Methane generation from Miocene lacustrine coals and organic-rich sedimentary rocks containing different types of organic matter

Ten selected samples with varying types and amounts of organic matter from two Miocene lacustrine basins in northwestern Turkey were analyzed by programmed-temperature open-system pyrolysis to determine methane generation potential and reaction kinetics. Open-system pyrolysis was performed at heating rates 0.1, 0.7 and 5.0 K/min, where generated gases were measured using an on-line gas chromatograph. Frequency factors and activation energy distributions of reaction kinetics for methane generation from the investigated lacustrine coals and sedimentary rocks indicated that type of kerogen controls the sequential order of methane generation. Methane from Type-III kerogen is generated at lower temperatures, which will be followed by methane from Type-II and Type-I kerogen. Methane generation potentials in the range 14-35 mg CH₄/g TOC correlates also with type of organic matter. For Type-III kerogen up to 28% of the total hydrocarbon generation potential belongs to methane. The respective value is only 2% for a Type-I kerogen.     

Merging Allosteric and Active Site Binding Motifs: De novo Generation of Target Selectivity and Potency via Natural‐Product‐Derived Fragments

The de novo design of molecules from scratch with tailored biological activity is still the major intellectual challenge in chemical biology and drug discovery. Herein we validate natural‐product‐derived fragments (NPDFs) as excellent molecular seeds for the targeted de novo discovery of lead structures for the modulation of therapeutically relevant proteins. The application of this de novo approach delivered, in synergy with the combination of allosteric and active site binding motifs, highly selective and ligand‐efficient non‐zinc‐binding ( 3 : 4‐{[5‐(2‐{[(3‐methoxyphenyl)methyl]carbamoyl}eth‐1‐yn‐1‐yl)‐2,4‐dioxo‐1,2,3,4‐tetrahydropyrimidin‐1‐yl]methyl}benzoic acid) as well as zinc‐binding ( 4 : 4‐({5‐[2‐({[3‐(3‐carboxypropoxy)phenyl]methyl}carbamoyl)eth‐1‐yn‐1‐yl]‐2,4‐dioxo‐1,2,3,4‐tetrahydropyrimidin‐1‐yl}methyl)benzoic acid) uracil‐based MMP‐13 inhibitors presenting IC₅₀ values of 11 nM ( 3 : LE=0.35) and 6 nM ( 4 : LE=0.31).     

Synthetic and Biological Studies of Sesquiterpene Polygodial: Activity of 9‐Epipolygodial against Drug‐Resistant Cancer Cells

Polygodial, a terpenoid dialdehyde isolated from Polygonum hydropiper L., is a known agonist of the transient receptor potential vanilloid 1 (TRPV1). In this investigation a series of polygodial analogues were prepared and investigated for TRPV1‐agonist and anticancer activities. These experiments led to the identification of 9‐epipolygodial, which has antiproliferative potency significantly exceeding that of polygodial. 9‐Epipolygodial was found to maintain potency against apoptosis‐resistant cancer cells as well as those displaying the multidrug‐resistant (MDR) phenotype. In addition, the chemical feasibility for the previously proposed mechanism of action of polygodial, involving the formation of a Paal–Knorr pyrrole with a lysine residue on the target protein, was demonstrated by the synthesis of a stable polygodial pyrrole derivative. These studies reveal rich chemical and biological properties associated with polygodial and its direct derivatives. These compounds should inspire further work in this area aimed at the development of new pharmacological agents, or the exploration of novel mechanisms of covalent modification of biological molecules with natural products.     

Identification of the Thermodynamically Stable Fe‐Containing Phase in Aged Cement Pastes

Current developments in cement chemistry increasingly rely on predictive thermodynamic modeling of the phase composition in cementitious composites with the aim of linking the performance of the material with the phase composition of the material. This approach requires identification of the cement phases that form in hydrating cementitious materials using standard techniques, such as X‐ray diffraction (XRD) and thermal analysis (DTA, TGA), but also state‐of‐the‐art synchrotron‐based techniques, in particular for those cases in which the signals of solid solutions overlap in XRD and TGA measurements. In this study, two ordinary Portland cements, with different chemical compositions and subject to different hydration times (~10, ~50 yr), were investigated aiming at identifying the most stable Fe‐containing cement phase in the cement pastes. The Fe‐containing cement phases and their solid solutions with the Al analogues in the complex cement matrix were analyzed with X‐ray absorption spectroscopy, indicating the formation of a mixed Fe–Al siliceous hydrogarnet as the major Fe‐containing phase. The presence of this phase after long hydration periods and upon selective dissolution of the pastes further indicates that, independent of the chemical compositions of cements, formation of the mixed Fe–Al siliceous hydrogarnet is thermodynamically favored in aged pastes, which is supported by published thermodynamic calculations.     

Frequency and phase estimation in time series with quasi periodic components

In this article, we consider frequency and phase estimation in a noisy oscillation with potentially non‐constant phase increments resulting from an underlying non‐constant frequency. A maximum periodogram method on segments is used to estimate the time‐varying frequency and a subsequent least squares approach to estimate the phase. A key problem addressed in this article is the question how to set up a meaningful concept of asymptotic statistics for this model. This problem is solved by a special infill asymptotics concept. We use this concept to prove consistency and asymptotic normality of the estimates. Furthermore, the phase estimate is compared to the Hilbert transform in a simulation.     

Controlled reversible debundling of single-walled carbon nanotubes by photo-switchable dendritic surfactants

Stimulus responsive surfactants based on dendritic glycerol azobenzene conjugates were used to solubilize and debundle single-walled carbon nanotubes in aqueous media. Their debundling property as well as their reaggregation behavior upon irradiation with light was examined and light triggered reversible bundling and precipitation are shown.     

Analytical Methods for the Rapid Determination of Solid Biofuel Quality

Fuel properties of solid biofuels are essential aspects for the energy-efficient and low-emission operation of biomass heat and power plants. Hence, fuel quality parameters are often defined and used for pricing in supply contracts. To simplify and accelerate analytical approaches, rapid analysis devices are required to determine fuel properties such as water- and ash content, calorific value, and chemical composition on-site. This article gives an overview about available technologies and, if applicable, their current state of use as rapid analysis devices for solid biofuels.     

NONLINEAR PI CONTROLLER FOR pH PROCESS

The control of pH is one of the most difficult challenges in the process industry because of the severe nonlinearities and high precision required in manipulating the flow rate. The Wiener model, which consists of a linear dynamic element followed by a nonlinear static element, is used for representing such nonlinear processes. Piecewise continuous polynomials are used for mapping the nonlinear static gain accurately. A nonlinear PI controller was designed based on the Wiener model. Simulation results on the nonlinear mathematical model are presented to highlight the superior performance of the Wiener model based nonlinear PI controller in comparison to that of the local linear PI controller. The performance of the nonlinear PI controller was further improved upon by using the method of inequalities to obtain a single set of PI controller settings that takes into account the parametric variations in the linear dynamic element at different operating points. Simulation and experimental results are presented to support the work.