The effect of the counter anion on the transport of thiourea in a PVC-based polymer inclusion membrane using Capriquat as carrier

This paper describes the effect of four counter anions (CH₃COO⁻, Cl⁻, NO₃⁻, ClO₄⁻) of the trioctylmethylammonium (TOMA) cation on the rate of solvent extraction of thiourea and its transport across poly(vinyl chloride) (PVC)-based polymer inclusion membranes (PIMs). The membranes also contained 2-nitrophenyl octyl ether (NPOE) as the plasticizer while chloroform was used as diluent in the solvent extraction studies. It is demonstrated that the counter anion affects substantially the rate of membrane transport and the degree of extraction follows the order: CH₃COO⁻ > Cl⁻ > NO₃⁻ ? ClO₄⁻. The transport rate is negligible for the perchlorate anion. This order is consistent with thiourea interacting with the counter anion through hydrogen bonding to form a heteroconjugate anion.     

Single-run ion chromatographic separation of inorganic and low-molecular-mass organic anions under isocratic elution: Application to environmental samples

For the isocratic ion chromatography (IC) separation of low-molecular-mass organic acids and inorganic anions three different anion-exchange columns were studied: IonPac AS14 (9 μm particle size), Allsep A-2 (7 μm particle size), and IC SI-50 4E (5 μm particle size). A complete baseline separation for all analyzed anions (i.e., F⁻, acetate, formate, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, HPO₄²⁻ and SO₄²⁻) in one analytical cycle of shorter than 17 min was achieved on the IC SI-50 4E column, using an eluent mixture of 3.2 mM Na₂CO₃ and 1.0 mM NaHCO₃ with a flow rate of 1.0 mL min⁻¹. On the IonPac AS14 column, it was possible to separate acetate from inorganic anions in one run (i.e., less than 9 min), but not formate, under the following conditions: 3.5 mM Na₂CO₃ plus 1.0 mM NaHCO₃ with a flow rate of 1.2 mL min⁻¹. Therefore, it was necessary to adapt a second run with a 2.0 mM Na₂B₄O₇ solution as an eluent under a flow rate of 0.8 mL min⁻¹ for the separation of organic ions, which considerably enlarged the analysis time. For the Allsep A-2 column, using an eluent mixture of 1.2 mM Na₂CO₃ plus 1.5 mM NaHCO₃ with a flow rate of 1.6 mL min⁻¹, it was possible to separate almost all anions in one run within 25 min, except the fluoride-acetate critical pair. A Certified Multianion Standard Solution PRIMUS for IC was used for the validation of the analytical methods. The lowest RSDs (less than 1%) and the best LODs (0.02, 0.2, 0.16, 0.11, 0.06, 0.05, 0.04, 0.14 and 0.09 mg L⁻¹ for F⁻, Ac⁻, For⁻, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, HPO₄²⁻ and SO₄²⁻, respectively) were achieved using the IC SI-50 4E column. This column was applied for the separation of concerned ions in environmental precipitation samples such as snow, hail and rainwater.     

Supramolecular networks through second-sphere coordination based on 1D metal-4,4′-dipyridyldisulfide coordination polymers and hydrogenfumarate or sulfonate anions

Four hydrogen-bonded assemblies of formula [M(dpds)₂(OH₂)₂]A₂·nH₂O (A = anion) are described. These assemblies result from the second-sphere coordination interactions between the 1D coordination polymers [M(dpds)₂(OH₂)₂]²⁺, M = Zn(II) and Cu(II), dpds = 4,4′-dipyridyldisulfide, and the pyridine-3-sulfonate (3pySO₃⁻) or hydrogenfumarate (Hfum⁻) anions. Significantly, supramolecular structural variations are observed depending on the presence of water lattice molecules, which formed discrete aggregates when the Hfum⁻ anion was used. The effects of geometrical variations in the building blocks are also evident on using Jahn-Teller-distorted divalent Cu(II) ions or regular octahedral species based on Zn(II) ions. The second-sphere effects on the stabilization of the compounds are illustrated by TGA experiments.     

