Antioxidant Sensors Based on Iron Diethylenetriaminepentaacetic Acid, Hematin, and Hemoglobin Modified TiO2 Nanoparticle Printed Electrodes

Antioxidant amperometric sensors based on iron-containing complexes and protein modified electrodes were developed. Indium tin oxide glass was printed with TiO2 nanoparticles, onto which iron-containing compounds and protein were adsorbed. When applied with negative potentials, the dissolved oxygen is reduced to H2O2 at the electrode surface, and the H2O2 generated in situ oxidizes Fe-II to Fe-III, and then electrochemical reduction of Fe-III therefore gives rise to a catalytic current. In the presence of antioxidants, H2O2 was scavenged, the catalytic current was reduced, and the decreased current signal was proportional to the quantity of existing antioxidants. A kinetic model was proposed to quantify the H2O2 scavenging capacities of the antioxidants. With the use of the sensor developed here, antioxidant measurements can be done quite simply: put the sensor into the sample solutions (in aerobic atmosphere), perform a cathodic polarization scan, and then read the antioxidant activity values. The present work can be complementary to the previous studies of antioxidant sensor techniques based on OH radicals and superoxide ions scavenging methods, but the sensor developed here is much easier to fabricate and use.

2,4-Dichlorophenoxyacetic acid (2,4-D) degradation promoted by nanoparticulate zerovalent iron (nZVI) in aerobic suspensions

Reactive species generated by Fe0 oxidation promoted by O2 (catalyzed or not by ligands) are able to degrade contaminant compounds like the herbicide 2,4-dichlorophenoxyacetic acid. The degradation of 2,4-D was influenced by the concentrations of zero valent iron (ZVI) and different ligands, as well as by pH. In the absence of ligands, the highest 2,4-D degradation rate was obtained at pH 3, while the highest percentage degradation (50%) was achieved at pH 5 after 120 min of reaction. Among the ligands studied (DTPA, EDTA, glycine, oxalate, and citrate), only ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) significantly enhanced oxidation of 2,4-D. This increase in oxidation was observed at all pH values tested (including neutral to alkaline conditions), indicating the feasibility of the technique for treatment of contaminated water. In the presence of EDTA, the oxidation rate was greater at pH 3 than at pH 5 or 7. Increasing the EDTA concentration increased the rate and percentage of 2,4-D degradation, however increasing the Fe0 concentration resulted in the opposite behavior. It was found that degradation of EDTA and 2,4-D occurred simultaneously, and that the new methodology avoided any 2,4-D removal by adsorption/coprecipitation. © 2013 Elsevier Ltd.

Studies on metal complex formation of environmentally friendly aminopolycarboxylate chelating agents

Aminopolykarboksyylaatteja, kuten etyleenidiamiinitetraetikkahappoa (EDTA), on käytetty useiden vuosikymmenien ajan erinomaisen metalli-ionien sitomiskyvyn vuoksi kelatointiaineena lukuisissa sovelluksissa sekä analytiikassa että monilla teollisisuuden aloilla. Näiden yhdisteiden biohajoamattomuus on kuitenkin herättänyt huolta viime aikoina, sillä niiden on havaittu olevan hyvin pysyviä luonnossa. Tämä työ on osa laajempaa tutkimushanketta, jossa on tavoitteena löytää korvaavia kelatointiaineita EDTA:lle. Tutkimuksen aiheena on kuuden kelatointiaineen metalli-ionien sitomiskyvyn kartoitus. EDTA:a paremmin luonnossa hajoavina nämä ovat ympäristöystävällisiä ehdokkaita korvaaviksi kelatointiaineiksi useisiin sovelluksiin. Työssä tutkittiin niiden kompleksinmuodostusta useiden metalli-ionien kanssa potentiometrisella titrauksella. Metalli-ionivalikoima vaihteli hieman kelatointiaineesta riippuen sisältäen magnesium-, kalsium-, mangaani-, rauta-, kupari-, sinkki-, kadmium-, elohopea-, lyijy- ja lantaani-ionit. Tutkittavat metallit oli valittu tähtäimessä olevien sovellusten, synteesissä ilmenneiden ongelmien tai ympäristönäkökohtien perusteella. Tulokset osoittavat näiden yhdisteiden metallinsitomiskyvyn olevan jonkin verran heikompi kuin EDTA:lla, mutta kuitenkin riittävän useisiin sovelluksiin kuten sellunvalkaisuprosessiin. Myrkyllisten raskasmetallien, kadmiumin, elohopen ja lyijyn kohdalla EDTA:a heikompi sitoutuminen on eduksikin, koska se yhdistettynä parempaan biohajoavuuteen saattaa alentaa tutkittujen yhdisteiden kykyä mobilisoida kyseisiä metalleja sedimenteistä. Useimmilla tutkituista yhdisteistä on ympäristönäkökulmasta etuna myös EDTA:a pienempi typpipitoisuus.

