Traces of antibiotics within domestic and industrial effluents have toxic impact on human health as well as surrounding flora and fauna. Potential increase in antibiotic resistance of microorganisms is likely to rise due to the incomplete removal of antibiotics by traditional wastewater processing, methods such as membrane filtration and biological treatment. In this study, we investigated a novel class of material termed polymer of intrinsic Microporosity (piM) that is based on amorphous microporous organic materials for the application of antibiotic removal form aqueous environments. the adsorption of four commonly used antibiotics (doxycycline, ciprofloxacin, penicillin G, and amoxicillin) was evaluated and found that at least 80% of the initial concentrations was eliminated under the optimized conditions. Langmuir and freundlich models were then employed to correlate the equilibria data; the Freundlich model fit well the data in all cases. For kinetic data, pseudo-first and second order models were examined. Pseudo-second order model fit well the kinetic data and allowed the calculation of the adsorption rate constants. thermodynamic parameters were obtained by conducting the adsorption studies at varied reaction temperatures. Surface potential, adsorption at various solution pHs, thermogravimetric analysis (TGA), Infrared spectroscopy (IR), and surface area experiments were conducted to draw possible adsorption mechanisms. The removal of antibiotics from water by PIM-1 is likely to be governed by both surface and pore-filling adsorption and could be facilitated by electrostatic interactions between the aromatic rings and charged functional groups as well as hydrogen bond formation between the adsorbent and adsorbate. Our work shows that the application of such novel microporous material could contribute to the removal of such challenging and persistent contaminants from wastewater with further optimizations of large-scale adsorption processes. Antibiotics are chemical compounds with a wide spectrum of applications in humans and veterinary medicine 1. They are used for treatment of diseases caused by various bacterial infections in addition to their wide usage in animal farming and aquaculture activity for disease prevention and growth promotion purposes 2-4. For example, the yearly consumption of antibiotics was estimated to be 162,000 tons for China 5 , 13,000 tons for United Sates 5 , and, 10,000 tons for European countries 5. Significant portions of the administered doses (30-90%) are excreted unmetabolized as active forms 6,7. These active antibiotic residues are found in the environment (surface water, ground water, and soil) as a result of runoff of domestic, agricultural, and industrial effluents 8. Some of the commonly used antibiotics were found to be persistent with long half-lives. Thus, they potentially pose adverse effects to water quality and aquatic life 9,10. Widespread use of antibiotics alters microbial ecosystems and exerts selective pressure on susceptible bacteria and lead to the surviva...
The polymer of intrinsic microporosity PIM-1 was modified by reaction with ethanolamine and with diethanolamine, and the modified polymers characterized by infrared spectroscopy, solid-state NMR spectroscopy, elemental analysis, thermogravimetric analysis and nitrogen adsorption. Various possible reaction products were considered, and the results indicated that hydroxyalkylaminoalkylamide structures were obtained. Gas adsorption measurements showed that ethanolamine modification increased the ideal CO 2 /N 2 selectivity. Studies of dye adsorption from aqueous solution demonstrated that the reaction products showed strong selectivity for the anionic dye Orange II, compared to the cationic dye Safranin O. Mass uptakes of the anionic dye by ethanolamine-modified PIM-1 samples were up to 2 orders of magnitude higher than for the parent polymer.
Three β-triketimine ligands, (L(1): [CH{CMeN(2,4,6-Me3-C6H2)}2C(CMe3N(2-MeO-C6H4)], L(2): [CH{CMeN(2,4-Me2-C6H3)}2C(CMe3N(2-MeO-C6H4)] and L(3): [CH{CMeN(2-Me-C6H4)}2C(CMe3N(2-MeO-C6H4)]), were synthesized and then characterized by (1)H and (13)C{(1)H} NMR spectroscopy, elemental analysis and electrospray (ES) MS. β-triketimine cobalt(ii) complexes were then prepared by the interaction of cobalt(ii) bromide with L(1-3) in the presence of NaBArF (BArF = [{3,5-(CF3)2-C6H3}4B](-) ). Five-coordinate dimeric bromide-bridged species [(LCoμ-Br)2][BArF]2 were obtained. The geometry of the complexes was found by single-crystal X-ray diffraction to be slightly distorted square-pyramidal. The polymerization of 1,3-butadiene catalysed by these complexes upon activation with methylaluminoxane (MAO) in chlorobenzene yielded high cis-1,4-polybutadiene (>97% cis). The effect of steric and electronic properties of the ligands on the performance of the catalytic system was investigated: it was found that ligands with fewer methyl substituents gave more active catalytic systems. It was also found that increasing MAO: Co ratio resulted in higher activity. Stereoselectivity of all catalysts slightly decreased at higher temperature, whereas activities were maximised at 20 °C, where very high values of activity were recorded.
Four new b-triketimine cobalt complexes [(LCo-m-Br) 2 ][BArF] 2 where L ¼ N,N 0 ,N 00 -triaryl-b-diketimine were synthesised and then characterized by single-crystal X-ray diffraction, MALDI-MS and elemental analysis. In combination with three previously reported, they provided a series of seven subtly different complexes which were screened for activity in the catalysis of isoprene polymerization: the structure of the ligand (L) had strong effects on activity and stereoselectivity. The produced polyisoprene contained a mixture of cis-1,4, trans-1,4 and 3,4-enchained monomers; 4,1-errors followed 3,4 errors. The highest percentage of cis-1,4 content (80%) was obtained with complex 5 where two electron-withdrawing fluorine substituents occupied the 2-and 6-positions of two of the imino-aryl rings. This polymer was obtained in 98.5%conversion. Both cis-1,4 content and activity decreased when electron donor substituents were present on the aryl rings, so that complex 1, with three methyl substituents in positions 2, 4 and 6 gave the lowest cis-1,4 content (73.6%), with a conversion of only 58.5%, under identical conditions. The temperature of the polymerization, the type of aluminium co-catalyst used, and the Al/Co ratio strongly affected the activity and microstructure of the polyisoprene produced. Ethylaluminiumsesquichloride was the most active of a range of organoaluminiums screened. A kinetic study using complex 6 as catalyst demonstrated that the polymerization was first-order in monomer, and that approximately 12% of cobalt formed active centers. The combination of high molecular weight (>10 5 ) with moderately high activity at conveniently accessible temperatures to give predominantly cis-1,4-polyisoprene but with 3,4 units to promote efficient crosslinking is potentially attractive, and has not previously been attained with 3d elements.
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