Electrochemical behavior of hexafluoroniobate, heptafluorotungstate, and oxotetrafluorovanadate anions in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide room temperature ionic liquid

Electrochemical behavior of hexafluoroniobate (Nb(V)F₆⁻), heptafluorotungstate (W(VI)F₇⁻), and oxotetrafluorovanadate (V(V)OF₄⁻) anions has been investigated in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPyrTFSA) ionic liquid at 298 K by means of cyclic voltammetry and chronoamperometry. Cyclic voltammograms at a Pt electrode showed that Nb(V)F₆⁻ anion is reduced to Nb(IV)F₆²⁻ by a one-electron reversible reaction. Electrochemical reductions of W(VI)F₇⁻ and V(V)OF₄⁻ anions at a Pt electrode are quasi-reversible and irreversible reactions, respectively, according to cyclic voltammetry. The diffusion coefficients of Nb(V)F₆⁻, W(VI)F₇⁻ and V(V)OF₄⁻ determined by chronoamperometry are 1.34 × 10⁻⁷, 7.45 × 10⁻⁸ and 2.49 × 10⁻⁷ cm² s⁻¹, respectively. The Stokes radii of Nb(V)F₆⁻, W(VI)F₇⁻, and V(V)OF₄⁻ in BMPyrTFSA have been calculated to be 0.23, 0.38, and 0.12 nm, from the diffusion coefficients and viscosities obtained.     

Organic tin compounds combined with anionic additives-an ionophore system leading to a phosphate ion-selective electrode?

The potentiometric response characteristics of electrodes based on organic trialkyl/aryl-tin compounds combined with various amounts of anionic additive (NaTFPB) were investigated in 0.1 M bis-Tris-H₂SO₄ buffer solution at pH 7.0. The best result for phosphate sensing was obtained for the electrode membrane containing tributyltin chloride and 25 mol% NaTFPB, where the electrode exhibits high selectivity towards phosphate anions with a slope of −60 mV per decade. It was demonstrated that the interference from more lipophilic anions is drastically suppressed (, i=H₂PO₄⁻: salicylate, 0.5; SCN⁻, −0.8; ClO₄⁻, −2.3) under this optimized measurement conditions.     

New interlocked molecules generated from a podand containing urea units and imidazolium salts using an anion template

A podand containing urea units (L) was found to form interlocked structures with 2,5-dihexylamide imidazolium salts (3·X), 2,5-dihexyl imidazolium salts (4·X), and 2,5-dihexyl benzoimidazolium salts (5·X), where X=Cl⁻, Br⁻, and PF₆⁻ using anions as templates. The binding ability of L and guest molecules was evaluated by ¹H NMR titrations in CDCl₃. It was found that L could form complexes with guest molecules in the following order, 3·X > 5·X > 4·X. Stabilities of the complexes also depended on shape of the templated anions: Cl⁻>Br⁻?PF₆⁻. Hydrogen bonding and π-π stacking interactions played an important role in the self-assembling of these interlocked molecules.     

Synthesis, optical and electrochemical properties of new receptors and sensors containing anthraquinone and benzimidazole units

Novel anion receptors and sensors, HBIMANQ and BIMANQ fabricated from the imidazolole unit and anthraquinone moieties were synthesized. ¹H NMR spectroscopy and UV-vis titrations in DMSO-d₆ and DMSO, respectively, showed that both receptors underwent deprotonation at the NH- moiety of the amide-anthraquinone unit in the presence of basic anions such as F⁻ and AcO⁻. These phenomena gave a dramatic color change due to charge transfer transition corresponding to the shift of λ_max from 371 nm to 489 nm. Redox chemistry of HBIMANQ and BIMANQ in the presence of anions (F⁻, Cl⁻, AcO⁻, BzO⁻, and H₂PO₄⁻) using cyclic voltammetry showed the different CV responses upon addition of various anions. In the case of HBIMANQ with various anions, the CV changes are dependent on the basic strength of anions in order of F⁻>AcO⁻, BzO⁻>H₂PO₄⁻>Cl⁻, Br⁻. Interestingly, the CV responses of BIMANQ with H₂PO₄⁻ exhibited the most significant changes. BIMANQ, thus, has an excellent electrochemical selectivity toward H₂PO₄⁻.     

