一种新型吡嗪铱（Ⅲ）配合物的合成及其磷光性质

利用5-甲基-2,3-二苯基吡嗪（MDPP）和水合三氯化铱（IrCl3•H2O）,合成了一种新型吡嗪铱配合物Ir (MDPP)2 (acac).通过1H NMR、元素分析和质谱方法对配合物结构进行了表征,并研究了配合物的吸收光谱和光致发光光谱.结果表明,配合物Ir (MDPP)2(acac)在393和528 nm处存在单重态1MLCT（金属到配体的电荷跃迁）和三重态3MLCT的吸收;在588 nm 处有较强的金属配合物三重态的磷光发射,是一种绿色磷光材料.     

Synthetic Crystalline Calcium Silicate Hydrate (I): Cation Exchange and Caesium Selectivity

Summary.  Solid crystalline calcium silicate hydrate (I) synthesized from equimolar amounts of Ca and Si under hydrothermal conditions at 120°C shows cation exchange properties towards divalent metal cations such as Ni, Cu, Cd, or Hg. It also exhibits caesium selectivity in the presence of Na⁺. The exchange capacity and selectivity of the solid can be increased by 10 and 28%, respectively, upon substitution of 0.01 mol of the Ca²⁺ in its structure by Na⁺. The ability of metal cation uptake by the solid was found to obey the order Ni²⁺ > Hg²⁺ > Cu²⁺ > Cd²⁺. The different affinities of calcium silicate hydrate (I) towards these ions can be used for their separation from solutions and also in nuclear waste treatment. The mechanism of the exchange reaction is discussed. Received June 11, 2001. Accepted September 10, 2001     

Trace metal speciation measurements in waters by the liquid binding phase DGT device

The speciation measurements of trace metals by the diffusive gradients in thin-films technique (DGT) using a poly(4-styrenesulfonate) (PSS) aqueous solution as a binding phase and a cellulose dialysis membrane (CDM) as a diffusive layer, CDM-PSS DGT, were investigated and showed good agreement with computer modelling calculations. The diffusion coefficients of ethylenediaminetetraacetic acid (EDTA) complexes with Cd²⁺ and Cu²⁺ were measured and compared with those of the inorganic metal ions. CDM-PSS DGT device was tested for speciation measurement in sample solutions containing EDTA, tannic acid (TA), glucose (GL), dodecylbenzenesulfonic acid (DBS) and humic acid (HA) as complexing ligands forming organic complexes with varying stability constants. Lower percentages of DGT labile copper concentrations over total filterable copper concentrations obtained from the deployments in freshwater sites indicated that copper complexes with organic matter were basically not measured by the devices.     

Influence of solvents on the insertion of methacrolein into zirconacyclopropenes

The reaction of Cp₂Zr(L)(η²-Me₃SiC₂) (L = THF, py) with equimolar amounts of H₂C = CMe-CHO at room temperature depends strongly on the ligands L and the solvents that are used. With L = THF, in the THF solution the insertion product

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1 was isolated, whereas by conducting the reaction in n-hexane solution an alkyne substitution with 1,4-coordination of the methacrolein takes place and the binuclear complex [

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2 was obtained. In conttrast, with L = py (a stronger ligand) only a 1:1 ratio of 1 and 2 was observed in both THF and in n-hexane. At 50°C complex 1 was converted into 2 and the alkyne was eliminated quantitatively.

Complexes 1 and 2 were characterized by IR and NMR spectroscopical measurements and 1 by an additional X-ray structure determination.     

