Chromium(III) selective membrane sensors based on Schiff bases as chelating ionophores

The two chromium chelates of Schiff bases, N-(acetoacetanilide)-1,2-diaminoethane (L₁) and N,N′-bis(acetoacetanilide)-triethylenetetraammine (L₂), have been synthesized and explored as neutral ionophores for preparing poly(vinylchloride) (PVC) based membrane sensors selective to Cr(III). The addition of lipophilic anion excluder (NaTPB) and various plasticizers viz. o-Nitrophenyloctyl ether (o-NPOE), dioctylpthalate (DOP), dibutylphthalate (DBP), tris(2-ethylhexyl)phosphate (TEHP), and benzyl acetate (BA) have found to improve the performance of the sensors. The best performance was obtained for the membrane sensor having a composition of L₁:PVC:DBP:NaTPB in the ratio 5:150:250:3 (w/w). The sensor exhibits Nernstian response in the concentration range 8.9 × 10⁻⁸ to 1.0 × 10⁻¹ M Cr³⁺ with limit of detection 5.6 × 10⁻⁸ M. The proposed sensor manifest advantages of relatively fast response (10 s) and good selectivity over some alkali, alkaline earth, transition and heavy metal ions. The selectivity behavior of the proposed electrode revealed a considerable improvement as compared to the best previously PVC-membrane electrode for chromium(III) ion. The potentiometric response of the proposed sensor was independent of pH of the test solution in the range of 2.0-7.0. The sensor has found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol and acetonitrile and could be used for a period of 3 months. The proposed electrode was used as an indicator electrode in potentiometric titration of chromium ion with EDTA and in direct determination in different water and food samples.     

Optical determination of ionophore diffusion coefficients in plasticized poly(vinyl chloride) sensing films

The knowledge of accurate diffusion coefficients of electrically neutral ionophores in solvent polymeric membranes is important in view of understanding and optimizing important sensor characteristics of ion-selective electrodes (ISEs) and their corresponding optical sensors. A spectroscopic imaging technique is introduced here to determine the diffusion coefficient of the chromoionophore (N,N-diethyl-5-(octadecanoylimino)-5H-benzo[a]phenoxazine-9-amine, ETH 5294) in solvent polymeric membranes with different types of plasticizers and varying polymer-plasticizer ratio. This method is based on following the changes in the absorbance profiles of the chromoionophore as a function of space and time. The desired membrane composition is solvent cast onto a glass slide and placed under a microscope objective. The membrane is then exposed to light from a mercury arc lamp which photobleaches the dye in a circular area, providing an interface from which the time rate of absorbance change is studied. Spectral images are acquired over fixed time intervals with a microscope equipped with a charge-coupled device (CCD) camera providing 0.41 μm nominal resolution. Two plasticizers, ortho-nitrophenyl octyl ether (o-NPOE) and bis(2-ethylhexyl) sebacate (DOS), are examined in poly(vinyl chloride) (PVC) by varying the ratio of polymer to plasticizer content and measuring the diffusion coefficient of the chromoionophore. Corresponding membrane compositions containing 10 wt.% of an inert lipophilic salt (ETH 500) are also examined. Near linear relationships between the logarithmic diffusion coefficients and the PVC content are observed that obey the following relationships: -0.0459 wt.% PVC (for PVC-DOS), -0.0468 wt.% PVC (for PVC-DOS-ETH 500), -0.0508 wt.% PVC (for PVC-NPOE), -0.0473 wt.% PVC (for PVC-NPOE-ETH 500).     

Comparative evaluation of Dy(III) selective poly(vinyl) chloride based membrane electrodes of macrocyclic tetraimine Schiff's bases

Three different derivatives of macrocyclic tetraimine Schiff's base have been synthesized and explored as a neutral ionophores for preparing poly(vinyl chloride) based membrane sensors selective to Dy³⁺. The addition of sodium tetraphenyl borate and various plasticizers, viz., o-NPOE, DBP, DBBP, DOP and CN has been found to substantially improve the performance of the sensors. The best performance was obtained with the sensor no. 1 having membrane of Schiff's base (SL-1) with composition (w/w) SL-1 (4.5%): PVC (30.5%): o-NPOE (59.5%): NaTPB (5.5%). This sensor exhibits Nernstian response with slope 19.4 mV/decade of activity in the concentration range of  10⁻⁸ to 1.0 × 10⁻² M Dy³⁺, performs satisfactorily over wide pH range of (2.8-7.2) with a fast response time (10 s). The sensor was also found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of acetonitrile, methanol or ethanol. The proposed sensor can be used over a period of 1.5 months without significant drift in potentials. The sensor has been also utilized for the determination of Dy³⁺ level in different soil samples.     

