Synthesis,characterization, and adsorption behavior of aminophosphinic grafted on poly(styrene‐Co‐divinylbenzene) for divalent metal ions in aqueous solutions

In the present work, two novel aminophosphinic acid ligands grafted on poly(styrene‐1%divinylbenzene) (St‐1%DVB) have been synthesized by reacting polymer precursors bearing primary amino groups with benzaldehyde (or propionaldehyde) and phenylphosphinic acid by the “one‐pot” Kabatachnik‐Fields reaction. The resins functionalized with aminophosphinic pendant groups were characterized by means of Fourier transform infrared spectroscopy (FTIR), thermal analysis, energy dispersive X‐ray microanalysis (EDX), and Scanning electron microscopy (SEM) imaging. Its adsorption capacity for divalent metal ions such as Cu(II) and Ni(II) were investigated. The adsorption procedure of Cu(II) and Ni(II) ions on polymer‐grafted aminophosphinic acid ligands was carried out by batch experiments. The result also shows that the adsorption process was best described by a pseudo‐second‐order kinetic equation and by the Langmuir adsorption isotherm. The best maximum adsorption capacity was obtained for resin with aminobenzylphosphinic acid groups [1.46 mg Cu(II)/g and 1.36 mg Ni(II)/g]. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Removal of reactive dyes using organofunctionalized mesoporous silicas

Mesoporous inorganic–organic hybrids with mono- or bifunctional pendant chains anchored onto the silica backbones were investigated for reactive dye removal. The organofunctionalized silicas obtained from silylating agents contain the functional groups: 3-aminopropyl, octadecyldimethyl(silylpropyl)ammonium and 3-mercaptopropyl. The pendant electrophilic chains attached on the new porous silicas interact with the negative charge of industrial textile reactive dyes: yellow GR, red RB and blue RN. The best maximum sorption results were obtained for both mercapto and amino groups, to give 351, 388 and 203 mg g^?1 for GR, RN and RB dyes. These silicas also have the advantage of undergoing sorption without initial pH adjustment and surface saturation in short times. The high sorption capacity is due to the combination of properties associated with higher pore volume, surface area, smaller particle and the presence of two different functional groups, also emphasizing the presence of one mercapto group in the hybrid. These silicas, mainly the structurally bifunctional arrangement, with available disposition of pendant chains, are promising for textile effluent removal.     

Evaluation of ion exchange resins for recovery of metals from electroplating sludge

In the present study, the recovery of metal ions from industrial solid residues from a galvanoplasty industry (Rio de Janeiro, Brazil) was investigated by cationic and anionic ion exchange resins. The electroplating residues were composed of the metals Cu²⁺, Fe³⁺, Al³⁺, Ni²⁺, and Cr³⁺. The studies of sorption were conducted under batch and column conditions. Based on these studies, the sorption parameters and the breakthrough curves for both resins were determined. Studies of the sorption equilibrium and kinetics were also performed. The maximum sorption capacities q _e (mg g^?1) of the cationic resin were: Cu²⁺: 1.9, Fe³⁺: 0.6 and Al³⁺: 0.4. For the anionic resin, the maxim values of q _e were Cu²⁺: 0.4 and Fe³⁺: 0.1. The Freundlich model was more adequate to describe the ion exchange equilibrium and the sorption mechanism fit the pseudo second-order kinetic model for both resins. The breakpoint of Cu²⁺ (100 ppm) occurred after passing 1,860 and 2,220 cm³ of residue solution through 20.0 g of the resins (column with h:6.0 cm and d:4.3 cm, flow rate: 60 cm³ min^?1). The column regeneration was carried out for five sorption–desorption cycles using H₂SO₄ 2.4 mol L^?1 (cationic) and HCl 2.0 mol L^?1 (anionic).     

