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1.
Chemistry ; : e202401233, 2024 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-38825747

RESUMO

The reaction of Re(CO)5Br with deprotonated 1H-(5-(2,2':6',2''-terpyridine)pyrid-2-yl)tetrazole yields a triangular assembly formed by tricarbonyl Re(I) vertices. Photophysical measurements reveal blue-green emission with a maximum at 520 nm, 32% quantum yield, and 2430 ns long-lived excited state decay lifetime in deaerated dichloromethane solution. Coordination of lanthanoid ions to the terpyridine units red-shifts the emission to 570 nm and also reveals efficient (90%) and fast sensitisation to both Eu(III) and Yb(III) at room temperature, with a similar rate constant kET of the order of 107 s-1. Efficient sensitisation of Eu(III) from Re(I) is unprecedented, especially when considering the close proximity in energy between the donor and acceptor excited states. On the other hand, comparative measurements at 77 K reveal that energy transfer to Yb(III) is two orders of magnitude slower than that to Eu(III). A two-step mechanism of sensitisation is therefore proposed, whereby the rate-determining step is a thermally activated energy transfer step between the Re(I) centre and the terpyridine functionality, followed by rapid energy transfer to the respective Ln(III) excited states. At 77 K, the direct Re(I) to Eu(III) energy transfer seems to proceed via a ligand-mediated superexchange Dexter-type mechanism.

2.
J Environ Manage ; 324: 116279, 2022 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-36170782

RESUMO

Phosphate shortages and the ensuing pressures on food security have led to an interest in processed sewage sludge as a substitute for commercial fertilisers. The presence of heavy metals in this nutrient source causes concerns around environmental release and pollution. This work builds towards a resin-in-pulp sludge detoxification process. It showcases the kinetic and thermodynamic adsorption capabilities of the ion-exchange resins C107E (carboxylic acid functionality), MTS9301 (iminodiacetic acid) and TP214 (thiourea), with respect to Cu(II), Fe(II), Pb(II) and Zn(II), within a simulated sewage sludge weak acid (acetate) leachate. The isotherms produced in this complex system were quite different to those generated when single metals were investigated in isolation, with desorption of lower affinity species clearly observed at higher equilibrium concentration values. Mixed-metal isotherm data were fitted to common two-parameter isotherm models and also a novel modified Langmuir model, which better accounted for the effects of desorption and competition. Kinetic data were also fit to common two-parameter models; results suggesting the system was likely film diffusion-controlled and followed pseudo-2nd-order kinetics. C107E displayed rapid adsorption of lead (t1/2 = 26 ± 3min), and significant uptake of all metals. MTS9301 showed high affinity for copper ions, with concurrent desorption of all the other metals, and also displayed the fastest kinetics (t1/2 = 14.1 ± 0.9, 130 ± 20, 25 ± 5 and 49 ± 6 min for copper, iron(II), lead and zinc, respectively). C107E and MTS9301 showed far slower adsorption for iron(II) than the other three metals, which invited the possibility of kinetic separations. TP214 had reasonable effectiveness in removal of copper, but poor affinity for all other metals. The greatest difficulty in modelling the multi-metal system was the two-stage trends observed in equilibrium experiments, as metal-proton exchanges become metal-metal exchanges. While not having the highest capacity, MTS9301 was recommended as the most appropriate resin for rapid and efficient removal of Cu, Pb and Zn from the acetate medium.


Assuntos
Metais Pesados , Poluentes Químicos da Água , Esgotos , Adsorção , Cobre , Fosfatos , Chumbo , Cinética , Compostos Ferrosos , Acetatos , Concentração de Íons de Hidrogênio
3.
Analyst ; 146(12): 3818-3822, 2021 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-34036982

RESUMO

There is a lack of molecular probes for imaging bacteria, in comparison to the array of such tools available for the imaging of mammalian cells. Here, organometallic molecular probes have been developed and assessed for bacterial imaging, designed to have the potential to support multiple imaging modalities. The chemical structure of the probes is designed around a metal-naphthalimide structure. The 4-amino-1,8-naphthalimide moiety, covalently appended through a pyridine ancillary ligand, acts as a luminescent probe for super-resolution microscopy. On the other hand, the metal centre, rhenium(i) or platinum(ii) in the current study, enables techniques such as nanoSIMS. While the rhenium(i) complex was not sufficiently stable to be used as a probe, the platinum(ii) analogue showed good chemical and biological stability. Structured illumination microscopy (SIM) imaging on live Bacillus cereus confirmed the suitability of the probe for super-resolution microscopy. NanoSIMS analysis was used to monitor the uptake of the platinum(ii) complex within the bacteria and demonstrate the potential of this chemical architecture to enable multimodal imaging. The successful combination of these two moieties introduces a platform that could lead to a versatile range of multi-functional probes for bacteria.