Development of a new fluorimetric bulk optode membrane based on 2,5-thiophenylbis(5-tert-butyl-1,3-benzexazole) for nickel(II) ions

A highly sensitive and selective fluorimetric optode membrane for the determination of ultra trace amounts of Ni²⁺ ions was prepared. The plasticized PVC-membrane incorporating potassium tetrakis(p-chlorophenyl)borate (KTpClPB) and 2,5-thiophenylbis(5-tert-butyl-1,3-benzexazole) (TTBB), as a highly fluorescent chromoionophore, displays a calibration response for Ni²⁺ ions over a wide concentration range of 1.0×10⁻³ to 1.0×10⁻⁸ M. It has a relatively fast response of <40 s. In addition to high stability and reproducibility, and relatively long working lifetime, the sensor possesses good selectivity for nickel ions over several common diverse ions. The fluorescence signal of the optode membrane can be easily recovered by immersion in EDTA solution. The optode was applied successfully to the determination of traces of Ni²⁺ ion in edible oil and a wastewater sample from nickel electroplating industries.     

Comparative study on 2-amino-1,4-naphthoquinone derived ligands as indium (III) selective PVC-based sensors

The three different ligands (Q₂ to Q₄) based on 2-amino-1,4-naphthoquinone (Q₁), have been synthesized and explored as neutral ionophores for preparing polyvinyl chloride-based membrane sensors selective to indium (III). The addition of potassium tetrakis(4-chlorophenyl) borate and various plasticizers, viz., o-NPOE, DBP, DBBP, DOP and CN has been found to substantially improve the performance of the sensors. The best performance was obtained with the sensor no. 16 having membrane of ligand (Q₂) with composition (%, w/w) ionophore Q₂ (3.0%):PVC (30.0%):o-NPOE (63.0%):KTpClPB (4.0%). This sensor exhibits Nernstian response with slope 19.8 mV/decade of activity in the concentration range 2.5 × 10⁻⁷ to 1.0 × 10⁻² M indium (III), performs satisfactorily over wide pH range of (2.5-7.5) with a fast response time (10 s). The sensor was also found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of acetonitrile, ethanol and methanol. The proposed sensor can be used over a period of 3.5 months without significant drift in potentials. The quantitative application of sensor was also evaluated by comparative analysis of artificially made sea water with AAS.     

Comparative studies of ONNO-based ligands as ionophores for palladium ion-selective membrane sensors

Palladium sensors based on two neutral ionophores, N,N′-bis(acetylacetone) cyclohexanediamine (L₁) and N,N′-bis(o-hydroxyacetophenone)-1,2-cyclohexanediamine (L₂) for quantification of palladium ions are described. Effect of various plasticizers (o-NPOE, DBP, DEP, DOP, TBP, and CN) and anion excluder, sodium tetra phenyl borate (NaTPB) has been studied. The best performance is obtained with a membrane composition of PVC:o-NPOE:ionophore (L₁):NaTPB of 150:300:5:5 (%, w/w). The sensor exhibits significantly enhanced selectivity towards palladium ion over the concentration range 1.0 × 10⁻⁸ to 1.0 × 10⁻¹ M with a lower detection limit of 4.0 × 10⁻⁹ M and a Nernstian compliance (29.1 ± 0.3 mV decade⁻¹ of activity) within pH range 2.0-6.0 and fast response time of 10 s. Influence of the membrane composition and possible interfering ions has also been investigated on the response properties of the electrode. Fast and stable response, good reproducibility and long-term stability of the sensor are demonstrated. The sensor has been found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol and acetonitrile and could be used for a period of 4 months. Selectivity coefficients determined with fixed interference method (FIM) indicate high selectivity for palladium. The proposed electrode shows fairly good discrimination of palladium from other cations. The application of prepared sensor has been demonstrated in determination of palladium ions in spiked water sample.     

Bulk optode sensors for batch and flow-through determinations of lead ion in water samples

A sensitive optode consisting of highly lead-selective ionophore (Lead IV), proton-selective chromoionophore (ETH 5294) and lipophilic anionic sites (KTpClPB) in plasticized polyvinyl chloride (PVC) membrane was fabricated. The optode membranes were used for determination of Pb²⁺ by absorption spectrophotometry in batch and flow-through systems. The influence parameters such as pH, type of buffer solution, response time and concentration of regenerating solution were optimized. The membrane responded to Pb²⁺ by changing its color from blue to pinkish purple in Tris buffer containing different concentration of Pb²⁺ at pH 7.0. The optode provided the response range of 3.16 × 10⁻⁸ to 5.00 × 10⁻⁵ mol L⁻¹ Pb²⁺ with the detection limit of 2.49 × 10⁻⁸ mol L⁻¹ in the batch system within the response time of 30 min. The dynamic range of 1.26 × 10⁻⁸ to 3.16 × 10⁻⁵ mol L⁻¹ Pb²⁺ with detection limit of 8.97 × 10⁻⁹ mol L⁻¹ were obtained in the flow-through system within the response time of 15 min. Moreover, the proposed optode sensors showed good selectivity towards Pb²⁺ over Na⁺, K⁺, Mg²⁺, Cd²⁺, Hg²⁺ and Ag⁺. It was successfully applied to determine Pb²⁺ in real water samples and the results were compared with well-established inductively coupled plasma optical emission spectrometry (ICP-OES). No significant different value (t_critical = 4.30 > t_exp = 1.00-3.42, n = 3 at 95% of confidence level) was found.     

