Functionalized polyglycidol-CuCl-complexes as catalysts in the oxidative coupling reaction of terminal acetylenes

Summary Novel hyperbranched amino-terminated polyglycidoles have been synthesized and tested as macromolecular ligands in the oxidative coupling reaction of phenylacetylene. Amino-terminated polyglycidoles-CuCl complexes showed to be more effective catalysts than the reference monomeric tertiary amines-CuCl ones, but less effective than the most efficient N,N,N'N'-tetramethylethylenediamine-(TMDA) CuCl complex. The difference in performance of monomeric and hyperbranched ligands is probably due to two factors. The first one is better complexation abilities and the second is the local increase of reagent concentration. Received: 28 April 2001/Revised version: 29 August 2001/Accepted: 5 September 2001     

Investment optimization model for freshwater acquisition and wastewater handling in shale gas production

Major challenges of water use in the drilling and fracturing process in shale gas production are large volumes required in a short‐period of time and the nonsteady nature of wastewater treatment. A new mixed‐integer linear programming (MILP) model for optimizing capital investment decisions for water use for shale gas production through a discrete‐time representation of the State‐Task Network is presented. The objective is to minimize the capital cost of impoundment, piping, and treatment facility, and operating cost including freshwater, pumping, and treatment. The goal is to determine the location and capacity of impoundment, the type of piping, treatment facility locations and removal capability, freshwater sources, as well as the frac schedule. In addition, the impact of several factors such as limiting truck hauling and increasing flowback volume on the solution is examined. A case study is optimized to illustrate the application of the proposed formulation. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1770–1782, 2015     

Mono‐Estolide Synthesis from trans‐8‐Hydroxy‐Fatty Acids by Lipases in Solvent‐Free Media and Their Physical Properties

Pseudomonas aeruginosa 42A2 is known to produce two hydroxy‐fatty acids, 10(S)‐hydroxy‐8(E)‐octadecenoic and 7,10(S,S)‐dihydroxy‐8(E)‐octadecenoic acids, when cultivated in a mineral medium using oleic acid as a single carbon source. These compounds were purified, 91 and 96 % respectively, to produce two new families of estolides: trans‐8‐estolides and saturated estolides from the monohydroxylated monomer. trans‐8‐estolides were produced by three different lipases (Novozym 435, Lipozyme RM IM and Lipozyme TL IM) with reaction yields between 68.4 ± 2.1 and 94.7 ± 2.4 % in a solvent‐free medium at 80 °C in 168 h under vacuum. Novozym 435 was found to be the most efficient biocatalyst for both hydroxy‐fatty acids with reaction yields of 71.7 ± 2.3 and 94.7 ± 2.4 %, respectively. Moreover, saturated estolides were also produced from a saturated 10(S)‐hydroxy‐8(E)‐octadecenoic. These estolides were chemically and enzymatically synthesized with Novozym 435, under the previous described reaction conditions with yields of 60.7 ± 2.1 and 71.2 ± 2.3 % respectively. Finally, viscosity, glass transition temperature, decomposition temperatures and enthalpies were determined to characterize both types of estolides. Thermal applications for both types of polyesters were improved since glass transition temperatures were lowered and decomposition temperatures were increased, with respect to their corresponding substrates.     

Burial grounds’ impact on groundwater and public health: an overview

The most common practice for disposal of dead bodies is inhumation in soil, which favours interactions with the surrounding environment and returns nutrients to the life cycle. However, when the burial ground is located where hydrogeological, geological and climatic conditions are not favourable to the process, contamination of soils and groundwater may occur, and decomposition may be inhibited, leading to social, economic and political problems. The most critical parameters when assessing the pollution potential of a burial ground are inhumation depth, geological formation, depth of the water table, density of inhumations, soil type and climate. Considering that, this paper presents an overview of the potential threat that cemeteries can pose, analysing and discussing the influence of the main variables causing environmental impacts and public health risks.     

Antecedents of construction project coalitions: a study of the Spanish construction industry

Research into the formation of alliances, relevant in the field of strategic management and especially, in the construction industry, is often explained in terms of interdependency and complementarities (exogenous factors). In contrast, the influence of a firm’s social relations networks (endogenous factors) has hardly been studied at all. Thus, a model is needed that includes both exogenous and endogenous factors as antecedents to the formation of strategic alliances in the construction industry. Cooperation in the construction sector is especially frequent, above all in public works programmes, as their scale requires coalitions of different‐sized firms. Accordingly, to explore how both exogenous and endogenous factors influence the formation of alliances, a social network analytical method—Multiple Regression Quadratic Assignment Procedure (MRQAP)—was applied to cooperative project coalitions in the Spanish public works construction sector from 2001–2007. Empirical findings confirm that construction companies form coalitions, principally on the basis of past alliances. Membership of business associations and groups is also a key factor, though the influence of geographic proximity is the most debatable result. In the construction industry, the formation of alliances is conditioned, among other factors, by previous social and economic relations that can generate the necessary information and trust for the selection of whichever partner is considered the most suitable for the development of the joint project.     

