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1.
New poly(ether-amide) nanocomposite containing phosphine oxide was prepared via solution polymerization process from synthesized poly(ether-amide) and Fe3O4 nanoparticles in a solution of N,N-dimethylformamide. Uniform monodisperse Fe3O4 nanoparticles were synthesized at room temperature via a facile sonochemical reaction. Poly(ether-amide) (PEA) as the polymer matrix was synthesized from reaction of 1,4-(4-carboxy phenoxy)butane (1) and bis(3-amino phenyl)phenyl phosphine oxide (2) via a direct polycondensation reaction. Nanoparticle and nanocomposite were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Fourier transform infrared. The effect of the presence of Fe3O4 nanoparticles on the thermal properties of PEA was studied using thermogravimetric analysis in nitrogen atmospheres. The magnetic properties of the sample were also investigated using an alternating gradient force magnetometer. We found that the Fe3O4 nanoparticles exhibit a ferromagnetic behaviour with a saturation magnetization of 59 emu/g and a coercivity of 104 Oe at room temperature. The coercivity of PEA/Fe3O4 nanocomposites is found to be 126 Oe, higher than 104 Oe which is obtained for Fe3O4.  相似文献   

2.
For the first time a comparative study of rhombohedral LaNiO3 and LaCuO3 oxides, using 57Fe Mössbauer probe spectroscopy (1% atomic rate), has been carried out. In spite of the fact that both oxides are characterized by similar crystal structure and metallic properties, the behavior of 57Fe probe atoms in such lattices appears essentially different. In the case of LaNi0.99Fe0.01O3, the observed isomer shift (δ) value corresponds to Fe3+ (3d5) cations in high-spin state located in an oxygen octahedral surrounding. In contrast, for the LaCu0.99Fe0.01O3, the obtained δ value is comparable to that characterizing the formally tetravalent high-spin Fe4+(3d4) cations in octahedral coordination within Fe(IV) perovskite-like ferrates. To explain such a difference, an approach based on the qualitative energy diagrams analysis and the calculations within the cluster configuration interaction method have been developed. It was shown that in the case of LaNi0.99Fe0.01O3, electronic state of nickel is dominated by the d7 configuration corresponding to the formal ionic “Ni3+-O2−” state. On the other hand, in the case of LaCu0.99Fe0.01O3 a large amount of charge is transferred via Cu-O bonds from the O:2p bands to the Cu:3d orbitals and the ground state is dominated by the d9L configuration (“Cu2+−O” state). The dominant d9L ground state for the (CuO6) sublattice induces in the environment of the 57Fe probe cations a charge transfer Fe3++O(L)→Fe4++O2−, which transforms “Fe3+” into “Fe4+” state. The analysis of the isomer shift value for the formally “Fe4+” ions in perovskite-like oxides clearly proved a drastic influence of the 4s iron orbitals population on the Fe−O bonds character.  相似文献   

3.
In this study, a novel method was used to synthesize the poly(N-isopropylacrylamide-co-acrylic acid)/Fe3O4 (poly(NIPAAm-AA)/Fe3O4) magnetic composite latex. The crosslinked poly(NIPAAm-AA) polymer latex particles were first synthesized by the method of soapless emulsion polymerization, then Fe2+ and Fe3+ ions were introduced to bond with the -COOH groups of AA segments in poly(NIPAAm-AA) polymer latex particles. Further by a reaction with NH4OH, Fe3O4 nanoparticles were generated in situ. The concentrations of acrylic acid (AA), crosslinking agent (N,N′-methylene bisacrylamide (MBA)), and Fe3O4 nanoparticles were important factors to influence the morphology and lower critical solution temperature (LCST) of poly(NIPAAm-AA)/Fe3O4 magnetic composite latex particles. The poly(NIPAAm-AA)/Fe3O4 latex particles were used as a thermosensitive drug carrier to load caffeine. The control release of caffeine was studies. Morphology-based schematic models were proposed to explain the control release behavior of the composite particles with different compositions. Moreover, the protein (albumin, acetylated from bovine serum (BSA)) was bound on the surface of poly(NIPAAm-AA)/Fe3O4 composite latex particles. The effects of AA, crosslinking agent and Fe3O4 contents on the amount of BSA binding were investigated at different temperatures and pH values. The composition-morphology-BSA conjugation relationship was established.  相似文献   

