A ratiometric fluorescent chemosensor for iron: discrimination of Fe2+ and Fe3+ and living cell application

A newly designed probe, 6-thiophen-2-yl-5,6-dihydrobenzo[4,5]imidazo-[1,2-c] quinazoline (HL(1)) behaves as a highly selective ratiometric fluorescent sensor for Fe(2+) at pH 4.0-5.0 and Fe(3+) at pH 6.5-8.0 in acetonitrile-HEPES buffer (1/4) (v/v) medium. A decrease in fluorescence at 412 nm and increase in fluorescence at 472 nm with an isoemissive point at 436 nm with the addition of Fe(2+) salt solution is due to the formation of mononuclear Fe(2+) complex [Fe(II)(HL)(ClO(4))(2)(CH(3)CN)(2)] (1) in acetonitrile-HEPES buffer (100 mM, 1/4, v/v) at pH 4.5 and a decrease in fluorescence at 412 nm and increase in fluorescence at 482 nm with an isoemissive point at 445 nm during titration by Fe(3+) salt due to the formation of binary Fe(3+) complex, [Fe(III)(L)(2)(ClO(4))(H(2)O)] (2) with co-solvent at biological pH 7.4 have been established. Binding constants (K(a)) in the solution state were calculated to be 3.88 × 10(5) M(-1) for Fe(2+) and 0.21 × 10(3) M(-1/2) for Fe(3+) and ratiometric detection limits for Fe(2+) and Fe(3+) were found to be 2.0 μM and 3.5 μM, respectively. The probe is a "naked eye" chemosensor for two states of iron. Theoretical calculations were studied to establish the configurations of probe-iron complexes. The sensor is efficient for detecting Fe(3+)in vitro by developing a good image of the biological organelles.     

Ionic specificity in pH regulated charged interfaces: Fe3+ versus La3+

We determine the distribution of two trivalent ions Fe(3+) and La(3+) next to two different amphiphilic charged interfaces as ions or complexes, consisting of the phosphate lipid dihexadecyl phosphate (DHDP) and the fatty acid arachidic acid (AA). These amphiphiles provide a wide range of pK(a) values, from 2.1 (DHDP) to 5.1 (AA), thus allowing manipulation of the surface charge over extremely low pH (pH ～1 or larger), and the two ions provide two limiting cases of specificity for the amphiphiles. We find that La(3+) distribution is mostly sensitive to the surface charge, whereas the Fe(3+) binding depends on its character in the solution and is highly specific, as indicated by the crucial role played by iron complexes (Fe(OH)(3) or Fe(OH)(2+)) forming covalent bonds even for an uncharged interface. The implications of the results to other ions and/or amphiphilic interfaces are also discussed.     

Colorimetric detection of Fe3+ ions using pyrophosphate functionalized gold nanoparticles

A sensitive, selective colorimetric Fe(3+) detection method has been developed by using pyrophosphate functionalized gold nanoparticles (P(2)O(7)(4-)-AuNPs). Gold nanoparticles were prepared by reducing HAuCl(4) with sodium borohydride, in the presence of Na(4)P(2)O(7). IR spectra suggested that pyrophosphates were capped on the surface of the gold nanoparticles. Aggregation of P(2)O(7)(4-)-AuNPs was induced immediately in the presence of Fe(3+) ions, yielding a color change from pink to violet. This Fe(3+)-induced aggregation of P(2)O(7)(4-)-AuNPs was monitored using first the naked eye and then UV-vis spectroscopy with a detection limit of 5.6 μM. The P(2)O(7)(4-)-AuNPs bound by Fe(3+) showed excellent selectivity compared to other metal ions (Ca(2+), Cd(2+), Co(2+), Fe(2+), Hg(2+), K(+), Mg(2+), Mn(2+), Na(+), Ni(2+), Pb(2+), and Zn(2+)). The best detection of Fe(3+) was achieved in a pH range from 3 to 9. In addition, the P(2)O(7)(4-)-AuNPs were also used to detect Fe(3+) in lake water samples, with low interference.     

