Vibration Spectra of Coprecipitated Fe(III)-Ni(II) and Fe(III)-Cu(II) Hydroxides and of the Products of Their Thermolysis

A range of coprecipitated Fe(III)-Me(II) (Me(II) = Ni, Cu) hydroxides and of the products of their thermolysis have been investigated by the IR spectroscopy method. The basic absorption bands has been assigned, and the chemistry of the process of formation of coprecipitated hydroxides has been discussed from the standpoint of generation of heteronuclear hydrococomplexes.     

非分离状态下FI-KR-FAAS测定铁的价态

建立了流动注射(FI)编结反应器(KR)在线预富集与火焰原子吸收光谱(FAAS)联用非分离状态下测定铁的价态的新方法。进样流速6.0 mL.min-1;进样时间60s,测定0.04 mg.L-1的Fe(Ⅲ)和Fe(Ⅱ),Fe(Ⅲ)和Fe(Ⅱ)的浓集系数(EF)分别为41和9;检出限分别为2.5和14.3μg.L-1;相对标准偏差(RSD,n=11)分别为2.3%和3.1%。以0.1‰φ的三乙醇胺为掩蔽剂,Fe(Ⅲ)和Fe(Ⅱ)在水样中的回收率分别为97%～101%和96%～100%。     

Fluorescence and Biological Evaluation of the La(III) and Eu(III) Complexes with 7-methoxychromone-3-carbaldehyde Benzoyl Hydrazone Schiff Base

A novel Schiff base ligand (L = 7-methoxychromone-3-carbaldehyde benzoyl hydrazone) and its La(III) and Eu(III) complexes have been successfully prepared. The crystal structure of [LaL(2)(NO(3))(3)].H(2)O was characterized by X-ray crystallography. It crystallizes in monoclinic, space group C2/c with crystallographic data: a = 27.7173(17) A, b = 10.0002(6) A, c = 14.7884(9) A, beta = 102.6870(10) degrees and Z = 4. In the structure, the La(III) ion satisfies 12 coordination and three nitrate coordinate as bidentate ligand. The biological experiments show that the ligand and its two complexes can strongly bind to DNA through intercalation mode, and the three compounds also exhibit good antioxidant activities against OH(*) and O(2) (-*). Moreover, it is found that the Eu(III) complex exhibits characteristic fluorescence of europium ion in different organic solvent.     

Enhanced fluorescence of Tb(III), Dy(III) perchlorate by salicylic acid in bis(benzoylmethyl) sulfoxide complexes and luminescence mechanism

Two novel ternary rare earth perchlorate complexes had been synthesized by using bis(benzoylmethyl) sulfoxide as first ligand (L=C₆H₅COCH₂SOCH₂COC₆H₅), salicylic acid as second ligand (L^′=C₆H₄OHCOO⁻). The compounds were characterized by elemental analysis, TG-DSC and molar conductivities in DMF solution. The composition was suggested as [REL₅L′](ClO₄)₂·nH₂O (RE=Tb, Dy; n=6, 8 ). Based on IR, ¹HNMR and UV spectra, it showed that the first ligand, bis(benzoylmethyl) sulfoxide (L), bonded with Tb(III), Dy(III) ions by the oxygen atom of sulfinyl group. The second ligand, salicylic acid group (L′), not only bonded with RE(III) ions by one oxygen atom of carboxyl group but also bonded with RE(III) ions by oxygen atom of phenolic hydroxyl group. In bis(benzoylmethyl) sulfoxide system, fluorescent spectra of the complexes showed that the luminescence of Tb(III), Dy(III) ions was enhanced by the second ligand salicylic acid. The ternary complexes had stronger fluorescence than the binary ones where only bis(benzoylmethyl) sulfoxide acted as ligand. Phosphorescent spectra of the two ligands indicated that the coordination of salicylic acid resulted in the matching extent increasing between the triplet state of ligand and excited state of the rare earths. The relationship between fluorescence lifetime and fluorescence intensity was also discussed.     