Assuntos
Iluminação , Naftalimidas , Animais , Bactérias , Lipídeos , Luminescência , Naftalimidas/toxicidade
4.
Inorg Chem ; 59(22): 16194-16204, 2020 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-33121245

RESUMO

Enhanced near-infrared (NIR) luminescence from two structurally related heterobinuclear NaIYbIII eight-cooridnate and heterobinuclear YbIIINaI eight-coordinate (CN = 8) complexes is reported and compared to a nine-coordinate (CN = 9) homoleptic complex. For the heteroleptic complex, [Yb(MPQ2)(acac)], the YbIII cation is coordinated to two tridentate 2-(5-methylpyridin-2-yl)-8-quinolinate (MPQ) anions, with a bidentate acetylacetonate (acac) anion completing the coordination sphere. Instead, the heterobinuclear [NaYb(MPQ)4] complex comprises a total of four anionic MPQ ligands, two of which exhibit κ3-coordination to the YbIII cation. The remaining two MPQ anions are unidentate toward the lanthanide and form µ2-bridges via the deprotonated quinolinate oxygens to a bound NaI cation which is also coordinated to the remaining nitrogen donor atoms. The structural properties of these complexes were evaluated by single-crystal X-ray diffraction (SXRD), continuous shape measure (CShM) analysis, and 1H NMR spectroscopy using a diamagnetic LuIII analogue. The corresponding photophysical properties were examined in CH2Cl2 solution by using absorption and emission spectroscopy. For both the complexes, characteristic YbIII emission is observed at ca. 980 nm, with recorded photoluminescence quantum yields (Φobs) and NIR luminescence lifetimes (τobs) of 2.0% and 14.0 µs vs 1.5% and 11.6 µs for the [NaYb(MPQ)4] and [Yb(MPQ)2(acac)] complexes, respectively. Interestingly, the eight-coordinate YbIII complexes both have higher photoluminescence quantum yields when compared to the homoleptic [Yb(MPQ)3] complex, which has a reported quantum yield of 1.0% and a NIR lifetime determined herein of 13.3 µs under identical conditions. These results have been rationalized by considering the overall efficiency of the ligand-centered sensitization process (ηsens = Φisc × Φeet), together with subsequent radiative (kr) and nonradiative (knr) deactivation of the YbIII cation. Moreover, the efficiency of the intersystem crossing (Φisc) and electronic energy transfer (Φeet) processes involved in the antennae effect have been quantified for the new complexes using a combination of nanosecond and femtosecond transient absorption techniques and have been compared to our previous results using [Ln(MPQ)3] complexes with Ln = Yb and Lu.

5.
Chemistry ; 25(45): 10566-10570, 2019 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-31197892

RESUMO

A family of three neutral iridium(III) tetrazolato complexes are investigated as bacterial imaging agents. The complexes offer a facile tuning of the emission colour from green (520 nm) to red (600 nm) in aqueous media, while keeping the excitation wavelength unchanged. The three complexes do not inhibit the bacterial growth of Bacillus Cereus, used as a model in this study, and exhibit extremely fast cellular uptake. After a minute incubation time, the nontoxic complexes show subcellular localisation in spherical structures identified as lipid vacuoles. Confocal Raman imaging has been exploited for the first time on live bacteria, to provide direct and label-free mapping of the lipid-enriched organelles within B. cereus, complementing the use of luminescent probes. Examination of the Raman spectra not only confirmed the presence of lipophilic inclusions in B. cereus but offered additional information about their chemical composition, suggesting that the lipid vacuoles may contain polyhydroxybutyrate (PHB).


Assuntos
Bacillus cereus/metabolismo , Complexos de Coordenação/química , Irídio/química , Lipídeos/química , Microscopia Confocal/métodos , Complexos de Coordenação/metabolismo , Substâncias Luminescentes/química , Análise Espectral Raman
6.
Soft Matter ; 13(5): 1006-1011, 2017 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-28083581

RESUMO

The thermal annealing behaviour of an electrolyte-triggered calixarene hydrogelator is found to depend strongly on the specific metal chloride used. While the lithium chloride gel showed typical gel-sol transitions as a function of temperature, the magnesium chloride gel was found to repeatedly strengthen with heat-cool cycles. Structural investigations using small-angle neutron scattering, and scanning probe microscopy, suggest that the annealing behaviour is associated with a change in morphology of the fibrous structures supporting the gel. On prolonged standing at room temperature, the magnesium chloride gel underwent a gel-crystal transition, with the collapsing gel accompanied by the deposition of crystals of a magnesium complex of the proline-functionalised calix[4]arene gelator.

