Modelling the semi-batch vinyl acetate emulsion polymerization in a real-life industrial reactor

A detailed dynamic model of the polymerization reaction of vinyl acetate in a real-life industrial reactor is presented. With the recipe and the operating procedures observed in the factory as inputs, the model predicts with reasonable accuracy the final conversion, the average particle diameter, the solid content and the viscosity. The manual and semi-manual operations, and the decision process followed by the operator, are also modelled in order to replicate closely the process carried out in the factory. The model provides further insight into the reaction kinetics and allows us to make knowledge-based decisions. The model is intended to be used for the optimization of the policy of adding monomer in order to reduce the batch time.     

The Lysozyme Inhibitor Thionine Acetate Is Also an Inhibitor of the Soluble Lytic Transglycosylase Slt35 from Escherichia coli

Lytic transglycosylases such as Slt35 from E. coli are enzymes involved in bacterial cell wall remodelling and recycling, which represent potential targets for novel antibacterial agents. Here, we investigated a series of known glycosidase inhibitors for their ability to inhibit Slt35. While glycosidase inhibitors such as 1-deoxynojirimycin, castanospermine, thiamet G and miglitol had no effect, the phenothiazinium dye thionine acetate was found to be a weak inhibitor. IC₅₀ values and binding constants for thionine acetate were similar for Slt35 and the hen egg white lysozyme. Molecular docking simulations suggest that thionine binds to the active site of both Slt35 and lysozyme, although it does not make direct interactions with the side-chain of the catalytic Asp and Glu residues as might be expected based on other inhibitors. Thionine acetate also increased the potency of the beta-lactam antibiotic ampicillin against a laboratory strain of E. coli.     

An efficient and highly selective approach for the construction of novel dispiro heterocycles in guanidine-based task-specific [TMG][Ac] ionic liquid

A simple, efficient and highly selective one-pot approach for the synthesis of biologically important novel dispiro heterocycles assembling three pharmacophoric moieties such as piperidinone, 1,3-indanedione, and pyrrolidine in a single molecular framework by means of three-component reaction between ninhydrin, sarcosine, and 1-benzyl/methyl-3,5-bis[(E)-arylidene]-piperidin-4-one is reported in task-specific 1,1,3,3-tetramethylguanidine acetate [TMG][Ac] ionic liquid as a environmentally benign solvent in excellent yields without using any catalyst. The TMG-based ionic liquid could be recovered and used at least four times without considerable reduction in its activity and selectivity. Good functional group tolerance and broad scope of usable substrates are other prominent features of the present methodology with high degree of chemo-, regio-, and stereoselectivity. The structure and relative stereochemistry of final products were established by single crystal X-ray structure and spectroscopic techniques.     

Luminescent properties of europium (III) acetate monohydrate in synthetic opal pores

Abstract

This paper presents a systematic photoluminescence spectra study of the (111) growth surface of an opal photonic crystal whose pores were filled with salt Europium (III) acetate monohydrate (C₆H₉EuO₆×H₂O). Ultraviolet excitation was provided by semiconductor laser operating at wavelengths of 405?nm. Emission spectra were measured both for free-form salt samples and for salt in opal pores annealed at various temperatures up to 1000?°C. The influence of changes in the coordination environment of europium ions on the luminescence spectra in the process of dehydration and salt decomposition up to Eu₂O₃ is established. Differences in the spectra of salt in the pores of opal were revealed compared with the spectra in the free state.     

Kinetics of chemical absorption of carbon dioxide into aqueous calcium acetate solution

Increasing energy demand in the world leads to more electricity generation mainly at fossil fuel power plants. Greenhouse gases are thus produced and mostly emitted to the atmosphere directly, resulting in global warming and climate change. Carbon dioxide is believed to be a main pollutant among greenhouse gases responsible from global warming. Conventional systems using mostly amine solutions to capture carbon dioxide at the source have some disadvantages, and alternatives are constantly being searched. In this work, a benign system of aqueous calcium acetate solution was investigated for this purpose. Calcium acetate is easy to produce, relatively cheap, environmentally friendly, nonhazardous, and noncorrosive. These properties make it a great alternative for use in capturing carbon dioxide. This absorption process is accompanied by chemical reaction. Therefore, the reaction kinetics needs to be investigated before its use in absorbers. A stirred cell reactor was used in the experiments using aqueous calcium acetate solution of different concentrations (2-20% w/w) and different carbon dioxide concentrations in gas mixtures (4.5-100% v/v dry carbon dioxide) at temperatures ranging from 286 to 352 K. The Gibbs free energy change for the overall reaction between carbon dioxide and aqueous calcium acetate solution was found to be –2.75 kJ/mol that shows the reaction is exergonic and occurs spontaneously. It was also found out that the reaction is pseudo–first order with respect to carbon dioxide which was also proven by calculating the Hatta number. Activation energy and Arrhenius (frequency) constant were also determined experimentally.     