Local structure of Mn4+ and Fe3+ spin probes in layered LiAlO2 oxide by modelling of zero-field splitting parameters

The zero-field splitting parameters (ZFS) of Mn(4+) and Fe(3+) ions in LiAlO(2) with a layered structure are analyzed experimentally and theoretically by using high-frequency electron paramagnetic resonance spectroscopy, Neuman superposition model (NSM), DFT and multiconfigurational calculations. The interpretation of ZFS is based on the comparison of the experimentally determined values with the calculated ones. This approach allows assessing the performance of different methods for computation of ZFS of Fe(3+) and Mn(4+) in layered oxide matrices. DFT and multiconfigurational calculations are used to analyze the effect of oxygen, aluminium, and lithium neighbours on ZFS of Fe(3+) and Mn(4+). These calculations are based on a cluster comprising Fe(3+) or Mn(4+) ions in a trigonally compressed octahedron with 6 metal ions (Al(3+) or Co(3+)) as first metal neighbours and 6 O(2-) and 2 Li(+) (above and below the layer) as second neighbours. A satisfactory agreement with the experimental data is achieved when the local structure of Mn(4+) and Fe(3+) deviates from the trigonal host-site geometry. The local structure of Fe(3+) comprises an axial distortion, while trigonal environment with reduced extent of distortion appears around Mn(4+).     

Thiacalix[4]arene based fluorescent probe for sensing and imaging of Fe3+ ions

A thiacalix[4]arene based fluorescent chemosensor 3 in the cone conformation has been synthesized and its recognition behaviour is evaluated toward various metal ions in mixed aqueous media. The chemosensor 3 showed high selectivity towards Fe(3+) ions by fluorescence quenching of excimer emission. Further, evaluation of the 3·Fe(3+) complex prepared in situ demonstrated great promise for the detection of the Fe(3+) ion in the presence of amino acids, blood serum and bovine serum albumin (BSA) solution. The compound 3 has suitable permeability into the PC3 cells and can be utilized as a Fe(3+) selective sensor in living cells (PC3 cells).     

水热合成Fe3+掺杂ZnO复合材料及其光催化活性

以Zn(Ac)2·2H2O、Fe(NO3)3·9H2O和NaOH为原料,采用水热法合成了Fe3+掺杂ZnO复合材料. 并用X射线衍射和扫描电子显微镜测试技术对合成样品的结构和形貌进行了表征. 结果表明,Fe3+掺杂ZnO合成产物为直棒状,直径为500 nm,长度为3 μm左右. 样品的紫外可见漫反射分析结果表明,在300～500 nm紫外可见光区域均有强的吸收. Fe3+掺杂ZnO作为光催化剂降解有机染料性能优于纯ZnO材料.     

EPR and ENDOR analysis of Fe3+ impurity centers in fluoroelpasolite lattices

Fe(3+) ions in hexagonal and cubic fluoroelpasolite crystals (A(1)(2)B(I)M(III)F(6)) have been investigated in a combined Electron Paramagnetic Resonance (EPR) and Electron Nuclear Double Resonance (ENDOR) study. A detailed analysis of the ENDOR spectra for the nearest (19)F and (23)Na shells in X (9.5 GHz) and Q band (34 GHz) allowed the complex EPR spectra to be disentangled and to determine the spin Hamiltonian parameters for the various S = 5/2 Fe(3+) centres. W-band (95 GHz) EPR measurements as a function of temperature were performed to provide unambiguous evidence about the absolute signs of the Zero Field Splitting (ZFS) and SuperHyperFine (SHF) parameters for Fe(3+) in Cs(2)NaAlF(6) as already determined from the ENDOR work. It could be concluded that all principal (19)F hyperfine values were positive, in agreement with earlier assignments in the literature for related systems. A comparative analysis of the (19)F SHF data for Fe(3+) at a perfectly octahedral site in the cubic crystal, and at two slightly trigonally distorted environments in the hexagonal crystals, indicates that the metal-to-ligand distance changes upon doping. The obtained set of parameters concerning one defect in various analogous environments can furthermore be used to test different methods of theoretical calculations for ZFS and SHF values.     