Thermal transitions and degradative processes in Fe(III)-tetracarboxyphthalocyanine-grafted poly(N-vinylcarbazole)

The introduction of 2,9,16,23-tetracarboxy-Fe(III)phthalocyanine [Fe(III)tcPc] units onto fractions of poly(N-vinylcarbazole) (PVK) by Friedel-Crafts reaction leads to amorphous PVK-based grafted compounds that show major interchain distances by the wide-angle x-ray scattering (WAXS) technique. Glass transition temperatures of the products are lower than the main glass transition temperature of PVK and are attributed to local movements of the voluminous added groups. Dynamic thermogravimetric experiments show decarboxylation processes within the 250°C-500°C range and little weight loss. The large remaining residue, up to 70% of the sample at 800°C, is suggested to be the consequence of successive cross-linking reactions. The Fourier transform infrared (FTIR) spectrum of the residue is similar to that of the grafted sample before degradation.     

Simultaneous observation of low temperature 4f-4f and 3d-3d emission spectra in a series of Cr(III)(ox)Ln(III) assembly

We report here the low temperature emission spectra in the heterometal dinuclear 3d-4f assembled molecular system [(acac)₂Cr^III(μ-ox)Ln^III(HBpz₃)₂] (Cr(ox)Ln:acac⁻=acetylacetonate, ox²⁻=oxalate, HBpz₃⁻=hydrotris(pyrazol-1-yl)borate; Ln=La, Nd, Ho, Er , Tm and Yb) in comparison with those of Na[Cr(acac)₂(ox)] and [(HBpz₃)₂Ln(μ-ox)Ln(HBpz₃)₂](Ln=Nd and Er). From 10 to 150 K the Cr(ox)Ln complexes show a broad emission band around 800 nm from the ²E state of Cr(III) moiety. At room temperature no ²E-⁴A₂ emission was observed in the Cr(ox)Ln except for the La and Lu complexes. On warming from 10 to 300 K rapid quenching of the ²E-⁴A₂ emission of Cr(III) is suggested to result from the energy transfer from Cr to Ln in the Cr(ox)Ln. The excitation spectra and the life-time were also measured with monitoring the 4f-4f emission peaks of the Cr(ox)Yb complex.     

Luminescent Eu(III) and Tb(III) Complexes: Developing Lanthanide Luminescent-Based Devices

This mini review gives some highlights of the work recently carried out in our research group in Dublin on the developments of lanthanide luminescent devices, where the future goal is to produce devices that can operate as sensors. A few examples demonstrate our design principles for targeting both anion and cations that are of biological or pharmaceutical relevance, where the recognition occurs in aqueous competitive media. We also discuss the possibility of developing mixed f-d metal complexes and conjugates that can be employed as novel supramolecular architectures.     

Chemical tuning of high-spin complexes based on 3- and 4-hydroxy-pentadentate-Fe (III) complex-units investigated by Mössbauer spectroscopy

The pentadentate ligands 3-OH-⁵L?=?[N,N′-Bis(1,3-dihydroxy-2-benzylidene)-1,7-diamino-4-azaheptane] and 4-OH-⁵L?=?[N,N′-Bis(1,4-dihydroxy-2-benzylidene)-1,7-diamino-4-azaheptane] has been prepared by a Schiff base condensation between 1,7-diamino-4-azaheptane and the dihydroxybenzaldehyde. Complexation with Fe(III) yields high-spin (S?=?5/2) complexes of [Fe^III(3-OH-⁵L)Cl] and [Fe^III(4-OH-⁵L)Cl]. These precursors were combined with [M(CN) _x ] ^y? (M?=?W(IV), Mo(IV), Ru(II), Co(III)) and heptanuclear and nonanuclear clusters of [M{(CN-Fe^III(3-OH-⁵L)} _x ]Cl _y and [M{(CN-Fe^III(4-OH-⁵L)} _x ]Cl _y resulted. Such starshaped hepta- and nonanuclear compounds are high-spin systems at room temperature. On cooling to 10 K some of the iron(III) centers switch to a second high-spin state as proven by Mössbauer spectra, i.e. multiple electronic transitions. Parts of the compounds perform a high-spin to high-spin transition.     

