<Superscript>1</Superscript>H-NMR Spectroscopy as a New Tool in the Assessment of the Oxidative State in Edible Oils

Within the course of lipid peroxidation, hydroperoxides are formed as primary products. They can be used as analytical markers to assess the deterioration status of oils and fats. Here a new ¹H-NMR assay to determine the hydroperoxide amount in edible oils is presented. We were able to show that the analytical performance of the method is similar to that of the commonly used peroxide value (PV) according to Wheeler. A total of 290 edible oil samples were analyzed using both methods. For some oil varieties considerable discrepancies were found between the results obtained. In the case of black seed and olive oil, two substances could be identified that cause positive (black seed oil) and negative (olive oils) deviations from the theoretical PV expected from the NMR values.     

A Novel Coenzyme A Analogue in the Anaerobic,Sulfate-Reducing,Marine Bacterium Desulfobacula toluolica Tol2T

Coenzyme A (CoA) thioesters are formed during anabolic and catabolic reactions in every organism. Degradation pathways of growth-supporting substrates in bacteria can be predicted by differential proteogenomic studies. Direct detection of proposed metabolites such as CoA thioesters by high-performance liquid chromatography coupled with high-resolution mass spectrometry can confirm the reaction sequence and demonstrate the activity of these degradation pathways. In the metabolomes of the anaerobic sulfate-reducing bacterium Desulfobacula toluolica Tol2^T grown with different substrates various CoA thioesters, derived from amino acid, fatty acid or alcohol metabolism, have been detected. Additionally, the cell extracts of this bacterium revealed a number of CoA analogues with molecular masses increased by 1 dalton. By comparing the chromatographic and mass spectrometric properties of synthetic reference standards with those of compounds detected in cell extracts of D. toluolica Tol2^T and by performing co-injection experiments, these analogues were identified as inosino-CoAs. These CoA thioesters contain inosine instead of adenosine as the nucleoside. To the best of our knowledge, this finding represents the first detection of naturally occurring inosino-CoA analogues.     

How Phosphorous Flame Retardant Additives Affect Benzoxazine-Based Monomer and Polymer Properties

The phosphorous-based flame retardant additives poly(m-phenylene methylphosphonate) (PMP) and resorcinol bis(diphenyl phosphate) (RDP) are reacted with bisphenol F and aniline–based benzoxazine (BF-a). DSC, rheological analysis, FT-IR, and soxhlet extraction reveal the covalent incorporation of both FR additives—initiating phenols in PMP structure as well as free phenols generated via transesterification reaction in the case of RDP. In contrast to PMP, RDP elongates the processing window but decreases the thermo–mechanical properties. Both additives increase the resistance in reactions against small flames with solely a phosphorous loading of 0.3 wt%, resulting in a V-0 rating and an improvement in the OI value by up to 2% for RDP and 4% for PMP. Both FRs reduce the heat release rate but increase the smoke production and the smoke toxicity in the case of RDP.     

New light-sensitive nucleosides for caged DNA strand breaks

Phototriggered bod cleavage has found wide application in chemistry as well as in biology. Nevertheless, there are only a few methods available for site-specific photochemical induction of DNA strand scission despite numerous potential applications. In this study we report the development of new photocleavable nucleotides based on the photochemistry of o-nitrobenzyl esters. The light-sensitive moieties were generated through introduction of o-nitrophenyl groups at the 5'C position of the nucleoside sugar backbone. The newly synthesized, modified nucleosides were incorporated in oligonucleotides and are able to build stable DNA duplexes. In such a way modified oligonucleotides ca cleaved site-specifically upon irradiation with > 360 nm light with high efficiency. Furthermore, we show that these modifications can be bypassed in DNA synthesis promoted by Thermus aquaticus DNA polymerase.     

