Synthesis of AB and ABA block copolymers as compatibilizers in nylon 6/polycarbonate blends

Nylon 6 (Ny6) and Bisphenol A polycarbonate (PC) are immiscible and form biphasic blends. To improve the compatibility of Ny6 and PC several ABA and AB Ny6/PC block copolymers were synthesized, and their compatibilizing behavior on the blends were tested. Block copolymers were prepared by reacting monoamino- or diamino-terminated Ny6 homopolymers with high molecular weight PC at 130°C in anhydrous DMSO. The reaction of diamino- and monoamino-terminated Ny6 with polycarbonate produces block copolymers of the type PC-Ny6-PC (ABA) and PC-Ny6 (AB), respectively, plus a certain amount of unconverted PC degradated to lower molecular weights. To separate the block copolymer from the unconverted PC, a selective fractionation with tetrahydrofuran (THF) and trifluoroethanol (TFE) was carried out. Three different fractions were obtained: THF-soluble fraction, TFE-soluble fraction, and the TFE-insoluble fraction. The scanning electron microscopy (SEM) analysis of a 75/25 (wt/wt) Ny6/PC blend added with 2% of ABA or AB block copolymers, showed the presence of smaller PC particles more adherent to the polyamide matrix, with respect to the same blend nonadded, which is clearly biphasic. The size of the PC particles decreases from ABA to AB compatibilized blends and the adhesion with the matrix is increases in the same way. © 1996 John Wiley & Sons, Inc.     

Practical aspects of chemometrics for oil spill fingerprinting

Tiered approaches for oil spill fingerprinting have evolved rapidly since the 1990s. Chemometrics provides a large number of tools for pattern recognition, calibration and classification that can increase the speed and the objectivity of the analysis and allow for more extensive use of the available data in this field. However, although the chemometric literature is extensive, it does not focus on practical issues that are relevant to oil spill fingerprinting. The aim of this review is to provide a framework for the use of chemometric approaches in tiered oil spill fingerprinting and to provide clear-cut practical details and experiences that can be used by the forensic chemist. The framework is based on methods for initial screening, which include classification of samples into oil type, detection of non matches and of weathering state, and detailed oil spill fingerprinting, in which a more rigorous matching of an oil spill sample to suspected source oils is obtained. This review is intended as a tutorial, and is based on two examples of initial screening using respectively gas chromatography with flame ionization detection and fluorescence spectroscopy; and two of detailed oil spill fingerprinting where gas chromatography-mass spectrometry data are analyzed according to two approaches: The first relying on sections of processed chromatograms and the second on diagnostic ratios.     

Use of 2,2-dimethoxypropane for the direct gas chromatographic-mass spectrometric determination of some organic compounds in water

The well known reaction between 2,2-dimethoxypropane and water allows for the conversion of an aqueous into an organic solution ready to be injected directly into a gas chromatographic-mass spectrometric (GC-MS) system. Only time, temperature and water/ketal ratio were the parameters studied among those which influence the equilibrium reaction. The reaction environment is not suitable for all compounds: acids, esters, alcohols, amines, ketones and phenols may react with methanol, acetone and ketal owing to Amberlyst being present as catalyst. This method is proposed for the GC-MS analysis of aqueous solutions containing hydrocarbons, halogenated hydrocarbons and ethers. The determination of some pesticides in water is reported.     

Syntheses of polysubstituted pyrroles and of 2,3-disubstituted quinoxalines and substituted benzo[g]quinoxalines

Tetraacetylethylene ( 1 ), and cis-diacetylethylene ( 4 ) reacted under mild conditions with 3-amino-2-butenoic acid methyl ester ( 6 ), benzene-1,2-diamine and naphthalene-2,3-diamine to give polysubstituted pyrroles, 2,3-disubstituted quinoxalines and 2,3-disubstituted benzo[g]quinoxalines respectively. Some aspects of the reactions mechanisms are discussed.     

A new apparatus for the extraction of organic compounds from aqueous solutions

A new apparatus for the extraction of organic compounds from sea water is described. With this apparatus it is possible to extract 54 standard compounds with high recovery percentages from 9 1 of sea water with 3 ml ofn-hexane. The analysis time (about 1 h) is appreciably lower than those of the extraction methods based on RP-18 and Carbopack-B adsorption (about 15 h). Furthermore, it is possible to analyze samples without filtration. An application of this method to the analysis of Tirreno sea water is reported.     