4.
Five new fluorescent indicators for Ca2+ were synthesized using the Stille reaction. They all consist of the tricarboxylate chelator APTRA (o-aminophenol-N,N,O-triacetic acid) linked to a (substituted) bithiophene or terthiophene fluorophore. The dissociation constants Kd measured via fluorimetric titrations at 21 °C in 100 mM KCl buffered solution, pH 7.05, for the Ca2+ complexes with the new probes are in the range between 10 and 40 μM.  相似文献   

5.
Complexation in the Fe2+–Fe3+N-(carboxymethyl)aspartic acid (H3L) system in aqueous solutions was studied by pH- and redox-potentiometric titration at 25°C and at an ionic strength of 0.1 (KCl). Depending on the H3L concentration and pH, neutral, protonated, and hydroxo complexes of iron(III) can be formed in the solutions. The stability constants for all the detected complexes were calculated, and the distribution plots for the fractions of complexes vs. the solution pH were constructed.  相似文献   

6.
The electrochemical properties of n-sulfonatothiacalyx[4]arene (H4XNa4) complexes with [Co(dipy)3]3+ and Fe3+ ions were studied by means of cyclic voltammetry in aqueous solution at pH 2.5. The observed single-electron reduction of [Co(dipy)3]3+ bound extraspherically to the upper rim and Fe3+ ion bound intraspherically to the lower rim of n-sulfonatothiacalyx[4]arene in binary [Co(dipy)3]3+ · H3X5?, H3X5? · Fe3+, and ternary [Co(dipy)3]3+ · H3X5? · Fe3+ heterometal complexes was more difficult than in the free state. The reversible single-electron transfer to the metal ion results in lower binding energy ([Co(dipy)3]3+, ΔΔG 0 = 3.9 kJ/mol) or in full fast dissociation of the complex (Fe3+). The ternary complex in the solution forms the aggregates, in which inner encapsulated Fe(III) and Co(III) ions are not reduced on the electrode. Their quantitative reduction takes place by the relay mechanism of intra- and intermolecular electron transfer through electrochemically generated [Co(dipy)3]2+ outer ions.  相似文献   

7.
《Tetrahedron letters》2019,60(20):1363-1369
A Fe3+-specific probe (N-TC) based on Rhodamine B was designed and synthesized. N-TC has a good spectral response to Fe3+ in the EtOH/H2O solution (1:1, v/v, HEPES, 0.5 mM, pH = 7.38) with low detection limits and high binding constants. N-TC displays the reversible “turn-off-on” fluorescence response with 1:1 binding stoichiometry. It is further proven to be practical in sensitively monitoring trace Fe3+ in environmental water specimens. Biological experiments demonstrated that N-TC can be respectively used as a probe for detection of Fe3+ in living cells, animals and plant tissues.  相似文献   

8.
Heme and nonheme-type flavone synthase enzymes, FS I and FS II are responsible for the synthesis of flavones, which play an important role in various biological processes, and have a wide range of biomedicinal properties including antitumor, antimalarial, and antioxidant activities. To get more insight into the mechanism of this curious enzyme reaction, nonheme structural and functional models were carried out by the use of mononuclear iron, [FeII(CDA-BPA*)]2+ (6) [CDA-BPA = N,N,N’,N’-tetrakis-(2-pyridylmethyl)-cyclohexanediamine], [FeII(CDA-BQA*)]2+ (5) [CDA-BQA = N,N,N’,N’-tetrakis-(2-quinolilmethyl)-cyclohexanediamine], [FeII(Bn-TPEN)(CH3CN)]2+ (3) [Bn-TPEN = N-benzyl-N,N’,N’-tris(2-pyridylmethyl)-1,2-diaminoethane], [FeIV(O)(Bn-TPEN)]2+ (9), and manganese, [MnII(N4Py*)(CH3CN)]2+ (2) [N4Py* = N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine)], [MnII(Bn-TPEN)(CH3CN)]2+ (4) complexes as catalysts, where the possible reactive intermediates, high-valent FeIV(O) and MnIV(O) are known and well characterised. The results of the catalytic and stoichiometric reactions showed that the ligand framework and the nature of the metal cofactor significantly influenced the reactivity of the catalyst and its intermediate. Comparing the reactions of [FeIV(O)(Bn-TPEN)]2+ (9) and [MnIV(O)(Bn-TPEN)]2+ (10) towards flavanone under the same conditions, a 3.5-fold difference in reaction rate was observed in favor of iron, and this value is three orders of magnitude higher than was observed for the previously published [FeIV(O)(N2Py2Q*)]2+ [N,N-bis(2-quinolylmethyl)-1,2-di(2-pyridyl)ethylamine] species.  相似文献   

