Dissipativity‐based distributed model predictive control with low rate communication

Distributed or networked model predictive control (MPC) can provide a computationally efficient approach that achieves high levels of performance for plantwide control, where the interactions between processes can be determined from the information exchanged among controllers. Distributed controllers may exchange information at a lower rate to reduce the communication burden. A dissipativity‐based analysis is developed to study the effects of low communication rates on plantwide control performance and stability. A distributed dissipativity‐based MPC design approach is also developed to guarantee the plantwide stability and minimum plantwide performance with low communication rates. These results are illustrated by a case study of a reactor‐distillation column network. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3288–3303, 2015     

Study of the bio‐production of carotenoids by Sporidiobolus salmonicolor (CBS 2636) using pre‐treated agro‐industrial substrates

BACKGROUND: The increasing industrial demand for carotenoids has aroused interest in their bio‐production, and the need to reduce production costs has encouraged the use of low cost industrial substrates, such as agro‐industrial residues. Thus the objective of this research was the bio‐production of carotenoids by Sporidiobolus salmonicolor using agro‐industrial substrates (corn steep liquor and sugarcane molasses), pre‐treated with acids (sulphuric and phosphoric). RESULTS: Bio‐production was carried out in an orbital shaker using a 10% (v/v) inoculum, incubation at 25 °C, and agitation at 180 rpm for 120 h in a non‐illuminated environment. The carotenoids were recovered using liquid N₂ combined with dimethylsulphoxide for cell rupture, and an acetone/methanol mixture (7:3 v/v) for extraction. CONCLUSION: The complete second‐order design allowed for optimisation of the carotenoid concentration obtained from industrial substrates pre‐treated with acids (sulphuric and phosphoric), obtaining a total carotenoid content of 541.5 µg L^?1 using 10 g L^?1 sugarcane molasses, 5 g L^?1 corn steep liquor and 5 g L^?1 yeast hydrolysate at 25 °C, with agitation at 180 rpm and an initial pH of 4.0. Copyright © 2008 Society of Chemical Industry     

The effect of crystallites on the rheological properties of microphase‐separated PVC‐PBA‐PVC triblock copolymers obtained by single electron transfer‐degenerative chain transfer living radical polymerization

Linear and nonlinear rheological properties of poly(vinyl chloride) (PVC)‐poly(n‐butyl acrylate)‐PVC triblocks of different compositions, obtained by single electron transfer‐degenerative chain transfer living radical polymerization, are investigated, focusing on the effect of crystallites. Dynamic mechanical thermal analysis results show the existence of two glass transition temperatures, denoting microphase segregation. However, rather than phase separation, it is the presence of two types of crystals that melt at T_m1 = 127 ± 0.8°C and T_m2 = 185 ± 2°C, respectively, the factor that determines the rheological response of the copolymers. To the difference with PVC homopolymers, extrusion flow measurements at very low temperatures (T = 100°C) are possible with the copolymers. A change in the viscosity‐temperature dependence is observed below and above the lowest melting temperature. Notwithstanding the microphase separation and the presence of crystallites, experiments carried out in conditions similar to industrial processing reveal a remarkable viscosity reduction for our copolymers with respect to PVC obtained by single electron transfer‐degenerative chain transfer living radical polymerization, conventional PVC, and PVC/[diethyl‐(2‐ethylhexyl) phthalate] compounds. Extrudates free of surface instabilities are obtained at low extrusion temperatures, such as 90–100°C. J. VINYL ADDIT. TECHNOL., 21:24–32, 2015. © 2014 Society of Plastics Engineers     

Phosphorus‐Carbon Bond Formation: Palladium‐Catalyzed Cross‐Coupling of H‐Phosphinates and Other P(O)H‐Containing Compounds

Two generally applicable systems have been developed for the cross‐coupling of P(O)H compounds with C_sp2 X and related partners. Palladium catalysis using a ligand/additive combination, typically either xantphos/ethylene glycol or 1,1′‐bis(diphenylphosphino)ferrocene/1,2‐dimethoxyethane, with diisopropylethylamine as the base, proved to be generally useful for the synthesis of numerous P C containing compounds. Routinely, 2 mol% of catalyst are employed (less than half the amount typically employed in most other literature reports). In most cases, excellent results are obtained with a variety of electrophiles (RX, where R=alkenyl, allyl, alkynyl, etc.). The full account of our studies is disclosed, including tandem hydrophosphinylation/coupling and coupling/coupling for doubly catalytic phosphorus‐carbon bond formation. The methodology compares favorably with any existing literature report. The use of an additive appears to be a generally useful strategy to control the reactivity of phosphinylidene compounds.     