Complexes based on ethylene- and propylene-bridged-pentadentate-Fe(III)-units allow interplay between magnetic centers and multistability investigated by Mössbauer spectroscopy

The propylene-based ⁵3,3-L?=?[N,N′-Bis(1-hydroxy-2-benzylidene)-1,7-diamino-4-azaheptane] and ethylene-based pentadentate ligand ⁵2,2-L?=?[N,N′-Bis(1-hydroxy-2-benzylidene)-1,5-diamino-3-azapentane] has been prepared. Complexation with Fe(III) yields high-spin (S?=?5/2) complexes of [Fe^III(⁵2,2-L)Cl] and [Fe^III(⁵3,3-L)Cl]. Such precursors were combined with [M(CN) _x ] ^y? (M?=?W(IV), Mo(IV), Ru(II), Co(III)) and heptanuclear and nonanuclear clusters of [M{(CN-Fe^III(⁵2,2-L)} _x ]Cl _y and [M{(CN-Fe^III(⁵3,3-L)} _x ]Cl _y resulted. Such starshaped hepta- and nonanuclear compounds are high-spin systems at room temperature. On cooling to 20 K in all presented ethylene compounds the iron(III) centers switch to a second high-spin state as proven by Mössbauer spectra with a yield of about 30%, i.e., multiple electronic transitions. The propylene compounds, however, perform a high-spin to low-spin transition. Mössbauer spectra taken during green light irradiation indicate changes in the population of the different electronic states, i.e. concerted inorganic reaction.     

Removal of lead from aqueous solutions by using the natural and Fe(III)-modified zeolite

In the present study, the sorption of lead by the natural and Fe(III)-modified zeolite (clinoptilolite) is described. The characterization of the natural zeolite-rich rock and the Fe(III)-modified form was performed by chemical analysis, point of the zero charge (pH_pzc), X-ray powder diffraction, applying the Rietveld/RIR method for the quantitative phase analysis, and scanning electron microscopy. The effects of sorbents dose and the initial lead concentrations on its sorption by two sorbents were investigated. For both sorbents, it was determined that at lower initial concentrations of lead, ion exchange of inorganic cations in zeolites with lead, together with uptake of hydrogen dominated, while at higher initial lead concentrations beside these processes, chemisorption of lead occurred. Significantly higher sorption of lead was achieved with Fe(III)-modified zeolite. From sorption isotherms, maximum sorbed amounts of lead, under the applied experimental conditions, were 66 mg/g for the natural and 133 mg/g for Fe(III)-modified zeolite. The best fit of experimental data was achieved with the Freundlich model (R² ≥ 0.94).     

Sonochemical synthesis of a new nano-structures bismuth(III) supramolecular compound: New precursor for the preparation of bismuth(III) oxide nano-rods and bismuth(III) iodide nano-wires

A new nanostructured Bi(III) supramolecular compound, {[Bi₂(4,4′-Hbipy)_1.678(4,4′-Hbipy)_0.322(μ-I)₂I_5.678] (4,4′-bipy)} (1), 4,4′-bipy = 4,4′-bipyridine} was synthesized by a sonochemical method. The nano-structure of 1 was investigated using scanning electron microscopy, powder X-ray powder diffraction (XRD), IR spectroscopy and elemental analysis, and the crystal structure of compound 1 was determined by single-crystal X-ray diffraction. The thermal stability of bulk compound 1 and of nano sized particles was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). Bi₂O₃ and BiI₃ nano-structures were obtained by calcinations of nano-structures of compound 1 at 400 °C under air and nitrogen atmospheres, respectively.     

Highly Selective and Anions Controlled Fluorescent Sensor for Hg<Superscript>2+</Superscript> in Aqueous Environment

A highly selective PET fluorescent sensor B1 for Hg²⁺ containing a BODIPY fluorophore and a NS₂O₂ penta-chelating receptor has been synthesized and characterized. Its absorption maximum wavelength (498 nm) and emission maximum wavelength (512 nm) are both in the visible range. The fluorescence quantum yields of the B1 and Hg²⁺-bound states of BHg1 are 0.008 and 0.58 in 70% aqueous ethanol solution, respectively. The pKa of 1.97 is the lowest in metal ions PET chemo sensors reported up till now as we know. Thus, B1 can detect the Hg²⁺ in a wide pH span, which indicates that it has more potential and further practical applications for biology and toxicology. Furthermore, BHg1 also displays response to some anions such as Cl⁻(Br⁻), , SCN⁻ and CH₃COO⁻, which is attributed to the significant coordinating ability of these anions to Hg²⁺.     