7.
Inorg Chem ; 56(15): 8975-8985, 2017 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-28696105

RESUMO

The reaction of the ß-triketonate ligands tris(4-methylbenzoyl)methanide and tribenzoylmethanide with the trivalent lanthanoids Eu3+, Er3+, and Yb3+ in the presence of Cs+ afforded polymeric structures where the repeating units are represented by bimetallic tetranuclear assemblies of formulation {[Ln(Cs)(ß-triketonate)4]2}n. The only exception is the structure formed by the reaction of tris(4-methylbenzoyl)methanide, Yb3+, and Cs+, which yielded a polymeric assembly where the repeating units are mononuclear Yb3+ complexes bridged by Cs+ cations. Photophysical measurements on the obtained materials confirmed efficient sensitization from the ligand excited states to the 4f* excited states of the three lanthanoids. According to transient absorption data, Er3+ and Yb3+ are sensitized via energy transfer from the triplet state of the ß-triketonate ligands. On the other hand, energy transfer to Eu3+ seems to occur via an alternative pathway, possibly directly via the singlet state or through ligand to metal charge transfer states. The emission measurements confirm efficient sensitization for all three lanthanoids and bright near-infrared emission for Er3+ and Yb3+, a characteristic that seems to be linked to the specific chemical structure of the ß-triketonate ligands.

8.
Chemistry ; 21(50): 18354-63, 2015 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-26511032

RESUMO

The reaction of hydrated lanthanoid chlorides with tribenzoylmethane and an alkali metal hydroxide consistently resulted in the crystallization of neutral tetranuclear assemblies with the general formula [Ln(Ae⋅HOEt)(L)4 ]2 (Ln=Eu(3+) , Er(3+) , Yb(3+) ; Ae=Na(+) , K(+) , Rb(+) ). Analysis of the crystal structures of these species revealed a coordination geometry that varied from a slightly distorted square antiprism to a slightly distorted triangular dodecahedron, with the specific geometrical shape being dependent on the degree of lattice solvation and identity of the alkali metal. The near-infrared (NIR)-emitting assemblies of Yb(3+) and Er(3+) showed remarkably efficient emission, characterized by significantly longer excited-state lifetimes (τobs ≈37-47 µs for Yb(3+) and τobs ≈4-6 µs for Er(3+) ) when compared with the broader family of lanthanoid ß-diketonate species, even in the case of perfluorination of the ligands. The Eu(3+) assemblies show bright red emission and a luminescence performance (τobs ≈0.5 ms, ${{\Phi}{{{\rm L}\hfill \atop {\rm Ln}\hfill}}}$≈35-37 %, ηsens ≈68-70 %) more akin to the ß-diketonate species. The results highlight that the ß-triketonate ligand offers a tunable and facile system for the preparation of efficient NIR emitters without the need for more complicated perfluorination or deuteration synthetic strategies.

9.
Faraday Discuss ; 179: 343-57, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-25877791

RESUMO

The various roles of mellitic acid during barium sulfate crystallization from nucleation to mesocrystal formation are explored and elucidated.

10.
J Am Chem Soc ; 136(43): 15122-5, 2014 Oct 29.
Artigo em Inglês | MEDLINE | ID: mdl-25283579

RESUMO

Large metal-oxo clusters consistently assume spherical or regular polyhedral morphologies rather than high-aspect-ratio structures. Access to elongated core structures has now been achieved by the reaction of lanthanoid salts with a tetrazole-functionalized calixarene in the presence of a simple carboxylate co-ligand. The resulting Ln19 and Ln12 clusters are constructed from apex-fused Ln5O6 trigonal bipyramids and are formed consistently under a range of reaction conditions and reagent ratios. Altering the carboxylate co-ligand structure reliably controls the cluster length, giving access to a new class of rod-like clusters of variable length.

