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- Synthesis and characterization of a 3-hydroxy-4-pyridinone chelator functionalized with a polyethylene glycol (PEG) chain aimed at sequential injection determination of iron in natural watersPublication . Mesquita, Raquel; Moniz, Tânia; Miranda, Joana L. A.; Gomes, Vânia; Silva, André M. N.; Rodriguez-Borges, J. E.; Rangel, António O. S. S.; Rangel, MariaThe synthesis of a highly water soluble 3-hydroxy-4-pyridinone ligand, functionalized with a hydrophilic ethylene glycol chain (PEG-HPO), was successfully achieved and is reported together with that of its iron (III) complex. The improved hydrophilicity of both the PEGylated 3,4-HPO ligand and its iron(III) complex were fully investigated in an analytical application and, the new chelator is proposed for the spectrophotometric sequential injection determination of iron in waters. The new ligand provided better sensitivity and a lower LOD for iron determination than that obtained for N-alkyl-3-hydroxy-4-pyridinone ligands. The developed sequential injection method presents a dynamic working range of 0.10-1.00 mg Fell. with a LOD of 48 mu g/L. Due to the use of a sequential injection system, the overall effluent production was <2 mL corresponding to the consumption of 44 mu g of PEG-HPO, 0.71 mg of NaHCO3, 0.92 mg of HNO3 and 500 mu L of sample. Two reference samples were assessed for accuracy studies and a relative deviation <5% was obtained; eight waters samples were analyzed and the results compared with the reference procedure, and no statistical difference was observed for the two sets of results.
- Effect of tris(3-hydroxy-4-pyridinonate) iron(III) complexes on iron uptake and storage in soybean (Glycine max L.)Publication . Santos, Carla S.; Carvalho, Susana M.P.; Leite, Andreia; Moniz, Tânia; Roriz, Mariana; Rangel, António O. S. S.; Rangel, Maria; Vasconcelos, Marta W.Iron deficiency chlorosis (IDC) is a serious environmental problem affecting the growth of several crops in the world. The application of synthetic Fe(III) chelates is still one of the most common measures to correct IDC and the search for more effective Fe chelates remains an important issue. Herein, we propose a tris(3-hydroxy-4-pyridinonate) iron(III) complex, Fe(mpp)3, as an IDC corrector. Different morphological, biochemical and molecular parameters were assessed as a first step towards understanding its mode of action, compared with that of the commercial fertilizer FeEDDHA. Plants treated with the pyridinone iron(III) complexes were significantly greener and had increased biomass. The total Fe content was measured using ICP-OES and plants treated with pyridinone complexes accumulated about 50% more Fe than those treated with the commercial chelate. In particular, plants supplied with compound Fe(mpp)3 were able to translocate iron from the roots to the shoots and did not elicit the expression of the Fe-stress related genes FRO2 and IRT1. These results suggest that 3,4-HPO iron(III) chelates could be a potential new class of plant fertilizing agents.
- A combined physiological and biophysical approach to understand the ligand-dependent efficiency of 3-hydroxy-4-pyridinone Fe-chelatesPublication . Santos, Carla S.; Leite, Andreia; Vinhas, Sílvia; Ferreira, Sofia; Moniz, Tânia; Vasconcelos, Marta W.; Rangel, Maria da ConceiçãoLigands of the 3‐hydroxy‐4‐pyridinone (3,4‐HPO) class were considered eligible to formulate new Fe fertilizers for Iron Deficiency Chlorosis (IDC). Soybean (Glycine max L.) plants grown in hydroponic conditions and supplemented with Fe‐chelate [Fe(mpp)3] were significantly greener, had increased biomass, and were able to translocate more iron from the roots to the shoots than those supplemented with an equal amount of the commercially available chelate [FeEDDHA]. To understand the influence of the structure of 3,4‐HPO ligand on the role of the Fe‐chelate to improve Fe‐uptake, we investigated and report here the effect of Fe‐chelates ([Fe(mpp)3], [Fe(dmpp)3], and [Fe(etpp)3]) in addressing IDC. Chlorosis development was assessed by measurement of morphological parameters, quantification of chlorophyll and Fe, and other micronutrient contents, as well as measurement of enzymatic activity (FCR) and gene expression (FRO2, IRT1, and Ferritin). All [Fe(3,4‐HPO)3] chelates were able to provide Fe to plants and prevent IDC but with a different efficiency depending on the ligand. We hypothesize that this may be related with the distinct physicochemical characteristics of ligands and complexes, namely, the diverse hydrophilic–lipophilic balance of the three chelates. To test the hypothesis, we performed an EPR biophysical study using liposomes prepared from a soybean (Glycine3 max L.) lipid extract and spin probes. The results showed that the most effective chelate [Fe(mpp)3] shows a preferential location close to the surface while the others prefer the hydrophobic region inside the bilayer.