Synthesis,extraction, and anti‐bacterial studies of some new bis‐1,2,4‐triazole derivatives part I

A series of new bis triazole Schiff base derivatives (4) were prepared in good yields by treatment of 4‐amino‐3,5‐diphenyl‐4H‐1,2,4‐triazole (3) with bisaldehydes (1). Schiff bases (4) were reduced with NaBH₄ to afford the corresponding bisaminotriazoles (5). All the new compounds were characterized by IR, ¹H NMR and ¹³C NMR spectral data. Their overall extraction (log K_ex) constants for 1 : 1 (M : L) complexes and CHCl₃/H₂O systems were determined at 25 ± 0.1°C to investigate the relationship between structure and selectivity toward various metal cations. The extraction equilibrium constants were estimated using CHCl₃/H₂O membrane transfer with inductively coupled plasma‐atomic emission spectroscopy spectroscopy. The stability sequence of the triazole derivatives in CHCl₃ for the metal cations was exhibited a characteristic preference order of extractability to metal ions [Fe(III) > Cu(II) > Pb(II) > Co(II) > Ni(II) > Mn(II) > Zn(II) > Mg(II) > Ca(II)]. The compounds were tested for anti‐microbial activity applying agar diffusion technique for 11 bacteria. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Investigation of a 6‐MSA Synthase Gene Cluster in Aspergillus aculeatus Reveals 6‐MSA‐derived Aculinic Acid,Aculins A–B and Epi‐Aculin A

Aspergillus aculeatus, a filamentous fungus belonging to the Aspergillus clade Nigri, is an industrial workhorse in enzyme production. Recently we reported a number of secondary metabolites from this fungus; however, its genetic potential for the production of secondary metabolites is vast. In this study we identified a 6‐methylsalicylic acid (6‐MSA) synthase from A. aculeatus, and verified its functionality by episomal expression in A. aculeatus and heterologous expression in A. nidulans. Feeding studies with fully ¹³C‐labeled 6‐MSA revealed that 6‐MSA is incorporated into aculinic acid, which further incorporates into three compounds that we name aculins A and B, and epi‐aculin A, described here for the first time. Based on NMR data and bioinformatic studies we propose the structures of the compounds as well as a biosynthetic pathway leading to formation of aculins from 6‐MSA.     

Multinuclear solid‐state NMR investigation of the moisture distribution in PEEK‐PBI and PEKK‐PBI blends

Blends of polyaryletherketones (PAEK), such as polyetheretherketones (PEEK) and polyetherketoneketones (PEKK), with polybenzimidazole (PBI) are of commercial interest due to their improved high‐temperature stability and wear properties. The changes of PBI and its PEEK‐ and PEKK‐blends (50 : 50 wt %) after immersing them in liquid H₂O and D₂O, and exposing them to D₂O steam at elevated temperatures and pressures are investigated by multinuclear solid‐state NMR and IR spectroscopy. Macroscopic morphological and chemical changes on the molecular scale, which take place upon high‐temperature steam‐treatment and the extent and reversibility of moisture uptake have been investigated. Interactions and reactions of water, steam, and aqueous solutions of LiCl and ZnBr₂ with the functional groups of the polymer components have been studied using D₂O in combination with IR, ¹H wideline, ²H, ⁷Li, and ⁷⁹Br MAS, as well as ¹³C and ¹⁵N CP/MAS NMR spectroscopy. Different locations and types of water and protons in the blends have been described and PBI has been proven to be mainly responsible for water and salt uptake into the blends. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41421.     

Synergistic Effect of a Palladium‐on‐Carbon/Platinum‐on‐Carbon Mixed Catalyst in Hydrogen/Deuterium Exchange Reactions of Alkyl‐Substituted Aromatic Compounds

We have found a synergistic effect in the H‐D exchange reaction of alkyl‐substituted aromatic compounds using the Pd/C‐Pt/C‐D₂O‐H₂ system. This system would lead to fully H‐D exchange results even on the sterically hindered sites which were only low‐deuterium incorporated by Pd/C or Pt/C independently. Since the reaction was general for a variety of aromatic compounds, it could be applied to the deuteration of dianiline derivatives as raw materials for polyimides.     