Conversion of ethyl acetate into benzene–toluene–xylene fraction over MFI zeolite-based catalysts

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Reversible addition‐fragmentation chain transfer polymerization of vinyl acetate under high pressure

In this work, high molecular weight polyvinyl acetate (PVAc) (M_n,GPC = 123,000 g/mol, M_w/M_n = 1.28) was synthesized by reversible addition‐fragmentation chain transfer polymerization (RAFT) under high pressure (5 kbar), using benzoyl peroxide and N,N‐dimethylaniline as initiator mediated by (S)‐2‐(ethyl propionate)‐(O‐ethyl xanthate) (X1) at 35 °C. Polymerization kinetic study with RAFT agent showed pseudo‐first order kinetics. Additionally, the polymerization rate of VAc under high pressure increased greatly than that under atmospheric pressure. The “living” feature of the resultant PVAc was confirmed by ¹H NMR spectroscopy and chain extension experiments. Well‐defined PVAc with high molecular weight and narrow molecular weight distribution can be obtained relatively fast by using RAFT polymerization at 5 kbar. © 2015 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym. Chem. 2015 , 53, 1430–1436     

Ultra‐performance liquid chromatography–tandem mass spectrometry assay for determination of plasma nomegestrol acetate and estradiol in healthy postmenopausal women

A highly sensitive and selective ultra‐performance liquid chromatography–tandem mass spectrometry method is described for the simultaneous determination of nomegestrol acetate (NOMAC), a highly selective progestogen, and estradiol (E2), a natural estrogen in human plasma. NOMAC was obtained from plasma by solid‐phase extraction, while E2 was first separated by liquid–liquid extraction with methyl tert‐butyl ether followed by derivatization with dansyl chloride. Deuterated internal standards, NOMAC‐d5 and E2‐d4 were used for better control of extraction conditions and ionization efficiency. The assay recovery of the analytes was within 90–99%. The analytes were separated on UPLC BEH C₁₈ (50 × 2.1 mm, 1.7 μm) column using a mobile phase comprising of acetonitrile and 3.0 mm ammonium trifluoroacetate in water (80:20, v/v) with a resolution factor (R_s) of 3.21. The calibration curves were linear from 0.01 to 10.0 ng/mL for NOMAC and from 1.00 to 1000 pg/mL for E2, respectively. The intra‐ and inter‐batch precision was ≤5.8% and the accuracy of quality control samples ranged from 96.7 to 103.4% for both analytes. The practical applicability of the method is demonstrated by analyzing samples from 18 healthy postmenopausal women after oral administration of 2.5 mg nomegestrol acetate and 1.5 mg estradiol film‐coated tablets under fasting.     

Phytochemical variations among four distinct varieties of Indian cardamom Elettaria cardamomum (L.) Maton

Abstract

Elettaria cardamomum (L.) Maton prestigiously called as Indian cardamom and is mostly cultivated in south India at higher altitudes ranging from 900 to 1400 msl. The chemical composition of dry capsules essential oil of the four distinct varieties was chemo-profiled by gas chromatography-mass spectrometry (GC-MS). Results revealed a higher concentration of major monoterpene 1, 8-Cineole ranging between 28.94% and 34.91% in PV 1 and PV 2 varieties respectively. Other monoterpenes like α-Pinene, Sabinene, Linalool, α-Terpineol and Nerol were present considerable quantities in all of the four cardamom varieties. Two sesquiterpenic constituents namely, ç-Elemene and 1,6,10-dodecatrien-3-ol (Nerolidol) were identified in all varieties. Three ester constituents were also obtained in PV 1 in which α-Terpinyl acetate (26.68%) exhibited as a major ester constituent followed by Ocimenyl acetate (0.80%) and E5-Dodecenyl acetate (0.30%). This is the first published report on the phytochemical concentration of recent varieties of Indian cardamom.

     

A highly efficient layered double hydroxide catalyst for direct ethoxylation of butyl acetate to oligo‐ethylene glycol butyl ether acetates

A novel synthetic route that directly inserts ethylene oxide into butyl acetate without any labile hydrogen to produce oligo‐ethylene glycol butyl ether acetates is developed using an efficient acid–base bifunctional catalyst. The layered double hydroxide materials, which have structures similar to that of hydrotalcite, are synthesized using co‐precipitation methods. After modification by organic acid, the as‐prepared catalysts exhibit higher butyl acetate conversion and ethylene oxide catalytic activity with narrow ethylene glycol butyl ether acetate adduct distribution. Copyright © 2016 John Wiley & Sons, Ltd.