Cross‐metathesis of methyl 10‐undecenoate with diethyl maleate: Formation of an α,ω‐diester via a metathesis reaction network

The cross‐metathesis of methyl 10‐undecenoate 1 derived from castor oil as a renewable raw material with diethyl maleate 2 was investigated. These reactions were carried out with several phosphine and N‐heterocyclic carbene ruthenium catalysts. The reaction conditions were optimised for high conversions in combination with high cross‐metathesis selectivity. This single‐step and atom‐economic synthetic method illustrates an efficient and selective preparation procedure of linear α,ω‐dicarboxylic acid esters starting from renewable resources and comparatively inexpensive base chemicals. Further by‐products are hardly obtained due to their consumption in secondary metathesis reactions. Hence, a sustainable alternative for polyamide and polyester monomers is presented.     

Laminar flame speed measurements of dimethyl ether in air at pressures up to 10 atm

Laminar flame speed measurements of dimethyl ether/air mixtures were made at 1, 5, and 10 atm with equivalence ratios ranging from 0.7 to 1.6. All experiments were performed in a large cylindrical constant-volume bomb with optical access. A new method for converting flame images into flame radii was used. Results reported in other studies were investigated, and some explanations on the disparities found are presented. A full uncertainty analysis was performed combining precision errors from data scatter with predicted systematic errors. Uncertainties ranging between 4.2% and 8.6% were found depending on the equivalence ratio and initial pressure. Experimental results agreed well with some other spherical flame experiments and counterflow flame measurements, but were found to be much lower than PIV-based stagnation flame results. Also, two spherical flame studies deviated significantly both in magnitude and trend. Critical radii and Peclet numbers, defined by the onset of rapid flame acceleration, were recorded for all high-pressure experiments. Markstein lengths were measured and showed a decreasing trend with increasing equivalence ratio. Three different methods were used to define the laminar flame thickness, and large disparities were found between them. In this study, the modeled temperature gradient method for the definition of flame thickness is preferred over other methods. Modeling was performed with the latest version of a C3 chemical kinetics mechanism. Good agreement is seen between the experimental results and the model at all pressures. Emphasis is placed in this paper on reporting experimental uncertainties, calculated density ratios, flame temperatures, and flame radii ranges used for data analysis, and the results resolve some discrepancies seen in the literature for dimethyl ether flame speeds.     

Synthesis and Characterization of Novel Surfactants: Combination Products of Fatty Acids,Hydroxycarboxylic Acids and Alcohols

The reaction of hydroxycarboxylic acids, such as citric, malic and tartaric species with an excess of fatty acid chlorides produces the corresponding O-acylated hydroxycarboxylic anhydrides in one step and in a near quantitative yield. These molecules are excellent electrophiles which react readily with a variety of nucleophiles including alcohols, diols and polyols. Their reaction with triethylene glycol and triethylene glycol monomethyl ether leads to two series of novel anionic surfactants, which are unsymmetrical gemini surfactants. The determination of their properties (CMC, foaming, HLB) revealed that these molecules are—depending on the chain length of the fatty acid—excellent emulsifiers, and that they also display interesting antimicrobial activity. These novel functional surfactants are of interest for applications in food and personal care products and for the formulation of pharmaceuticals.     

Effects of environmental factors on seasonal and spatial changes in surface zooplankton in Golden Horn Estuary (Istanbul,Turkey)

The abundance and spatial distribution of zooplankton at monthly intervals were studied in polluted Golden Horn Estuary (Istanbul, Turkey), from July 2006 to December 2007. Selected water quality parameters also were measured. The zooplankton community was characterized by the presence of freshwater, estuarine and marine species, with a total of 59 taxa. Rotifers were the most important fraction of the total zooplankton, comprising 36.52% of all the samples. The zooplankton exhibited seasonal patterns, with the highest abundance occurring in the summer (979 ind. L^?1) and the lowest in the spring (856 ind. L^?1). Rotifera was the most abundant group in the upper and middle estuary, whereas Copepoda usually reaches the maximum densities in the higher salinity waters in the lower estuary. The study results indicated that both the sampling time (seasons) and sampling sites jointly had significant effects on the zooplankton densities (manova P < 0.05), and horizontal patterns were related to electrical conductivity, water temperature, dissolved oxygen, suspended particulate matter, pH and chlorophyll a measured in the estuary.     

