13‐Phenyltridec‐9‐enoic and 15‐phenylpentadec‐9‐enoic acids in Arum maculatum seed oil

The seed oil of Arum maculatum has been found to contain 13‐phenyltridec‐9‐enoic (0.4%) and 15‐phenyl‐pentadec‐9‐enoic (1%) acids, detected by gas chromatographymass spectrometry of the picolinyl ester and related derivatives.     

Mid‐chain grafting in PVB‐graft‐PVB

The polymer commonly referred to as poly(vinyl butyral) is actually the statistical terpolymer poly(vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate), the main component of the polymeric interlayer in automotive and architectural safety glass, amongst other uses. Here, the effects of ‘self‐grafting’ or ‘auto‐grafting’ in this polymer are examined using size‐exclusion chromatography (SEC) with triple detection. These and supporting experiments (eg, batch‐mode multi‐angle light scattering) allow study of the effects of induced branching in the resultant PVB‐graft‐PVB molecule, and comparison with the ungrafted (though not linear) base polymer. This was done by application and extension of the classic Zimm–Stockmayer long‐chain branching (LCB) theory, by determination of the fractal dimension (d_f) of the polymers and of the change in d_f as a function of molar mass, as well as by the multiplicity of size parameters that are measured in a multi‐detector SEC experiment. Copyright © 2004 Society of Chemical Industry     

Analysis of Polar Precursors of 1,3,5,7‐Tetranitro‐1,3,5,7‐tetrazocine (HMX) Using Hydrophilic Interaction Chromatography

Octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) is currently one of the most widely used explosives. 1,3,5,7‐Tetraacetyl‐1,3,5,7‐tetraazacyclooctane (TAT) is an attractive precursor for the synthesis of HMX; the nitration of this key precursor results in both high yield and purity under mild condition. TAT can be prepared either by acetylation of 2,6‐diacetyl‐pentamethylenetetramine (DAPT) or by the condensation of ACN and 1,3,5‐trioxane. However, TAT and DAPT are polar compounds, and are difficult to analyze using reverse phase liquid chromatography. Herein, a chromatography method for the direct separation of these polar compounds was developed using hydrophilic interaction chromatography (HILIC) using a Venusil HILIC column, with ACN/water (95/5, v/v) as the mobile phase. The chromatographic analysis and identification of these polar compounds provide valuable information for the optimization of the synthetic process of TAT.     

Selective Extraction of N‐Heterocyclic Precursors of 1,3,5,7‐Tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) Using Molecularly Imprinted Polymers

N‐heterocyclic compounds are key nitration precursors for some high energy density explosives such as 1,3,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX). Nitration of 1,3,5,7‐tetraacetyl‐1,3,5,7‐tetraazacyclooctane (TAT) yields HMX in high yields and purity. However, the analogue 1,3,5‐triacetyl‐1,3,5‐triazacyclohexane (TRAT) is easily co‐produced via the condensation of acetonitrile and 1,3,5‐trioxan. To selectively extract TAT from a mixture of TAT and TRAT, the molecular imprinting technology (MIT) was developed in this study. The capacity of the dry polymer is 16 mg g⁻¹ and the recovery surpasses 75 %.     

Characterization of macroporous 1‐vinyl‐2‐pyrrolidone copolymers obtained by suspension polymerization

Radical suspension copolymerization of 1‐vinyl‐2‐pyrrolidone (VP) with three different cross‐linkers: divinylbenzene (DVB), trimethylolpropane trimethacrylate (TRIM), and di(methacryloxymethyl) naphthalene (DMN) was used to prepare macroporous microspheres. During the copolymerization, the mixture of toluene and n‐dodecane as a pore‐forming diluent was used. All samples were characterized in terms of particle size and distribution, nitrogen content, specific surface area total pore volume, and pore size distribution. It was found that specific surface area of the obtained beads is strongly dependent on the diluent system and the type of cross‐linker and achieves value from 27 to 845 m²/g. To determine the influence of chemical structure of cross‐linkers on the selectivity and polarity of the copolymers, inverse gas chromatography was applied. In addition, VP–DVB and VP–DMN copolymers were modified by sulfonation into cation‐exchangers with cation exchange capacity equal 1.98 and 2.31 mmol/g, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Bis‐methylene‐interrupted octadecadienoic fatty acids in Bulgarian bovine butter fats