TiO2‐Oligoaldaramide nanocomposites as efficient core‐shell systems for wood preservation

Homogeneous core‐shell systems were obtained with a growth, in controlled steps, of several oligoamides on TiO₂ nanoparticles. Derivatives of natural compounds, such as l ‐tartaric acid and α,α′‐trehalose, were used as diesters in the polycondensation reactions with ethylenediamine. TiO₂ anatase was chosen because of its high photo‐activity and its antimicrobial activity. The TiO₂ nanoparticles had been previously activated then functionalized using two different coupling agents, and finally, the TiO₂‐oligoamide nanocomposites were synthesized using two synthetic pathways. The final products were characterized by ¹H NMR, ¹³C NMR, FT‐IR, and transmission electron microscope. These nanocomposites can show improved properties in comparison with the single components (TiO₂ nanoparticles or oligoamides), which are useful in many fields, such as antimicrobial coatings for surfaces in cultural heritage conservation. A nanocomposite (TiO₂‐polyethylenetartaramide) was used for applicative studies, and it has shown a good efficacy against fungal attack by Trametes versicolor on wood specimens (Fagus sylvatica). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42047.     

Synthesis,characterization, thermal stability,and compatibility properties of poly(vinyl p‐nitrobenzal acetal)‐g‐polyglycidylazides

A series of energetic polymers, poly(vinyl p‐nitrobenzal acetal)‐g‐polyglycidylazides (PVPNB‐g‐GAPs), are obtained via cross‐linking reactions of poly(vinyl p‐nitrobenzal acetal) (PVPNB) with four different molecular weights polyglycidylazides (GAPs) using toluene diisocyanate as cross‐linking agent. The structures of the energetic polymers are characterized by ultraviolet visible spectra (UV‐Vis), attenuated total reflectance‐Fourier transform‐infrared spectroscopy (ATR‐FT‐IR), ¹H nuclear magnetic resonance spectrometry (¹H NMR), and ¹³C nuclear magnetic resonance spectrometry (¹³C NMR). Differential scanning calorimetry (DSC) is applied to evaluate the glass‐transition temperature of the polymers. DSC traces illustrate that PVPNB‐g?2^#GAP, PVPNB‐g?3^#GAP, and PVPNB‐g?4^#GAP have two distinct glass‐transition temperatures, whereas PVPNB‐g?1^#GAP has one. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) are used to evaluate the thermal decomposition behavior of the four polymers and their compatibility with the main energetic components of TNT‐based melt‐cast explosives, such as cyclotetramethylene tetranitramine (HMX), cyclotrimethylene‐trinitramine (RDX), triaminotrinitrobenzene (TATB), and 2,4,6‐trinitrotoluene (TNT). The DTA and TGA curves obtained indicate that the polymers have excellent resistance to thermal decomposition up to 200°C. PVPNB‐g?4^#GAP also exhibits good compatibility and could be safely used with TNT, HMX, and TATB but not with RDX. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42126.     

Antichagasic,Leishmanicidal, and Trichomonacidal Activity of 2‐Benzyl‐5‐nitroindazole‐Derived Amines

Three different series of new 5‐nitroindazole derivatives—1‐(ω‐aminoalkyl)‐2‐benzylindazolin‐3‐ones (series A ; ten compounds), 3‐(ω‐aminoalkoxy)‐2‐benzylindazoles (series B ; four compounds) and 3‐alkylamino‐2‐benzylindazoles (series C ; five compounds)—have been synthesized and evaluated against the protozoan parasites Trypanosoma cruzi, Leishmania amazonensis, and Trichomonas vaginalis: etiological agents of Chagas disease, cutaneous leishmaniasis, and trichomoniasis, respectively. Many indazoles of series A , B , and C were efficient against T. cruzi. Some compounds in series A , after successfully passing the preliminary screening for epimastigotes, exhibited activity values against amastigotes of several T. cruzi strains that were better than or similar to those shown by the reference drug benznidazole and displayed low nonspecific toxicity against mammalian cells. On the other hand, preliminary studies against promastigotes of L. amazonensis showed high leishmanicidal activity for some derivatives of series A and C . With regard to activity against T. vaginalis, some indazoles of series B and C were rather efficient against trophozoites of a metronidazole‐sensitive isolate and showed low nonspecific toxicities toward Vero cell cultures. Additionally, some of these compounds displayed similar activity against metronidazole‐sensitive and resistant isolates, showing the absence of cross‐resistance between these derivatives and the reference drug.     