The Application of Two-dimensional Fluorescence Correlation Spectroscopy on the Interaction Between Bovine Serum Albumin and Paeonolum in the Presence of Fe(III)

The effect of Fe³⁺ on the interaction between bovine serum albumin (BSA) and paeonolum (PAL), which was extracted from the traditional Chinese herb, Paeonia suffruticosa Andr, was investigated by UV and fluorescence spectroscopy. Two-dimensional correlation spectroscopy was applied to the analysis of fluorescence spectra. The results of spectroscopic measurements suggested that PAL had a strong ability to quench the intrinsic fluorescence of BSA through static quenching procedure in the presence of Fe(III). Thermodynamic parameter enthalpy changes (ΔH) and entropy changes (ΔS) were calculated. The binding parameters including binding constant (K), and the distance (r) between PAL and BSA were evaluated on the basis of the theory of Föster energy transfer. Owing to the spectral resolution enhancement in 2D correlation spectroscopy, the structure change of PAL–Fe³⁺ can be observed.     

Theoretical Calculations of Transition Probabilities and Oscillator Strengths for Sc(III) and Y(III)

利用最弱受约束电子势模型理论计算了二价钪离子和二价钇离子的能级间跃迁几率和振子强度的数值. 二价钪离子的计算结果与美国国家标准技术研究院(NIST)所给出的可接受值吻合良好. 二价钇离子的计算结果也与现有的其他理论方法的计算结果十分接近.     

Concentrated Fe(III)–nitrilotriacetate solutions: study by Raman spectroscopy and ab initio calculations

Fe(III)–nitrilotriacetate(NTA) aqueous solutions are used in various redox desulfurization processes. The nature of stable Fe–NTA complexes depends highly on parameters such as [Fe(III)] concentration, NTA/Fe ratio and pH value. These complexes can be characterized by potentiometric measurements or UV‐vis spectroscopy, but only at rather low concentrations. Using synthesis of solids, Raman spectra of these solids and ab initio calculations, a rational determination of the nature of complexes stable in water at high iron concentrations was proposed from the position sensitivity of the main low wavenumber band to the coordination sphere of iron cations. This band was assigned to ν(Fe N) stretching vibrations from ab initio calculations. Depending on the pH and NTA/Fe ratio of the prepared solutions, different species were identified from the Raman spectra. The present methodology can be extended to other metal–ligand systems to elucidate the nature of stable complexes in aqueous solution. Copyright © 2006 John Wiley & Sons, Ltd.     

Kinetics and mechanism of uncatalysed and ruthenium(III) catalysed oxidation of allyl alcohol by diperiodatoargentate(III) in aqueous alkaline medium

The oxidation of allyl alcohol by diperiodatoargentate(III) (DPA) is carried out both in the absence and presence of ruthenium(III) catalyst in alkaline medium at 298 K and a constant ionic strength of 1.1 mol dm^?3 was studied spectrophotometrically. The oxidation products in both the cases were acrolein and Ag(I), identified by spectral studies. The stoichiometry is same in both the cases, that is, [AA]/[DPA] = 1:1. The reaction shows first order in [DPA] and has less than unit order dependence each in both [AA] and [Alkali] and retarding effect of [IO] in both the catalysed and uncatalysed cases. The order in [Ru(III)] is unity. The active species of DPA is understood to be as monoperiodatoargentate(III) (MPA) in both the cases. The uncatalysed reaction in alkaline medium has been shown to proceed via a MPA–allyl alcohol complex, which decomposes in a rate determining step to give the products. In catalysed reaction, it has been shown to proceed via a Ru(III)‐allyl alcohol complex, which further reacts with one molecule of MPA in a rate determining step to give the products. The reaction constants involved in the different steps of the mechanisms were calculated for both reactions. The catalytic constant (K_c) was also calculated for catalysed reaction at different temperatures. The activation parameters with respect to slow step of the mechanisms were computed and discussed for both the cases. The thermodynamic quantities were also determined for both reactions. Copyright © 2007 John Wiley & Sons, Ltd.     

