One-dimensional coordination polymers of praseodymium(III)–vanadium(V) complexes with pyridine-2,6-dicarboxylic acid

This paper represents the hydrothermal synthesis of new isomorphous lanthanide–vanadium complexes with one-dimensional coordination polymers: [Pr₂(VO₂)₂(dipic)₄(H₂O)₉] · nH₂O with dipic = pyridine-2,6-dicarboxylic acid and n = 7.75. The structure determination shows a unique one-dimensional structure in which three types of chains run along the c-axis: the chain of positively charged praseodymium complexes bridged by a dipic ligand ([Pr(dipic)(H₂O)₅]⁺), the chain of negatively charged, stacked vanadium complexes ([VO₂(dipic)]⁻), and the chain of neutral praseodymium complexes with a bridged dipic ligand and a coordinating dipic ligand ([Pr(dipic)[VO₂(dipic)](H₂O)₄]). Such one-dimensional chains provide open channels which can accommodate water molecules. Not only accommodated water molecules but also ones coordinated to praseodymium ions were easily removed and absorbed upon heating at 200 °C and exposure of humidity at room temperature, respectively.     

Photophysical properties of clozapine and determination of its concentration by using Eu(III)–dipicolinic acid complex as photo probe

Clozapine drug is photo-stable under irradiation of light for a long time, so we can store it in difficult and hot conditions. In addition the activity of clozapine is inhibited of the absorption spectra in the presence of glucose and enhanced in the presence of iron(III). We succeeded in detecting the concentration of clozapine in the range 1–60 × 10^?9 M using Eu(III)–dipicolinic acid complex as photo probe type and using Stern–Völmer equation to determine the Stern–Völmer constant, critical radius and the mechanism of quenching of luminescence of Eu(III)–dipicolinic acid complex is found to be of dipolar–dipolar interaction.     

Luminescence of ytterium(III) β-diketonate complexes containing different ligands

The spectral and luminescent characteristics of ytterbium(III) β-diketonate complexes containing different nitrogen- and phosphorus-containing ligands are determined. The most intensive luminescence in the IR region is observed for the neutral phosphorus-containing ligands.     

Luminescence of the europium(III) cryptate [Eu3+⊂2.2.1] in the solid state

The luminescence properties of solid [Eu³⁺ ⊂ 2.2.1]Cl₃·2H₂O are reported. Measurements were performed down to liquid-helium temperature. There are some striking differences between the present results and those reported earlier for the same cryptate in aqueous solution. These differences are discussed.     

Determination of carbamates and organophosphorus pesticides by SDME–GC in natural water

Water contamination due to the wide variety of pesticides used in agriculture practices is a global environmental pollution problem. Analytical methods with low quantification limits are necessary. The application of a new extraction technique, solvent drop microextraction (SDME), followed by gas chromatography with a nitrogen-phosphorus detector, was assessed for determining carbamates and organophosphorus pesticides in natural water. Experimental parameters which control the performance of SDME such as selection of microextraction solvent, optimization of organic drop volume, effects of sample stirring, salt addition, and, finally, sorption time profiles were studied. Once SDME was optimized, analytical parameters such as linearity (r ²>0.99), precision (<13%), and detection limits (0.2 to 5 μg/L), plus matrix effects were evaluated (no matrix effects were found). SDME is a dynamic technique able to extract pesticides from water in 14 min; the use of organic solvents and water samples for SDME is negligible compared to other extraction techniques.     

The selective recognition of mismatched d(GCGAGC)_2 by the cobalt(III) complex

Base mismatches arise naturally in the life cycleof a cell as a result of either polymerase error or DNAdamage. Under most circumstances the cell correctsthese mispairings using a complex repair system toprevent mutations in the genetic code. Experimental…     

Kinetics and mechanism of the oxidation of neutralized α-hydroxy acids by tris(pyridine-2-carboxylato)manganese(III)

The kinetics of oxidation of the neutralized -hydroxy acids: lactic, -hydroxyisobutyric, mandelic, benzilic and atrolactic acids by tris(pyridine-2-carboxylato)manganese(III) have been studied. The reactions were carried out in a Na(pic)-picH [Na(pic) = sodium salt of pyridine-2-carboxylic acid and picH = pyridine-2-carboxylic acid] buffer medium in the 4.89–6.10pH range. The oxidation rate was found to be independent of pH, and rate follows the order: benzilate > mandelate >atrolactate>lactate > -hydroxy isobutyrate. The oxidation products are MeCHO, Me2CO, PhCHO, Ph2CO and PhCOMe for the respective reactions. A mechanism is proposed involving intermediate formation of hepta-coordinated MnIII complexes in a fast step. The complexes then decompose to give free radicals and MnII in the rate determining step. The free radicals subsequently react with another molecule of the MnIII species to give the respective carbonyl compounds in a fast step.     

