Sulphonated macroporous resin catalysts: Studies on the dehydration of 2-butanol

Sulphonated styrene-divinylbenzene resins with various cross-linking have been synthesized and the dehydration of 2-butanol has been studied on these acid catalysts. The pore structure of the resin controls the rate of dehydration. Thecis totrans ratio of the 2-butene formed indicate that the resin catalysts behave like aqueous solution of acids, i.e.dissociated protons are responsible for catalysis.     

Synthesis of the One-dimensional Compound (Ph4P)[In(P2Se6)] in a Ph4P+-Containing Selenophosphate Flux,and Structure of [In(P2Se6)2]5– – a Discrete Molecular Fragment of the [In(P2Se6)]nn– Chain

The reaction of one equivalent of In with a molten flux of (Ph₄P)₂Se₅ and P₂Se₅ (1 : 2), at 250 °C gave the (Ph₄P)[In(P₂Se₆)] ( I ). Stoichiometric elemental synthesis at 750 °C produced the Cs₅In(P₂Se₆)₂ ( II ). The thin, yellow crystals of ( I ), and the irregular, dark orange crystals of ( II ), appear to be air- and water-stable. Compound ( I ) crystallizes in the monoclinic space group C2/c (no. 15) and at 23 °C: a = 23.127(7) Å, b = 6.564(1) Å, c = 19.083(3) Å, β = 97.42(2)°, V = 2873(1) ų, Z = 4, final R/R_w = 4.4/5.2%. Compound ( II ) crystallizes in the tetragonal space group P4₂/m (no. 84) and at 23 °C: a = b = 13.886(1) Å, c = 7.597(2) Å, V = 1464.9(3) ų, Z = 2, final R/R_w = 3.9/5.1%. Compound ( I ) contains infinite [In(P₂Se₆)]_n^n– with a structure related to that of K₂FeP₂Se₆. Compound ( II ) contains the discrete [In(P₂Se₆)₂]^5– which can be viewed as a fragment of the [In(P₂Se₆)]_n^n– chain.     

Stereospecific Formal [3+2] Dipolar Cycloaddition of Cyclopropanes with Nitrosoarenes: An Approach to Isoxazolidines

The MgBr₂‐catalyzed formal [3+2] cycloaddition of donor–acceptor activated cyclopropanes with nitrosoarenes offers a novel approach to various structurally diverse isoxazolidines. The reactions, which are experimentally easy to conduct, occur with complete stereospecificity and perfect control of regioselectivity. Product isoxazolidines can be readily transformed into α‐amino lactones by reductive or decarboxylative N? O cleavage and subsequent lactonisation, and the N‐aryl bond cleavage is also possible under oxidative conditions.     

Low band‐gap diketopyrrolopyrrole‐containing polymers for near infrared electrochromic and photovoltaic applications

Donor–acceptor type polymers bearing diketopyrrolopyrrole and 3,4‐ethylenedioxythiophene units are reported. The polymers are green and exhibit very low band‐gaps (1.19 eV) with strong and broad absorption (maxima of about 830 nm) in the near infrared (NIR) region in their neutral film states. The polymers display color changes between dark green and light blue with exceptional optical contrasts in the NIR regions of up to 78 and 63% as thin films and single‐layer electrochromic devices, respectively. Fast switching, good stabilities as well as high coloration efficiencies (743–901 cm² C^?1) were also observed. The polymers could also be potentially used as photovoltaic material, with a power conversion efficiency of up to 1.68%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1287–1295     

LC–MS Simultaneous Determination of Itopride Hydrochloride and Domperidone in Human Plasma

A rapid, simple, sensitive and specific liquid chromatography–tandem mass spectrometry method was developed and validated for simultaneous quantification of itopride hydrochloride and domperidone in human plasma. Both drugs were extracted by liquid–liquid extraction with ethyl acetate and saturated borax solution. The chromatographic separation was performed on a reversed-phase C18 column with a mobile phase of water–methanol (2:98, v/v) containing 0.5% formic acid. The protonated analyte was quantitated in positive ionization by multiple reaction monitoring with a mass spectrometer. The assay exhibited linearity over the concentration range of 3.33–500 ng mL^?1 for itopride hydrochloride and 3.33–100 ng mL^?1 for domperidone in human plasma. The precursor to product ion transitions of m/z 359.1–72.3 and 426.0–147.2 were used to measure itopride hydrochloride and domperidone respectively. The method was found suitable for the analysis of plasma samples collected during phase 1 pharmacokinetics study of itopride HCl 50 mg and domperidone 20 mg in 12 healthy volunteers after single oral doses of the combination drug.     