Thermal properties of N-alkyl-N-methylpyrrolidinium and N-butylpyridinium fluorometallates and physicochemical properties of their melts

A series of N-alkyl-N-methylpyrrolidinium (RMPyr⁺, where R = E: ethyl, B: butyl, and H: hexyl) and N-butylpyridinium (BPy⁺) salts based on the fluorocomplex anions, BF₄⁻, PF₆⁻, SbF₆⁻, NbF₆⁻, TaF₆⁻, and WF₇⁻, have been synthesized and their thermal behavior has been investigated. The melting points of the RMPyr⁺ salts are above room temperature with the trend; BMPyrAF₆ < HMPyrAF₆ < EMPyrAF₆ for the hexafluorocomplex salts. Some of the salts containing BMPyr⁺ and HMPyr⁺ exhibit phase transitions in the solid states. Similar melting points of BPy⁺ salts of PF₆⁻, SbF₆⁻, NbF₆⁻, TaF₆⁻, and WF₇⁻ are observed at around 350 K. Ionic conductivity and viscosity for BMPyrNbF₆ (3.0 mS cm⁻¹ and 164 cP at 328 K) are similar to those for BMPyrTaF₆ (3.0 mS cm⁻¹ and 165 cP at 328 K), resulting from the similarity of the anions in size. The activation energies of ionic conductivity for the NbF₆⁻ and TaF₆⁻ salts are 18 and 20 kJ mol⁻¹, and those for viscosity are 23 and 25 kJ mol⁻¹, respectively calculated by Arrhenius equation in the temperature range between 328 and 348 K. Electrochemical windows of BMPyrNbF₆, BMPyrTaF₆, and BMPyrWF₇ are about 4.0, 5.0 and 3.1 V, respectively.     

Optimum conditions for intercalation of lacunary tungstophosphate(V) anions into layered Ni(II)-Zn(II) hydroxyacetate

Acetate containing nickel-zinc hydroxysalts (LHS-Ni-Zn) have been synthesized by coprecipitation and hydrothermal treatment. The acetate anions were exchanged with PW₁₂O₄₀³⁻ anions, and optimum conditions to attain the maximum level of W in the compound have been identified. The W intercalated compound was characterized by powder X-ray diffraction, FT-IR spectroscopy, thermogravimetric and differential thermal analyses, scanning electron microscopy and transmission electron microscopy.The exchange of LHS-Ni-Zn with PW₁₂O₄₀³⁻ at pH=3 for 72 h leads to a solid with a basal spacing of 9.62 Å and a W content (weight) of 37%. The hydrothermal treatment at 90 °C for 24 h increases this value to 48% with a W/Zn molar ratio of 1.38, which corresponds to a layered compound with lacunary tungstophosphate anions in the interlayer space. The intercalated solid is stable up to 250 °C, the layer structure collapses on dehydroxylation and amorphous compounds were identified at 500 °C. Two crystalline phases, NiO (rock salt) and a solid solution (Zn_1−xNi_x)WO₄, were identified by powder X-ray diffraction at high temperature (ca. 1000 °C).     