Kinetic study of the protonations and substitutions of different cobalt(III)–nta complexes

The behaviour of the Cobalt(III)–nta (nta = nitrilotriacetate) system in an acidic medium was investigated. The acid dissociation constant, pK _a1, of [(nta)(H₂O)Co(-OH)Co(H₂O)(nta)]^– was determined as 3.09(3) and the pK _a of the cis-[Co(nta)(H₂O)₂]/[Co(nta)(H₂O)(OH)]^– equilibrium was determined as 6.71(1). cis-[Co(nta)(H₂O)₂] undergoes ring-opening upon acidification below pH = 2.0. The formation of [Co( ³-nta)(H₂O)₃]⁺ was also studied. The substitutions between cis-[Co(nta)(H₂O)₂] and NCS^– ions were investigated in the pH = 2–7 ranges. [Co(nta) (H₂O)(OH)]^– reacts ca. 70 times faster at 24.7 °C with NCS^– ions than cis-[Co(nta)(H₂O)₂], indicating a cis-labilising effect of the OH^– ligand.     

Synthesis of Eu(III) and Tb(III) Complexes with Two New Amide Type Podands and Their Luminescence Properties

ＩｎｔｒｏｄｕｃｔｉｏｎＬａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｈａｖｅａｔｔｒａｃｔｅｄｍｕｃｈａｔｔｅｎｔｉｏｎｂｅｃａｕｓｅｏｆｔｈｅｉｒｉｍｐｏｒｔａｎｔａｐｐｌｉｃａｔｉｏｎｓ .1ＩｎｐａｒｔｉｃｕｌａｒＥｕ(ＩＩＩ)ａｎｄＴｂ(ＩＩＩ)ｃａｎｂｅｃｈａｒａｃｔｅｒｉｚｅｄｂｙｌｏｎｇ ｌｉｖｅｄ(ｍｓｔｉｍｅｓｃａｌｅ)ａｎｄｓｔｒｏｎｇｌｕｍｉｎｅｓｃｅｎｔｅｌｅｃｔｒｏｎｉｃａｌｌｙｅｘ ｃｉｔｅｄｓｔａｔｅｓ ,ｗｈｉｃｈｍａｋｅｓｔｈｅｍｉｍｐｏｒｔａｎｔｉｎａｎａｌｙｔｉｃａｌｃｈｅｍ…     

An unprecedented two-dimensional Eu(III) coordination polymer Eu(OOC–C5H4N–CH2–CH2–COO)(OOC–COO)·2H2O formed by in situ reaction of fumaric acid and isonicotinic acid: Crystal structure and luminescent properties

Hydrothermal reaction of fumaric acid and isonicotinic acid in presence of trace quantity of nitric acid produced an unprecedented two-dimensional coordination polymer Eu(OOC–C₅H₄N–CH₂–CH₂–COO)(OOC–COO)·2H₂O containing in situ formed new ligands, 3-(4-pyridinecarboxylate)propionic acid (inpro) and oxalate (ox) moieties. The formation of inpro ligand from isonicotinic acid and fumaric acid is presumably through dehydration between 3-hydroxylpropionic acid and 4-carboxypyridinium moieties present under the above conditions, and the oxalate formation due to the reductive coupling of CO₂ radicals generated from 2-hydroxysuccinic acid through C–C bond cleavage. The compound crystallizes in monoclinic P2₁/C space group and contains nine-coordinated Eu³⁺ ion having a distorted mono-capped square-antiprismatic geometry. While two chelatively bridging oxalate moieties coordinating through four of their O atoms lead to the formation of zigzag Eu(III)–oxalate chains, four uniquely bridging anionic inpro ligands which coordinate through five O centers altogether make the system take an overall two-dimensional network arrangement. Upon excitation at 359 nm the compound exhibits interesting luminescent properties in solid state with several intense bands in the visible region; the most intense and sharp emission being in the red region at 615 nm due to ⁵D₀ → ⁷F₂ transition, facilitated by the low-symmetry coordination environment around Eu³⁺ ion by the ligands.     

Eu(III)-modified properties of thermosensitive core–shell microspheres

We successfully prepared PNIPAM-g-P(NIPAM-co-St) (PNNS) core–shell microsphere by an emulsifier-free emulsion polymerization method. When PNNS with a core–shell structure is interacted with Eu(III), Eu(III) mainly bonds to oxygen of the carbonyl groups of PNNS, forming the novel PNNS-Eu(III) complex. It was found that the complex showed thermosensitive and fluorescent properties at one time. Especially, the maximum emission intensity of Eu(III) in the complex at 614 nm is significantly enhanced in comparison with that of pure Eu(III), demonstrating that there exists an efficient intermolecular energy transfer from the polymer ligand to Eu(III) and then the excited Eu(III) generates the enhanced fluorescence. When the weight ratio of Eu(III) and the PNNS is 8 wt%, the enhancement of the emission fluorescence intensity at 614 nm is highest.     