Identification of Cyclopropaneoctanoic Acid 2-Hexyl in Human Adipose Tissue and Serum

Fatty acids containing a cyclopropane ring in their structure (cyclopropane FA) have been found in a wide variety of bacteria, a number of protozoa, and Myriapoda. Little is known about cyclopropane FA in mammal, especially in human tissues. The present study deals with the identification of cyclopropane FA in adipose tissue and serum of humans and rats. Fatty acids extracted from the adipose tissue and serum obtained from obese women during bariatric surgery were methylated and analyzed on GC–MS. We have identified: cyclopropaneoctanoic acid 2-hexyl, cyclopropaneoctanoic acid 2-octyl, cyclopropanenonanoic acid, and 2-[[2-[(2-ethylcyclopropyl)methyl]cyclopropyl]methyl] acid in human adipose tissue. We confirmed the presence of cyclopropaneoctanoic acid 2-hexyl by derivatization of FA extracted from human adipose tissue to picolinyl esters. Cyclopropaneoctanoic acid 2-hexyl was the main cyclopropane FA (approximately 0.4 % of total fatty acids in human adipose tissue, and about 0.2 % of total fatty acids in the serum). In adipose tissue cyclopropaneoctanoic acid 2-hexyl was found mainly in triacylglycerols, whereas in serum in phospholipids and triacylglycerols. The cyclopropaneoctanoic acid 2-hexyl has also been found in serum, and adipose tissue of rats in amounts comparable to humans. The content of cyclopropaneoctanoic acid 2-hexyl decreased in adipose tissue of rats maintained on a restricted diet for 1 month. In conclusion, we demonstrated that cyclopropaneoctanoic acid 2-hexyl is present in human adipose tissue and serum. Adipose tissue cyclopropaneoctanoic acid 2-hexyl is stored mainly in triacylglycerols and the storage of this cyclopropane FA is affected by food restriction.     

Kinetic evaluation of phenol/aniline mixtures adsorption from aqueous solutions onto activated carbon and hypercrosslinked polymeric resin (MN200)

Kinetic adsorption of phenol and aniline from aqueous solution onto activated carbon and hypercrosslinked polymeric resin MN200 were evaluated in single and binary system. Larger phenol and aniline uptakes were observed for activated carbon in single as well as binary system, which can be attributed to the better physical properties of activated carbon, for instance larger surface area and micropore area. The kinetic experimental data was properly fitted by the pseudo-first and pseudo-second-order rate equations. A synergetic effect between solutes was observed since phenol and aniline sorption kinetic in binary system was faster than the individual sorption of each solute in single system, as well as a slight increase in the kinetic parameters obtained in binary system. The particle diffusion rate was defined as the rate limiting mechanism in the singles and binary system for phenol and aniline kinetic adsorption on both adsorbents. Two steps were markedly defined by the Weber and Morris intraparticle diffusion analysis for phenol and aniline onto both adsorbents. In binary systems, the intraparticle diffusion was influenced by the physical properties of adsorbents.     

Increased Serum Level of Cyclopropaneoctanoic Acid 2-Hexyl in Patients with Hypertriglyceridemia-Related Disorders

We recently reported the presence of various cyclopropane fatty acids—among them, cyclopropaneoctanoic acid 2‐hexyl—in the adipose tissue of obese women. The aim of this study was to verify whether the presence of cyclopropaneoctanoic acid 2‐hexyl in human serum was associated with obesity or chronic kidney disease (both being related to dyslipidemia), and to find potential associations between the serum level of this compound and specific markers of the these conditions. The serum concentration of cyclopropaneoctanoic acid 2‐hexyl was determined by gas chromatography–mass spectrometry (GC–MS) in non‐obese controls, obese patients, obese patients after a 3‐month low‐calorie diet, and individuals with chronic kidney disease. Obese patients and those with chronic kidney disease presented with higher serum levels of cyclopropaneoctanoic acid 2‐hexyl than controls. Switching obese individuals to a low‐calorie (low‐lipid) diet resulted in a reduction in this fatty acid concentration to the level observed in controls. Cyclopropaneoctanoic acid 2‐hexyl was also found in foods derived from animal fat. Serum concentrations of triacylglycerols in the analyzed groups followed a pattern similar to that for serum cyclopropaneoctanoic acid 2‐hexyl, and these variables were positively correlated with each other among the studied groups. Patients with hypertriglyceridemia‐related conditions presented with elevated serum levels of cyclopropaneoctanoic acid 2‐hexyl. Our findings suggest that its high serum level is related to high serum triacylglycerol concentrations rather than to body mass or BMI.     

