Kadriye Ertekin

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.

Photophysical and photochemical characteristics of an azlactone dye in sol-gel matrix; a new fluorescent pH indicator

Abstract The photophysical and photochemical properties of an azlactone derivative, 4-(p-N,N-dimethylaminophenylmethylene)-2-phenyl-5-oxazolone, (DPO) in a sol-gel matrix have been examined. The fluorescence quantum yield, radiative lifetime, fluorescence lifetime, fluorescence rate constant and singlet energy values of the DPO dye were determined in a modified tetraethyl orthosilicate (TEOS) solid matrix by absorption and emission spectroscopy and obtained data were compared with the results of measurements in acetonitrile (MeCN) and tetrahydrofuran (THF) solution. The sol-gel matrix enhanced the fluorescence quantum yield (Qf=0.296) and fluorescence emission lifetime (τf=0.47 ns) compared to Qf=0.0027–0.0025 and τf=0.02–0.03 ns for solutions in MeCN and THF. The acidity constant of DPO was found to be as pKa=5.1 in the transparent sol-gel matrix. The dye doped sol-gel exhibited a pH sensitivity in pH range 3.0–7.0.

An ultra sensitive fluorescent nanosensor for detection of ionic copper

A stable and ultra sensitive nano-scale fluorescent chemo-sensor for trace amounts of Cu(2+) was proposed. The Cu(2+) selective fluoroionophore 2-{[(2-aminophenyl)imino]methyl}-4,6-di-tert-butylphenol (DMK-7) was encapsulated in polymeric ethyl cellulose. The sensing membranes were fabricated in form of nanofibers and thin films. When embedded in polymers, the exploited DMK-7 dye exhibited enhanced photophysical characteristics in absorbance, Stokes shift, fluorescence quantum yield, and short and long-term photostability with respect to the solution phase. Sensing abilities of the nanofibers and thin films were tested by steady state and time resolved fluorescence spectroscopy. To our knowledge, this is the first attempt using the DMK-7-doped electrospun nanofibrous materials for copper sensing. The offered sensor displayed a sensitive response with a detection limit of 3.3×10(-13) M for Cu(2+) ions over a wide concentration range of 5.0×10(-12)-5.0×10(-5). Additionally, exhibited high selectivity over convenient cations; Na(+), K(+), Ca(2+), Mg(2+), NH4(+) and Ag(+), Al(3+), Ba(2+), Co(2+), Cr(3+), Fe(3+), Fe(2+), Hg(2+), Li(+), Mn(2+), Ni(2+), Pb(2+), Sn(2+) and Zn(2+).

Fiber optic sodium and potassium sensing by using a newly synthesized squaraine dye in PVC matrix.

In recent years squarines received attention as fluorescent labels. Their very promising spectral properties such as long wavelength absorption and emission, high extinction coefficients and quantum yields could lead novel sensing technologies. In this work newly synthesized fluoroinophores named bis[4-N-(1-aza-4,7,10,13-tetraoxacyclopentadecyl)-3,5-dihydroxyphenyl]squaraine, azacrown-1 and 2 bis[4-N-(1-aza-4,7,10,13,16-pentaoxacyclooctadecyl)-3,5-dihydroxyphenyl]squaraine, azacrown-2 have been used for sodium and potassium sensing in plasticized PVC matrix. The squaraine derivatives exhibited fluorescence emission based optical responses to sodium and potassium with a detection limit of 1.10(-9) M. The sensor compositions exhibited wide response ranges between 10(-9) and 10(-5) M Na(+)or K(+), and, therefore, may be an alternative method to flame emission spectroscopy. The sensor is fully reversible within the dynamic range and the response time is 3 min under batch conditions. Cross sensitivity to pH is negligible in the pH range of 6.2-7.3. Throughout fiber optic based studies a relative signal change of 54-56% has been achieved. The azacrown dyes have the advantage that they can be excited with long wavelength light and, are, therefore, LED compatible. The cross sensitivity of azacrown-1 and -2 to Ba(2+), Ca(2+) and NH(4)(+)were also tested in separate solutions.

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.

