Mono‐, di‐ and trimethylated homologues of isoprenoid tetraether lipid cores in archaea and environmental samples: mass spectrometric identification and significance

Higher homologues of widely reported C₈₆ isoprenoid diglycerol tetraether lipid cores, containing 0–6 cyclopentyl rings, have been identified in (hyper)thermophilic archaea, representing up to 21% of total tetraether lipids in the cells. Liquid chromatography‐tandem mass spectrometry confirms that the additional carbon atoms in the C_87‐88 homologues are located in the etherified chains. Structures identified include dialkyl and monoalkyl (‘H‐shaped’) tetraethers containing C_40‐42 or C_81‐82 hydrocarbons, respectively, many representing novel compounds. Gas chromatography‐mass spectrometric analysis of hydrocarbons released from the lipid cores by ether cleavage suggests that the C₄₀ chains are biphytanes and the C₄₁ chains 13‐methylbiphytanes. Multiple isomers, having different chain combinations, were recognised among the dialkyl lipids. Methylated tetraethers are produced by Methanothermobacter thermautotrophicus in varying proportions depending on growth conditions, suggesting that methylation may be an adaptive mechanism to regulate cellular function. The detection of methylated lipids in Pyrobaculum sp. AQ1.S2 and Sulfolobus acidocaldarius represents the first reported occurrences in Crenarchaeota. Soils and aquatic sediments from geographically distinct mesotemperate environments that were screened for homologues contained monomethylated tetraethers, with di‐ and trimethylated structures being detected occasionally. The structural diversity and range of occurrences of the C_87‐89 tetraethers highlight their potential as complementary biomarkers for archaea in natural environments. Copyright © 2015 John Wiley & Sons, Ltd.     

Selective Activation of C=C Bond in Sustainable Phenolic Compounds from Lignin via Photooxidation: Experiment and Density Functional Theory Calculations

Lignocellulosic biomass can be converted to high‐value phenolic compounds, such as food additives, antioxidants, fragrances and fine chemicals. We investigated photochemical and heterogeneous photocatalytic oxidation of two isomeric phenolic compounds from lignin, isoeugenol and eugenol, in several nonprotic solvents, for the first time by experiment and the density functional theory (DFT) calculations. Photooxidation was conducted under ambient conditions using air, near‐UV light and commercial P25 TiO₂ photocatalyst, and the products were determined by TLC, UV–Vis absorption spectroscopy, HPLC‐UV and HPLC‐MS. Photochemical and photocatalytic oxidation of isoeugenol proceeds via the mild oxidative “dimerization” to produce the lignan dehydrodiisoeugenol (DHDIE), while photooxidation of eugenol does not proceed. The DFT calculations suggest a radical stepwise mechanism for the oxidative “dimerization” of isoeugenol to DHDIE as was calculated for the first time.     

Probing the Diastereoselectivity of Staudinger Reactions Catalyzed by N‐Heterocyclic Carbenes

The reaction of ethylphenylketene with 1,3‐dimesitylimidazol‐2‐ylidene (IMes) or 1,3‐dimesitylimidazolin‐2‐ylidene (SIMes) afforded the corresponding azolium enolates in high yields. The two zwitterions were fully characterized by various analytical techniques. Their thermal stabilities were monitored by thermogravimetric analysis and the molecular structure of SIMes ? EtPhC?C?O was determined by means of X‐ray crystallography. A mechanism was proposed to account for the trans‐diastereoselectivity observed in the [2+2] cycloaddition of ketenes and N‐protected imines catalyzed by N‐heterocyclic carbenes and an extensive catalytic screening was performed to test its validity. The steric bulk of the NHC catalyst markedly affected the cis/trans ratio of the model β‐lactam product. The nature of the solvent used to carry out the Staudinger reaction also significantly influenced its diastereoselectivity. Conversely, the nature of the substituent on the N‐sulfonated imine reagent and the reaction temperature were less critical parameters.     

