Experimental study of the performances of a modified diesel engine operating in homogeneous charge compression ignition (HCCI) combustion mode versus the original diesel combustion mode

Homogeneous charge compression ignition (HCCI) combustion mode provides very low NO_x and soot emissions; however, it has some challenges associated with hydrocarbon (HC) emissions, fuel consumption, difficult control of start of ignition and bad behaviour to high loads. Cooled exhaust gas recirculation (EGR) is a common way to control in-cylinder NO_x production in diesel and HCCI combustion mode. However EGR has different effects on combustion and emissions, which are difficult to distinguish. This work is intended to characterize an engine that has been modified from the base diesel engine (FL1 906 DEUTZ-DITER) to work in HCCI combustion mode. It shows the experimental results for the modified diesel engine in HCCI combustion mode fueled with commercial diesel fuel compared to the diesel engine mode. An experimental installation, in conjunction with systematic tests to determine the optimum crank angle of fuel injection, has been used to measure the evolution of the cylinder pressure and to get an estimate of the heat release rate from a single-zone numerical model. From these the angle of start of combustion has been obtained. The performances and emissions of HC, CO and the huge reduction of NO_x and smoke emissions of the engine are presented. These results have allowed a deeper analysis of the effects of external EGR on the HCCI operation mode, on some engine design parameters and also on NO_x emission reduction.     

Extrusion deactivation of rice bran enzymes by pH modification

Rice bran is considered in Mexico as “waste”, useful only for feeds. As considerable amounts of oil are available in rice bran, it might be worthwhile to stabilize it and extract the edible oil before using it for feedstuffs. Precisely these oils are responsible for rice bran rapid deterioration, particularly in climatic conditions such as those prevalent in Mexico's tropical areas (high humidity and high temperature). This paper deals with the study of the effect of pH during extrusion of fresh rice bran in order to inactivate lipid‐breaking enzymes. Hydrochloric acid or calcium hydroxide, Ca(OH)₂, were added at 0, 1, 5, 10% (dry basis), and moisture content of the bran samples was varied (20, 30, 40%, dry basis) in a 3² factorial design to corroborate its effect at acid and alkaline pH range. Free fatty acids (FFA) increase was the control variable. Extruded samples were stored at room temperature (between 20 and 28 °C) using a non‐extruded sample as control to assess the shelf life effects. Results indicate that in acid‐extruded samples, the increase in FFA concentration after 98 days was much less than in the unmodified‐pH or alkaline samples. The lowest FFA increase after 3 months of storage time was <10 mg FFA/g rice bran using extrusion with no water or chemicals added or using extrusion adding HCl, irrespective of the moisture content of rice bran.     

Effect of Coordinating Solvents on Solution Speciation and the Crystallisation via ROP of a Triphos-Silver Coordination Cage

There is a general lack of understanding of how coordination polymers (metal-organic frameworks) form. Some insight can be gained from observations of formal ROP (ring-opening polymerisation) relationships between coordination polymers and their discrete soluble precursors. Most ROP examples reported previously have involved bidentate bridging ligands. Here we present an unusual example of a ROP relationship based on a tripodal ligand. In particular, 1,3,5-tris(diphenylphosphino)benzene (L1) is found to form a symmetrical coordination cage of stoichiometry Ag₃(L1)₂ in solution in acetonitrile. This contrasts with previous observations in less-coordinating solvents in which higher nuclearity cages are also formed, and shows that the coordinating acetonitrile solvent reduces anion-templating effects. On crystallization from acetonitrile a one-dimensional polymeric structure [Ag₃(L1)₂(NCCH₃)(OTf)₃] _n is obtained. The structure is noteworthy in being a ROP isomer of the trinuclear cage observed in solution. The structure also exhibits solvent-filled channels (maximum diameter 6.1 Å) but the material is not stable to desolvation. The structure of the polymer contrasts with that obtained from less-coordinating solvents, the latter being a stable hexagonal 2-dimensional structure with nanoporosity.     