Design of oxygen sensing nanomaterial: synthesis, encapsulation of phenylacetylide substituted Pd(II) and Pt(II) meso-tetraphenylporphyrins into poly(1-trimethylsilyl-1-propyne) nanofibers and influence of silver nanoparticles

Room temperature phosphorescent oxygen sensors have been designed by embedding symmetric palladium(II) or platinum(II) meso-tetraphenylporphyrins in poly(1-trimethylsilyl-1-propyne) in the form of nanofibers along with/without silver nanoparticles. These materials combine the advantages of the high oxygen sensitivity of porphyrins and the enhanced surface area of porous nanofibers. Phenylacetylide bearing palladium(II) or platinum(II) meso-tetraphenylporphyrins (Pd-TPA, Pt-TPA, Pd-TPP and Pt-TPP) were designed to enhance phosphorescence quantum yields as well as sensitivity towards oxygen. Their syntheses were achieved by 2 alternative methods including successive metallation reactions and Sonogashira coupling via optimization of the synthetic strategies and conditions. The respective effect of the metal (Pd or Pt) and substituent on phosphorescence quantum yield as well as other photophysical properties was considered. The sensing performances of the corresponding silver-free and silver doped nanofibers were tested in the oxygen concentration range of 0.0–100.0%. The offered composites provided the advantages of fast response, enhanced sensitivity, reversible and long lasting response, higher Stern–Volmer constants (KSV) and low limit of detection values extending to 7.5 ppm for oxygen.

Photostability studies of thermomesomorphic derivatives of 2, 5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione

Abstract In this study, the photophysical characteristics, like molar extinction coefficients, Stokes shifts, quantum yields, radiative and fluorescence lifetimes, fluorescence rate constants, radiationless deactivation rate constants, and singlet energies of the fluorescent mesomorphic diketopyrrolopyrrole derivatives, (DPPDs), 3,6-bis(4-octyloxyphenyl)-2,5-dihydro-2,5-dimethylpyrrolo[3,4-c]pyrrole-1,4-dione (DPPD-1) and 3,6-bis(4′-butylbiphenyl-4-yl)-2,5-dihydro-2,5-dimethylpyrrolo[3,4-c]pyrrole-1,4-dione (DPPD-2) have been determined. The photostability studies were carried out under xenon arc lamp, direct and concentrated sunlight in solution of chloroform and tetrahydrofuran as well as in solid state, embedded in matrices of polyvinyl chloride (PVC) and sol-gel. The studies reveal that the photostabilities of the DPPD derivatives in PVC and sol-gel matrices are enhanced compared to solutions of chloroform and tetrahydrofuran.

Significant sensitivity and stability enhancement of tetraphenylporphyrin-based optical oxygen sensing material in presence of perfluorochemicals

Emission-based oxygen sensing properties of highly luminescent tetraphenylporphyrin molecules were investigated in polystyrene, ethyl cellulose, poly(1-trimethylsilyl-1-propyne) and poly(isobutylmethacrylate) matrices. The effect of perfluorochemicals (PFCs) on oxygen sensitivity and stability of the sensor materials was also examined. Fluorescence intensity and lifetime measurements of meso-tetraphenylporphyrinato Zn(II) (ZnTPP) and meso-tetraphenylporphyrin (H2TPP) materials were performed in the concentration range of 0–100% pO2. The fluorescence intensity variation of H2TPPvs. oxygen was 86%. H2TPP-based composite also yielded higher Stern–Volmer constant, faster response and regeneration time, excellent long term photostability and larger linear response range with respect to ZnTPP. The detection limit of oxygen for H2TPP was less than 0.5%. When stored in sealed bags protected from sunlight, no decrease in oxygen sensitivity was observed during approximately five months. As far as we know, the gathe...

Determination of pKa values of clinically important perfluorochemicals in nonaqueous media

Perfluorochemicals (PFCs) are clinically and biotechnologically important species. In this work, the potentiometric titration method in nonaqueous media is proposed for the determination of acidity constant values of six different perfluorinated compounds. The saturated and nonsaturated perfluoroacids, perfluorocarnosine, and perfluoroalkyl-β-alanine were potentiometrically titrated in acetonitrile, N,N-dimethylformamide, acetone, ethanol, methanol, and pyridine with tetrabutylammonium hydroxide. The half-neutralization potentials and acidity constants of PFCs have been calculated from the titration curves by using the computerized derivative method. Except for RF-Carnosine, all of the potentiometric titration curves of the PFCs exhibited one stoichiometric and well-defined endpoints in all of the solvents employed. The reproducibility and sensitivity of the method were evaluated.

Enhanced optical oxygen sensing using a newly synthesized ruthenium complex together with oxygen carriers

In this article, an emission based, simple and fast method is proposed for the determination of gaseous oxygen. A newly synthesized fluorophore, dichloro-{2,6-bis[1-(4-dimethylamino-phenylimino) ethyl]pyridine}ruthenium(II) has been used for oxygen sensing together with oxygen carrier perfluorochemicals (PFCs) in silicon matrix. It should be noted that the solubility of oxygen in fluorocarbons is about three to ten times large as that observed in the parent hydrocarbons or in water, respectively. Employed PFCs are chemically and biochemically inert, have high dissolution capacities for oxygen, and, once doped into sensing film, considerably enhance the response of sensing agent.