Synthesis and evaluation of Gd-DTPA-labeled arabinogalactans as potential MRI contrast agents

Arabinogalactan derivatives conjugated with gad olinium-diethylenetriaminepentaacetic acid (Gd-DTPA) by ethylenediamine (Gd-DTPA-CMAG-A(2)) or hexylamine (Gd-DTPA-CMAG-A(6)) have been synthesized and characterized by means of Fourier transform infrared spectra (FTIR), C-13 nuclear magnetic resonance (C-13 NMR), size exclusion chromatography (SEC), and inductively coupled plasma atomic emission spectrometry (ICP-AES).

Comparison between Gd-DTPA and several bisamide derivatives as potential MRI contrast agents

Four neutral gadolinium complexes of diethylenetriaminepentaacetic acid (DTPA)-bisamide derivatives have been synthesized and characterized. Their potential application as tissue-specific and low-osmolarity MRI contrast agents has been evaluated by in vitro and in vivo experiments. Their measured relaxivities in D2O, bovine serum albumin and human serum transferrin solutions showed favorable relaxation ability. In vivo studies have proven that Gd(DTPA-BDMA), Gd(DTPA-BIN), and Gd(cyclic-DTPA-1,2-pn) could be promising liver-specific MRI contrast agents and Gd(DTPA-BDMA), and Gd(cyclic-DTPA-1,2-pn) have favorable renal excretion capability. Among them, Gd(cyclic-DTPA-1,2-pn) is a more powerful hepatic contrast agent and Gd(DTPA-BIN) provides the stable imaging contrast for several hours. They also show a lower toxicity.

Laser-time-resolved fluorescence spectroscopy in immunoassays

This paper described a laser-excited time-resolved fluoroimmunoassay set. It made lanthanide ion to couple the anhydrde of diethylenetriaminepentaacetic acid (DTPAA) for labeling antibodies. The experiment used polystyrene tap coated with HCV antigen as the solid phase and a chelate of the rare earth metal europium as fluorescent label. A nitrogen laser beam was used to excite the Eu3+ chelates and after 60 ys delay time,the emission fluorescence was measured. Background fluorescence of short lifetimes caused by serum components and Raman scattering can be eliminated by set the delay rime. In the system condition, fluorescent spectra and fluorescent lifetimes of Eu3+ beta-naphthoyltrifluroacetone (NTA) chelates were measured. The fluorescent lifetime value is 650 mu s. The maximum emssion wavelength is 613 nm. The linear range of europium ion concentration is 1 x 10(-7)- 1 x 10(-11) g.mL(-1) and the detection limit is 1 x 10(-13) g.mL(-1). The relative standard deviation of determination ( n = 12) for samples at 0.01 ng.mL(-1) magnitude is 6.4%. Laser-TRFIA was also found to be suitable for diagnosis of HCV. The sensitvity and specificity were comparable to enzyme immunoassay. The result was obtained with laser-TRFIA for 29 human correlated well with enzyme immunoassay.

Studies on the solution structures of lanthanide(III) complexes of DTPA-BIN by NMR

The solution structures of diamagnetic lanthanide (III) complexes of DTPA-BIN (Ln = La, Y, Lu, Sc) have been investigated by H-1 NMR, C-13 NMR and 2D NMR. For each complex, two or more species of asymmetric conformations with little distinction were identified at room temperature. And their solution structures vary with the radius of the central metals. NMR spectra support the hypothesis that Sc3+ with smaller radius formed an eight-coordinated structure with DTPA-BIN, La3+ with larger radius formed nine- or ten-coordinated structures with DTPA-BIN, and Y (DTPA-BIN) and Lu (DTPA-BIN) had nine-coordinated solution structures. The solution structure of Gd (DTPA-BIN) was obtained from the similarity of radius between Gd3+ and Y3+, which is a nine-coordinated structure formed by three nitrogens, three acetate oxygens, two acetyl oxygens, one water molecule and a gadolinium(III) cation.

H-1 NMR Titration Studies of Two Novel DTPA Derivatives

Polyaminopolycarboxylate gadolinium (III) complexes have been studied intensively in recent years because of their potential uses as contrast agents for magnetic resonance imaging (MHI)([1]). The research interests are mainly focussed on Gd3+ complexes of DTPA, DOTA and their various derivatives. Four kinds of Gd3+ complexes can be used presently in clinical MRI, which are GD(DTPA)([2]), Gd(DOTA)([3]), Gd(DTPA-BMA)([4]) and Gd(HP-DO3A)([5]). Here report two new DTPA bis (amide) derivatives-diethylenetriaminepentaacetic acid-N, N ''-bis (dimethylamide) (DTPA-BDMA) and -bis (diethylamide) (DTPA-BDEA).