Selective detection of Fe2+ by combination of CePO4:Tb3+ nanocrystal-H2O2 hybrid system with synchronous fluorescence scan technique

A new method for quenching kinetic discrimination of Fe(2+) and Fe(3+), and sensitive detection of trace amount of Fe(2+) was developed by using synchronous fluorescence scan technique. The principle of this assay is based on the quenching kinetic discrimination of Fe(2+) and Fe(3+) in CePO(4):Tb(3+) nanocrytals-H(2)O(2) hybrid system and the Fenton reaction between Fe(2+) and H(2)O(2). Stable, water-soluble and well-dispersible CePO(4):Tb(3+) nanocrystals were synthesized in aqueous solutions, and characterized by transmission electron microscopy (TEM) and electron diffraction spectroscopy (EDS). We found that both Fe(2+) and Fe(3+) could quench the synchronous fluorescence of CePO(4):Tb(3+) nanocrytals-H(2)O(2) system, but their quenching kinetics velocities were quite different. In the presence of Fe(3+), the synchronous fluorescent intensity was unchanged after only one minute, but in the presence of Fe(2+), the synchronous fluorescent intensity decreased slowly until 28 min later. The Fenton reaction between Fe(2+) and H(2)O(2) resulted in hydroxyl radicals which effectively quenched the synchronous fluorescence of the CePO(4):Tb(3+) nanocrystals due to the oxidation of Ce(3+) into Ce(4+) by hydroxyl radicals. Under optimum conditions, the linear range for Fe(2+) is 3 nM-2 μM, and the limit of detection is 2.0 nM. The method was used to analyze water samples.     

Local coordination of Fe3+ in Li[Co(0.98)Fe(0.02)]O2 as cathode material for lithium ion batteries-multi-frequency EPR and Monte-Carlo Newman-superposition model analysis

The local coordination of the Fe(3+)-centers in Li[Co(0.98)Fe(0.02)]O(2) cathode materials for lithium-ion batteries has been investigated by means of XRD and multi-frequency EPR spectroscopy. EPR clearly showed the Fe(3+) being in a high-spin state with S = 5/2. The set of spin-Hamiltonian parameters obtained from multi-frequency EPR experiments with Larmor frequencies ranging between 9.8 and 406 GHz was transformed into structural information by means of an expansion to standard Newton-superposition modeling, termed as Monte-Carlo Newman superposition modeling. Based on this analysis, an isovalent incorporation of the Fe(3+)-ions on the Co(3+)-sites, i.e. Fe(x)(Co), has been shown. With that respect, the positive sign of the axial second-order fine-structure interaction parameter B(0)(2) is indicative of an elongated oxygen octahedron, whereas B(0)(2) < 0 points to a compressed octahedron coordinated about the Fe(3+)-center. Furthermore, the results obtained here suggest that the oxygen octahedron about the Fe(3+)-ion is slightly distorted as compared to the CoO(6) octahedron, which in turn may impose mechanical strain to the cathode material.     

Three rhodamine-based "off-on" chemosensors with high selectivity and sensitivity for Fe3+ imaging in living cells

Three new rhodamine-based probes Y1-Y3 were synthesized as "off-on" chemosensors for Fe(3+) imaging in living cells. The recognizing behaviors were investigated both experimentally and computationally. The crystal structure of the complex Y3-Fe(3+) revealed that Fe(3+) preferred to coordinate with the N atom of benzothiazole moiety rather than the O atom of carboxyl group.     