Static and Dynamic Mechanical Behavior of Electron Beam‐Cured Monomer and Monomer/Liquid Crystal Systems

Summary: This paper discusses static and dynamic mechanical properties of electron beam‐cured mixtures made of the nematic liquid crystal (LC) E7 and either tripropyleneglycol diacrylate (TPGDA) or propoxylated glycerol triacrylate (GPTA) as monomers differing essentially by their functionality. Dilution of the initial mixture with LC leads to a significant weakening of the film mechanical strength. Strong effects were found on Young modulus and rubbery state modulus. As the concentration of LC increases, these mechanical parameters drop significantly together with the glass transition temperature of the polymer showing a plasticizing effect. The results for the glass transition temperatures for the polymer and the LC were confirmed by thermograms obtained by differential scanning calorimetry.

Storage tensile modulus versus temperature of EB‐cured TPGDA/E7 films for different LC concentrations.     

Self-diffusion of low-generation PAMAM dendrimers with hydroxyl surface groups in solutions: a general regularity

An experimental study of the self-diffusion and nuclear magnetic relaxation of poly(amidoamine) dendrimers with hydroxyl surface groups (PAMAM-OH) dissolved in methanol over a wide range of concentration (?) is reported. It is shown that experimental concentration dependences of PAMAM-OH self-diffusion coefficients (D) can be reduced to the so-called generalized ? dependence. Over macromolecular concentration range studied, the generalized concentration dependence of PAMAM-OH D coincides with analogous curve obtained for poly(allylcarbosilane) dendrimers of high generations. This result confirms the existence of common regularities of the dendritic macromolecule self-diffusion, and their independence of the individual physicochemical and structural properties of dendrimer, solvent, and features of their interactions in the given systems. The concentration dependence of the PAMAM-OH diffusion also exhibits a clear signature of an inflexible molecule.     

Selective oxidation of alcohols by combinatorial catalysis

High-throughput synthesis and screening of polyoxometalate (POM) and supported-metal libraries have been developed for the selective aerobic oxidation of alcohols to the corresponding aldehydes/ketones in the liquid phase. Libraries consisting of 96 catalysts were prepared in multi-well reactors and screened for catalytic activity using TLC, GC and NMR detection methods. Promising hits identified in the high-throughput primary screens were successfully scaled up and optimized in conventional laboratory test units. Isolated yields confirm high selectivities of more than 90% with quantitative conversions. Substrates tested include primary and secondary alcohols. Specific results will be presented for hydroxymethyl-substituted heterocycles and bicyclo-octanols.     

Mullite Coatings on SiC and C/C–Si–SiC Substrates Characterized by Infrared Spectroscopy

Mullite (3Al₂O₃·2SiO₂) coatings on SiC substrates and SiC precoated carbon/carbon composite (C/C-Si-SiC) substrates were produced by pulsed laser deposition (PLD) using pressed mullite powder targets. The layers can be characterized efficiently by IR reflection spectroscopy in the spectral range between 650 and 5000 cm⁻¹. The deposited coatings turn into mullite upon oxidation in air at temperatures between 1400° and 1600°C. Fabry-Perot interferences indicate a high quality and homogeneity of the mullite coating/SiC substrate interface. Amorphous SiO₂ gradually forms during prolonged heating or at higher temperatures.     

Aging of anhydride‐hardened epoxies in lubricants at elevated temperatures

In automotive under‐the‐hood applications, electronics respectively their packaging materials come in contact with automotive fluids. The effect of automatic transmission fluid (ATF) on an anhydride‐cured epoxy was investigated at temperatures up to 180 °C for up to 1000 h. This study has shown that ATF retards the oxidative aging of the epoxy, presumably due to oxygen consumption. Whereas in air the material underwent a thermo‐oxidative aging with a mass loss of up to 4% and a strong broadening of T_g to higher temperatures, in ATF a temperature dependent distinctive drop of T_g from 142 to 126 °C after 1000 h aging at 180 °C, and a mass loss of maximum 1% was observed which might be a thermal decomposition of the epoxy material. A slight broadening of the damping factors might indicate an intrusion of ATF components. A color change of the samples could be observed after aging in air and ATF, with the discoloration in air being more intense. An explanation for the color change might be either a minor amount of oxygen causing an oxidative discoloration reaction or the intrusion of colored ATF degradation products. While the oxidation‐kinetics in air exhibited Arrhenius temperature‐dependence the mechanism in ATF changed above 165 °C. An acceleration of aging tests at temperatures beyond 150 °C is, therefore, not possible. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44877.