An improved flow analysis-ion chromatography method for determination of cationic and anionic species at trace levels in Antarctic ice cores

A method was developed for the quantitative determination of cations and anions in Antarctic ice cores at μg L⁻¹ and sub-μg L⁻¹ levels by ion chromatography (IC), after ultra-clean decontamination procedures. Strict manipulation and decontamination procedures were used in sub-sampling, in order to minimise sample contamination. Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺ were determined by 12-min isocratic elution (H₂SO₄ eluent). Contemporaneously, in a parallel device, F⁻, MSA (methanesulfonic acid), Cl⁻, NO₃⁻ and SO₄²⁻ were analysed in a single 12-min run with multiple-step elution using Na₂CO₃/NaHCO₃ as eluent. Melted ice samples were pumped from their still-closed containers (polystyrene accuvettes with polyethylene caps), shared between the two ion chromatographic systems, online filtered (0.45 μm Teflon membrane) and pre-concentrated (anions and cations pre-concentration columns) using a flow analysis system, thus avoiding uptake of contaminants from the laboratory atmosphere. Sensitivity, linear range, reproducibility and detection limit were evaluated for each chemical species. Anion or cation detection limits ranged from 0.01 to 0.15 μg L⁻¹ by using a relatively small sample volume (1.5 mL). Such values are significantly lower than those reported in literature for almost all the components. These methods were successfully applied to the analysis of cations and anions at trace levels in the Dome C ice core. The composition of the atmospheric aerosol for the last 850 kyr was reconstructed by high-resolution continuous chemical stratigraphies. Concentration trends in the last nine glacial-interglacial climatic cycles were shown and briefly discussed.     

Ionic liquids monolithic columns for protein separation in capillary electrochromatography

A series of ionic liquids (ILs) monolithic capillary columns based on 1-vinyl-3-octylimidazolium (ViOcIm⁺) were prepared by two approaches (“one-pot” approach and “anion-exchange” approach). The effects of different anions (bromide, Br⁻; tetrafluoroborate, BF₄⁻; hexafluorophosphate, PF₆⁻; and bis-trifluoromethanesulfonylimide, NTf₂⁻) on chromatography performance of all the resulting columns were investigated systematically under capillary electrochromatography (CEC) mode. The results indicated that all these columns could generate a stable reversed electroosmotic flow (EOF) over a wide pH range from 2.0 to 12.0. For the columns prepared by “one-pot” approach, the EOF decreased in the order of ViOcIm⁺Br⁻ > ViOcIm⁺BF₄⁻ > ViOcIm⁺PF₆⁻ > ViOcIm⁺NTf₂⁻ under the same CEC conditions; the ViOcIm⁺Br⁻ based column exhibited highest column efficiencies for the test small molecules; the ViOcIm⁺NTf₂⁻ based column possessed the strongest retention for aromatic hydrocarbons; and baseline separation of four standard proteins was achieved on ViOcIm⁺NTf₂⁻ based column corresponding to the highest column efficiency of 479 000 N m⁻¹ for cytochrome c (Cyt c). These results indicated that the property of ILs based columns could be tuned successfully by changing anions, which gave these columns potential to separate both small molecules and macro biomolecules.     

2, 2′-Dihydroxyazobenzene-based fluorescent system for the colorimetric ‘turn-on’ sensing of cyanide

2, 2′-Dihydroxyazobenzene (DHAB) demonstrated high sensitivity and low selectivity toward three anions: CN⁻, CO₃²⁻, and HCO₃⁻. In the presence of Cu(II), complex DHAB-Cu(II) could give rise to enhanced fluorescence intensity by about 45-fold at 590 nm and visible red-to-reddish orange color change upon the addition of cyanide by utilizing an indirect method, while no changes were observed in the presence of other anions, including F⁻, Cl⁻, Br⁻, I⁻, H₂PO₄⁻, CH₃COO⁻, NO₃⁻, CO₃²⁻ and HCO₃⁻, and SO₄²⁻, making the DHAB-Cu(II) complex a selective and sensitive cyanide chemosensor.     