9.
Three novel compounds bearing 2,7-dihydroxylnaphthalene capable of detecting Cu2+ or Fe3+ have been synthesised based on photoinduced electron transfer. The ability of these compounds for complex transition metal ions has been studied, and complex stoichiometry for Cu2+ and Fe3+ complex has been determined in the Tris–HCl (0.01 M DMSO/H2O (v/v) 1:1, buffer, pH 7.4) solution system by fluorescence titration experiments. These chemosensors form a 1:1 complex with Cu2+ or Fe3+ and show a fluorescent quenching with a binding constant of (4.46 ± 0.29) × 103 and (8.04 ± 0.26) × 104, respectively.  相似文献   

10.
A new glucose-based C2-derivatized colorimetric chemo-sensor (L1) has been synthesized by a one-step condensation of glucosamine and 2-hydroxy-1-naphthaldehyde for the recognition of transition metal ions. Among the eleven metal ions studied, viz., Mg2+, Ca2+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Hg2+, L1 results in visual colour change only in the presence of Fe2+, Fe3+and Cu2+ in methanol. However, in an aqueous HEPES buffer (pH 7.2) it is only the Fe3+ that gives a distinct visual colour change even in the presence of other metal ions, up to a concentration of 280 ppb. The changes have been explained based on the complex formed, and the composition has been determined to be 2:1 between L1 and Fe3+ based on Job’s plot as well as ESI MS. The structure of the proposed complex has been derived based on HF/6-31G calculations.  相似文献   

11.
The alkali sodium ferrate (IV) Na4FeO4 has been prepared by solid-state reaction of sodium peroxide Na2O2 and wustite Fe1−xO, in a molar ratio Na/Fe=4, at 400°C under vacuum. Powder X-ray and neutron diffraction studies indicate that Na4FeO4 crystallizes in the triclinic system P−1 with the cell parameters= a=8.4810(2) Å, b=5.7688(1) Å, c=6.5622(1) Å, α=124.662(2)°, β=98.848(2)°, γ=101.761(2)° and Z=2. Na4FeO4 is isotypic with the other known phases Na4MO4 (M=Ti, Cr, Mn, Co and Ge, Sn, Pb). The solid solution Na4FexCo1−xO4 exists for x=0-1 and we have followed the evolution of the cell parameters with x to determine the lattice parameters of the triclinic cell of Na4FeO4. A three-dimensional network of isolated FeO4 tetrahedra connected by Na atoms characterizes the structure. This compound is antiferromagnetic below TN=16 K. At 2 K the magnetic cell is twice the nuclear cell and the magnetic structure is collinear (μFe=3.36(12) μB at 2 K). This black compound is highly hygroscopic. In water or on contact with the atmospheric moisture it is disproportionated in Fe3+ and Fe6+. The Mössbauer spectra of Na4FeO4 are fitted with one doublet (δ=− 0.22 mm/s, Δ=0.41 mm/s at 295 K) in the paramagnetic state and with a sextet at 8K. These parameters characterize Fe4+ high-spin in tetrahedral FeO4 coordination.  相似文献   

12.
The absorption of Fe3+ ion from the aqueous phase to the solid phase was carried out by using p-tert-butyl calix[6]arene (L1), calix[6]arene (L2), p-tert-butyl calix[8]arene (L3), and calix[8]arene (L4). The effect of varying pH upon the absorption capability of parent calixarenes was examined. It was found that the compounds (L1, L2, L3, and L4) showed the highest extractability toward Fe3+ ion at 4.5–5.4. The calixarene L2 shows a strong binding ability to Fe3+ ion. Based on the continuous variation method, calixarene L2 formed 1:1 complex with Fe3+ ion.  相似文献   

