane analogue of baicalein. This substitution resulted in a decreased inhibitory activity toward 12-lipoxygenase, but led to increased toxicity in melanoma (A375, B16, B16F10) and colon cancer cell lines (SW480, HCT116, CT26CL25) with decreased tumour selectivity in comparison to baicalein. Surprisingly, borcalein displays a different mechanism of cytotoxicity with increased intracellular production of reactive oxygen species (ROS), reactive nitrogen species (RNS) and nitric oxide (NO).     

Identification,Synthesis, and Behavioral Activity of 5,11-Dimethylpentacosane,A Novel Sex Pheromone Component of the Greater Wax Moth,Galleria Mellonella (L.)

The greater wax moth, Galleria mellonella (L.), is a serious and widespread pest of the honeybee, Apis mellifera L. In contrast to most moths, for which long-range mate finding is mediated by female-produced sex pheromones, G. mellonella males attract conspecific females over long distances by emitting large amounts of a characteristic scent in combination with bursts of ultrasonic calls. The male scent for this species was previously identified as a blend of nonanal and undecanal. When these compounds were bioassayed, characteristic short-range sexual behavior, including wing fanning, was triggered in conspecific females, but the aldehyde blend failed to elicit attraction over longer distances. We identified, via analysis and synthesis, a third male-specific compound, 5,11-dimethylpentacosane. We show that it acts as a behavioral synergist to the aldehydes. In wind tunnel experiments, very few female moths responded to the aldehyde blend or to 5,11-dimethylpentacosane tested separately, but consistently showed orientation and source contact when a combination of all three compounds was applied. The level of attraction to the three-component mixture was still lower than that to male extract, indicating that the composition of compounds in the synthetic blend is suboptimal, or that additional pheromone components of G. mellonella are yet to be identified. The identification of 5,11-dimethylpentacosane is an important step for the development of an efficient long-range attractant that will be integrated with other environmentally safe strategies to reduce damage to beehives caused by wax moths.     

Cuticular Extracts from Acromis sparsa (Coleoptera: Cassidinae) Mediate Arrestment Behavior of the Commensal Canestriniid Mite Grandiella rugosita

Astigmatid mites in the family Canestriniidae are often closely associated with tortoise leaf beetles (Chrysomelidae: Cassidinae). For example, the survival of the commensal canestriniid mite Grandiella rugosita depends on dispersal to the cassidine beetle Acromis sparsa. Here, we tested whether the beetle cuticle provides chemical cues for host recognition for G. rugosita. In two-choice assays with cuticular extracts from A. sparsa and the co-occurring, non-host cassidine Chelymorpha alternans offered simultaneously, mites clearly preferred the area treated with extract from their host. In no-choice assays, G. rugosita spent three times longer and moved three times slower on host cuticular extracts compared to non-host extracts and the solvent control. Analyses of the chemical composition of cuticular extracts from males and females of A. sparsa and C. alternans revealed complex mixtures of mainly methyl branched hydrocarbons, which clearly separated both species in a principal component analysis. We found no qualitative difference between males and females of either species, but in C. alternans quantitative differences between males and females were detected. Our results demonstrate that G. rugosita is able to discriminate between cuticular extracts from its host A. sparsa and the non-host C. alternans. The components eliciting the observed arrestment behavior remain to be determined.     

Photoinitiierte Polymerisation mit Dialkoxythiocarbonyldisulfiden – eine Polymerisationsreaktion mit Primärradikalabbruch

Photoinitiated Polymerization with Dialkoxy Thiocarbonyl Disulfides – a Polymerization Reaction with Primary Radical Termination The photoinduced free radical polymerization of methyl methacrylate (MMA) and some other vinyl monomers using dialkoxy thiocarbonyl disulfides ( 1 – 4 ) as photoinitiators was studied. The photolysis of these initiators leads to cleavage of the S S bond, which was determined by spin trapping experiments with phenyl tert-butyl nitrone. No evidence was found for a further thermal decomposition of the primary alkoxy thiocarbonyl sulfide radicals (R·) at room temperature. In the absence of scavengers the primary radicals react back exclusively to the initial compounds, due to a strong cage effect. By means of UV spectroscopic measurements and in the presence of MMA the quantum yields of the initiator decomposition were detected to be 0.8. The polymerization of acrylic and methacrylic derivatives can be initiated by the R·, contrary to the situation with fumarates and maleates. The mechanism of MMA polymerization depends on the light intensity absorbed by the initiators. At high intensities the combination of primary and polymer radicals terminates the chain reaction. This follows from the measured monomer exponent of α = 2, the light intensity exponent of β = 0,2 and the number of thiocarbonyl end groups of 2 in the polymers isolated. Contrary to this, in the low intensity region the experimental data obey the ideal kinetic equation. Kinetic modelling gives evidence for an interaction of the monomer with the cage radicals.     

An Innovative Submerged Entry Nozzle Design for Billet and Bloom Casting

Fluid flow in the mold has a significant impact on the quality of continuously cast steel products.Since it is strongly influenced by the SEN design,attention h...     

Modeling Alcohol Dehydrogenase Catalysis in Deep Eutectic Solvent/Water Mixtures

The use of oxidoreductases (EC1) in non-conventional reaction media has been increasingly explored. In particular, deep eutectic solvents (DESs) have emerged as a novel class of solvents. Herein, an in-depth study of bioreduction with an alcohol dehydrogenase (ADH) in the DES glyceline is presented. The activity and stability of ADH in mixtures of glyceline/water with varying water contents were measured. Furthermore, the thermodynamic water activity and viscosity of mixtures of glyceline/water have been determined. For a better understanding of the observations, molecular dynamics simulations were performed to quantify the molecular flexibility, hydration layer, and intraprotein hydrogen bonds of ADH. The behavior of the enzyme in DESs follows the classic dependence of water activity (a_W) in non-conventional media. At low a_W values (<0.2), ADH does not show any activity; at higher a_W values, the activity was still lower than that in pure water due to the high viscosities of the DES. These findings could be further explained by increased enzyme flexibility with increasing water content.