11.
Materials (Basel) ; 17(8)2024 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-38673138

RESUMO

The UK's adoption of pyroprocessing of spent nuclear fuel as an alternative to the current aqueous processing routes requires a robust scientific underpinning of all relevant processes. One key process is the clean-up of the contaminated salt from the electroreducing and electrorefining processes. A proposed method for this clean-up is zone refining, whereby the tendency of the contaminants to remain in the liquid phase during melting and freezing is exploited to 'sweep' the contaminants to one end of the sample. Experiments were performed, utilising off-the-shelf laboratory equipment, to demonstrate the feasibility of zone refining for clean-up of electroreducing and electrorefining wastes. This was successful for the electrorefining simulant samples, with effective segregation coefficient, keff, values, which provide a measure of the degree of separation in the sample, between 0 and 1. Lower values indicate greater separation, with values of as low as 0.542 achieved here, corresponding to a reduction in RECl3 content from 10.0 wt.% to 8.4 wt.% (for 80% salt reuse). Due to difficulties in obtaining a fully homogeneous electroreducing simulant waste, it was not possible to demonstrate the feasibility of zone refining using the current experimental setup. Further research is required to elucidate the correct preparation conditions for production of homogeneous electroreducing waste simulants.

12.
J Am Coll Cardiol ; 83(2): 291-299, 2024 01 16.
Artigo em Inglês | MEDLINE | ID: mdl-38199706

RESUMO

BACKGROUND: Exercise electrocardiographic stress testing (EST) has historically been validated against the demonstration of obstructive coronary artery disease. However, myocardial ischemia can occur because of coronary microvascular dysfunction (CMD) in the absence of obstructive coronary artery disease. OBJECTIVES: The aim of this study was to assess the specificity of EST to detect an ischemic substrate against the reference standard of coronary endothelium-independent and endothelium-dependent microvascular function in patients with angina with nonobstructive coronary arteries (ANOCA). METHODS: Patients with ANOCA underwent invasive coronary physiological assessment using adenosine and acetylcholine. CMD was defined as impaired endothelium-independent and/or endothelium-dependent function. EST was performed using a standard Bruce treadmill protocol, with ischemia defined as the appearance of ≥0.1-mV ST-segment depression 80 ms from the J-point on electrocardiography. The study was powered to detect specificity of ≥91%. RESULTS: A total of 102 patients were enrolled (65% women, mean age 60 ± 8 years). Thirty-two patients developed ischemia (ischemic group) during EST, whereas 70 patients did not (nonischemic group); both groups were phenotypically similar. Ischemia during EST was 100% specific for CMD. Acetylcholine flow reserve was the strongest predictor of ischemia during exercise. Using endothelium-independent and endothelium-dependent microvascular dysfunction as the reference standard, the false positive rate of EST dropped to 0%. CONCLUSIONS: In patients with ANOCA, ischemia on EST was highly specific of an underlying ischemic substrate. These findings challenge the traditional belief that EST has a high false positive rate.


Assuntos
Doença da Artéria Coronariana , Isquemia Miocárdica , Doenças Vasculares , Humanos , Feminino , Pessoa de Meia-Idade , Idoso , Masculino , Teste de Esforço , Doença da Artéria Coronariana/diagnóstico , Acetilcolina , Eletrocardiografia , Isquemia Miocárdica/diagnóstico , Isquemia
13.
Front Chem ; 10: 997147, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36329859

RESUMO

This paper is part of a growing body of research work looking at the synthesis of an optimal adsorbent for the capture and containment of aqueous radioiodine from nuclear fuel reprocessing waste. 32 metalated commercial ion exchange resins were subjected to a two-tier screening assessment for their capabilities in the uptake of iodide from aqueous solutions. The first stage determined that there was appreciable iodide capacity across the adsorbent range (12-220 mg·g-1). Candidates with loading capacities above 40 mg·g-1 were progressed to the second stage of testing, which was a fractional factorial experimental approach. The different adsorbents were treated as discrete variables and concentrations of iodide, co-contaminants and protons (pH) as continuous variables. This gave rise to a range of extreme conditions, which were representative of the industrial challenges of radioiodine abatement. Results were fitted to linear regression models, both for the whole dataset (R 2 = 59%) and for individual materials (R 2 = 18-82%). The overall model determined that iodide concentration, nitrate concentration, pH and interactions between these factors had significant influences on the uptake. From these results, the top six materials were selected for project progression, with others discounted due to either poor uptake or noticeable iodide salt precipitation behaviour. These candidates exhibited reasonable iodide uptake in most experimental conditions (average of >20 mg·g-1 hydrated mass), comparing favourably with literature values for metallated adsorbents. Ag-loaded Purolite S914 (thiourea functionality) was the overall best-performing material, although some salt precipitation was observed in basic conditions. Matrix effects not withstanding it is recommended that metalated thiourea, bispicolylamine, and aminomethylphosphonic acid functionalized silicas warrant further exploration.