A Promising MgII‐Ion‐Selective Luminescent Probe: Structures and Properties of Dy–Mn Polymers with High Symmetry

Two Dy–Mn polymers, {[Dy(L¹)₃Mn_1.5(H₂O)₃]?3.125 H₂O}_n ( 1 , L¹=pyridine‐2,6‐dicarboxylic acid) and {[Dy(L²)₃Mn_1.5(H₂O)₆]?8.25 H₂O}_n ( 2 , L² = 4‐hydroxylpyridine‐2,6‐dicarboxylic acid), with high symmetry (S₆) have been prepared. Polymer 1 has a nanoporous 3D framework with channel of about 17.6 Å diameter, while 2 has a honeycomb‐type 2D structure with the cavity of approximately 14.4 Å diameter. In the construction of multidimensional porous polymers with 3d–4f mixed metals, it is the first observation that a ligand substituent effect leads to dramatic differences in the structures formed. Luminescent studies reveal that the emission intensities of 1 and 2 increase significantly upon the addition of Mg²⁺, whereas the introduction of other metal ions leaves the intensity unchanged or even weakens it; hence, both of them may serve as good candidates of Mg²⁺ luminescent probes. To our knowledge, complex 1 is also the first example of a 3d–4f metal‐based nanoporous polymer to exhibit luminescent selectivity for Mg²⁺. Magnetic susceptibility measurements reveal a rather rare ferromagnetic interaction in 2 . Thermal gravimetric analyses and powder X‐ray diffraction investigations have also been performed, suggestive of high thermal stability of 1 .     

Thermal decompositions of some divalent transition metal complexes of triethanolamine

The thermal behaviours of the Ti(II), Mn(II), Fe(II), Ni(II), Cu(II) and Zn(II) complexes of triethanolamine were studied by means of thermogravimetry, differential thermogravimetry, differential thermal analysis infrared spectrophotometry and elemental analysis. The sequence of thermal stability of the metal complexes, determined by using the initial decomposition temperature, was found to be Ti(II)?Mn(II)>Fe(II)>Ni(II)>Zn(II)>Cu(II). Some of the kinetic parameters, such as the activation energy and order of reaction for the initial decomposition reaction, were calculated and the relationship between the thermal stability and the chemical structure of the complexes is discussed.     

Competition between pi and non-pi cation-binding sites in aromatic amino acids: a theoretical study of alkali metal cation (Li+, Na+, K+)-phenylalanine complexes

To understand the cation-pi interaction in aromatic amino acids and peptides, the binding of M(+) (where M(+) = Li(+), Na(+), and K(+)) to phenylalanine (Phe) is studied at the best level of density functional theory reported so far. The different modes of M(+) binding show the same order of binding affinity (Li(+)>Na(+)>K(+)), in the approximate ratio of 2.2:1.5:1.0. The most stable binding mode is one in which the M(+) is stabilized by a tridentate interaction between the cation and the carbonyl oxygen (O[double bond]C), amino nitrogen (--NH(2)), and aromatic pi ring; the absolute Li(+), Na(+), and K(+) affinities are estimated theoretically to be 275, 201, and 141 kJ mol(-1), respectively. Factors affecting the relative stabilities of various M(+)-Phe binding modes and conformers have been identified, with ion-dipole interaction playing an important role. We found that the trend of pi and non-pi cation bonding distances (Na(+)-pi>Na(+)-N>Na(+)-O and K(+)-pi>K(+)-N>K(+)-O) in our theoretical Na(+)/K(+)-Phe structures are in agreement with the reported X-ray crystal structures of model synthetic receptors (sodium and potassium bound lariat ether complexes), even though the average alkali metal cation-pi distance found in the crystal structures is longer. This difference between the solid and the gas-phase structures can be reconciled by taking the higher coordination number of the cations in the lariat ether complexes into account.     

Capillary electrophoresis of trace metals in highly saline physiological sample matrices

Trace metal ions in highly saline samples such as urine were determined with capillary electrophoresis (CE) without desalting or off-line preconcentration. By mixing with a dye, 4-(2-pyridylazo) resorcinol (PAR), the metal ions were converted into anionic complexes having strong absorbance near 500 nm. A large volume of the metal-PAR complex sample solution injected into a coated capillary was stacked isotachophoretically and separated under a reverse potential. The salt anion (chloride) and PAR in the sample matrix acted as the leading and terminating electrolytes, respectively. In a sample containing a 250 mM NaCl matrix, more than 400-fold enhancement in the absorbance detector response was realized compared to the normal CE injection mode. Combination of the dye complexation and isotachophoretic stacking provided excellent detection limits (S/N = 3) for three trace metal ions in the low ppb range (Fe(2+), 0.7 ppb, Ni(2+), 0.4 ppb; Zn(2+), 1.2 ppb) with absorbance detection. The migration time reproducibility was excellent (relative standard deviations: standard samples < 1%, urine samples approximately 1%). The proposed method is convenient and fast, and the sample analysis can be completed within 20 min.     