Preparative silver nitrate thin‐layer chromatography of fatty acid methyl esters and gas chromatography‐mass spectrometry of 4,4‐dimethyloxazoline derivatives were applied in combination to analyze the cis,cis octadecadienoic (18:2) fraction in commercial samples of bovine butter fat in Bulgaria. The main component, 9,12–18:2 was accompanied by a series of bis‐methylene‐interrupted isomers, cis,cis‐5,9‐; 6,10‐; 9,13‐ and 11,15–18:2, which were unambiguously identified by their specific mass spectra. The latter are characterized by the presence of very intensive diagnostic fragments which help to correctly locate the position of the double bond system in the carbon chain. The cis,cis‐5,9–18:2 isomer was found for the first time in butter fat, and the 6,10–18:2 isomer has not been described as yet.     

A comprehensive study on the size exclusion chromatography of kappa‐carrageenan for the identification of after‐peaks

Aqueous size exclusion chromatography (SEC) of polysaccharides in general and carrageenans in particular is complicated by a number of factors. The chromatograms of carrageenans which are sulfated anionic natural polymers contain a number of after‐peaks depending on the occlusion, adsorption, or association of various ionic species either naturally present or evolved during their processing. A systematic SEC analysis of after‐peaks appearing in the chromatograms was made to identify the species responsible for their formation. The five after‐peaks constantly appearing in the aqueous (0.1M NaNO₃) SEC of kappa‐carrageenan are attributed to sulfate, chloride, and nitrate anions whereas the first three and the fourth are due to divalent cations, mostly, and the fifth appears to result from the unknown impurities. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of biodegradable block copolymer pluronic‐b‐poly(L‐lysine)

This study presented the investigations on the synthesis of a novel biodegradable block copolymer of pluronic‐b‐poly(L ‐lysine) (pluronic‐b‐PLL), which combined the characteristics of aliphatic polyester and poly(amino acids). The synthesis work started with end‐capping of pluronic with N‐t‐butoxycarbonyl‐L ‐phenylalanine using dicyclohexylcarbodiimide in the presence of 4‐dimethylaminopyridine, followed by a deprotection process to obtain the amino‐terminated pluronic; the new primary amino group in the modified pluronic initiated ring‐opening polymerization of amino acid N‐carboxyanhydride, which afforded the pluronic‐b‐poly(N^ε‐(Z)‐L ‐lysine) block copolymer. Finally, removal of the side‐chain N^ε‐(carbonybenzoxy) end protecting groups yields the block copolymer of pluronic‐b‐PLL. The products were characterized by ¹H‐NMR, FTIR, DSC, and GPC. The block copolymer micelle containing the anticancer drug paclitaxel was prepared by the double emulsion method. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Surface DEAE groups facilitate protein transport on polymer chains in DEAE‐modified‐and‐DEAE‐dextran‐grafted resins

Sepharose FF was modified with diethylaminoethyl‐dextran (DEAE‐dextran, DexD) and/or DEAE (D) to fabricate three types of ion exchangers FF‐DexD (grafting‐ligand resin), FF‐D (surface‐ligand resin), and FF‐D‐DexD (mixed‐ligand resin), for protein adsorption equilibria and kinetics study. It was found that both adsorption capacity and uptake rate (effective diffusivity, D_e) were significantly enhanced by grafting DEAE‐dextran. Notably, the D_e values on FF‐DexD and FF‐D‐DexD (D_e/D₀ > 1.4) were six times greater than those on FF‐D (D_e/D₀ < 0.3). More importantly, the increase of surface‐ligand density greatly enhanced uptake kinetics on FF‐D‐DexD. The results indicate that the surface ligands assisted the transport of bound proteins on polymer chains in the mixed‐ligand resins. That is, surface ligands worked as “transfer stations” between two neighboring chains, resulting in enhanced transport of bound proteins on chains. The research thus disclosed the unique role of surface ligands in facilitating protein uptake kinetics onto polymer‐grafted ion‐exchangers. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3812–3819, 2016     

Determination of crystallinity ratio and some physicochemical properties of poly(4‐methyl‐1‐pentene)