Thermal and luminescent properties of Eu2+-doped aluminates prepared by the sol–gel method

Alkaline earth aluminates with the overall nominal compositions Ca_0.5Sr_0.5Al₂O₄, Ca_0.5Mg_0.5Al₂O₄ and Mg_0.5Sr_0.5Al₂O₄ doped with 1 mol% of Eu²⁺ ions were prepared by the modified aqueous sol–gel method. The thermal behaviour of the xerogels was studied by the TG/DSC-MS technique under an argon and a reductive atmosphere (Ar/H₂–5 %). Appropriate luminescent efficiency of the materials was achieved after annealing at temperatures lower than those in conventional solid state reactions. All three aluminates are mixtures of at least two phases; the monoclinic phase of CaAl₂O₄, the hexagonal phase of SrAl₂O₄ and the cubic phase of MgAl₂O₄ were identified. Solid solubility was recognised in the Ca_0.5Sr_0.5Al₂O₄:Eu²⁺ composition due to the similar ionic radii of Ca²⁺ and Sr²⁺. UV excited luminescence was observed in the blue region (λ_max = 441 nm) in the aluminates containing the monoclinic phase of CaAl₂O₄ and in the green region (λ_max = 520 nm) in the Mg_0.5Sr_0.5Al₂O₄:Eu²⁺ composition.     

Structures and luminescent properties of two heterotrimetallic Ln(III)–Sr(II)–K(I) complexes

Eu(III)–Sr(II)–K(I) and Tb(III)–Sr(II)–K(I) heterotrimetallic metal-organic frameworks with 2,4,6-pyridinetricarboxylic acid have been synthesized under hydrothermal conditions. The complexes are isomorphic and both in triclinic space group P-1. The ligands bond with three metal ions with two coordination modes. One connects seven metal ions and the other connects eight metal ions. IR spectra, thermal analysis, and photoluminescent properties have been studied. The results display strong characteristic emissions of Eu(III) or Tb(III) ions with excitation of ultraviolet radiation.     

New luminescent heteronuclear Ln(III)–Bi(III) complexes (Ln = Nd,Eu, Tb,Yb) based on aminopolycarboxylic acids

New heteronuclear Ln(III)–Bi(III) complexes (Ln?=?Nd, Eu, Tb, Yb, Lu) with ethylenediamine-N,N,N′,N′-tetraacetic (H₄edta), trans-1,2-cyclohexane-diamine-N,N,N′,N′-tetraacetic (H₄cdta), diethylenetriamine-N,N,N′,N″,N″-pentaacetic (H₅dtpa), and triethylenetetraamine-N,N,N′,N″,N″′,N″′-hexaacetic (H₆ttha) acids have been synthesized with a different synthetic approach. Bi(III) is a sensitizer of the 4f-luminescence in visible and near IR region. Emission spectra of Eu(III)–Bi(III) complexes were studied and the asymmetry of Eu(III) coordination environment was estimated, in good agreement with molecular models. The complexes synthesized by self-assembly are characterized by higher values of the 4f-luminescence quantum yield than other Ln(III)–Bi(III) complexes.     

A new 3-D microporous Ln(III)–Cu(I) framework constructed by pyridine-3,5-dicarboxylate

A new 3-D lanthanide-transition metal coordination polymer [LaCu(PDC)₂H₂O] _n (1) was hydrothermally synthesized from pyridine-3,5-dicarboxylic acid (H₂PDC) and characterized by single-crystal X-ray diffraction, IR spectroscopy, and thermal gravimetric analysis (TGA). The microporous framework of 1 can be viewed as constructed by planar binuclear Cu₂(PDC)₄ building blocks and La(III) chains, a new structural motif in 3d-4f heterometallic coordination polymers. The sample exhibits strong blue emission in the solid state and retains its framework integrity up to ca 380°C.     

Separation of Am(III) from nitric acid medium by phosphonium ionic liquid–hydroxyacetamide mixture

A strongly hydrophobic phosphonium ionic liquid, trihexyltet radecylphosphonium bis(trifluoromethanesulfonyl)imide ([P₆₆₆₁₄][NTf₂]) was employed as the diluent for the extraction behavior of Am(III) using N,N-dihexyl-2-hydroxyacetamide(DHHy) as extractant. The extractibility of americium(III) in [P₆₆₆₁₄][NTf₂] phase was measured as a function of various parameters such as aqueous phase acidity (0.1–8 M), extractant concentration (0.01–0.15 M), equilibration time (5–120 min) and temperature (298–333 K). The extraction performance observed in DHHy/[P₆₆₆₁₄][NTf₂] was compared with those observed in N,N-dihexyloctamide (DHOA) in [P₆₆₆₁₄][NTf₂] and DHHy in other diluents such as [C₄mim][NTf₂] and n-dodecane. The effect of temperature on D _Am(III) in ionic liquid system and recovery of Am(III) from the loaded phase were ascertained in detail.     

