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The current effort in environmental remediation is aimed at removing iodine-131 radionuclide from radioactive liquid waste produced by an Egyptian nuclear power plant using some synthesised alginate derivatives. Two different copolymers, namely sodium alginate poly (acrylic acid) (P1) and sodium alginate poly (acrylic acid-methacrylic acid) (P2), are prepared using gamma radiation. The ability of these polymers to remove 131I radionuclide as sorbents has been investigated. The synthesised polymers exhibit excellent adsorption performance for 131I ions, and the adsorption equilibrium requires only 30 min, which reveals that the sorption process is kinetically faster than most of the other materials reported previously. The removal percents for 131I radionuclide at a pH of 3.0 at room temperature on P1 and P2 are 77.7% and 84.2%, respectively. The sorption capacities of the two polymers demonstrate that P2 > P1, with capacities of 67.9 and 58.5 mg/g, respectively. Four linear kinetic models are investigated: pseudo-first order, pseudo-second order, Elovich, and Weber-Morris models. Regarding their calculated parameters, these models indicate that the adsorption process of I-ions on both P1 and P2 is controlled by chemisorption. Four equilibrium isotherm models (Redlich-Peterson, Langmuir, Freundlich, and Harkin-Jura) are investigated, revealing that the adsorption process is a monolayer and multilayer process on a heterogeneous surface.

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The study presents the achievement of a new assembly with antioxidant behaviour based on a copolymacrolactone structure that encapsulates erythritol (Eryt). Poly(ethylene brassylate-co-squaric acid) (PEBSA) was synthesised in environmentally friendly conditions, respectively, through a process in suspension in water by opening the cycle of ethylene brassylate macrolactone, followed by condensation with squaric acid. The compound synthesised in suspension was characterised by comparison with the polymer obtained by polymerisation in solution. The investigations revealed that, with the exception of the molecular masses, the compounds generated by the two synthetic procedures present similar properties, including good thermal stability, with a Tpeak of 456 °C, and the capacity for network formation. In addition, the investigation by dynamic light scattering techniques evidenced a mean diameter for PEBSA particles of around 596 nm and a zeta potential of -25 mV, which attests to their stability. The bio-based copolymacrolactone was used as a matrix for erythritol encapsulation. The new PEBSA-Eryt compound presented an increased sorption/desorption process, compared with the PEBSA matrix, and a crystalline morphology confirmed by X-ray diffraction analysis. The bioactive compound was also characterised in terms of its biocompatibility and antioxidant behaviour.

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Controlling the properties of supramolecular assemblies requires unveiling the specific interactions between their components. In the present work, the catalytic properties and structure of co-assemblies composed of a benzene-1,3,5-tricarboxamide (BTA) ligand coordinated to copper (the soldier) and seven enantiopure BTAs (the sergeants) have been determined. Whatever the sergeant, the enantioselectivity of the reaction is directly proportional to the optical purity of the supramolecular helices. More strikingly, the role played by the sergeant in the co-assembly process differs significantly: from almost pure intercalator (when it is incorporated in the stacks of the soldier and generates long homochiral helices) to pure chain capper (when it leads to the formation of partly helically biased and short assemblies). The former situation leads to optimal enantioselectivity for the catalytic system under study (58 % ee) while the latter situation leads to very low selectivity (8 % ee). The successful rationalization of this high and unexpected difference is crucial for the development of more efficient catalysts and more elaborate supramolecular systems.

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We report the development of a novel graft copolymer, diethylamino ethyl methacrylate grafted xanthan gum (mwXG-g-DEAEMA), by microwave heating. The synthesized graft copolymer was used for potential application of Cr(VI) adsorption. The structure, thermal stability and morphologies of XG and mwXG-g-DEAEMA were characterized to verify the adsorbent formed under optimized reaction conditions. FTIR, XRD, TGA and SEM techniques were used for characterization of XG and mwXG-g-DEAEMA. Furthermore, 1H NMR spectroscopic analyses predict the probable structure of copolymer. Based on the NMR data, a plausible mechanism for copolymer formation has been proposed. The effects of adsorbent loading, pH, contact time and equilibrium concentration of the Cr(VI) adsorption were investigated batch wise. The Cr(VI) adsorption process followed the pseudo-second-order rate model and equilibrium data were best described by Freundlich isotherm model. This work will encourage researchers to focus on this facile green technique for the synthesis of adsorbent with enhanced adsorption capacity.

