Speciation of selenium(IV) and selenium(VI) in environmental samples by the combination of graphite furnace atomic absorption spectrometric determination and solid phase extraction on Diaion HP-2MG

A simple solid phase extraction procedure for speciation of selenium(IV) and selenium(VI) in environmental samples has been proposed prior to graphite furnace atomic absorption spectrometry. The method is based on the solid phase extraction of the selenium(IV)-ammonium pyrrolidine dithiocarbamate (APDC) chelate on the Diaion HP-2MG. After reduction of Se(VI) by heating the samples in the microwave oven with 4 mol l⁻¹ HCl, the system was applied to the total selenium. Se(VI) was calculated as the difference between the total selenium content and Se(IV) content. The experimental parameters, pH, amounts of reagents, eluent type and sample volume were optimized. The recoveries of analytes were found greater than 95%. No appreciable matrix effects were observed. The adsorption capacity of sorbent was 5.20 mg g⁻¹ Se (IV). The detection limit of Se (IV) (3sigma, n = 11) is 0.010 μg l⁻¹. The preconcentration factor for the presented system was 100. The proposed method was applied to the speciation of selenium(IV), selenium(VI) and determination of total selenium in natural waters and microwave digested soil, garlic, onion, rice, wheat and hazelnut samples harvested various locations in Turkey with satisfactory results. In order to verify the accuracy of the method, certified reference materials (NIST SRM 2711 Montana Soil, NIST SRM 1568a Rice Flour and NIST SRM 8418 Wheat Gluten) were analyzed and the results obtained were in good agreement with the certified values. The relative errors and relative standard deviations were below 6 and 10%, respectively.     

Potassium Sensing by Using a Newly Synthesized Squaraine Dye in Sol-Gel Matrix

Squaraines are a group of fluorescent dyes and pigments derived from squaric acid and dialkylanilines well known in applications such as photoreceptors, organic solar cells, optical recording media, and non-linear optics. Their very promising spectral properties, long wavelength absorption and emission, and high absorptivity and quantum yields have not been exploited so far in relation to optical sensor design. They exhibit excellent solubility in sol-gel matrices, and the ligand is an integral part of the fluorophore system, which makes the molecule a fluoroionophore. In this work, potassium-sensing agent, bis[4-N-(1-aza-4,7,10,13,16-pentaox acyclooctadecyl)-3,5-dihydroxyphenyl] squaraine has been used for potassium sensing in a sol-gel matrix. The spectrofluorimetric response of dye-doped tetraethyl ortosilicate (TEOS) film after exposure to certain concentrations of K⁺ has been investigated, and 62% of relative signal change was achieved. The dynamic working range of the sensor membrane has been found between 10^–9 and 10^–6 M K⁺, in other terms from nanomolar to micromolar levels, which is an advantage over flame emission spectroscopy, in view of detection limit. The sensor is fully reversible within the dynamic range and the response time (₉₀) is found to be 2 min under batch conditions. The cross-sensitivity of the molecule to Na⁺, Ba²⁺, Ca²⁺, and NH⁺ ₄ was also tested in separate solutions.     

A Long Wavelength Excitable Fluorophore; Chloro Phenyl Imino Propenyl Aniline (CPIPA) for Selective Sensing of Hg (II)

In this study, a very sensitive and highly selective irreversible optical chemical sensor (optode) for mercury ions was described. The sensing scheme was based on the interaction of Hg (II) with a newly synthesized fluoroionophore; chloro phenyl imino propenyl aniline (CPIPA) in plasticized PVC membrane. The sensor membranes were tested for the determination of mercury ion in aqueous solutions by batch and flow-through methods. The optodes allow determination of Hg (II) in the working range of 1.0 × 10⁻⁹–1.0 × 10⁻⁵ M with a detection limit of 4.3 ppb. The sensor exhibited excellent selectivity for Hg (II) with respect to several common alkali, alkaline earth and transition metal ions. The association constant of the 1:1 complex formation for Hg (II) was found to be K_a = 1.86 × 10⁵ M⁻¹. The CPIPA exhibited high fluorescence quantum yield, long excitation and emission wavelength and high Stokes’ shift values in the solid matrix which makes it compatible with solid state optics.     

Ratiometric sensing of CO2 in ionic liquid modified ethyl cellulose matrix

In this study emission-based ratiometric response of ion pair form of 1-hydroxy-3,6,8-pyrenetrisulfonate (HPTS) to gaseous CO(2) has been evaluated in ionic liquid (IL) containing ethyl cellulose (EC) matrix. The ionic liquid: 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF(4)); provided longer storage time and highly stable microenvironment for the HPTS molecule due to the buffering effect. The utilization of ionic liquid in ethyl cellulose matrix resulted with superior spectral characteristics. The excitation spectra of HPTS exhibited an atypical isoemmissive point in modified EC matrix at 418 nm which allows ratiometric processing of the signal intensities. EMIMBF(4)-doped sensor films exhibited enhanced linear working range between 0 and 100% pCO(2). The signal changes were fully reversible and the shelf life of the EMIMBF(4)-doped films was extended from 15 to 95 days.     