14.
J Hazard Mater ; 401: 123351, 2021 01 05.
Artigo em Inglês | MEDLINE | ID: mdl-32653788

RESUMO

Aqueous leaching to recover salts from black dross is accompanied by hazardous gas generation. The gas-generating phases vary significantly across differently sourced black dross. The challenge for the industry is how to accurately qualify and quantify the problematic components of black dross, especially minor reactive phases. This paper employed XRF, EDX, XRD, Raman and FTIR to analyse two industrial black dross samples from various sources. A novel pre-treatment method before characterisation was devised using water-free glycerol and anhydrous ethanol to remove the major salt components, without reacting the gas-generating phases. The results show that around 80 % of the salts existent in the black dross had been removed successfully through pre-treatment. This method facilitated the determination of minor reactive phases characterised by XRD, XRF and EDX, and had little effect on the characterisation by Raman and FTIR spectroscopy. The ammonia-generating nitride phase was detected by XRD, Raman and FTIR. The FTIR, moreover, allowed the successful identification of carbide. Best practice guidelines for the industrial analysis of black dross has been proposed. The guidelines would provide industry with evidence to include or adjust gas treatment methods and operational parameters when dealing with compositional variability in industrially-sourced black dross.

15.
Micromachines (Basel) ; 11(10)2020 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-33027961

RESUMO

We introduce fluoride-selective anion exchange resin sorbents as sensitisers into membranes for water-gated field effect transistors (WGTFTs). Sorbents were prepared via metal (La or Al)-loading of a commercial macroporous aminophosphonic acid resin, PurometTM MTS9501, and were filled into a plasticised poly(vinyl chloride) (PVC) phase transfer membrane. We found a potentiometric response (membrane potential leading to WGTFT threshold shift) to fluoride following a Langmuir-Freundlich (LF) adsorption isotherm with saturated membrane potential up to ~480 mV, extremely low characteristic concentration c1/2 = 1/K, and picomolar limit of detection (LoD), even though ion exchange did not build up charge on the resin. La-loading gave a superior response compared to Al-loading. Membrane potential characteristics were distinctly different from charge accumulating sensitisers (e.g., organic macrocycles) but similar to the Cs+ (cation) selective ion-exchanging zeolite mineral 'mordenite'. We propose a mechanism for the observed threshold shift and investigate interference from co-solutes. Strong interference from carbonate was brought under control by 'diluting' metal loading in the resin. This work sets a template for future studies using an entirely new 'family' of sensitisers in applications where very low limit of detection is essential such as for ions of arsenic, mercury, copper, palladium, and gold.

16.
ACS Macro Lett ; 9(1): 56-60, 2020 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-35638650

RESUMO

The synthesis of the Rh(I)-aryl complex, Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) is reported and its efficacy as an initiator for the (co)polymerization of phenylacetylenes established. The X-ray crystal structure indicates that the complex adopts a slightly distorted square planar geometry whose purity and structure was also confirmed by elemental analysis and 1H, 13C, 31P, 19F, 103Rh, and 31P-103Rh{1H} HMQC NMR spectroscopy. We demonstrate that Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) mediates the (co)polymerization of phenylacetylenes in a controlled fashion with initiation efficiencies as high as 0.98, as evidenced by the pseudo-first-order kinetic and number-average molecular weight versus conversion profiles. The ability to form well-defined AB diblock copolymers, in a stereoregular manner, by sequential monomer addition is verified in the block copolymerization of phenylacetylene with 4-fluorophenylacetylene with quantitative crossover efficiency, as determined by size exclusion chromatography.