Novel Redox-Dependent Esterase Activity (EC 3.1.1.2) for DJ-1: Implications for Parkinson’s Disease

Mutations the in human DJ-1 (hDJ-1) gene are associated with early-onset autosomal recessive forms of Parkinson’s disease (PD). hDJ-1/parkinsonism associated deglycase (PARK7) is a cytoprotective multi-functional protein that contains a conserved cysteine-protease domain. Given that cysteine-proteases can act on both amide and ester substrates, we surmised that hDJ-1 possessed cysteine-mediated esterase activity. To test this hypothesis, hDJ-1 was overexpressed, purified and tested for activity towards 4-nitrophenyl acetate (pNPA) as µmol of pNPA hydrolyzed/min/mg·protein (U/mg protein). hDJ-1 showed maximum reaction velocity esterase activity (V_max = 235.10 ± 12.00 U/mg protein), with a sigmoidal fit (S_0.5 = 0.55 ± 0.040 mM) and apparent positive cooperativity (Hill coefficient of 2.05 ± 0.28). A PD-associated mutant of DJ-1 (M26I) lacked activity. Unlike its protease activity which is inactivated by reactive oxygen species (ROS), esterase activity of hDJ-1 is enhanced upon exposure to low concentrations of hydrogen peroxide (<10 µM) and plateaus at elevated concentrations (>100 µM) suggesting that its activity is resistant to oxidative stress. Esterase activity of DJ-1 requires oxidation of catalytic cysteines, as chemically protecting cysteines blocked its activity whereas an oxido-mimetic mutant of DJ-1 (C106D) exhibited robust esterase activity. Molecular docking studies suggest that C106 and L126 within its catalytic site interact with esterase substrates. Overall, our data show that hDJ-1 contains intrinsic redox-sensitive esterase activity that is abolished in a PD-associated mutant form of the hDJ-1 protein.     

Hydrogenation of vegetable oil using highly dispersed Pt/γ-Al2O3 catalyst: Effects of key operating parameters and deactivation study

In the present work, Pt/γ-Al₂O₃ catalysts with high metal dispersion were prepared and characterized using chloroplatinic acid and platinum acetylacetonate as metal precursors. The activity and selectivity of the catalysts were evaluated in the hydrogenation of sunflower oil. A comprehensive analysis of the effects of key operational parameters on catalytic performance was carried out. The experimental variables were hydrogen pressure (275.8–551.6 kPa), temperature (160–200°C), and catalyst loading (0.005–0.015 kg Pt_exp/m³_oil). Platinum catalysts were active, with a double bond conversion of 28% at 2 h. The metal precursor affected catalyst selectivity. The catalyst prepared with chloroplatinic acid exhibited a lower formation of trans-isomers compared with Pt acetylacetonate. The γ-Al₂O₃ supported platinum catalyst with a metal loading of 0.51 wt.% and a metal dispersion of 98% maintained its initial catalyst activity and selectivity after 10 consecutive uses (1200 min accumulate operation time), without changes in its catalytic properties. The obtained results suggested that Pt catalysts are an attractive alternative to conventional nickel catalysts for the hydrogenation of vegetable oil.     

Optimization models for shale gas water management

There are four key aspects for water use in hydraulic fracturing, including source water acquisition, wastewater production, reuse and recycle, and subsequent transportation, storage, and disposal. Water use life cycle is optimized for wellpads through a discrete‐time two‐stage stochastic mixed‐integer linear programming model under uncertain availability of water. The objective is to minimize expected transportation, treatment, storage, and disposal cost while accounting for the revenue from gas production. Assuming freshwater sources, river withdrawal data, location of wellpads, and treatment facilities are given, the goal is to determine an optimal fracturing schedule in coordination with water transportation, and its treatment and reuse. The proposed models consider a long‐time horizon and multiple scenarios from historical data. Two examples representative of the Marcellus Shale play are presented to illustrate the effectiveness of the formulation, and to identify optimization opportunities that can improve both the environmental impact and economical use of water. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3490–3501, 2014     

Optimal maintenance scheduling of a gas engine power plant using generalized disjunctive programming

A new continuous‐time model for long‐term scheduling of a gas engine power plant with parallel units is presented. Gas engines are shut down according to a regular maintenance plan that limits the number of hours spent online. To minimize salary expenditure with skilled labor, a single maintenance team is considered which is unavailable during certain periods of time. Other challenging constraints involve constant minimum and variable maximum power demands. The objective is to maximize the revenue from electricity sales assuming seasonal variations in electricity pricing by reducing idle times and shutdowns in high‐tariff periods. By first developing a generalized disjunctive programming model and then applying both big‐M and hull reformulation techniques, we reduce the burden of finding the appropriate set of mixed‐integer linear constraints. Through the solution of a real‐life problem, we show that the proposed formulations are very efficient computationally, while gaining valuable insights about the system. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2083–2097, 2014