Study on the effect of chain-length compatibility of mixed anionic–cationic surfactants on the cloud-point extraction of selected organophosphorus pesticides

The chain-length compatibility of mixed anionic-cationic surfactants was investigated for the extraction of organophosphorus pesticides (OPPs). Cationic surfactants with different chain lengths (n = 12 and 16) were mixed with sodium dodecyl sulfate (SDS; n = 12) for the mixed anionic-cationic surfactants-based extraction. Six OPPs were studied including azinphos-methyl, parathion-methyl, fenitrothion, diazinon, chlorpyrifos, and prothiophos. Reversed-phase high-performance liquid chromatography was used for the determination of the studied OPPs. The extraction was performed using mixtures of SDS and cationic surfactants including dodecyltrimethyl ammonium bromide or dodecyltrimethylammonium bromide (DTAB; n = 12) and cetyltrimethyl ammonium bromide or cetyltrimethyl ammonium bromide (CTAB; n = 16). The parameters affecting the extraction efficiencies of two extraction systems were studied and discussed. The optimum condition for SDS-DTAB was 15 mmol L(-1) SDS and 1 mmol L(-1) DTAB in the presence of 15% (w/v) sodium chloride (NaCl). Meanwhile, the condition for SDS-CTAB was 10 mmol L(-1) SDS and 1.0 mmol L(-1) CTAB with 10% (w/v) NaCl. Under the optimum conditions, the extraction efficiency of SDS-DTAB (66-85%) was slightly higher than that of SDS-CTAB (61-82%). In addition, the SDS-DTAB system also gave greater enrichment factor than SDS-CTAB for all the studied OPPs. This result may be due to the compatibility of chain length between SDS and DTAB. The extraction using SDS-DTAB was successfully applied to determine OPPs in fruit samples (i.e., pomelo, apple, and pineapple). No contamination by the studied OPPs in samples was observed. Good accuracy with recoveries ranging from 77 to 105% was obtained. Low limits of detection were in the range of 0.003-0.01 mg kg(-1) which are below the MRLs established by EU-MRLs for the OPPs residues in fruit samples.     

Effect of the Nature of the Polymer Matrix on the Luminescence of Tb(III) Complexes with β-Diketone Copolymers

The formation conditions and luminescence of Tb(III) complexes with synthesized copolymers of unsaturated acetylacetone derivatives with styrene and methyl methacrylate were studied. The luminescence intensity of these Tb(III) complexes was found to depend on the β-diketone substituent nature (CH₃, CF₃, C₆H₅) and structure (linear, branched) and the β-diketone to monomer ratio in the polymerizing mixture.     

Spectroscopic investigations of hematoxylin–Eu(III) complex interacting with Herring-sperm DNA

The interaction of HE–Eu(III) complex (HE?=?hematoxylin) with Herring-sperm DNA (hsDNA) has been studied by absorption spectra, fluorescence, and viscosity measurements in physiological buffer (pH?=?7.40). The binding constant of HE–Eu(III) complex to hsDNA was obtained by double reciprocal method at 298 and 310?K and the corresponding thermodynamic parameters (Δ_r Hm??=?8.55?×?10⁴?J?mol^?1, Δ_r Gm??=??3.01?×?10⁴?J?mol^?1, Δ_r Sm??=?387.95?J?mol^?1?K^?1) were calculated, showing that the interaction between HE–Eu(III) complex and hsDNA was driven mainly by entropy. The value of K indicated that the binding mode of HE–Eu(III) complex with DNA was not classical intercalation. These results were further supported by viscosity method and competitive binding experiment. Scatchard analysis suggests that the interaction mode was a mixed binding, which contains partial intercalation and groove binding.     

Kinetics and mechanism of the reduction of diaquatetrakis (2,2′-bipyridine)-μ-oxo diruthenium(III) by ascorbic acid

Summary The kinetics of the oxidation of ascorbic acid by diaquatetrakis (2,2-bipyridine)--oxo diruthenium(III) in aqueous HClO₄ were investigated. The dependence of the second order rate constantk ₂ on [H⁺] is given by k ₂=a+b[H⁺]^–, indicating that both the undissociated form and the monoanion of ascorbic acid are reactive. Marcus theory was used to estimate the redox potential for the Ru^III-O-Ru^III/Ru^III-O-Ru^II couple and a feasible mechanism has been proposed to explain the results.