1,2-fused pyrimidines. V. Synthesis of 1-alkyl or phenyl-2H-dipyrido-[1,2-a:2′,3′-d]pyrimidine-2,5(1H)-diones

The reaction of 2-[(N-acyl, N-alkyl or phenyl)amino]-4H-pyrido[1,2-a]pyrimidin-4-ones 8a-g with the N,N-dimethylformamide/phosphorus oxychloride Vilsmeier reagent 1 (95°, 90 minutes) afforded 1-alkyl or phenyl-2H-dipyrido[1,2-a:2′,3′-d]pyrimidine-2,5(1H)^?diones, 3-alkyl substituted or not, 10a-g . The starting compounds 8 were prepared by treating 2-amino-4H-pyrido[1,2-a]pyrimidin-4-ones N-alkyl substituted 7a,b or N-phenyl substituted 4 with excess anhydrides (130°, 7 hours) when the 2-(alkylamino) derivatives 7 were used in the reaction, compounds 8 were obtained along with very small amounts of 3-acyl-2-(alkylamino)-4H-pyrido[1,2-a]pyrimidin-4-ones 9 .     

4,5-Dihydroisoxazole and 4,5-dihydro-1,2,4-oxadiazole derivatives from cycloaddition reactions of nitrile oxides to alkyl N-(diphenylmethylene)-α,β-dehydroamino acids

The alkyl N-(diphenylmethylene)-α,β-dehydroamino acids 1 have been submitted to 1,3-dipolar cycloadditions with nitrile oxides. The reactivity of these compounds depends on the type and on the stereochemistry of the β-substituents. With the unsubstituted terms 1a,b the reaction occurs on the C,C double bond, providing a good method for the synthesis of the 4,5-dihydroisoxazole derivatives 3a,b,c and for the gem-functionalized 4,5-dihydroisoxazoles amino carboxylic ester 5. The β-substituted compounds 1c,d,e , inert to 1,1-dimethylethylnitrile oxide, undergo the reaction to the N,C double bond, thus giving with 2a,b the 4,5-dihydro-1,2,4-oxadiazole derivatives 4. All the reactions occur with high site- and regioselectivity.     

Chemical Composition of Volatile Compounds in Apis mellifera Propolis from the Northeast Region of Pará State,Brazil

Propolis is a balsamic product obtained from vegetable resins by exotic Africanized bees Apis mellifera L., transported and processed by them, originating from the activity that explores and maintains these individuals. Because of its vegetable and natural origins, propolis is a complex mixture of different compound classes; among them are the volatile compounds present in the aroma. In this sense, in the present study we evaluated the volatile fraction of propolis present in the aroma obtained by distillation and simultaneous extraction, and its chemical composition was determined using coupled gas chromatography, mass spectrometry, and flame ionization detection. The majority of compounds were sesquiterpene and hydrocarbons, comprising 8.2–22.19% α-copaene and 6.2–21.7% β-caryophyllene, with additional compounds identified in greater concentrations. Multivariate analysis showed that samples collected from one region may have different chemical compositions, which may be related to the location of the resin’s production. This may be related to other bee products.     

Tuning the properties of a black TiO2-Ag visible light photocatalyst produced by a rapid one-pot chemical reduction

A highly efficient black TiO₂-Ag photocatalytic nanocomposite, active under both UV and visible light illumination, was synthesized by decorating the surface of 25 nm TiO₂ particles with Ag nanoparticles. The material was obtained via a rapid, one-pot, simple (surfactant and complexing agent free) chemical reduction method using silver nitrate and formaldehyde as a metal salt and reducing agent, respectively. The nanocomposite shows an increase of over 800% in the rate of photocatalytic methylene blue dye degradation, compared to commercial unmodified TiO_2, under UV-VIS illumination. Unlike pure TiO₂, the nanocomposite exhibits visible light activation, with a corresponding drop in optical reflectance from 100% to less than 10%. The photocatalytic properties were shown to be strongly enhanced by post-reduction annealing heat treatments in air, which were observed to decrease, rather than coarsen, silver particle size, and increase particle distribution. This, accompanied by a variation in the silver surface oxidation states, appear to dramatically affect the photocatalytic efficiency under both UV and visible light. This highly active photocatalyst could have wide ranging applications in water and air pollution remediation and solar fuel production.