- Microsequential injection lab-on-valve system for the spectrophotometric bi-parametric determination of iron and copper in natural watersPublication . González, Alba; Mesquita, Raquel B. R.; Avivar, Jessica; Moniz, Tânia; Rangel, Maria; Cerdà, Víctor; Rangel, António O. S. S.The determination of iron and copper exploiting a microsequential injection lab-on-valve system with online spectrophotometric detection is described. A new, environmental friendly 3-hydroxy-4-pyridinone chelator, functionalized with a polyethylene glycol chain (MRB12) to improve water solubility, was used for iron determination. For copper determination, 1-(2-pyridylazo)-2-naphthol (PAN) was used. Different parameters affecting the formation of the complexes were studied, namely sample volume, reagent concentration, and buffer composition and concentration. The optimized conditions, 150 mu L of sample volume and 250 mg L-1 of MRB12 for iron determination, and 200 mu L of sample and 120 mg L-1 of PAN for copper determination, enabled an LOD of 15 and 18 mu g L-1 for iron and copper, respectively. The robustness of the developed procedure was assessed by the calculation of the relative standard deviation (RSD), 5% for iron determination and 2% for copper determination. The accuracy of the method was assessed comparing the results with two certified samples (RD < 7.5%) and calculating recovery percentages with five river water samples (average < 107%).
- New hydrophilic 3-hydroxy-4-pyridinone chelators with ether-derived substituents: synthesis and evaluation of analytical performance in the determination of iron in watersPublication . Moniz, Tânia; Cunha-Silva, Luís; Mesquita, Raquel B.R.; Miranda, Joana L.A.; Silva, André M.N.; Silva, Ana M.G.; Rangel, António O.S.S.; Castro, Baltazar de; Rangel, MariaThree new hydrophilic 3-hydroxy-4-pyridinone chelators containing ether-derived substituents were prepared by a more sustainable synthetic protocol that involves the use of microwave heating and commercially available amines, allowing the successful production of highly water soluble chelators with improved reaction yields and reaction times. Compared with parent 3-hydroxy-4-pyridinone ligands, the new compounds were obtained faster and in higher amounts, facilitating the scale up of the synthesis, which is crucial to produce these ligands and their respective iron(III) complexes for many biological, analytical and agricultural applications. Ligands were fully characterized by 1H and 13C Nuclear Magnetic Resonance, High Resolution Mass Spectrometry and Single Crystal X-Ray Diffraction and their performance in the analytical determination of iron(III) in water samples was evaluated by sequential injection methods. The results obtained are scientifically relevant, pointing out the potential of the new and straightforwardly synthesized ligands as analytical reagents for determination of iron(III).
- Iron speciation in natural waters by sequential injection analysis with a hexadentate 3-hydroxy-4-pyridinone chelator as chromogenic agentPublication . Miranda, Joana; Mesquita, Raquel; Ana, Nunes; Rangel, Maria; Rangel, António O. S. S.A sequential injection method for iron speciation in various types of natural waters was developed using a synthesised hexadentate 3-hydroxy-4-pyridinone chelator (CP256). The denticity of the ligand that allow formation of the corresponding iron (III) complex in a 1:1 stoichiometry proved to be highly advantageous, in comparison with parent bidentate, hydroxy-4-piridinone chelators, with a two fold increase of reaction sensitivity and over 65% decrease of the LOD. A solid phase extraction approach was employed to attain matrix elimination, facilitating iron (III) determination and application to high salinity waters. The combination with the total iron determination obtained by the direct reaction of the ligand resulted in iron speciation. Two detection spectrophotometric cells were tested, a conventional flow cell (CFC) and a liquid waveguide capillary cell (LWCC). The dynamic concentration ranges were 0.1–2 mg/L with the CFC detection and 0.005–0.1mg/L with the LWCC, with limit of detection of 30 mg/L and 6 mg/L, respectively. The developed method was successfully applied to a variety of natural waters.