Application of solid phase microextraction in the determination of paralytic shellfish poisoning toxins

A SPME-HPLC-post-column fluorescent derivatization method for the direct determination of saxitoxin (STX), the most potent paralytic shellfish poisoning (PSP) toxin, in water has been developed. Commercially available SPME devices with 50 microm Carbowax templated resin (CW/TPR) coating was found to be able to pre-concentrate STX from aqueous media. A special pre-conditioning treatment of soaking the SPME coating in 0.1 M NaOH solution significantly improved the extraction efficiency. The optimal pH for the SPME process is 8.1 and the equilibration time is 40 min. The partition coefficient, K, of the distribution of STX between the SPME coating and the aqueous media was measured to be 2.99 +/- 0.04 x 10(3). Extracted toxin on the SPME stationary phase was difficult to be desorbed by the HPLC mobile phase under dynamic desorption mode. A static ion-pairing desorption technique using a desorption solvent mixture of 20 mM sodium 1-heptanesulfonate in 30% aqueous acetonitrile acidified with 50 mM sulfuric acid was developed to overcome this problem. The method detection limit and repeatability achieved by this SPME-HPLC method were 0.11 ng ml(-1) and 3.7%, respectively, with a sample volume of just 5 ml of water. This analytical method is adequate for the monitoring of the PSP toxin in fresh/drinking waters. However, serious interference was observed when this technique was applied to saline water samples. This is probably due to competition of sodium ions with the cationic STX for absorption into the SPME stationary phase.     

Separation of lignosulfonate from its aqueous solution using supported liquid membrane

This paper presents an experimental and theoretical study on facilitated transport of lignosulfonate (LS) through a flat sheet supported liquid membrane using trioctylamine (TOA) as carrier and dichloroethane as diluent. The studies were carried out with various support materials and operating conditions (viz. carrier concentration, strip phase concentration, salt concentration, etc.) and their effects on the transport of LS. The results were analyzed to identify a suitable combination of support and operating condition that would yield best performance of the supported liquid membrane (SLM) in terms of fast and efficient transport of LS. The stability of the SLM was assessed in terms of loss of liquid from the pores of membrane support. The SLM is found to be stable till 10 h. Co-transport mechanism has been adopted in this work by using NaOH as the strip phase. It was observed that extraction of LS is increased with increase in concentration of NaOH up to a limiting value of 0.5 M NaOH. Difference of salt concentration between feed and strip phase considerably affect the separation process. The diffusional resistances of organic membrane (Δorg) and aqueous solution (Δaq) calculated from the permeation model, which is again a combination of three unique mechanisms viz., diffusion through a feed aqueous layer, a fast interfacial chemical reaction, and diffusion of carrier–complex through the organic membrane, are found to be 609.9 and 176.6 s cm⁻¹, respectively. The values of the diffusion coefficient in the membrane (D_org) and in the bulk organic phase (D_complex) are 1.67×10⁻⁹ and 6.68 × 10⁻⁸ m²s⁻¹, respectively. The extraction of LS is about 90%. Nearly 43% of LS can be recovered at optimum condition.     

Laser induced optoacoustic spectroscopy of benzil: Evaluation of structural volume change upon photoisomerization

The cis-skew to trans-planar photoisomerization of benzil in the photoexcited state was studied by laser-induced optoacoustic spectroscopy (LIOAS) in a series of normal alkane solvents at room temperature. The structural volume change due to the photoisomerization process has been estimated and compared with the same calculated from the optimized skew and trans structures. The magnitude of the structural volume change is estimated to be 22.9 ± 1.2 mL/mol. This study reveals that an expansion in volume occurs during the photoinduced isomerization process. In non-polar alkane solvents, the estimated volume change has been argued to be free from electrostrictional contribution.     

Simultaneous separation of mercury and lignosulfonate from aqueous solution using supported liquid membrane

This paper presents an experimental investigation on facilitated and simultaneous transport of mercury and lignosulfonate (LS) through a flat sheet supported liquid membrane (SLM) having Nylon 6,6 as support, trioctylamine (TOA) as carrier and dichloroethane as solvent. The experiments were performed at various operating conditions such as strip phase concentration, feed pH, carrier concentration and feed concentration to find the best set of parameters that would yield the maximum separation of pure mercury as well as its mixture with LS. The experiments were performed in co-transport mode using NaOH as the strip phase. It was observed that extraction of mercury as well as its mixture increases with increase in concentration of NaOH up to a certain limit 0.1 M NaOH in case of pure solution and 0.2 M NaOH in case of mixture). Feed phase pH significantly affects the mercury separation process. However, initial feed concentration does not affect the extraction process appreciably. Separation of mixture of mercury and LS behaves in a similar way as their pure solution; however the extraction is low in comparison to pure solution. The extraction of mercury from its pure solution is about 81% in 1 h. The extraction of mercury and LS from their mixture is about 52.6% and 50.2%, respectively at optimum condition and in a period of 2 h.     

Semi-invariants of binary forms and Sylvester’s theorem

The Ramanujan Journal - We obtain a combinatorial formula related to the shear transformation for semi-invariants of binary forms, which implies the classical characterization of semi-invariants in...