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Poly(limonene carbonate) (PLC) has been highlighted as an attractive substitute to petroleum derived plastics, due to its utilisation of CO2 and bio-based limonene as feedstocks, offering an effective carbon capture and utilisation pathway. Our study investigates the techno-economic viability and environmental sustainability of a novel process to produce PLC from citrus waste derived limonene, coupled with an anaerobic digestion process to enable energy cogeneration and waste recovery maximisation. Computational process design was integrated with a life cycle assessment to identify the sustainability improvement opportunities. PLC production was found to be economically viable, assuming sufficient citrus waste is supplied to the process, and environmentally preferable to polystyrene (PS) in various impact categories including climate change. However, it exhibited greater environmental burdens than PS across other impact categories, although the environmental performance could be improved with a waste recovery system, at the cost of a process design shift towards energy generation. Finally, our study quantified the potential contribution of PLC to mitigating the escape of atmospheric CO2 concentration from the planetary boundary. We emphasise the importance of a holistic approach to process design and highlight the potential impacts of biopolymers, which is instrumental in solving environmental problems facing the plastic industry and building a sustainable circular economy.

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Electrochemical polymerisation is reported to be a method for readily producing copolymers of various conjugated molecules. We employed this method for mixtures of indole, carbazole or fluorene with 3-hexylthiophene (HT), in order to obtain their soluble copolymers. Although polymer films were obtained, infrared (IR) and Raman investigations showed that instead of the expected linear copolymers, polyindole and polycarbazole N-substituted with HT, as well as a poly(3-hexylthiophene) (PHT)/polyfluorene blend were produced instead. Boron trifluoride diethyl etherate was also used in an attempt to promote copolymerisation, but the produced deposits were found to be highly degraded.

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The continuous amalgamation of photocatalysis into existing reversible deactivation radical polymerisation (RDRP) processes has initiated a rapidly propagating area of polymer research in recent years. We introduce bismuth oxide (Bi2 O3 ) as a heterogeneous photocatalyst for polymerisations, operating at room temperature with visible light. We demonstrate formidable control over degenerative chain-transfer polymerisations, such as macromolecular design by interchange of xanthate (MADIX) and reversible addition-fragmentation chain-transfer (RAFT) polymerisation. We achieved narrow molecular weight distributions and attribute the excellent temporal control of a photo-induced electron transfer (PET) process. This methodology was employed to synthesise diblock copolymers combining differently activated monomers. The Bi2 O3 catalyst system has the additional benefits of low toxicity, reusability, low-cost, and ease of removal from the reaction mixture.

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Natural rubber latex was initially deproteinised (DNRL) and then subjected to physicochemical modifications to make high functional membranes for drug delivery applications. Initially, DNRL was prepared by incubating with urea, sodiumdodecylsulphate and acetone followed by centrifugation. The deproteinisation was confirmed by CHN analysis. The DNRL was then chemically modified by grafting (dimethylaminoethyl methacrylate) onto NR particles by using a redox initiator system viz; cumene hydroperoxide/tetraethylenepentamine, followed by dialysis for purification. The grafting was confirmed by dynamic light scattering, Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. The grafted system was blended with a hydrophilic adhesive polymer PVA and casted into membranes. The membranes after blending showed enhanced mechanical properties with a threshold concentration of PVA. The moisture uptake, swelling and water contact angle experiments indicated an increased hydrophilicity with an increased PVA content in the blend membranes. The grafted DNRL possessed significant antibacterial property which has been found to be retained in the blended form. A notable decrease in cytotoxicity was observed for the modified DNRL membranes than the bare DNRL membranes. The in-vitro drug release studies using rhodamine B as a model drug, confirmed the utility of the prepared membranes to function as a drug delivery matrix.