Determination of fluoride and oxalate using the indicator reaction of Zr(IV) with methylthymol blue adsorbed on silica gel

Solid-phase spectrophotometric and visual test-methods of fluoride and oxalate determination are proposed. The methods are based on the competitive reactions of ZrOCl₂ with methylthymol blue immobilized on silica gel and fluoride or oxalate in solution. Absorbance of the solid-phase reagent at 590 nm decreases with the growth of fluoride and oxalate contents in solution. The developed methods demonstrate high selectivity. The interference of Bi(III) and SO₄²⁻, PO₄³⁻ is eliminated by the addition of 0.01 mol L⁻¹ solution of ascorbic acid and 0.01 mol L⁻¹ of BaCl₂, respectively. To eliminate the fluoride interference with oxalate determination 1 × 10⁻³ mol L⁻¹ solution of Ca(NO₃)₂ at pH 1.5 was added. The anions of the organic acids were destructed prior to F⁻ determination by ultrasonic exposition (44 kHz, intensity of ≤10 W cm⁻² for 3 min). The proposed methods were applied to the analysis of mineral water, toothpaste and biological fluids.     

Thermal aggregation of bovine serum albumin studied by asymmetrical flow field-flow fractionation

The use of asymmetrical flow field-flow fractionation (AsFlFFF) in the study of heat-induced aggregation of proteins is demonstrated with bovine serum albumin (BSA) as a model analyte. The hydrodynamic diameter (d_h), the molar mass of heat-induced aggregates, and the radius of gyration (R_g) were calculated in order to get more detailed understanding of the conformational changes of BSA upon heating. The hydrodynamic diameter of native BSA at ambient temperature was ∼7 nm. The particle size was relatively stable up to 60 °C; above 63 °C, however, BSA underwent aggregation (growth of hydrodynamic diameter). The hydrodynamic diameters of the aggregated particles, heated to 80 °C, ranged from 15 to 149 nm depending on the BSA concentration, duration of incubation, and the ionic strength of the solvent. Heating of BSA in the presence of sodium dodecyl sulfate (1.7 or 17 mM) did not lead to aggregation. The heat-induced aggregates were characterized in terms of their molar mass and particle size together with their respective distributions with a hyphenated technique consisting of an asymmetrical field-flow fractionation device and a multi-angle light scattering detector and a UV-detector. The carrier solution comprised 8.5 mM phosphate and 150 mM sodium chloride at pH 7.4. The weight-average molar mass (M_w) of native BSA at ambient temperature is 6.6 × 10⁴ g mol⁻¹. Incubation of solutions with BSA concentrations of 1.0 and 2.5 mg mL⁻¹ at 80 °C for 1 h resulted in aggregates with M_w 1.2 × 10⁶ and 1.9 × 10⁶ g mol⁻¹, respectively. The average radius of gyration and the average hydrodynamic radius of the heat-induced aggregate samples were calculated and compared to the values obtained from the size distributions measured by AsFlFFF. For comparison static light scattering measurements were carried out and the corresponding average molar mass distributions of solutions with BSA concentrations of 1.0 and 2.5 mg mL⁻¹ at 80 °C for 1 h gave aggregates with M_w 1.7 × 10⁶ and 3.5 × 10⁶ g mol⁻¹, respectively.     

Syntheses, crystal structures and Raman spectra of Ba(BF4)(PF6), Ba(BF4)(AsF6) and Ba2(BF4)2(AsF6)(H3F4); the first examples of metal salts containing simultaneously tetrahedral BF4 and octahedral AF6 anions