Polyether–maleimide‐based crosslinked self‐healing polyurethane with Diels–Alder bonds

The Diels–Alder (DA) reaction is particularly desirable for the preparation of heat‐stimuli self‐healing polymeric materials because of its thermal reversibility, high yield, and minimal side reactions. Some attempts were conducted to synthesize polyether–maleimide‐based crosslinked self‐healing polyurethane with DA bonds (C‐PEMIPU–DA) through the reactions of the prepolymer (polymeric MDI/PBA‐1000) functionalized by furfuryl amine and polyether–maleimide without benzene in this study. The structures of intermediates and C‐PEMIPU–DA were first confirmed by ¹H‐NMR, Fourier transform infrared spectroscopy, and differential scanning calorimetry. Next, the thermal reversibility and the self‐healing performance of C‐PEMIPU–DA were studied by ¹H‐NMR, polarizing optical microscopy, tensile testing, and a sol–gel process. The results show that C‐PEMIPU–DA exhibited interesting properties of thermal reversibility and self‐healing. The polymers could be applied to self‐healing materials or recyclable materials in the fields of the repair of composite structures and aging parts because of their thermosetting properties at room temperature and thermoplasticity at higher temperatures. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41944.     

Multiple Oxidative Dehydrogenative Functionalization of Arylacetaldehydes Using Molecular Oxygen as Oxidant Leading to 2‐Oxo‐acetamidines

A novel copper‐catalyzed, multiple oxidative dehydrogenative functionalization of arylacetaldehydes leading to 2‐oxo‐acetamidine compounds has been developed. This transformation is highly efficient with dissociation of six hydrogens including two sp³ C H and one sp² C H bond activations. This method not only provides an efficient approach to 2‐oxo‐acetamidine compounds, but also offers a valuable mechanistic insight into this novel copper catalysis.     

Mathematical Modelling of Proton‐Conducting Solid Oxide Fuel Cells and Comparison with Oxygen‐Ion‐Conducting Counterpart

Proton‐conducting solid oxide fuel cells (H‐SOFC), using a proton‐conducting electrolyte, potentially have higher maximum energy efficiency than conventional oxygen‐ion‐conducting solid oxide fuel cells (O‐SOFC). It is important to theoretically study the current–voltage (J–V) characteristics in detail in order to facilitate advanced development of H‐SOFC. In this investigation, a parametric modelling analysis was conducted. An electrochemical H‐SOFC model was developed and it was validated as the simulation results agreed well with experimental data published in the literature. Subsequently, the analytical comparison between H‐SOFC and O‐SOFC was made to evaluate how the use of different electrolytes could affect the SOFC performance. In addition to different ohmic overpotentials at the electrolyte, the concentration overpotentials of an H‐SOFC were prominently different from those of an O‐SOFC. H‐SOFC had very low anode concentration overpotential but suffered seriously from high cathode concentration overpotential. The differences found indicated that H‐SOFC possessed fuel cell characteristics different from conventional O‐SOFC. Particular H‐SOFC electrochemical modelling and parametric microstructural analysis are essential for the enhancement of H‐SOFC performance. Further analysis of this investigation showed that the H‐SOFC performance could be enhanced by increasing the gas transport in the cathode with high porosity, large pore size and low tortuosity.     

Copper‐Catalyzed Cascade Reactions of Substituted 4‐Iodopyrazolecarbaldehydes with 1,2‐Phenylenediamines and 2‐Aminophenols

A new approach for the synthesis of novel annulated‐pyrazoles is presented. This protocol includes an intermolecular condensation followed by a copper‐mediated intramolecular C N or C O coupling reaction. The method is applied to a range of substituted 4‐iodopyrazolecarbaldehydes which react with 1,2‐phenylenediamines or 2‐aminophenols to yield substituted 2,4‐ or 1,4‐dihydrobenzo[b]pyrazolo[4,3‐e][1,4]diazepines or substituted‐2H‐ or 1H‐benzo[b]pyrazolo[3,4‐f][1,4]oxazepines, respectively.     

Fourier transform infrared spectroscopy study of poly(1‐trimethylsilyl‐1‐propyne) aging

The influence of various factors on the aging of poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) during long‐term storage in air was investigated with Fourier transform infrared spectroscopy. Most attention was paid to the differentiation of oxidation, the reduction of the free volume, and the absorption of low‐molecular‐weight compounds from the environment. IR spectra of PTMSP samples stored from 1–2 months to 6.5 years revealed C?O, C? O, and C? H bands that had been earlier attributed to polymer oxidation products. It was established, however, that these bands completely disappeared from IR spectra of the aged samples after their soaking in ethanol. Spectra of dried residues of ethanol extracts displayed all these bands and did not show any bands of polymer chain fragments. Gas chromatography/mass spectrometry analysis proved that the residues were composed mainly of various dialkyl phthalates. Special experiments showed that PTMSP films easily absorbed di‐n‐butyl phthalate vapors. IR spectra of the films stored for a long time showed no decrease in double‐bond and methyl group bands. It was concluded that the polymer did not undergo oxidation in air at room temperature for at least 6.5 years. The absorption of plasticizer vapors (and possibly other compounds) from the environment and the reduction of the free volume were the main reasons found for PTMSP aging. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2523–2527, 2007     

