Fluorescent and Electrochemical Sensing of Polyphosphate Nucleotides by Ferrocene Functionalised with Two ZnII(TACN)(pyrene) Complexes

The [Fc? bis{Zn^II(TACN)(Py)}] complex, comprising two Zn^II(TACN) ligands (Fc=ferrocene; Py=pyrene; TACN=1,4,7‐triazacyclononane) bearing fluorescent pyrene chromophores linked by an electrochemically active ferrocene molecule has been synthesised in high yield through a multistep procedure. In the absence of the polyphosphate guest molecules, very weak excimer emission was observed, indicating that the two pyrene‐bearing Zn^II(TACN) units are arranged in a trans‐like configuration with respect to the ferrocene bridging unit. Binding of a variety of polyphosphate anionic guests (PPi and nucleotides di‐ and triphosphate) promotes the interaction between pyrene units and results in an enhancement in excimer emission. Investigations of phosphate binding by ³¹P NMR spectroscopy, fluorescence and electrochemical techniques confirmed a 1:1 stoichiometry for the binding of PPi and nucleotide polyphosphate anions to the bis(Zn^II(TACN)) moiety of [Fc? bis{Zn^II(TACN)(Py)}] and indicated that binding induces a trans to cis configuration rearrangement of the bis(Zn^II(TACN)) complexes that is responsible for the enhancement of the pyrene excimer emission. Pyrophosphate was concluded to have the strongest affinity to [Fc? bis{Zn^II(TACN)(Py)}] among the anions tested based on a six‐fold fluorescence enhancement and 0.1 V negative shift in the potential of the ferrocene/ferrocenium couple. The binding constant for a variety of polyphosphate anions was determined from the change in the intensity of pyrene excimer emission with polyphosphate concentration, measured at 475 nm in CH₃CN/Tris‐HCl (1:9) buffer solution (10.0 mM , pH 7.4). These measurements confirmed that pyrophosphate binds more strongly (K_b=(4.45±0.41)×10⁶ M ^?1) than the other nucleotide di‐ and triphosphates (K_b=1–50×10⁵ M ^?1) tested.     

Preparation and evaluation of solid-phase microextraction fibres based on functionalized latex nanoparticle coatings for trace analysis of inorganic anions

The use of a functionalized latex nanoparticle coating as a new sorbent phase for solid-phase microextraction (SPME) was examined. By means of electrostatic absorption onto ionized silanol groups, a fused-silica rod was coated with polymeric nanoparticles functionalized with quaternary ammonium groups. Optimum conditions for the preparation of the coated fibre are presented. The fibre was used for the extraction of a mixture of seven anions from water samples which are analysed by coupling the SPME fibre to an ion chromatographic system via a special interface. The results obtained proved the suitability of this novel coating as a new SPME fibre. A linear calibration for the target analytes was achieved over the concentration range from 5 μg L⁻¹ to 5 mg L⁻¹ (r² > 0.988), while limits of detection for these ions were all below 3.7 μg L⁻¹ (S/N = 3). The reproducibility of a single fibre (n = 4) under similar conditions was between 7 and 12%, while the fibre to fibre reproducibility (n = 5) was between 8.9 and 14%.     

1,3-双(1-苯基-1H-四唑-5-巯基)-乙酰苯腙钳形受体对卤素阴离子的识别机理

采用密度泛函B3LYP(Becke, three-parameter, Lee-Yang-Parr)和HF(Hatree-Fock)方法, 从理论上探讨了1,3-双(1-苯基-1H-四唑-5-巯基)-乙酰苯腙(DAPHZ)钳形受体对卤素阴离子的识别机理,结果发现DAPHZ受体以其钳形结构中的-N-H基团与卤素阴离子间形成双侧红移氢键进行识别. 经BSSE校正后DAPHZ•••F-, DAPHZ•••Cl-和DAPHZ•••Br-体系的分子识别相互作用能ΔECP分别为-327.5,-163.5和-148.3 kJmol-1, 说明钳形DAPHZ受体对F-具有最好的识别能力. 此外, 采用自然键轨道(NBO)计算, 相关H原子化学位移计算及分子中原子(AIM)等理论分析了识别体系中红移氢键的电子结构和性质, 结果表明APHZ受体对卤素阴离子的识别能力的相对顺序为DAPHZ•••F- >> DAPHZ•••Cl- ≈ DAPHZ•••Br-.     