It was determined that the thermal stability of poly(4‐methyl‐1‐pentene) (P4MP) was maintained up to 424°C in an inert atmosphere by thermogravimetric analysis. The retention diagrams of ethyl acetate, tert‐butyl acetate, and benzene on P4MP were plotted at temperatures between 30 and 280°C by inverse gas chromatography (IGC) technique. Melting temperature of the polymer was determined as 230 and 239.5°C by IGC and differential scanning calorimetry (DSC), respectively. The percent crystallinity of P4MP was obtained from the retention diagrams at temperatures below melting point. The percent crystallinity obtained by IGC is in good agreement with the ones obtained by DSC. Then, specific retention volume, V, weight fraction activity coefficient, Ω, Flory‐Huggins polymer‐solvent interaction parameter, χ, equation‐of‐state polymer‐solvent interaction parameter, χ, and effective exchange energy parameter, X_eff of octane, nonane, decane, undecane, dodecane, tridecane, n‐butyl acetate, isobutyl acetate, isoamyl acetate with P4MP, were determined between 240 and 280°C by IGC. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of novel aromatic polyamides derived from 2,2′‐bis(p‐phenoxyphenyl)‐4, 4′‐diaminodiphenyl ether

BACKGROUND: Wholly aromatic polyamides (aramids) are high‐performance polymeric materials with outstanding heat resistance and excellent chemical stabilities due to chain stiffness and intermolecular hydrogen bonding of amide groups. Synthesis of structurally well‐designed monomers is an effective strategy to prepare modified forms of these aramids to overcome lack of organo‐solubility and processability limitations. RESULTS: A novel class of wholly aromatic polyamides was prepared from a new diamine, namely 2,2′‐bis(p‐phenoxyphenyl)‐4,4′‐diaminodiphenyl ether (PPAPE), and two simple aromatic dicarboxylic acids. Two reference polyamides were also prepared by reacting 4,4′‐diaminodiphenyl ether with the same comonomers under similar conditions. M?_w and M?_n of the resultant polymers were 8.0 × 10⁴ and 5.5 × 10⁴ g mol^?1, respectively. Polymers resulting from PPAPE exhibited a nearly amorphous nature. These polyamides exhibited excellent organo‐solubility in a variety of polar solvents and possessed glass transition temperatures up to 200 °C. The 10% weight loss temperatures of these polymers were found to be up to 500 °C under a nitrogen atmosphere. The polymers obtained from PPAPE could be cast into transparent and flexible films from N,N‐dimethylacetamide solution. CONCLUSION: The results obtained show that the new PPAPE diamine can be considered as a good monomer to enhance the processability of its resultant aromatic polyamides while maintaining their high thermal stability. The observed characteristics of the polyamides obtained make them promising high‐performance polymeric materials. Copyright © 2009 Society of Chemical Industry     

Large‐scale isolation and purification of C‐phycocyanin from the cyanobacteria Anabaena marina using expanded bed adsorption chromatography

BACKGROUND: Phycobiliproteins are water soluble proteins useful as fluorescent markers of cells and macromolecules, and as natural colorants, and are anticarcinogenic. Although phycobiliproteins have many applications, their use is limited by the high cost of the purified macromolecules, mainly related with the cost of extraction and purification. In this study a fast and scalable method for preparative extraction and purification of C‐phycocyanin (C‐PC) from Anabaena marina is developed. RESULTS: The method developed consists in the extraction of phycobiliproteins using repeated single contact strategy, separation being performed by expanded bed adsorption (EBA) chromatography using Streamline‐DEAE. Optimal conditions for EBA were obtained at small scale, using a 15 mm internal diameter column, these being a sample load of 0.9 mg C‐PC mL^?1 adsorbent, an expanded bed volume twice the settled bed volume and a sample viscosity of 1.109 mP. The process was then scaled up 36 times, the success of the scale‐up process being verified. Finally, to obtain pure C‐PC conventional ion‐exchange chromatography was utilized. CONCLUSION: Small diameter columns was shown to be useful to simulate the behavior of larger diameter columns for use in scaled up systems. Expanded bed adsorption was demonstrated to be a scalable technology allowing large quantities of C‐PC to be obtained, maintaining high protein recovery while reducing both processing cost and time. The proposed methodology allows recovery of more than 62% of the C‐PC contained in the biomass in the form of pure C‐PC concentrates. Copyright © 2010 Society of Chemical Industry     

Characterization of 4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine

4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine (DANT) was prepared with a 35 % yield from cyanuric chloride in a three step process. DANT was characterized by IR and NMR spectroscopy (¹H, ¹³C, ¹⁵N), single‐crystal X‐ray diffraction, and DTA. The crystal density of DANT is 1.849 g cm⁻³. The cyclization of one azido group and one nitrogen atom of the triazine group giving tetrazole was observed for DANT in a dimethyl sulfoxide solution using NMR spectroscopy. An equilibrium exists between the original DANT molecule and its cyclic form at a ratio of 7 : 3. The sensitivity of DANT to impact is between that for PETN and RDX, sensitivity to friction is between that for lead azide and PETN, and sensitivity to electric discharge is about the same as for PETN. DANT′s heat of combustion is 2060 kJ mol⁻¹.     