In the system BaF₂/BF₃/PF₅/anhydrous hydrogen fluoride (aHF) a compound Ba(BF₄)(PF₆) was isolated and characterized by Raman spectroscopy and X-ray diffraction on the single crystal. Ba(BF₄)(PF₆) crystallizes in a hexagonal space group with a=10.2251(4) Å, c=6.1535(4) Å, V=557.17(5) Å³ at 200 K, and Z=3. Both crystallographically independent Ba atoms possess coordination polyhedra in the shape of tri-capped trigonal prisms, which include F atoms from BF₄⁻ and PF₆⁻ anions. In the analogous system with AsF₅ instead of PF₅ the compound Ba(BF₄)(AsF₆) was isolated and characterized. It crystallizes in an orthorhombic Pnma space group with a=10.415(2) Å, b=6.325(3) Å, c=11.8297(17) Å, V=779.3(4) Å³ at 200 K, and Z=4. The coordination around Ba atom is in the shape of slightly distorted tri-capped trigonal prism which includes five F atoms from AsF₆⁻ and four F atoms from BF₄⁻ anions. When the system BaF₂/BF₃/AsF₅/aHF is made basic with an extra addition of BaF₂, the compound Ba₂(BF₄)₂(AsF₆)(H₃F₄) was obtained. It crystallizes in a hexagonal P6₃/mmc space group with a=6.8709(9) Å, c=17.327(8) Å, V=708.4(4) Å³ at 200 K, and Z=2. The barium environment in the shape of tetra-capped distorted trigonal prism involves 10 F atoms from four BF₄⁻, three AsF₆⁻ and three H₃F₄⁻ anions. All F atoms, except the central atom in H₃F₄ moiety, act as μ₂-bridges yielding a complex 3-D structural network.     

Preparation of a new solid state fluoride ion selective electrode and application

A new solid state fluoride ion selective electrode composed of 70% Ag₂S, 10% Cu₂S and 20% CaF₂ has been developed. An analytically useful potential change occurred, from 1 × 10⁻⁶ to 1 × 10⁻¹ M fluoride ion. The slope of the linear portion (1 × 10⁻¹-1 × 10⁻⁵ M) was about 26 ± 2 mV/10-fold concentration changes in fluoride. It was found that pH change between 1 and 8 had no effect on the potential of the electrode. There was no interference of most common cations such as K^+, Na⁺, Ca²⁺ and Mg²⁺ and anions such as Cl⁻, NO₃⁻, SO₄²⁻ and PO₄³⁻. The lifetime of the electrode was more than 2 years, when used at least 4-5 times a day, and the response time was about 60 s.The measurements were made at constant ionic strength (0.1 M NaNO₃) and at room temperature. This electrode has been used for the determination of fluoride ion in Ankara city tap water and in bottled spring water using standard addition method. The validation of the electrode has been made with a commercial fluoride ion selective electrode (Orion) and high consistency was obtained.     

A new tool for inorganic nitrogen speciation study: simultaneous determination of ammonium ion, nitrite and nitrate by ion chromatography with post-column ammonium derivatization by Nessler reagent and diode-array detection in rain water samples

The paper presents a new method for a simultaneous determination of inorganic nitrogen species in the oxidized (NO₂⁻, NO₃⁻) and reduced (NH₄⁺) form in rain water samples. The method is based on a system of nitrogen species separation employing ion exchange and diode-array detection. The ions are separated in a strong ion-exchanger, nitrites and nitrates are determined directly at 208 and 205 nm, respectively, while the ammonium ions are determined in the column hold-up time after a post-column derivatization by the Nessler reagent, at 425 nm. The use of a diode-array detector permits a simultaneous identification of the inorganic nitrogen species in 8 min. The detection limits obtained are: NO₂⁻, 0.1 mg L⁻¹; NO₃⁻, 0.05 mg L⁻¹; NH₄⁺, 1 mg L⁻¹. The method proposed has been successfully used for speciation analysis of inorganic nitrogen in precipitation.     