Mechanosynthesis and Thermal Stability of Piezoelectric Perovskite 0.92Pb(Zn1/3Nb2/3)O3–0.08PbTiO3 Powders

The mechanosynthesis of piezoelectric perovskite 0.92Pb(Zn_1/3Nb_2/3)O₃–0.08PbTiO₃ (PZN–PT) by direct mechanochemical activation of the constituent oxides has been studied by X-ray diffraction (XRD) and transmission electron microscopy (TEM). This and the PbO flux method are the only two procedures that have succeeded in synthesizing this phase, which has recently been shown to present very high electromechanical response. The thermal stability of the single perovskite phase powders has been studied by differential thermal analysis/thermogravimetry and by high-temperature XRD as a function of mechanical activation time and pressure. The phase was found to transform into a pyrochlore type structure at temperatures above 400°C. The transformation presented a significant time dependence, and it was slowed down by increasing mechanical activation time and by the application of pressures by hot pressing. Sintering experiments were accomplished and 85% density, 77% perovskite-phase ceramics were obtained after heating at 1000°C for 1 h. Hot pressing at this temperature failed to increase the percentage of perovskite phase. Results are discussed, and procedures for obtaining dense single-phase PZN–PT-based ceramics with ultrahigh piezoelectricity are proposed.     

EPR characterisation of carbon black in loose and tight contact with Al2O3 and CeO2 catalysts

The intensity of contact between soot and catalyst is one of the major parameters that determine the soot oxidation reactivity. In the present work the EPR study is focused on the mixtures of carbon black with Al₂O₃ and CeO₂ in loose and tight contacts in order to provide the physicochemical characterisation of the contact. For tight contact CB-catalyst mixtures a new paramagnetic species is observed and can be considered as a fingerprint of the contact between the two solids. These new paramagnetic species increase the catalytic reactivity of CB combustion in the presence of cerium oxide.     

Environmental aspects of metals removal from waters and gold recovery

Mining and metals processing are not invisible activities and are heavy industries, which require energy, water, chemicals, and land area. Recently more emphasis is given to environmental and societal aspects in mining and processing. Development of good practices with improved resource efficiency, new recovery methods and sustainability thinking are increasingly required. This work shows pH titration method for acid mine drainage (AMD) water incorporated with aqueous thermodynamic model for selective metals precipitation from complex solution. Also two examples on gold recovery methods from aqueous streams are shown: biosorption using fungal matter and solvent extraction using a task‐specific ionic liquid. By understanding chemical thermodynamics and natural phenomena, there is a better chance of developing solutions for environmental problems and new industrial processes. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2739–2748, 2015     

Phenylalanine Ammonia‐Lyase‐Catalyzed Deamination of an Acyclic Amino Acid: Enzyme Mechanistic Studies Aided by a Novel Microreactor Filled with Magnetic Nanoparticles

Phenylalanine ammonia‐lyase (PAL), found in many organisms, catalyzes the deamination of l ‐phenylalanine (Phe) to (E)‐cinnamate by the aid of its MIO prosthetic group. By using PAL immobilized on magnetic nanoparticles and fixed in a microfluidic reactor with an in‐line UV detector, we demonstrated that PAL can catalyze ammonia elimination from the acyclic propargylglycine (PG) to yield (E)‐pent‐2‐ene‐4‐ynoate. This highlights new opportunities to extend MIO enzymes towards acyclic substrates. As PG is acyclic, its deamination cannot involve a Friedel–Crafts‐type attack at an aromatic ring. The reversibility of the PAL reaction, demonstrated by the ammonia addition to (E)‐pent‐2‐ene‐4‐ynoate yielding enantiopure l ‐PG, contradicts the proposed highly exothermic single‐step mechanism. Computations with the QM/MM models of the N‐MIO intermediates from l ‐PG and l ‐Phe in PAL show similar arrangements within the active site, thus supporting a mechanism via the N‐MIO intermediate.     