Ion chromatography of nitrite at the ppb level with photometric measurement of iodine formed by post-column reaction of nitrite with iodide

The difficulty in ion-chromatographic determination of nitrite in aqueous solutions containing a high concentration of chloride arises mainly from incomplete resolution of the peaks for these anions on the separation column whose efficiency is not high. A photometric measurement of iodine formed by a reaction of nitrite with iodide has been found to make it possible to determine, chromatographically, trace amounts of nitrite without any interference from chloride; chloride does not oxidize iodide to produce iodine. The proposed method was based on the separation of nitrite from matrix anions on a silica-based anion-exchange column with a 1.5·10⁻³ M phthalate eluent (pH 5.0), followed by photometric measurement of the iodine (as triiodide) formed via a post-column reaction of the separated nitrite with iodide. The optimal conditions for the post-column reaction were established by varying the concentrations of iodide, copper(II) and nitric acid in a post-column-reaction solution and the length of a reaction tube. A calibration graph for nitrite, plotted as peak heights versus concentrations, was linear up to 1.50·10⁻⁵ M (690 ppb). The detection limit, defined at S/N=3, was 1.00·10⁻⁷ M (4.60 ppb) nitrite. The presence of chloride ions up to 0.01 M did not give any interference to the determination of nitrite. This method was successfully applied to the determination of nitrite in lake water, river water, sewage works water and snow samples without any pretreatment.     

LCAO-MO Calculation of Dipole Transition Moment of Some First-Row Transition Metal Tetroxy Anions

Abstract

Recently very encouraging results of semiempirical parameteric calculation of dipole transition moments of the lowest energy t₁ ? 2e (¹A₁ - ¹T₂) transition of permanganate and chromate ions have been reported. In the case of vanadate ion, which is isoelectronic with the permanganate and chromate ion, no such study of spectral intensities appears to have been reported so far. A parameteric calculation in terms of a single parameter β, the ligand mixing coefficient using Richardson's orbitals⁴ and both dipole velocity and dipole length operators have been reported in the present paper.     

Sensitive fluorescence probes for dihydrogen phosphonate anion based on calix[4]arene bearing naphthol-hydrazone groups

t-Butyl and t-pentylcalix[4]arenes bearing two 2-naphthol-1-hydrazone groups at the lower rim were synthesized,and showed excited-state intermolecular proton transfer fluorescent signal with basic anion.They are more sensitive to dihydrogen phosphate anion than to fluoride anion,although the latter has stronger basicity.Compared with t-butylcalix[4]arene bearing two 2-naphthol-1-hydrazone groups,t-pentylcalix[4]arenes derivative has a larger fluorescent difference between dihydrogen phosphate and fluoride a...     

Radii of Redox Components from Absolute Redox Potentials Compared with Covalent and Aqueous Ionic Radii

Aqueous standard potentials, referred to that of the SHE as zero, were recently shown to vary linearly with gaseous ionization potentials, with the absolute potential of SHE as the intercept. This enabled arriving at the absolute redox potentials of elements. Here, the distances between the oxidized and reduced forms in aqueous solutions have been evaluated. From the linear dependence of these distances on the covalent radii of atoms, the radii of the redox components have been obtained. The latter also vary linearly with the aqueous ionic radii estimated earlier from ion‐water distances, and indicate the presence of aqueous molecular anions.     

Electron transfer versus nucleophilic pathways in the ion-pair annihilation of organoborate anions by carbonylmanganese(I) cations

Substituted carbonylmanganese cations [Mn(CO)₅L]⁺, where L=py, PPh₃ and PPh₂Me, readily react with various organoborate anions (tetramethylborate, methyltriphenylborate and tetraphenylborate) in THF solution to afford a mixture of dimanganese carbonyls, hydridomanganese carbonyls and alkylmanganese carbonyls. The formation of the dimanganese carbonyl dimers as well as the hydridomanganese carbonyls suggests the involvement of 19-electron carbonylmanganese radicals that stem from an initial electron transfer. On the other hand, the acetonitrile-substituted analogue [Mn(CO)₅(CH₃CN)]⁺ reacts with the same borate anions to afford the alkylated RMn(CO)₅, where R=CH₃ and C₆H₅, as the sole carbonylmanganese product. As such, this alkylative annihilation is best formulated as a direct attack on the carbonyl carbon by the borate nucleophile. The two different pathways can be understood in terms of the balance between the electrophilicity of the carbonyl ligand and the electron affinity of the carbonylmanganese cation.