Quantitative Determination of Natural Glycolipids from Oil Seed by Automated High‐Performance Thin‐Layer Chromatography (HPTLC)

The role of glycolipids in vegetable oil refining and production of bio‐based fuels has not been disclosed so far. Such investigations required a reliable and reproducible quantitative determination of these compounds. Fundamental data were therefore established on the quantitative determination of glycolipids in vegetable oil gums by means of high‐performance thin‐layer chromatography (HPTLC). Concentrating on five abundant natural glycolipid classes found in these oils, identification of a suitable separation method for the employed glycolipid mixture and those parameters relevant for successful detection were considered in detail. The special importance of sample volume when employing quantitative HPTLC was discussed. Acetone/chloroform/water 6:3:0.4 (v/v/v) was identified as a convenient mobile phase for the investigated issue. A derivatization reagent comprising methanol, copper(II)sulfate pentahydrate, sulfuric acid 98 %, and phosphoric acid 85 % was identified. Subsequent heating at 135 °C for 10 min finished the derivatization and enabled detection at λ = 370 nm. Calibration curves ranging from 1500 to 31.25 ng/mL, regarding both peak area and peak height, were determined. The good correlation of parameters enabled the application of the method to real oil gum samples from sunflower and soybean oil. This revealed that digalactosyldiglycerides in combination with either sterylglucosides or acylated sterylglucosides represented the major glycolipid classes in these oils.     

Lecithin‐enhanced biotransformation of cholesterol to androsta‐1,4‐diene‐3,17‐dione and androsta‐4‐ene‐3,17‐dione

A biotransformation process using Mycobacterium sp was studied for androsta‐1, 4‐diene‐3,17‐dione (ADD) and androsta‐4‐ene‐3,17‐dione (AD) production from cholesterol. Cholesterol has a poor solubility in water (～1.8 mg dm^?3 at 25 °C), which makes it difficult to use as the substrate for biotransformation. Lecithin is a mixture of phospholipids of phosphatidylcholine (PC) and phosphatidylethanolamine (PE), which behave like surfactants and can form planar bi‐layer structures in an aqueous medium. Therefore, a small amount of lecithin (<1 g dm^?3) can be used to form stable colloids with cholesterol at a relatively high concentration (20 g dm^?3) in water. In this work, an energy density of 1000 J cm^?3 from sonication was provided to overcome the self‐association of cholesterol and to generate a stable lecithin–cholesterol suspension that could be used for enhanced biotransformation. The lecithin–cholesterol suspension was stable and could withstand typical autoclaving conditions (121 °C, 15 psig, 20 min). In contrast to conventional surfactants, such as Tween 80, that are commonly used to help solubilize cholesterol, lecithin did not change the surface tension of the aqueous solution nor cause any significant foaming problem. Lecithin was also biocompatible and showed no adverse effect on cell growth. Compared with the medium with Tween 80 as the cholesterol‐solubilizing agent, lecithin greatly improved the biotransformation process in regard to its final product yield (～59% w/w), productivity (0.127–0.346 g dm^?3 day^?1), ADD/AD ratio (6.7–8), as well as the long‐term process stability. Cells can be reused in repeated batch fermentations for up to seven consecutive batches, but then lose their bioactivity due to aging problems, possibly caused by product inhibition and nutrient depletion. © 2002 Society of Chemical Industry     

Characterization and thermal properties of poly(n‐butyl acrylate‐g‐styrene) graft copolymers

Poly(butyl acrylate‐g‐styrene) graft copolymers were prepared by free‐radical polymerization using a polystyrene macromonomer carrying a methacryloyloxy group at the chain end and they were characterized by size‐exclusion chromatography, and Fourier transform infrared spectroscopy. Glass transition temperatures and degradation behavior were determined by thermal analysis. Only a single glass transition temperature was observed for the resulting graft copolymers, indicating the miscibility between the poly(styrene) phase and poly(butyl acrylate) (pBA) phase in the graft copolymer. The incorporation of polystyrene segments in the graft copolymer improved the thermal stability of pBA and enhanced the apparent activation energy for the thermal degradation of pBA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 783–789, 2001