Structural studies of Na-montmorillonite exchanged with Fe2+, Cr3+, and Ti4+ by N2 adsorption and EXAFS

The structures of Fe(2+)-, Cr(3+)-, and Ti(4+)-modified montmorillonite prepared from ion exchange of the Na-clay with Fe(2+), Cr(3+), and Ti(4+) were investigated. Conventional BET surface area and spectroscopic analysis by extended adsorption fine structure (EXAFS) were applied. It was shown that the BET surface area of Na-clay was similar to that of Fe-clay, but somewhat different from those of Cr- and Ti-clay; it decreased in the order Na- > Fe- > Ti- > Cr-montmorillonite. This sequence appeared to be consistent with the ion size Na(+) (0.95 nm)>Fe(2+) (0.65 nm)>Cr(3+) (0.62 nm), except for Ti(4+) (0.69 nm). EXAFS data showed that some Si atoms within montmorillonite were replaced by Ti atoms and that a neostructure of titanium oxide was formed.     

基于香豆素与胍的荧光探针的合成及对Co2+、Fe3+的识别研究(英文)

本论文设计合成了基于1,3-二氨基胍盐酸盐、氨基胍盐酸盐的新型香豆素类荧光探针L1、L2。通过紫外-可见、荧光光谱的变化研究探针L1、L2对金属离子的识别效应。利用Job’s plot曲线确定探针L1与Co²⁺形成了1∶2的配合物,探针L2和Fe³⁺形成了3∶1的配合物,且表现为明显的荧光增强。探针L1对Co²⁺的检出限可达到10^-6mol/L,探针L2对Fe³⁺的检出限可达到10^-7mol/L。两种高灵敏度荧光探针有望应用于生物和环境监测领域。     

Terbium hybrid particles with spherical shape as luminescent probe for detection of Cu2+ and Fe3+ in water

A novel green emissive terbium inorganic-polymeric hybrid particle was designed and this material could detect cations in water. Polyvinyl alcohol as an amphiphilic surfactant rendered the powders dispersible in water with regular round shape (10-20 μm). Interestingly, we noticed that not only Cu(2+) (detection limit 10(-4)M) but also Fe(3+) (detection limit 10(-4) M) can give rise to emission quenching to this target material in comparison with K(+), Na(+), Fe(2+), Mn(2+), Pd(2+), Cd(2+) and Co(2+) (10(-3) mol L(-1)). We regarded that the coordination interactions between ligand and metal ions resulted in these quenching processes. Additionally, it was found that the sensing material can be repeatedly used at least 5 cycles. More importantly, this novel material demonstrated higher thermal-stability in aqueous media than pure silica hybrid material.     

Selective sensing of Fe3+ based on fluorescence quenching by 2,6-bis(benzoxazolyl)pyridine with beta-cyclodextrin in neutral aqueous solution

A selective and sensitive fluorescent chemosensor (BBOZP-CD) for Fe(3+) was composed of water-soluble beta-cyclodextrins and 2,6-bis(benzoxazolyl)pyridine which was synthesized through the reaction of 2,6-pyridinedicarboxylic acid and o-aminophenol catalyzed by polyphosphoric acid under microwave irradiation. The chemosensor BBOZP-CD for metal ions were carefully investigated by fluorescent quenching in present of metal ions. The result showed BBOZP-CD chemosensor was remarkable fluorescence quenching and a highly selectivity and sensitivity for Fe(3+) in neutral aqueous solution, and the other common metal ions did not notably disturb the detection of Fe(3+). Additionally, the effect of pH to the chemosensor for Fe(3+) was also studied. The result indicated the respond signals of BBOZP-CD to Fe(3+) was stable and hardly influenced while the pH value was greater than 3.6.     

New oxides showing an intense orange color based on Fe3+ in trigonal-bipyramidal coordination

Hexagonal YIn(1-x)Fe(x)O(3) phases have been prepared and characterized. The coordination for the In/Fe site in this structure is trigonal-bipyramidal. The colors of the phases change from yellow to orange to dark red with increasing Fe content. Magnetic measurements confirm high-spin Fe(3+) for all phases.     