Performance characteristics of suspended particulate reagent-iminodiacetate as a binding agent for diffusive gradients in thin films

The performance characteristics of an alternative binding agent, suspended particulate reagent-iminodiacetate (SPR-IDA), for use with DGT methodology were investigated. The parameters investigated during this study included gel hydration, blank levels, elution factor (f_e), capacity, the effects of pH on the binding of trace metals by DGT. The novel application of this resin for use as a quantitative standard for laser ablation ICP-MS was also evaluated. To further constrain the results for the SPR-IDA binding agent, parallel experiments were performed using resin gel containing Chelex 100, which has been widely reported in the literature. Hydration results showed that the SPR-IDA resin gel reached a stable dimension and weight within ∼30 min and was dimensionally stable for ≤6 months. The measured DGT blanks for the SPR-IDA resin were 0.0023, 0.15, 0.21, 0.0033 and 0.011 ng disc⁻¹ for Co, Ni, Cu, Cd and Pb, respectively. The elution factor differed for the two resin types with the Chelex 100 recoveries slightly lower than previous reports and the SPR-IDA resin showing on average ∼5-9% better recoveries than DGT containing Chelex 100. The measured capacity of DGT discs containing the SPR-IDA binding agent was 0.26 mg Cd, similar to the calculated value of 0.29 mg Cd, indicating the entire resin layer was available for metal uptake.Both resin types performed equally well when deployed in 1 mM NaNO₃ solutions with DGT measurements of ∼100% of direct solution measurements for Co, Ni and Cd. However, DGT measurements of Cu and Pb systematically decreased with increasing solution pH down to ∼50% of solution values at pH 8.0, due to artifacts resulting from colloid formation during the addition of the metals. This was remedied by adding the metals as dilute salt standards and addition of Mg(NO₃)₂ to eliminate adsorption to the container walls. In the latter experiments, DGT measured concentrations of Co, Ni, Cu, Cd and Pb were in agreement with solution concentrations. Deployment of DGT in solutions with increasing concentrations of trace metals yielded linear results, suggesting that quantitative analysis using simplified laser ablation techniques should be possible using this newly characterized SPR-IDA resin gel.     

Removal of Mn(II) and Cd(II) from wastewaters by natural and modified clays

The adsorption capacities of commercial and Brazilian natural clays were evaluated to test their applications in wastewater control. We investigated the process of sorption of manganese(II) and cadmium(II) present in synthetic aqueous effluents, by calculating the adsorption isotherms at 298 K using batch experiments. The influence of temperature and pH on the adsorption process was also studied. Adsorption of metals was best described by a Langmuir isotherm, with values of Q ₀ parameter, which is related to the sorption capacity, corresponding to 6.3 mg g^{− 1} for K-10/Cd(II), 4.8 mg g^{− 1} for K-10/Mn(II), 11.2 mg g^{− 1} for NT-25/Cd(II) and 6.0 mg g^{− 1} for NT-25/Mn(II). We observed two distinct adsorption mechanisms that may influence adsorption. At the first 5 min of interaction, a cation exchange mechanism that takes place at exchange sites located on (001) basal planes is predominant. This process is inhibited by low pH values. After this first and fast step, a second sorption mechanism can be related to formation of inner-sphere surface complexes, which is formed at edges of the clay. The rate constants and the initial sorption rates correlate positively with temperature in all studied systems, denoting the predominance of a physisorption process. The addition of complexing agents that are incorporated within the K10 structure, enhance metal uptake by the adsorbent. The results have shown that both Cd(II) and Mn(II) were totally retained from a 50 mg L^{− 1} solution when K10 grafted with ammonium pyrrolidinedithiocarbamate (APDC) was used as adsorbent.