13.
The existence of homoserine lactone in Pisum sativum seedlings is demonstrated. L-Homoserine lactone reacts with hydroxylamine, at neutral or alkaline pH, to form homoserine hydroxamic acid. Procedures are described for preparing L-homoserine lactone and L-homoserine hydroxamic acid. The hydroxamic acid yields a color with maximum absorbance at 492 nm with Fe3+ in 0.25 N HCl. This reaction permitted assay for total homoserine and homoserine lactone. Six-day old Pisum sativum seedlings, with cotyledons removed, were extracted with 90% ethanol. Evaporation of the ethanol and addition of Na2SO4 solution and toluene and centrifugation removed protein lipids and esters. After clarification with activated charcoal, homoserine lactone content was estimated by reaction with NH2OH and Fe3+ reagents. For total homoserine, protein precipitation was with 2 N HCl and toluene. Evaporation to dryness at 60 °C under vacuum converted all homoserine to the lactone. The values found for total homoserine (μmols/g, wet weight) and preformed lactone (%) with the various growth media used were as follows: nitrate 87.4 (14.7%), NH2OH 75.2 (6.3%), water 70.5 (7.9%), urea 56.4 (18.9%). Acetic anhydride added to homoserine hydroxamic acid forms acetohydroxamic acid, which yields a color with maximum absorbance at 505 nm with Fe3+. This color reaction is seven times as sensitive as the reaction of Fe3+ with homoserine hydroxamic acid itself.  相似文献   

14.
In this work, we synthesised and characterised three novel fluorescence macrocyclic sensors containing optically active dansyl groups. The studies for the interaction of the synthesised compounds with various mental ions (Li+, Na+, K+, Ag+, Mg2+, Ca2+, Ba2+, Pb2+, Zn2+, Co2+, Cd2+, Hg2+, Ni2+, Cu2+, Mn2+, Cr3+, Al3+, Fe3+) were performed by fluorescence titration, Job’s plot, ESI-MS and DFT calculations. The results showed that the sensors 1a–1c displayed selective recognition for Cu2+ and Fe3+ ions and formed stoichiometry 1:1 complex through PET mechanism in DMSO/H2O solution (1:1, v/v, pH 7.4 of HEPES). The binding constant (K) and detection limit were calculated.  相似文献   

15.
Copper (II) complex of 2,4-dimethyl-1,5,9,12-tetraazacyclopentadeca-1,4-diene, [Me2(15)dieneN4] was synthesized and used in the fabrication of Cu2+ – selective ISE membrane in PVC matrix. The membrane having Cu(II) macrocyclic complex as electroactive material along with sodium tetraphenyl borate (NaTPB) as anion discriminator. Dibutyl phthalate (DBP) as plasticizer in poly(vinyl chloride) (PVC) matrix was prepared for the determination of Cu2+. The best performance was observed by the membrane having Cu(II) complex–PVC–NaTPB–DBP with composition 1:5:1:3. The sensor worked well over a concentration range 1.12 × 10−6 M–1.0 × 10−1 M between pH 2.1–6.2 and a fast response time 10±2 s and a lifetime of 6 months. Their performance in partially non-aqueous medium was found satisfactory. Electrodes exhibited excellent selectivity for Cu2+ ion over other mono-, di-, trivalent cations. It can also be used as indicator electrode in the potentiometric titration of Cu2+ against EDTA as well as in the determination of Cu2+ in real samples.  相似文献   

16.
A new HfIV‐based metal‐organic framework with UiO‐66 topology was synthesized via a one‐step solvothermal method by using 3‐methyl‐4‐phenylthieno[2,3‐b]thiophene‐2,5‐dicarboxylic acid (H2MPTDC) as a ligand. The MOF material showed a high stability in a broad pH range (from pH 2 to pH 12) in an aqueous medium. The presence of hydrophobic methyl and phenyl substituents in the carboxylic acid ligand and strong Hf?O bond play crucial roles in its stability. The new MOF material was systematically characterized by various techniques such as XRPD, N2 sorption, thermogravimetric analyses and FT‐IR spectroscopy. The photophysical properties of the MOF material were also examined by steady‐state and time‐resolved fluorescence studies. It was observed that the blue fluorescence of the MOF material was selectively quenched in the presence of Fe3+ ion in pure aqueous medium. A mechanistic study disclosed that quenching occurs via a strong inner filter effect (IFE) arising from Fe3+ ion in aqueous medium. Interestingly, the fluorescence of the MOF material can be recovered by elimination of the IFE of Fe3+ ion via reduction of Fe3+ ion by ascorbic acid (AA). Based on the fluorescence recovery by AA, a MOF based on‐off‐on probe was developed for the sensing of Fe3+ ion and AA in aqueous medium. Inspired by this reversible sensing event, we demonstrate basic (NOT, OR, YES, INHIBIT and IMP) and higher integrated logic operations utilizing this fluorescent MOF. This MOF‐based logic systems could be potentially used for next‐generation logic‐gate based analytical applications as well as for the detection and discrimination of targeted molecules in various complex domains.  相似文献   