- Use of an ether-derived 3-hydroxy-4-pyridinone chelator as a new chromogenic reagent in the development of a microfluidic paper-based analytical device for Fe(III) determination in natural watersPublication . Moniz, Tânia; Bassett, Chelsea R.; Almeida, M. Ines G. S.; Kolev, Spas; Rangel, Maria; Mesquita, Raquel B. R.This article reports on the development and validation of a disposable microfluidic paper-based analytical device (μPAD) for on-hand. in-situ, and cheap Fe(III) determination in natural waters complying with World Health Organization guidelines. The developed μPAD used 3-hydroxy-4-pyridinone (3,4-HPO) as a colour reagent due to its considerably lower toxicity than traditionally used iron analytical reagents. It was selected among a group of hydrophilic 3,4-HPO chelators containing ether-derived chains in their structure which were prepared using green methods. The relatively high water solubility of these chelators improved the detection limit and applicability as μPAD reagents. Under optimal conditions, the μPAD is characterised by a quantification range between 0.25-2.0 mg/L, a detection limit of 55 μg/L and 15 min of analysis time. The signal stability extends up to 4 hours and the device is stable for at least one month. The reagent consumption is below 0.2 mg per analysis and the μPAD method was validated by analysis certified reference materials and by comparison with atomic absorption results (RD < 10%). The newly developed μPAD was successfully applied to the determination of iron in river, well and tap waters with no need of any prior sample pre-treatment.
- Iron speciation by microsequential injection solid phase spectrometry using 3-hydroxy-1(H)-2-methyl-4-pyridinone as chromogenic reagentPublication . Suárez, Ruth; Mesquita, Raquel B. R.; Rangel, Maria; Cerdà, Víctor; Rangel, António O.S.S.The speciation of iron using the newly synthesized 3-hydroxy-1(H)-2-methyl-4-pyridinone by solid phase spectrophotometry in a microsequential injection lab-on-valve (µSI-LOV-SPS) methodology is described. Iron was retained in a reusable column, Nitrilotriacetic Acid Superflow (NTA) resin, and the ligand was used as both chromogenic and eluting reagent. This approach, analyte retention and matrix removal, enabled the assessment of iron (III) and total iron content in fresh waters and high salinity coastal waters with direct sample introduction, in the range of 20.0–100 µg/L. with a LOD of 9 µg/L. The overall effluent production was 2 mL, corresponding to the consumption of 0.48 µg of 2-metil-3-hydroxy-4-pyridinone, 0.34 mg of NaHCO3, 16 mg of HNO3, 4.4 µg H2O2 and 400 µL of sample. Four reference samples were analyzed and a relative deviation<10% was obtained; furthermore, several bathing waters (♯13) were analyzed using the developed method and the results were comparable to those obtained by atomic absorption spectrophotometry (relative deviations<6%).
- Determination of iron(III) in water samples by microsequential injection solid phase spectrometry using an hexadentate 3-hydroxy-4-pyridinone chelator as reagentPublication . Miranda, Joana L. A.; Mesquita, Raquel B. R.; Nunes, Ana; Rangel, Maria; Rangel, António O. S. S.In this work, the hexadentate 3,4–hydroxypyridinone ligand was used as reagent for the spectrophotometric quantification of iron(III) in fresh and sea waters, using a micro sequential injection lab-on-valve (μSI-LOV) system in a solid phase spectrometry (SPS) mode. To implement SPS, thus eliminating the sample matrix, a packed column in the flow cell was used; the chosen sorbent was Nitrilotriacetic Acid Superflow resin (NTA). The possibility of performing an analytical curve resorting to just one standard was also demonstrated. The consumption of the hexadentante ligand was about 30 μg per determination and the effluent production lower than 2.5 mL. The dynamic concentration range was 0.45–9.0 μmol L−1, with a limit of detection of 0.13 μmol L−1 and limit of quantification 0.43 μmol L−1. The proposed μSI-LOV-SPS methodology was successfully applied to river, ground, estuarine, tap, and sea waters.