An experimental and modeling study of the low- and high-temperature oxidation of cyclohexane

The experimental study of the oxidation of cyclohexane has been performed in a jet-stirred reactor at temperatures ranging from 500 to 1100 K (low- and intermediate temperature zones including the negative temperature-coefficient area), at a residence time of 2 s and for dilute mixtures with equivalence ratios of 0.5, 1, and 2. Experiments were carried out at quasi-atmospheric pressure (1.07 bar). The fuel and reaction product mole fractions were measured using online gas chromatography. A total of 34 reaction products have been detected and quantified in this study. Typical reaction products formed in the low-temperature oxidation of cyclohexane include cyclic ethers (1,2-epoxycyclohexane and 1,4-epoxycyclohexane), 5-hexenal (formed from the rapid decomposition of 1,3-epoxycyclohexane), cyclohexanone, and cyclohexene, as well as benzene and phenol. Cyclohexane displays high low-temperature reactivity with well-marked negative temperature-coefficient (NTC) behavior at equivalence ratios 0.5 and 1. The fuel-rich system (? = 2) is much less reactive in the same region and exhibits no NTC. To the best of our knowledge, this is the first jet-stirred reactor study to report NTC in cyclohexane oxidation. Laminar burning velocities were also measured by the heated burner method at initial gas temperatures of 298, 358, and 398 K and at 1 atm. The laminar burning velocity values peak at ? = 1.1 and are measured as 40 and 63.1 cm/s for T_i = 298 and 398 K, respectively. An updated detailed chemical kinetic model including low-temperature pathways was used to simulate the present (jet-stirred reactor and laminar burning velocity) and literature experimental (laminar burning velocity, rapid compression machine, and shock tube ignition delay times) data. Reasonable agreement is observed with most of the products observed in our reactor, as well as the literature experimental data considered in this paper.     

Recycling and Oligomerization Activity of Ni/Al Catalyst in a Biphasic System with Ionic Liquids

The catalyst decomposition in homogeneously catalyzed reactions is a very important factor that has been studied for the oligomerization of n‐butenes in a system of two liquid phases. A highly active catalyst [NiCl₂(PMe₃)₂] was investigated with an emphasis on the long‐term catalyst activity using N‐methylpyrrole as a buffer. The recycling experiments indicated that this catalyst is viable for five runs. Furthermore, introducing aluminum chloride or an ionic liquid in small concentrations led to increased stability, though fine adjustments were necessary to arrive at optimal results.     

Effects of the γ-irradiation strength and basalt additive content on the mechanical performance and dielectric response of polypropylene films

In this study, we investigated the effects of high-dose γ-ray irradiation on the mechanical and dielectric properties of polypropylene (PP)–basalt thick films. PP–basalt thick-film composites with various basalt contents from 0.5 to 10.0% were prepared by a hot-press method. The samples were exposed to γ radiation at different doses in the range 3–25 kGy. The mechanical properties of the samples, such as the Young's modulus, tensile strength, percentage strain at break, and energy at break, were examined in the context of the γ-irradiation process. Although the maximum elasticity was obtained for the unirradiated 0.5% basalt-added composite, the 6 kGy γ-irradiated PP–1.0% basalt sample exhibited the highest elasticity properties among all of the composites. The best mechanical properties, including the ultimate tensile strength and energy at break values, were achieved for the 12 kGy γ-irradiated neat PP. The dielectric properties of the PP–basalt composites were also investigated in the 100 Hz to 15 MHz frequency region at room temperature. According to the analysis of the dielectric properties, the 3 kGy γ-irradiated neat PP may have potential for microelectronic device applications that require low dielectric constant and dielectric loss materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47414.     

Data supply chain (DSC): research synthesis and future directions

In the digital economy, the volume, variety and availability of data produced in myriad forms from a diversity of sources has become an important resource for competitive advantage, innovation opportunity as well as source of new management challenges. Building on the theoretical and empirical foundations of the traditional manufacturing Supply Chain (SC), which describes the flow of physical artefacts as raw materials through to consumption, we propose the Data Supply Chain (DSC) along which data are the primary artefact flowing. The purpose of this paper is to outline the characteristics and bring conceptual distinctiveness to the context around DSC as well as to explore the associated and emergent management challenges and innovation opportunities. To achieve this, we adopt the systematic review methodology drawing on the operations management and supply chain literature and, in particular, taking a framework synthetic approach which allows us to build the DSC concept from the pre-existing SC template. We conclude the paper by developing a set of propositions and outlining an agenda for future research that the DSC concept implies.     

A new optimization model to support a bottom-up approach to facility design

The facility layout problem is typically solved in what is referred to as a “top-down approach” of block layout design followed by detailed layout determination. However, a number of research efforts recently have challenged this approach, producing a reformulated bottom-up approach to the facility layout problem. In this paper we consider the bottom-up approach, applying a tighter formulation than prior efforts and investigating the solvability limits of the new model. Empirical testing of the new bottom-up layout model indicates that although this model produces more usable output, as judged by industry experts, it is approximately three times harder to solve. Valid inequalities and special cases are identified to help improve the formulation's solvability.