光致变色Schiff碱N,N’-双(水杨醛缩)-1,2-环己二胺的荧光光谱

用稳态和时间分辨荧光光谱研究了Ｎ,Ｎ’ 双水杨醛缩 １,２ 环己二胺（Ｎ,Ｎ’ ｂｉｓ（ｓａｌｉ ｃｙｌｉｄｅｎｅ） １,２ ｃｙｃｌｏｈｅｘａｎｅｄｉａｍｉｎｅ,ＢＳＣ）在固态和四氯化碳、氯仿溶液中的光致变色行为。发现经过光照,ＢＳＣ的荧光光谱发生了明显、快速的改变,并且光致变色过程可重复进行。     

Rhod-5N as a Fluorescent Molecular Sensor of Cadmium(II) Ion

The photophysical and complexing properties of Rhod-5N (commercially available) in MOPS buffer are reported. This fluorescent molecular sensor consists of a BAPTA chelating moiety bound to a rhodamine fluorophore. Its fluorescence quantum yield is low and a drastic enhancement of fluorescence intensity upon cation binding was observed. Special attention was paid to the complexation with Cd²⁺, a well known toxic metal ion. Possible interference with other metal ions (Na⁺, K⁺, Mg²⁺, Ca²⁺, Zn²⁺, Pb²⁺) was examined. Rhod-5N was found to be highly selective of Cd²⁺ over those interfering cations except Pb²⁺. The limit of detection is 3.1 μg l⁻¹.     

Crystal structure of Ni(II) complex and fluorescence properties of Zn(II) complex with the Schiff base derived from diethenetriamine and PMBP

The Schiff base, H₂L, was derived from 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and diethenetriamine. The crystal structure of [NiL(C₂H₅OH)]·H₂O obtained from ethanol solution was determined by X-ray diffraction analysis. The coordination geometry of Ni(II) ion is a distorted octahedron with three oxygen atoms and three nitrogen atoms. Under the excitation of ultraviolet light, strong fluorescence of solid Zn(II) complex was observed. In addition, the fluorescence enhancement was obtained in the presence of Zn²⁺ in THF solution of the ligand, indicating that H₂L may be a potential fluorescent sensor for Zn²⁺.     

Oxygen-dependent Oxidation of Fe(II) to Fe(III) and Interaction of Fe(III) with Bovine Serum Albumin, Leading to a Hysteretic Effect on the Fluorescence of Bovine Serum Albumin

The serum albumin is the most abundant protein in blood plasma and the iron is essential for many cellular processes. However, the interaction between Fe³⁺ and haem-free serum albumin remains unclear. Here we provide evidence for the fact that haem-free BSA possesses one specific Fe³⁺-binding site. The binding of Fe³⁺ to BSA results in a significant quenching of the Trp fluorescence of BSA. The average apparent dissociation constant value for the interaction of Fe³⁺ and BSA is 3.46 × 10⁻⁸ ± 3 × 10⁻¹⁰ M at 37 °C and 3.30 × 10⁻⁸ ± 5 × 10⁻¹⁰ M at 25 °C, respectively, as determined by fluorescence titration. Addition of 50 μM Fe²⁺ to 1 μM BSA results in an obvious hysteretic effect on the fluorescence of BSA. The time-dependent fluorescence quenching of BSA by Fe²⁺ is not caused by the Fe²⁺-induced conformational change of BSA, but the oxygen-dependent oxidation of Fe²⁺ to Fe³⁺. Fe²⁺ undergoes an oxygen-dependent oxidation to Fe³⁺ under aerobic conditions, which is accelerated by the interaction of BSA with Fe³⁺ and extensively inhibited under anaerobic conditions. The results suggest that BSA may take part in non-transferrin bound iron transfer.