Fluorescent probe: complexation of Fe3+ with the myo-inositol 1,2,3-trisphosphate motif

Natural myo-inositol phosphate antioxidants containing the 1,2,3-trisphosphate motif bind Fe(3+) in the unstable penta-axial conformation.     

Magnetism of cyano-bridged hetero-one-dimensional Ln3+-M3+ complexes (Ln3+ = Sm,Gd, Yb; M3+ = FeLS,Co)

The reaction of Ln(NO(3))(3).aq with K(3)[Fe(CN)(6)] or K(3)[Co(CN)(6)] and 2,2'-bipyridine in water led to five one-dimensional complexes: trans-[M(CN)(4)(mu-CN)(2)Ln(H(2)O)(4) (bpy)](n)().XnH(2)O.1.5nbpy (M = Fe(3+) or Co(3+); Ln = Sm(3+), Gd(3+), or Yb(3+); X = 4 or 5). The structures for [Fe(3)(+)-Sm(3+)] (1), [Fe(3)(+)-Gd(3+)] (2), [Fe(3)(+)-Yb(3+)] (3), [Co(3)(+)-Gd(3+)] (4), and [Co(3)(+)-Yb(3+)] (5) have been solved; they crystallize in the triclinic space P1 and are isomorphous. The [Fe(3+)-Sm(3+)] complex is a ferrimagnet, its magnetic studies suggesting the onset of weak ferromagnetic 3-D ordering at 3.5 K. The [Fe(3+)-Gd(3+)] interaction is weakly antiferromagnetic. The isotropic nature of Gd(3+) allowed us to evaluate the exchange interaction (J = 0.77 cm(-)(1)).     

Collision-induced dissociation tandem mass spectrometry of desferrioxamine siderophore complexes from electrospray ionization of UO2(2+), Fe3+ and Ca2+ solutions

Desferrioxamine (DEF) is a trihydroxamate siderophore typical of those produced by bacteria and fungi for the purpose of scavenging Fe(3+) from environments where the element is in short supply. Since this class of molecules has excellent chelating properties, reaction with metal contaminants such as actinide species can also occur. The complexes that are formed can be mobile in the environment. Because the natural environment is extremely diverse, strategies are needed for the identification of metal complexes in aqueous matrices having a high degree of chemical heterogeneity, and electrospray ionization mass spectrometry (ESI-MS) has been highly effective for the characterization of siderophore-metal complexes. In this study, ESI-MS of solutions containing DEF and either UO(2)(2+), Fe(3+) or Ca(2+) resulted in generation of abundant singly charged ions corresponding to [UO(2)(DEF - H)](+), [Fe(DEF - 2H)](+) and [Ca(DEF - H)](+). In addition, less abundant doubly charged ions were produced. Mass spectrometry/mass spectrometry (MS/MS) studies of collision-induced dissociation (CID) reactions of protonated DEF and metal-DEF complexes were contrasted and rationalized in terms of ligand structure. In all cases, the most abundant fragmentation reactions involved cleavage of the hydroxamate moieties, consistent with the idea that they are most actively involved with metal complexation. Singly charged complexes tended to be dominated by cleavage of a single hydroxamate, while competitive fragmentation between two hydroxamate moieties increased when the doubly charged complexes were considered. Rupture of amide bonds was also observed, but these were in general less significant than the hydroxamate fragmentations. Several lower abundance fragmentations were unique to the metal examined: abundant loss of H(2)O occurred only for the singly charged UO(2)(2+) complex. Further, NH(3) was eliminated only from the singly charged Fe(3+) complex; this and fragmentation of C-C and C-N bonds derived from neither the hydroxamate nor the amide groups suggested that Fe(3+) insertion reactions were competing with ligand complexation. In no experiments were coordinating solvent molecules observed, attached either to the intact complexes or to the fragment ions, which indicated that both intact DEF and its fragments were occupying all of the coordination sites around the metal centers. This conclusion was based on previous experiments that showed that undercoordinated UO(2)(2+) and Fe(3+) readily added H(2)O and methanol in the ESI quadrupole ion trap mass spectrometer that was used in this study.     