Syntheses and characterization of mixed-chelate copper(II) complexes containing different counter ions; spectroscopic studies on solvatochromic properties

Solvatochromic mixed-chelate copper(II) complexes, [Cu(Cl-acac)(diamine)]X (where Cl-acac = 3-chloroacetylacetonate ion, diamine = N,N′-dimethyl,N′-benzyl-1,2-diaminoethane and X = B(Ph)₄⁻, PF₆⁻, BF₄⁻ and ClO₄⁻), have been prepared. The complexes were characterized on the basis of elemental analysis, molar conductance, UV-Vis and IR spectroscopies. Single crystals of [Cu(Cl-acac)(diamine)(H₂O)]PF₆, complex 2, were also characterized by X-ray diffraction. The influence of the solvent polarity and counter ions on the ν_max values of the d-d bands of the complexes have been investigated by means of visible spectroscopy. All the complexes demonstrated negative solvatochromism. A multi-parametric equation has been utilized to explain the solvent effect on the d-d transition of the complexes using SPSS/PC software. The stepwise multiple linear regression (SMLR) method demonstrated that the donor power of the solvent plays the most important role in the solvatochromism of the compounds. The relative donor power of the anions X was determined by visible spectra in the solvent dichloromethane.     

Spectroscopic and structural characterization of Na2[(VO)2(ttha)]·8H2O (ttha = triethylenetetraamine-N,N,N′,N″,N′″,N′″-hexaacetate): Interpreting the results with density functional theory

Na₂[(V^IVO)₂(ttha)]·8 H₂O (ttha = triethylenetetraamine–N,N,N′,N″,N′″,N′″–hexaacetate ion), prepared by treating [VO(H₂O)₅][(VO)₂(ttha)]·4 H₂O with Na₆(ttha), has been characterized by single crystal X-ray diffraction, infrared spectroscopy, UV–Vis absorption spectroscopy, electron spin resonance spectroscopy, and modeled by density functional theory (DFT). The X-ray structure revealed a distorted octahedral geometry around each vanadium center. The electronic absorption spectrum of [(VO)₂(ttha)]²⁻ (aq) features absorptions at ca. 200 nm (ε > 13900 L mol⁻¹ cm⁻¹), 255 nm (ε = 3480 L mol⁻¹ cm⁻¹), 586 nm (ε = 33 L mol⁻¹ cm⁻¹), and 770 nm (ε = 38 L mol⁻¹ cm⁻¹). The time-dependent density functional theory (TDDFT) calculated electronic absorption spectrum was remarkably similar to the actual spectrum, and TDDFT predicts absorption peaks at 297, 330, 458, 656, and 798 nm. TDDFT assigned the peak at 798 nm to be the α spin HOMO → LUMO transition. Hence, the peak at 770 nm in the actual spectrum is most likely the α spin HOMO → LUMO transition. Moreover, the TDDFT calculations revealed that the α spin HOMO and LUMO are partly comprised of d orbitals on both vanadium centers, and the first derivative electron spin resonance spectrum also suggests that the two unpaired electrons in [(VO)₂(ttha)]²⁻ are localized near the vanadium centers.     

Surface-modified CdSe quantum dots as luminescent probes for cyanide determination

Luminescent surface-modified CdSe semiconductor quantum dots (QDs), with nanoparticle (NP) size distribution in the order of 2-7 nm, have been synthesized for optical determination of cyanide ions. The nanoparticles have been functionalised with tert-butyl-N-(2-mercaptoethyl)-carbamate (BMC) groups and exhibit a strong fluorescent emission at about 580 nm with rather long fluorescence lifetimes (several hundred nanoseconds) in aerated methanolic solution. The observed luminescence emitted by the synthesized nanocrystals was tremendously increased by photo-activation under sunlight exposure. The functionalised QDs turned out to exhibit excellent long-term stability when stored in the dark (no significant changes in QDs luminescence emission intensity was observed even after two months from synthesis). The functionalisation of the NPs with carbamate ligand allowed a highly sensitive determination of free cyanide via analyte-induced changes in the photoluminescence (fluorescence quenching of intensity at 580 nm and lifetime changes) of the modified quantum dots (excited at 400 nm). A detection limit of 1.1 × 10⁻⁷ M (2.9 μg l⁻¹) of cyanide ions was obtained, while the interfering effect of other inorganic anions (including NO₃⁻, Cl⁻ or SCN⁻) was negligible even at 200-fold level concentrations in excess of cyanide.