Novel Tacrine‐Grafted Ugi Adducts as Multipotent Anti‐Alzheimer Drugs: A Synthetic Renewal in Tacrine–Ferulic Acid Hybrids

Herein we describe the design, multicomponent synthesis, and biological, molecular modeling and ADMET studies, as well as in vitro PAMPA‐blood–brain barrier (BBB) analysis of new tacrine–ferulic acid hybrids (TFAHs). We identified (E)‐3‐(hydroxy‐3‐methoxyphenyl)‐N‐{8[(7‐methoxy‐1,2,3,4‐tetrahydroacridin‐9‐yl)amino]octyl}‐N‐[2‐(naphthalen‐2‐ylamino)2‐oxoethyl]acrylamide (TFAH 10 n ) as a particularly interesting multipotent compound that shows moderate and completely selective inhibition of human butyrylcholinesterase (IC₅₀=68.2 nM ), strong antioxidant activity (4.29 equiv trolox in an oxygen radical absorbance capacity (ORAC) assay), and good β‐amyloid (Aβ) anti‐aggregation properties (65.6 % at 1:1 ratio); moreover, it is able to permeate central nervous system (CNS) tissues, as determined by PAMPA‐BBB assay. Notably, even when tested at very high concentrations, TFAH 10 n easily surpasses the other TFAHs in hepatotoxicity profiling (59.4 % cell viability at 1000 μM ), affording good neuroprotection against toxic insults such as Aβ_1–40, Aβ_1–42, H₂O₂, and oligomycin A/rotenone on SH‐SY5Y cells, at 1 μM . The results reported herein support the development of new multipotent TFAH derivatives as potential drugs for the treatment of Alzheimer′s disease.     

Perfume‐containing polyurea microcapsules with undetectable levels of free isocyanates

Core‐shell polyurea microcapsules with a 40% fragrance load were prepared by interfacial polymerization of guanidine and a technical polyisocyanate prepolymer containing mainly the biuret trimer derived from hexamethylene di‐isocyanate (HDI). Residual free polyisocyanates were still present at a level slightly above 100 mg NCO functional group per kg as determined by liquid chromatography hyphenated with tandem mass spectrometry of HDI and of its biuret trimer. This level was decreased by a factor of about 10 when the polymerization process was allowed to proceed for a longer time and by a factor of about 500 when guanidine or NaOH were added to the microcapsule suspension to act as scavengers. In these cases, polyisocyanate conversion was observed to proceed for about one month when the microcapsules were stored at room temperature before reaching a plateau at a level below 1 mg NCO/kg. Overall, ammonia was the most efficient polyisocyanate scavenger as no residual HDI biuret trimer and only less than 2 μg NCO/kg as HDI were detected at the end of the process, a level which had dropped below the limit of detection of 0.25 μg NCO/kg after about 40 days of aging at room temperature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Isolation of Non-methylene Interrupted or Acetylenic Fatty Acids from Seed Oils Using Semi-preparative Supercritical Chromatography

Preparative scale supercritical fluid chromatography was used for isolating and purifying uncommon non-methylene interrupted or acetylenic polyunsaturated fatty acids ethyl esters from seed oils. Fractionation of Biota orientalis seed oil ethyl esters was performed by supercritical fluid chromatography to obtain juniperonic acid [(5Z,11Z,14Z,17Z)-eicosa-5,11,14,17-tetraenoic acid], a non-methylene interrupted polyunsaturated fatty acid. Fractionation of sandalwood seed oil ethyl esters yielded ximenynic acid [(E)-octadec-11-en-9-ynoic acid], an acetylenic polyunsaturated fatty acid. The effects of CO₂ flow rate, column stationary phase and particle size were explored to optimize ximenynic and juniperonic ethyl ester recovery and purity from ethyl ester mixtures using online UV/Vis detection. Particle size, followed by the stationary phase, were found to be the most important parameters to achieving good separation. Under optimized conditions, ximenynic and juniperonic ethyl ester purities greater than 99 and 95%, respectively, were achieved in a one step process without co-solvent. The isolation and recovery of juniperonic acid from biota seed oil free fatty acids was also attempted. Using free fatty acids as the feed material, the non-methylene interrupted polyunsaturated sciadonic acid was also able to be separated from other compounds including juniperonic acid under some conditions, and gave an increase in concentration of more than 17 times.