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In the present project, graft polymerization was employed to synthesis a novel adsorbent using acrylic acid (AA) and xanthan gum (XG) for cationic methylene dye (MB+) removal from aqueous solution. The XG was rapidly grafted with acrylic acid (CH2=CHCOOH) under microwave heating. Fourier-transform infrared spectroscopy (FTIR), Proton Nuclear magnetic resonance spectroscopy (1H NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Thermal gravimetric analysis (TGA) techniques were used to verify the adsorbent formed under optimized reaction conditions. Optimum reaction conditions [AA (0.4M), APS (0.05M), XG (2gL-1), MW power (100%), MW time (80s)] offer maximum %G and %GE of 484 and 78.3, respectively. The removal ratio of adsorbent to MB+ reached to 92.8% at 100mgL-1. Equilibrium and kinetic adsorptions of dyes were better explained by the Langmuir isotherm and pseudo second-order kinetic model respectively. The results demonstrate xanthan gum grafted polyacrylic acid (mw XG-g-PAA) absorbent had the universality for removal of dyes through the chemical adsorption mechanism.

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Two new di-zinc-aryl complexes, [LZn2 Ph2 ] and [LZn2 (C6 F5 )2 ], coordinated by a diphenol tetraamine macrocyclic ligand have been prepared and fully characterised, including by single-crystal X-ray diffraction experiments. The complexes' reactivities with monomers including carbon dioxide, cyclohexene oxide, phthalic anhydride, isopropanol and phenol were investigated using both experimental studies and density functional theory calculations. In particular, [LZn2 Ph2 ] readily inserts carbon dioxide to form a carboxylate, at 1 bar pressure, whereas [LZn2 (C6 F5 )2 ] does not react. Under these conditions [LZn2 Ph2 ] shows moderate activity in the ring-opening copolymerisation of cyclohexene oxide/carbon dioxide (TOF=20 h-1 ), cyclohexene oxide/phthalic anhydride (TOF=33 h-1 ) and the ring-opening polymerisations of rac-lactide (TOF=99 h-1 ) and ϵ-caprolactone (TOF=5280 h-1 ).

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BACKGROUND: Mycotoxins are produced by fungi as secondary metabolites. They often multi-contaminate food and feed commodities posing a health risk to humans and animals. Fast and easy multiplex screening could be thought as a useful tool for detection of multi-contaminated food and feed commodities. RESULTS: A highly sensitive immune-affinity monolithic arrays for detecting the mycotoxins zearalenone, deoxynivalenol, T-2 toxin, HT-2 toxin, aflatoxins, ochratoxin A, and fumonisin B1 were fabricated using UV induced co-polymerisation. The mycotoxin antibodies firstly reacted with functional monomer to form antibody/functional monomer bio-conjugates. Subsequently, the antibody/functional monomer bio-conjugates co-polymerised with cross-linker to form mycotoxins immune-affinity arrays. With optimal fabrication conditions, all mycotoxin immune-affinity monolithic arrays exhibited a linear response spanning three orders of magnitude. And the immune-affinity monolithic array has a low detection limit and has a good uniformity (intra-assay CV, and inter-assay CV both <8%). CONCLUSION: The fabricated mycotoxin immune-affinity monolithic arrays were proved as a sensitive, stable and economical tool in real food samples detection. Moreover, the mycotoxin immune-affinity monolithic arrays would be able to minimise manipulation steps: add samples and enzyme labelled mycotoxins, and detect CL signals. © 2016 Society of Chemical Industry.

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In vitro mineralisation in simulated body fluid (SBF) of synthetic polymers continues to be an important area of research as the outcomes cannot be predicted. This study evaluates a series of ePTFE membranes grafted with carboxylate-containing copolymers, specifically using acrylic acid and itaconic acid for grafting. The samples differ with regards to graft density, carboxylate density and polymer topology. The type and amount of mineral produced in 1.5 × SBF was dependent on the sample characteristics as evident from XPS, SEM/EDX, and FTIR spectroscopy. It was found that the graft density affects the mineral phases that form and that low graft density appear to cause co-precipitation of calcium carbonate and calcium phosphate. Linear and branched graft copolymer topology led to hydroxyapatite mineralisation whereas crosslinked graft copolymers resulted in formation of a mixture of calcium-phosphate phases. This study demonstrates that in vitro mineralisation outcomes for carboxylate-containing graft copolymers are complex. The findings of this study have implications for the design of bioactive coatings and are important for understanding the bone-biomaterial interface.