Modeling and optimization of a high-pressure ethylene polymerization reactor using gPROMS

A gPROMS implementation of a comprehensive steady-state model of the high-pressure polymerization of ethylene in a tubular reactor is presented. Model outputs along the reactor length include the complete molecular weight distribution and branching indexes, as well as monomer conversion, average molecular weights, reactants’ compositions, and reactor temperature and pressure. A detailed calculation of physical and transport properties, such as the reaction mixture density, heat-transfer capacity, viscosity and global heat-transfer coefficient is also included. The reactor model is included in an optimization framework that is used to determine the best operating conditions for producing a polymer with tailor-made molecular structure in terms of the complete molecular weight distribution, branching and polydispersity.     

Helikauranoside A, a New Bioactive Diterpene

A new ent-kaurane glucoside, named helikauranoside A (4), was isolated from the aerial parts of Helianthus annuus L. together with three known ent-kaurane-type diterpenoids: (−)-kaur-16-en-19-oic acid (1), grandifloric acid (2), and paniculoside IV (3). The structure of 4 was determined by using a combination of 1D (¹H-NMR and ¹³C-NMR) and 2D (COSY, HSQC, and HMBC) NMR techniques. Bioactivity spectra of isolated compounds were tested by using the etiolated wheat coleoptile bioassay in aqueous solutions at concentrations ranging from 10⁻³ to 10⁻⁶M. Helikauranoside A (4) was the most active (−84%, 10⁻³M; −56%, 10⁻⁴M). These results suggest that this new compound may be involved in defense mechanisms of H. annuus.     

Study of the anticorrosive behaviour of epoxy binders containing non-toxic inorganic corrosion inhibitor pigments

The anticorrosive performance of epoxy coatings pigmented with non-toxic corrosion inhibitors pigments was investigated in this work. The coatings used contained the following pigments: zinc phosphate (ZP), zinc phosphomolybdate (ZPM) and zinc calcium phosphomolybdate (ZCPM). For comparative studies epoxy coatings with the following compositions were made up: one only with filler (CRG); one without pigments, varnish (VR) and other with zinc chromate (ZC) pigment. The corrosion inhibitor performance of the coatings was evaluated by immersion tests in 0.01 mol L⁻¹ NaCl aqueous solutions and accelerated tests in a salt spray chamber. The corrosion inhibitor performance of the samples was monitored using open-circuit potential (E_oc) measurements and electrochemical impedance spectroscopy (EIS) technique. Complementary tests were carried out using water vapour permeability of free-standing films and thermogravimetric (TG) analysis. The permeability test showed that the addition of the studied pigments did not modify the barrier properties of the free-films in comparison that pigmented with chromate. Thermal analysis indicated that the addition of the pigments improved the thermal stability of the coatings and it suggested a resin/pigment interaction. The total immersion tests and salt spray tests demonstrated that the barrier properties of the coatings pigmented with the inhibitors were not degrading as much as that pigmented with ZC. Therefore, all the three pigments could replace ZC as an anticorrosive pigment in similar conditions to those described here. The best corrosion inhibitor performance in the total immersion test was presented by the ZPM and ZCPM coatings while in the salt spray test the corrosion inhibitor performance of all the three pigmented coatings was similar, suggesting that only in the less aggressive test is possible to detect any difference between the coatings with the non-toxic pigments.     

Controlled degradation and crosslinking of polypropylene induced by gamma radiation and acetylene

Isotactic polypropylene (iPP) undergoes crosslinking and extensive main chain scissions when submitted to irradiation. The simultaneous irradiation of PP and acetylene is able to control chain scission and produce grafting. The grafted PP further reacts with PP radicals resulting in branching and crosslinking. In this work, commercial polypropylenes (iPP) of different molecular weights were irradiated with a ⁶⁰Co source at dose of 12.5 kGy in the presence of acetylene in order to promote the crosslinking. The mechanical and rheological tests showed a significant increase in melt strength and drawability of the modified samples obtained from resins with high melt flow index. The characterization of the molecular modifications induced by gamma irradiation of isotactic polypropylenes under acetylene atmosphere proved the existence of branching, crosslinking and chain scission in a qualitative way. The G′ and G″ indicated the presence of LCB in all samples. Therefore, PP irradiation under acetylene was proved to be an effective approach to achieve high melt strength polypropylene (HMSPP).