Influence of molecular weight upon drag reduction by polymers

Summary Drag reduction measurements have been made with samples of polyethyleneoxide and polyacrylamide with relatively narrow molecular weight distributions obtained by fractionation of commercial polymers. Relationships between the polymer molecular weight and the concentration required to give the same drag reduction have been determined. The influence of polymer degradation upon these relationships has been investigated.Molecular weight distributions of commercial polymers have been determined and their influence upon the drag-reducing properties is noted.The influence of wall shear stress has been investigated over the range 1.0 × 10² - 4.5 × 10³ dyn/cm². The results with unfractionated polymers were found to be consistent with other results in the literature.     

Effective elastic moduli of two dimensional solids with distributed cohesive microcracks

Effective elastic properties of a defected solid with distributed cohesive micro-cracks are estimated based on homogenization of the Dugdale–Bilby–Cottrell–Swinden (Dugdale–BCS) type micro-cracks in a two dimensional elastic representative volume element (RVE).Since the cohesive micro-crack model mimics various realistic bond forces at micro-scale, a statistical average of cohesive defects can effectively represent the overall properties of the material due to bond breaking or crack surface separation in small scale. The newly proposed model is distinctive in the fact that the resulting effective moduli are found to be pressure sensitive.     

Flow mechanisms in dense silica-metal oxide-water suspensions

The rheological properties of dense silica in water suspensions (approx. 50% solids by volume) containing additions of metal oxides were examined. Metal oxides used were ferric, zinc and stannic. To prevent settling, testing was performed in a rheometer which was modified to provide for continual stirring of the materials. Relatively small oxide additions had the effect of thickening the mixtures and making them non-Newtonian. Different rate-limiting steps for flow were identified depending on the particular mixture, testing temperature and shear strain rate. Flow could be described using empirical equations which are identical to those often used to describe plastic flow in solid crystalline materials.     

The characterisation of coumarins from selected structural classes by electrospray ionisation quadrupole time-of-flight tandem mass spectrometry

Electrospray ionisation quadrupole time-of-flight tandem mass spectrometry (ESI-QTOF-MS/MS) has been used for characterisation of a selection of naturally occurring and synthetic coumarins from different structural classes. The product ions, suggested in earlier studies by electrospray ionisation ion trap mass spectrometry (ESI-MS(n)), are unequivocally established for the representative coumarins by virtue of accurate mass measurement. Synthetic coumarins that are unsubstituted in the heterocyclic ring give rise to a major product ion by loss of CO(2), whereas those substituted in the heterocyclic ring generally undergo alternative fragmentation releasing neutral species such as ketene or methyl ketene. Naturally occurring coumarins, unsubstituted in the heterocyclic ring and substituted in the benzene ring with chains or rings of hydrocarbons and oxygen, principally fragment at the side chain releasing unsaturated hydrocarbons. The ESI-QTOF-MS/MS behaviour of some naturally occurring and synthetic quinolines which are structurally similar or fragment similarly are included where appropriate.     

Further results on an abstract model for branching and its application to mixed integer programming

Mathematical Programming - A key ingredient in branch and bound (B&B) solvers for mixed-integer programming (MIP) is the selection of branching variables since poor or arbitrary selection...     

A mean reverting process for pricing treasury bills and futures contracts

An analytically tractable, discrete-time single-factor model is developed for valuing treasury bills and futures contracts. It uses a multiplicative binomial foward process that creates neither negative nor implausibly large positive interest factors, and which can incorporate different possible degrees of mean reversion. The paper derives explicit formulae for bill prices, futures prices, their conditional variances and risk premia in a setting that relates the evolution of the term structure more closely to both model and data than do other similar works. In contrast to other term-structure constrained models, this paper emphasizes that in a one-factor model the martingale probabilities cannot be treated independently of the perturbation functions. The paper's empirical methods also differ from the customary approaches. Instead of comparing differences between model-predicted and observed prices, the paper applies ARCH methodology to test model-predicted ratios of conditional variances to risk premia. Our tests find influences exogenous to the model, but these factors do not seem capable of being explained with two-factor models using only interest rates.     

Scalarization and Kuhn-Tucker-Like Conditions for Weak Vector Generalized Quasivariational Inequalities

We consider a weak vector generalized quasivariational inequality. By introducing a method of scalarization which does not require any assumption on the data and by using previous results of the authors concerning scalar generalized quasivariational inequalities, we present Kuhn-Tucker-like conditions for this problem in the case in which the set-valued operator of the constraints is defined by a finite number of inequalities