Oxidation of low density lipoprotein by iron at lysosomal pH: implications for atherosclerosis

Low density lipoprotein (LDL) has recently been shown to be oxidised by iron within the lysosomes of macrophages and this is a novel potential mechanism for LDL oxidation in atherosclerosis. Our aim was to characterise the chemical and physical changes induced in LDL by iron at lysosomal pH and to investigate the effects of iron chelators and α-tocopherol on this process. LDL was oxidised by iron at pH 4.5 and 37°C and its oxidation monitored by spectrophotometry and HPLC. LDL was oxidised effectively by FeSO4 (5-50 µM) and became highly aggregated at pH 4.5, but not at pH 7.4. Cholesteryl esters decreased and after a pronounced lag 7-ketocholesterol increased greatly. Total hydroperoxides (measured by tri-iodide assay) increased up to 24 h and then decreased only slowly. The lipid composition after 12 h at pH 4.5 and 37°C was similar to that of LDL oxidised by copper at pH 7.4 and 4°C, i.e. rich in hydroperoxides but low in oxysterols. Previously oxidised LDL aggregated rapidly and spontaneously at pH 4.5, but not at pH 7.4. Ferrous was much more effective than ferric iron at oxidising LDL when added after the oxidation was already underway. The iron chelators diethylenetriaminepentaacetic acid and, to a lesser extent, desferrioxamine inhibited LDL oxidation when added during its initial stages, but were unable to prevent LDL aggregating after it had been partially oxidised. Surprisingly, desferrioxamine increased the rate of LDL modification when added late in the oxidation process. α-Tocopherol enrichment of LDL initially increased the oxidation of LDL, but inhibited it later. The presence of oxidised and highly aggregated lipid within lysosomes has the potential to perturb the function of these organelles and to promote atherosclerosis.

Transition metal rates in latosol twice treated with sewage sludge

A reciclagem agrícola do lodo de esgoto tem provocado o acúmulo de metais pesados no solo e na água, podendo atingir níveis tóxicos e causar danos às plantas cultivadas, aos animais e ao homem, por meio da cadeia trófica. Neste intuito foi desenvolvido o presente experimento, em condições de campo, entre 2000 e 2002, onde foram avaliados os efeitos da aplicação de lodo de esgoto por dois anos, sobre a extração de metais de transição (essenciais e não) pelo extrator DTPA em um Latossolo Vermelho distrófico (LVd) de textura média. As concentrações dos elementos metálicos: Mn, Fe, Cd, Ni, Co, Pb e Cr não foram detectados pelo método da absorção atômica na solução obtida com o extrator DTPA. A aplicação de lodo de esgoto causou inicialmente pequena elevação no pH do solo, posteriormente a diminuição do mesmo, e manteve-se próximo ao original. Foi possível concluir que, com a aplicação consecutiva do lodo, os teores extraíveis de Fe e Mn nas amostras de solos aumentaram gradativamente nos dois anos agrícolas, com as doses do lodo de esgoto aplicado, época de amostragens, e foram superiores ao tratamento testemunha. O extrator apresentou capacidade restrita para avaliação da fitodisponibilidade dos metais pesados decorrentes das baixas concentrações nas amostras de solo.

Tungsten permanent chemical modifier for fast estimation of Se contents in soil by graphite furnace atomic absorption spectrometry

A tungsten carbide coating on the integrated platform of a transversely heated graphite atomizer was used as a modifier for the direct determination of Se in soil extracts by graphite furnace atomic absorption spectrometry. Diethylenetriaminepentaacetic acid (0.0050 mol L-1) plus ammonium hydrogencarbonate (1.0 mol L-1) extracted predominantly available inorganic selenate from soil. The formation of a large amount of carbonaceous residue inside the atomizer was avoided with a first pyrolysis step at 600 degreesC assisted by air during 30 s. For 20 muL of soil extracts delivered to the atomizer and calibration by matrix matching, an analytical curve (10.0-100 mug of L-1) with good linear correlation (r = 0.999) between integrated absorbance and analyte concentration was established. The characteristic mass was similar to63 pg of Se, and the lifetime of the tube was similar to750 firings. The limit of detection was 1.6 mug L-1, and the relative standard deviations (n = 12) were typically <4% for a soil extract containing 50 mug of L-1. The accuracy of the determination of Se was checked for soil samples by means of addition/recovery tests. Recovery data of Se added to four enriched soil samples varied from 80 to 90% and indicated an accurate method.