Coagulation of bitumen with kaolinite in aqueous solutions containing Ca2+, Mg2+ and Fe3+: effect of citric acid

Heterocoagulation experiments of kaolinite with solvent-diluted-bitumen were carried out to investigate the effect of hydrolyzable metal cations and citric acid on the liberation of bitumen from kaolinite. The adsorption of Ca(2+) and Mg(2+) on kaolinite, and zeta potentials of kaolinite and bitumen droplets in solutions containing 10(-3)mol/L of Ca(2+), Mg(2+) and Fe(3+) with or without citric acid were also measured. It was found that the heterocoagulation of bitumen with kaolinite was enhanced in the presence of the metal cations from pH 7 to pH 10.5, accompanied by a decrease in the magnitude of the zeta potentials and an increase in the adsorption of the metal cations on kaolinite and possibly on bitumen droplets. The addition of 5 x 10(-4)mol/L citric acid reduced the degree of coagulation from 90% to less than 40% in the presence of 10(-3)mol/L Ca(2+) and Mg(2+) cations at pH approximately 10, and at pH approximately 8 for Fe(3+). It was found that hydrolyzable metal cations enhanced bitumen-kaolinite interactions through electrical double layer compression and specific adsorption of the metal hydrolysis species on the surface of kaolinite. The effect of metal cations was removed by citric acid through formation of metal-citrate complexes and/or the adsorption of citrate anions, which restored the zeta potentials of both kaolinite and bitumen. Therefore, electrostatic attraction or repulsion was responsible for the coagulation or dispersion of kaolinite particles from bitumen droplets in the tested system.     

A terpyridyl-imidazole (tpy-HImzPh3) based bifunctional receptor for multichannel detection of Fe2+ and F- ions

The X-ray crystal structures of the tridentate ligand, 4'-[4-(4,5-diphenyl-1H-imidazol-2-yl)-phenyl]-[2,2':6',2']terpyridine (tpy-HImzPh(3)) and its bis-homoleptic iron(ii) complex of composition [Fe(tpy-HImzPh(3))(2)](2+) have been determined, showing that the ligand crystallized in a monoclinic form with the space group P2(1)/c while its Fe(II) complex crystallizes in an orthorhombic form with space group Fddd. Both the anion and cation binding properties of the receptor were thoroughly investigated in dimethylformamide-acetonitrile (1?:?9) solution using absorption, emission, and (1)H NMR spectral studies which revealed that the receptor acts as a sensor for both F(-) and Fe(2+). In the presence of excess F(-) ion, deprotonation of the imidazole N-H fragment of the receptor occurs, an event which is signaled by the development of a yellow color visible with the naked eye. The estimated value of the equilibrium constant of the receptor with F(-) is 1.9 × 10(4) M(-1). Deprotonation is also observed in the presence of hydroxide. The receptor also shows colorimetric and fluorimetric sensing ability towards Fe(2+) ions. The binding site for the metal ion in the system has been unambiguously established by single-crystal X-ray diffraction studies of the Fe(II) complex of the receptor. The influence of solvents on the absorption and fluorescence spectra of the receptor has been investigated in detail. Cyclic voltammetric (CV) and square wave voltammetric (SWV) measurements carried out in dimethylformamide-acetonitrile (2?:?3) provided evidence in favor of cation (Fe(2+)) and anion (F(-)) concentration dependent electrochemical responses, enabling the ligand to act as a suitable electrochemical sensor for F(-) and Fe(2+) ions.