Stereoselective Synthesis of Phosphoryl‐Substituted Phenols

Copper‐catalyzed C X activation‐phosphorylation of aryls bearing different groups has been achieved using P(O) H compounds as efficient phosphorylation reagents without the assistance of any ligand. Optically active H‐phosphinates can also act as good substrates in the reaction, giving the (Sp)‐phosphoryl substituted phenolic compounds stereospecifically with retention of configuration at the phosphorus center. Furthermore, it is shown that the migration of phosphorus on O‐aryl phosphonates from oxygen to carbon also proceeds stereospecifically to produce the corresponding optically active (Rp)‐phosphoryl‐substituted phenolic compounds with retention of configuration at phosphorus via treatment with lithium diisopropylamide (LDA). Plausible mechanisms have been proposed for these reactions.

     

Production of alkenyl succinic anhydrides from low‐erucic and low‐linolenic rapeseed oil methyl esters

Fatty acid methyl esters from low‐erucic and low‐linolenic rapeseed oil were used to produce alkenyl succinic anhydrides. A second‐order Doehlert uniform network design was used to investigate the influence of the reaction temperature and the molar ratio between the maleic anhydride and the main unsaturated rapeseed oil methyl esters on the yield of alkenyl succinic anhydride from methyl oleate. Further subjects of investigation were the conversion of methyl oleate, the formation of side reaction products, the Gardner color of the product and its viscosity, and finally the content of maleic anhydride remaining in the medium after the reaction. Alkenyl succinic anhydride from methyl oleate was isolated by column chromatography and analyzed by IR, ¹H‐ and ¹³C‐NMR and MS. The optimal reaction conditions for obtaining the maximum yield of alkenyl succinic anhydride from methyl oleate in the experimental domain (80%) were 210‐220 °C and a maleic anhydride/rapeseed oil methyl ester molar ratio of 1.5. However, the products synthesized in these conditions showed a high degree of viscosity (0.45 kg m^?1 s^?1), a very dark color (18 Gardner color) and a high content of undesirable side products (6%), which could hinder their industrial use. A molar ratio of less than 1.5 led to a clearer and less viscous product, although with a lower alkenyl succinic anhydride content.     

Influence of hydrogen donors on peroxide‐initiated melt grafting of vinylsilane to poly(ethylene‐co‐vinyl acetate)

A technique has been examined for reducing the extent of crosslinking resulting from 1,1‐di(t‐butylperoxy)‐3,3,5‐trimethylcyclohexane (L‐231) initiating melt grafting of vinyltriethoxysilane (VTEOS) onto poly(ethylene‐co‐vinyl acetate) (EVA). Using measurements of crosslink density and VTEOS conversion, a standard of selectivity for the EVA/VTEOS/L‐231 system at 145 °C was defined and used to assess the influence of a range of additives (0.25 mol per mole VTEOS). The data indicated that compounds such as 4‐nonene, N,N‐dimethylaniline, and cumene improve reaction selectivity, whereas dodecane and cyclohexyl acetate have no effect. A strong correlation between the minimum C? H bond dissociation energy and the influence of a given compound is evident, suggesting that a labile C? H bond is the key element of an effective additive. A mechanism of additive function on the basis of hydrogen atom donation is proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2397–2402, 2002     

Synthesis and characterization of tetrakis‐ derivatives of bisphenol‐A with 4‐phenylazoaniline and 5‐(4‐aminophenylazo)‐25,26,27‐tribenzoyloxy‐ 28‐hydroxycalix[4]arene

The synthesis of tetrakis‐ derivatives of bisphenol‐A containing azo groups at their 2,2′,6,6′‐positions is reported. Novel examples of bisphenol‐A, coupled with diazonium salts and derived from 4‐phenylazoaniline and 5‐(4‐aminophenylazo)‐25,26,27‐tribenzoyloxy‐28‐hydroxycalix [4]arene, have been synthesized. It has been observed that the coupling reaction of diazonium salt obtained from 4‐phenylazoaniline with bisphenol‐A gives tetrakis‐ while those derived from 5‐(4‐aminophenylazo)‐25,26,27‐tribenzoyloxy‐28‐hydroxycalix [4]arene give partially substituted bisphenol‐A analogues. The newly prepared tetrakis‐azo substituted bisphenol‐A compounds ( 1 and 2 ) are characterized by using UV‐vis, FT‐IR, ¹H‐NMR spectroscopic methods as well as elemental analysis techniques. These azo compounds give rise to bathochromic shifts in the absorption spectra, which can even be detected by “naked eye.” © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011