17.
This work reports the preparation of new Cu2+ ion-imprinted polymeric nanoparticles using 1-hydroxy-4-(prop-2′-enyloxy)-9,10-anthraquinone (AQ) as a vinylated chelating agent. The Cu2+ ion found to form a stable 1:1 complex with AQ in methanol solution. The resulting Cu2+-AQ complex was copolymerized with ethyleneglycol dimethacrylate, as a cross-linking monomer, via precipitation polymerization method. The imprint copper ion was removed from the polymeric matrix using a 0.1 mol L−1 HNO3 solution. The Cu2+-imprinted polymeric nanoparticles were characterized by IR spectroscopy, scanning electron microscopy (SEM) and N2 adsorption-desorption isotherms. The SEM micrographs showed colloidal nanoparticles of 60-100 nm in diameter and slightly irregular in shape. Optimum pH for maximum sorption was 7.0. Sorption and desorption of Cu2+ ion on the IIP nanoparticles were quite fast and achieved completely over entire investigated time periods of 2-30 min. Maximum sorbent capacity and enrichment factor of the prepared IIP for Cu2+ were 73.8 μmol g−1 and 56.5, respectively. The relative standard deviation and limit of detection (CLOD = 3Sb/m) of the method were evaluated as 2.6% and 0.1 ng mL−1, using inductively coupled plasma-atomic emission spectrometry, respectively. It was found that the imprinting technology results in increased affinity of the prepared material toward Cu2+ ion over other metal ions with the same charge and close ionic radius. The relative standard deviations for six and twenty replicates with the same nanoparticles were found to be 1.7% and 2.1%, respectively.  相似文献   

18.
Here, we report an ultra-sensitive and colorimetric sensor for the detection of Fe3+ or Cu2+ successively using glutathione-functionalized Au nanoclusters (GSH-AuNCs). For GSH-AuNCs can catalytically oxidize peroxidase substrates, such as 3, 3′, 5, 5′-tetramethylbenzidine (TMB), colored products are formed in the presence of H2O2. While upon the addition of Fe3+ or Cu2+ into the GSH-AuNCs-TMB-H2O2 system, diverse color and absorbance of the system was obtained due to the self oxidation of Fe3+ and the inhibition of peroxidase-like activity of GSH-AuNCs. With the introduction of ethylene diamine tetraacetic acid (EDTA) or ammonium fluoride (NH4F) to GSH-AuNCs-TMB-H2O2+Cu2+ system or GSH-AuNCs-TMB-H2O2+Fe3+ system respectively, a restoration of color and absorbance of system was realized. On the basis of above phenomenon, a colorimetric and quantitative approach for detecting Fe3+ and Cu2+ was developed with detection limit of 1.25 × 10−9 M and 1.25 × 10−10 M respectively. Moreover, the concentration of Fe3+ and Cu2+ in human serums was also accurate quantified by this method. So this design strategy realized the simple and simultaneous detection of Fe3+ and Cu2+, suggesting significant potential in clinical diagnosis.  相似文献   

19.
ABSTRACT

Perimedine labelled rhodamine dye 1 has been designed and synthesised. Metal ion binding studies of 1 have been performed in CH3CN/H2O (3:1, v/v, 10 mM Tris-HCl buffer, pH = 6.90). Compound 1 senses multiple metal ions such as Al3+, Fe3+ and Fe2+ by exhibiting turn on fluorescence and colour change (colourless to pink) under different experimental conditions. Concentration variation distinguishes Al3+ from Fe3+ ion. At low concentration (c = 1 x 10?4 M), only Al3+ ion can exhibit turn on fluorescence with sharp colour change. Sensing of Fe2+ ion through turn on fluorescence and colour change has been possible via in situ oxidation by following Fenton’s reaction.  相似文献   

20.
A new tetraphenylethylene (TPE)-based sensor M1 bearing double 2-methylpyridyl-2-methylthiophenylamino units linked with triazole moieties was reported. Both UV–vis and fluorescence spectroscopic studies demonstrated that M1 was highly sensitive and selective toward Fe3+ over other metal ions in THF/H2O solution based on the aggregation-induced emission quenching mechanism. The lowest detection limit of M1 for Fe3+ is 0.7 μM. The detailed fluorescent titration study suggested that the binding stoichiometry of the M1–Fe3+ complex was 1:2, and the structure between M1 and the Fe3+ complex was confirmed by the 1H NMR titration.  相似文献   

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