17.
Dalton Trans ; 49(47): 17421-17432, 2020 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-33220677

RESUMO

Trinuclear lanthanoid clusters have been synthesised and investigated as toroidal spin systems. A pyridyl functionalised ß-diketonate, 1,3-bis(pyridin-2-yl)propane-1,3-dione (o-dppdH) has been used to synthesise a family of clusters of the form [Dy3(OH)2(o-dppd)3Cl2(H2O)4]Cl2·7H2O (1), [Tb3(o-dppd)3(µ3-OH)2(CH3CH2OH)3Cl3][Tb3(o-dppd)3(µ3-OH)2(H2O)(CH3CH2OH)2Cl3]Cl2·H2O (2), [Ho3(OH)2(o-dppd)3Cl(H2O)5]Cl3·3H2O (3) and [Er3(OH)2(o-dppd)3Cl2(H2O)3(CH3OH)]Cl2·3H2O·CH3OH (4). Despite the previous occurrence of this structural motif in the literature, these systems have not been widely investigated in terms of torodic behaviour. Magnetic studies were used to further characterise the complexes. DC susceptibility studies support weak antiferromagnetic exchange in the complexes. Slow magnetic relaxation behaviour is observed in the dynamic AC magnetic studies for complex 1. Theoretical studies predict that complex 1 and 3 have a non-magnetic ground state based on a toroidal arrangement of spins. Changes to the coordination environment in 2 do not support a toroic spin state. The prolate nature of the ErIII centres in complex 4 and large transverse anisotropy do not support the toroidal arrangement of lanthanoid spins in the complex.

18.
J Hazard Mater ; 361: 200-209, 2019 01 05.
Artigo em Inglês | MEDLINE | ID: mdl-30189369

RESUMO

Spent potlining (SPL) hazardous waste is a potentially valuable source of fluoride, which may be recovered through chemical leaching and adsorption with a selective sorbent. For this purpose, the commercially available chelating resin Purolite® S950+ was loaded with lanthanum ions, to create a novel ligand-exchange sorbent. The equilibrium fluoride uptake behaviour of the resin was thoroughly investigated, using NaF solution and a simulant leachate of SPL waste. The resin exhibited a large maximum defluoridation capacity of 187 ± 15 mg g-1 from NaF solution and 126 ± 10 mg g-1 from the leachate, with solution pH being strongly influential to uptake performance. Isotherm and spectral data indicated that both chemisorption and unexpected physisorption processes were involved in the fluoride extraction and suggested that the major uptake mechanism differed in each matrix. The resin demonstrates significant potential in the recovery of fluoride from aqueous waste-streams.

19.
ACS Appl Mater Interfaces ; 11(25): 22464-22473, 2019 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-31141662

RESUMO

Sulfonated hyper-cross-linked polymers based on 4,4'-bis(chloromethyl)-1,1'-biphenyl (BCMBP) were synthesized via metal-free (SHCP-1) and conventional Lewis acid-catalyzed (SHCP-2) Friedel-Crafts alkylation routes. The sulfonated polymers possessed BET surface areas in excess of 500 m2·g-1. SHCP-1 was investigated for its ability to extract Sr and Cs ions from aqueous solutions via the ion-exchange reaction of the sulfonic acid moiety. Equilibrium uptake data could be accurately modeled by the Dubinin-Radushkevich isotherm, with maximum calculated loading values of 95.6 ± 2.8 mg·g-1 (Sr) and 273 ± 37 mg·g-1 (Cs). Uptake of both target ions was rapid, with pseudo second-order rate constants calculated as 7.71 ± 1.1 (×10-2) for Sr and 0.113 ± 0.014 for Cs. Furthermore, the polymer was found to be highly selective toward the target ions over large excesses of naturally occurring competing metal ions Na, K, Mg, and Ca. We conclude that hyper-cross-linked polymers may offer intrinsic advantages over other adsorbents for the remediation of aqueous Sr and Cs contamination.

20.
Water Res ; 158: 257-267, 2019 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-31048195

RESUMO

A shortage of phosphate rock resources has led to a focus on the use of sewage sludge as a fertiliser. One factor preventing the unlimited application of sewage sludge in agriculture is the heavy metal content. This work looks at a process where weak acid leaching of sewage sludge would be coupled to ion exchange (IX) for heavy metal ion removal. IX offers an effective method for the recovery of these metals from a leachate. This study presents the pH performance of six selected IX resins in extracting Cu2+, Fe2+, Pb2+ and Zn2+ from acetic, lactic and citric acid media simulated weak acid leachate. Acetic acid media displayed limited suppression of metal extraction, whilst lactic and citric acid media rendered MTS9100 ineffective. Lactic acid media when combined with C107E resin allows for the targeted extraction of lead. Both MTS9570 and MTS9501 display high ferrous extraction in all media at all pH values, although citric acid hinders extraction by both resins at higher pH values. TP214 is selective for copper over all other metal ions in all weak acid media. MTS9301 is the most effective at extracting all metals from all media solutions, with separation of copper becoming more apparent when transitioning to citric acid.


Assuntos
Metais Pesados , Esgotos , Compostos Ferrosos , Troca Iônica , Chumbo , Zinco
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