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The choice of the anion has a surprisingly strong effect on the incorporation of CO2 into the polymer obtained during the zinc-catalysed copolymerisation of CO2 and cyclohexene oxide. The product span ranges from polyethercarbonates, where short polyether sequences alternate with carbonate linkages, to polycarbonates with a strictly alternating sequence of the repeating units. Herein, we report on the influence of the coordination ability of the anion on the selectivity and kinetics of the copolymerisation reaction.

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Interaction of p-tert-butylcalix[8]areneH8 (L(8) H8 ) with [NaVO(OtBu)4 ] (formed in situ from VOCl3 ) afforded the complex [Na(NCMe)5 ][(VO)2 L(8) H]⋅4 MeCN (1⋅4 MeCN). Increasing [NaVO(OtBu)4 ] to 4 equiv led to [Na(NCMe)6 ]2 [(Na(VO)4 L(8) )(Na(NCMe))3 ]2 ⋅10 MeCN (2⋅10 MeCN). With adventitious oxygen, reaction of 4 equiv of [VO(OtBu)3 ] with L(8) H8 afforded the alkali-metal-free complex [(VO)4 L(8) (µ(3) -O)2 ] (3); solvates 3⋅3 MeCN and 3⋅3 CH2 Cl2 were isolated. For the lithium analogue, the order of addition had to be reversed such that lithium tert-butoxide was added to L(8) H8 and then treated with 2 equiv of VOCl3 ; crystallisation afforded [(VO2 )2 Li6 [L(8) ](thf)2 (OtBu)2 (Et2 O)2 ]⋅Et2 O (4⋅Et2 O). Upon extraction into acetonitrile, [Li(NCMe)4 ][(VO)2 L(8) H]⋅8 MeCN (5⋅8 MeCN) was formed. Use of the imido precursors [V(NtBu)(OtBu)3 ] and [V(Np-tolyl)(OtBu)3 ] and L(8) H8 , afforded [tBuNH3 ][{V(p-tolylN)}2 L(8) H]⋅3 1/2 MeCN (6⋅3 1/2 MeCN). The molecular structures of 1 to 6 are reported. Complexes 1, 3, and 4 were screened as precatalysts for the polymerisation of ethylene in the presence of cocatalysts at various temperatures and for the copolymerisation of ethylene with propylene. Activities as high as 136 000 g (mmol(V) h)(-1) were sometimes achieved; higher molecular weight polymers could be obtained versus the benchmark [VO(OEt)Cl2 ]. For copolymerisation, incorporation of propylene was 7.1-10.9 mol % (compare 10 mol % for [VO(OEt)Cl2 ]), although catalytic activities were lower than [VO(OEt)Cl2 ].

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The present study focuses on electrospray ionisation (ESI) tandem mass spectrometry of novel copolyesters obtained by anionic ring-opening copolymerisation of ß-substituted ß-lactones. Detailed analysis of these copolyesters, including molecular chain architecture as well as the structures of the end groups, was performed using ESI-MS/MS collision-induced dissociation spectra. The random arrangement of comonomeric units along the copolyester chains was demonstrated by comparison of ESI-MS(n) fragmentation spectra and fragmentation pathways. Sequence distribution analysis of comonomeric units confirmed the copolymer's random structure. ESI-MS(n) proved to be a promising technique for structural analysis of copolyesters obtained via anionic ROP.

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A starch-graft-polyacrylamide (St-g-PAM) superabsorbent crosslinked by N,N'-methyl bisacrylamide (MBA) was prepared using 10 MeV simultaneous electron beam irradiation at room temperature and subsequent alkaline hydrolysis. The effects of the irradiation dose, acryliamide-to-anhydroglucose unit (AM-to-AGU) ratio and crosslinker amount on the properties of the obtained polymers were evaluated. The structure of the graft copolymer was confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM). Optimisation treatments were carried out and found for a total dose of 8 kGy, an AM-to-AGU ratio of 4.5 mol mol(-1) and a crosslinker-to-AM ratio of 0.4%mol mol(-1). The obtained superabsorbent polymer showed the maximum absorptions of 1,452 gg(-1) and 83 gg(-1) for distilled water and saline solution, respectively (relative to its own dry weight). The results suggest 10 MeV electron beam irradiation is more efficient than γ-ray irradiation due to its higher energy and dose rate.

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