Ação do ácido trissódio-cálcio-dietileno-triaminopentaacético (CaNa3DTPA) nas lesões de isquemia-reperfusão em membro posterior de rato

OBJETIVO: Ação do ácido trissódio-cálcio-dietileno-triaminopentaacético (CaNa3DTPA), quelante de ferro com ação ainda anti-viral, antiinflamatória e imunológica, na atenuação de lesões de reperfusão em músculos esqueléticos de ratos. MÉTODOS: 52 ratos Wistar, pesando 188±22g, foram anestesiados e submetidos a semi-amputação de membro posterior direito (MPD), poupando-se o fêmur, artéria e veia femorais. Foram então randomizados e distribuídos: G1-CTAN - controle anestesia, sem cirurgia e sem isquemia; G2-CTCIR - controle cirurgia, sem isquemia; G3-IRCT e G3-IRDTPA - com isquemia (4 hora) e reperfusão ( 2 horas). O G3-IRCT foi tratado, ao final da isquemia, com cloreto de sódio 0,9% e G3-IRDTPA com (CaNa3DTPA).Parâmetros: Circunferência do pé direito e peso do rato, dosagem sérica de CPK, dosagem de malonaldeído e microscopia óptica de músculos soleus bilateral. RESULTADOS: Aumento da circunferência nos G3-IRCT e G3-IRDTPA (significante no G3-IRCT quando comparado ao G1-CTAN); CPK elevado nos G3-IRCT e G3-IRDTPA comparados aos controles; MDA mais alto no membro contralateral do G3-IRDTPA, comparado ao MPD do G3-IRDTPA e ao G1-CTAN; maior edema intersticial em G3-IRCT, maior infiltrado inflamatório em G3-IRDTPA e recuperação dos níveis de glicogênio semelhantes em G3-IRCT e G3-IRDTPA. CONCLUSÃO: Apesar do menor edema no G3-IRDTPA comparado ao G3-IRCT, o CaNa3DTPA não alterou CPK sérico, MDA muscular e morfologia muscular dos animais.

Reação do solo e disponibilidade de micronutrientes, em solo de textura média, tratado com lodo de esgoto e cultivado com milho

The evaluation of micronutrient availability in agricultural soil treated with sewage sludge was developed in Field with maize cultivation on a Dystrophic Red Latosol. The experiment used a randomized complete block design, with the treatments in a split-plot scheme, in time, with six doses of sewage sludge (main-plot treatment) in relation to the five sampling periods for the soil (subplot treatment), with four replications. The sewage sludge was applied in the superficial layer (0-20 cm). The micronutrients Fe, Cu, Mn and Zn were extracted from the soils using a DTPA (diethylenetriaminepentaacetic acid) solution. The same micronutrients were analyzed in the plant tissue after the nitric-perchloric decomposition of the maize samples by spectrometric atomic absorption. The results showed an increasing amount of Fe, Mn, Zn, Cu, Cation Exchange Capacity (CEC) and a decreasing pH in the soil. The increasing doses of sewage sludge increased the Fe, Mn, Cu and Zn availability in the soil solution, and the uptake amount by maize plants were always greater than the control values.

Heavy Metals Extracted by DTPA and Organic Acids from Soil Amended with Urban or Industrial Residues

Understanding soil responses to the application of urban or industrial residues is necessary. In the current experiment, both sources of residues were applied to the soil surface of a Hapludox soil for 8 years. The four residues studied were biodigested and centrifuged sewage sludge (LB and LC, respectively), steel slag from the metallurgic industry (E), and limed mud from the pulp and cellulose industry (LCal). The residues were applied at 0, 2, 4, and 8 Mg ha(-1) four times from 2002 to 2010 when soybean was cultivated in the summer and lopsided oat and sorghum were cultivated during the winter. The contents of heavy metals were evaluated with diethylenetriaminepentaacetic acid (DTPA) and organic acids. The LB was the residue that increased the contents of soil micronutrients and heavy metals to their greatest levels, although within limits that impair the risks of environmental contamination.

Somatostatin receptors as targets for nuclear medicine imaging and radionuclide treatment

Radiolabeled peptides have been an important class of compounds in radiopharmaceutical sciences and nuclear medicine for more than 20 years. Despite strong research efforts, only somatostatin-based radiopeptides have a real impact on patient care, diagnostically and therapeutically. [(111)In-diethylenetriaminepentaacetic acid(0)]octreotide is commercially available for imaging. Imaging was highly improved by the introduction of PET radionuclides such as (68)Ga, (64)Cu, and (18)F. Two peptides are successfully used in targeted radionuclide therapy when bound to DOTA and labeled with (90)Y and (177)Lu.