Characterization of a reservoir-type capillary optical microsensor for pCO(2) measurements

A reservoir type of capillary microsensor for pCO₂ measurements is presented. The sensor is based on the measurement of the fluorescence intensity of the anionic form of the pH indicator 1-hydroxy-3,6,8-pyrenetrisulfonate in the form of its ion pair with a quaternary ammonium base in an ethyl cellulose matrix. The glass capillary containing the reservoir sensor was prepared by immersing the tip of the optical fiber into the sensing agent very close to the sensor tip thus providing a very small volume for the sensing reaction. The purpose of the sensing approach is to regenerate the dye/buffer system by diffusion, which may be poisoned by interfering acids, or bleach by photolysis. The fresh cocktail from the reservoir takes the place of protonated form of the dye. The internal buffer system also makes the protonation-deprotonation equilibria reversible. The distal tip of the internal buffer containing reservoir is coated with a gas-permeable but ion-impermeable teflon membrane. The dynamic range for the detection of pCO₂ is between 1 and 20 hPa, which corresponds to the range of dissolved CO₂ in water. The response time is 15 s and the detection limit is 1 hPa of pCO_2. The recovery performance of this sensor can be improved by means of mechanical adjustment of the sensor tip in a micrometric scale.     

Photocharacterization of Novel Ruthenium Dyes and Their Utilities as Oxygen Sensing Materials in Presence of Perfluorochemicals

Photophysical constants of three novel ruthenium dyes derived from tridentate pyridinediimine (pydim) ligands has been declared and their photoluminescent properties were investigated in solvents of dichloromethane (DCM), tetrahydrofuran (THF) and ethanol (EtOH) by UV-Visible absorption, emission and excitation spectra. The quantum yield, fluorescence decay time, molar extinction coefficient and Stoke’s shift values of the novel ruthenium complexes were determined. The perfluoro compound (PFC) nonadecafluorodecanoic acid which is also known as medical gas carrier has been used for the first time together with newly synthesized Ruthenium complexes in ethyl alcohol. The utilities of oxygen sensing materials were investigated in EtOH in presence of chemically and biochemically inert PFC.     

Synthesis and Characterization of New Binaphthyl‐Linked Phenanthroline‐, Bipyridine‐, or Pyridine‐Derived Ligands,and the Study of Their Cytotoxic Activity

In the present work, we describe the synthesis and characterization of five new versatile acyclic or macrocyclic ligands containing binaphthyl‐linked pyridine, bipyridine, or phenanthroline groups in their framework (see Schemes 1–4). The structures of the ligands were elucidated on the basis of elemental analyses, IR, ¹H‐NMR, ¹³C‐NMR, and FAB mass spectra. The cytotoxicity of these compounds was tested in vitro by using the tetrazolium salt reduction (MTT) assay on A549 (human lung carcinoma epithelial like) cells. All of the tested compounds induced time‐ and concentration‐dependent cytotoxic effect.     

Factors Associated With Mathematics Achievement and Participation in Advanced Mathematics Courses: An Examination of Gender Differences From an International Perspective

This paper reports results of an exploratory study examining factors that might be associated with achievement in mathematics and participation in advanced mathematics courses in Canada, Norway, and the United States of America (USA). These factors, which were not directly related to schooling accounted for large degrees of variability, 24% to 39%, in mathematics achievement scores. Confidence in mathematics was the strongest predictor of achievement for students from Canada and Norway, whereas for the students from the USA, parents' highest education level was the highest predictor of achievement. Student home environment related variables were stronger predictors of achievement for females than for males in all three countries. The participation in advanced mathematics courses could be predicted with 72% to 76% accuracy by the same variables. In all of the three countries, the strongest predictors of participation in advanced mathematics courses were students' attitudes toward mathematics. Parents' education level, a socioeconomic related variable, was one of the strongest predictors of participation for Canadian female students and all students from the USA.     

Optical CO<Subscript>2</Subscript> Sensing with Ionic Liquid Doped Electrospun Nanofibers

The first use of electrospun nanofibrous materials as highly responsive fluorescence quenching-based optical CO₂ sensors is reported. Poly(methyl methacrylate) and ethyl cellulose were used as polymeric materials. Sensing slides were fabricated by electrospinning technique. A fiber-optic bundle was used for the gas detection. CO₂ sensors based on the change in the fluorescence signal intensity of ion pair form of 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS). The sensor slides showed high sensitivities due to the high surface area-to-volume ratio of the nanofibrous membrane structures. The preliminary results of Stern-Volmer analysis show that the sensitivities of electrospun nanofibrous membranes to detect CO₂ are 24 to 120 fold higher than those of the thin film based sensors. The response times of the sensing reagents were short and the signal changes were fully reversible. The stability of ion pair form of HPTS in the employed matrix materials was excellent and when stored in the ambient air of the laboratory there was no significant drift in signal intensity after 7 months. Our stability tests are still in progress.