Near-infrared solid-state fluorescent naphthooxazine dyes attached with bulky dibutylamino and perfluoroalkenyloxy groups at 6- and 9-positions

No solid-state fluorescence is observed for 9-(diethylamino)benzo[a]phenoxazin-5-one (Nile Red). However, 9-dibutylamino-6-{perfluoro[4-methyl-3-(1-methylethyl)-2-penten]-2-oxy}benzo[a]phenoxazin-5-one showed fluorescence maximum at 717 nm in solid state with fluorescence quantum yield 0.024. X-ray crystallographic analysis suggests that prevention of network π−π interactions by the bulky fluorine-containing and dibutylamino groups is essential to show solid-state fluorescence.     

A selective artemisinin-sensor using metalloporphyrin as a recognition element entrapped in the Au-nanoparticles-chitosan modified electrodes

An amperometric artemisinin (ARN) sensor based on the supramolecular recognition of glycosylated metalloporphyrin, which is included in the Au-nanoparticles-chitosan film coated on the glass carbon electrodes, was developed. For the improvement of the selectivity of artemisinin detection, 5,10,15,20-tetrakis[2-(2,3,4,6-tetraacetyl-β-d-glucopyranosyl)-1-O-phenyl]porphyrin (T(o-glu)PPH) metal complex [FeT(o-glu)PPCl] was synthesized and employed as a ARN-sensitive and -selective material in the amperometric sensors. The proposed [FeT(o-glu)PPCl]/Au-nanoparticles modified electrodes showed excellent selectivity and sensitivity toward ARN with respect to a number of interferents and exhibited stable current response, which can be attributed to the coordination of ARN with the [FeT(o-glu)PPCl] in the electrodes. The calibration graph obtained with the proposed sensor was linear over the range of 1.8 × 10⁻⁷-1.7 × 10⁻⁹ mol l⁻¹, with a detection limit of 1.7 × 10⁻⁹ mol l⁻¹ for ARN. Significant advantages of the proposed procedure over the conventional reductive electrochemical methods are the selective detection and the relatively low applied potential requirement of the ARN-sensor. The prepared sensor is applied for the determination of ARN in plant samples and the results agreed with the values obtained by the pharmacopoeia method.     

Comparative study of Ag(I) selective poly(vinyl chloride) membrane sensors based on newly developed Schiff-base lariat ethers derived from 4,13-diaza-18-crown-6

The six Schiff-base lariat ether chelates based on 4,13-diaza-18-crown ether, have been synthesized and explored as a neutral ionophores for preparing poly(vinyl chloride) based membrane sensors selective to silver(I). The addition of potassium tetrakis(4-chlorophenyl) borate and various plasticizers, viz., o-NPOE, DBP, DBBP, DOP and CN has been found to substantially improve the performance of the sensors. The best performance was obtained with the sensor no. 5 having membrane of chelate (A₆) with composition (w/w) chelate (2.8%):PVC (45.7%):o-NPOE (48.6%):KTpClPB (2.8%). This sensor exhibits Nernstian response with slope 59.3 mV/decade of activity in the concentration range 5.6 × 10⁻⁸-1.0 × 10⁻¹ M Ag(I), performs satisfactorily over wide pH range of (3.0-8.0) with a fast response time (12 s). The sensor was also found to work satisfactorily in partially non-aqueous media up to 25% (v/v) content of acetonitrile, methanol or ethanol and can tolerate the concentration 1.0 × 10⁻² M of ionic (SDS, TBC) and nonionic (Triton X-100) surfactants. The proposed sensor can be used over a period of 4 months without significant drift in potentials. The response of the sensor was highly selective to Ag⁺ over a large number of cations and it could therefore be used for Ag⁺ estimation in blood of occupationally exposed persons.     

Ion-transport and diffusion coefficients of non-plasticised methacrylic-acrylic ion-selective membranes

The ion-transport behaviour of methacrylic-acrylic-based polymers for ion-selective electrode (ISE) membranes was investigated by a spectrophotometric method to determine the apparent diffusion coefficient. By observing the degree of deprotonation of the chromoionophore or chromogenic ionophore, the extent of penetration of cations into the polymer films was determined. The transport of the cations into the optode films depended on the stoichiometry of complexation by the ionophores. The apparent diffusion coefficients, estimated from the deprotonation data were of the order of 10⁻¹² to 10⁻¹¹ cm² s⁻¹. These values indicate that the apparent ion mobility in the methacrylic-acrylic ISE membranes is approximately a thousand times lower than that in plasticised PVC ISE membranes. For some ionophores, the value of the apparent diffusion coefficient could be modulated according to the ionophore content in the membrane and the data obtained for a calixarene containing membrane were tested against a model for facilitated diffusion with chained carriers. The data did not fit a model where intramolecular diffusion was limiting, but were consistent with a first-order rate-limiting mechanism involving an intermediate 1:2 complex between ion and ionophore. In this instance, the lowest values for D_app were thus not necessarily obtained for lowest ionophore loading and in the range examined, a trend of decreasing D_app with increasing ionophore was noted.     

Nickel pyrazolyl borate complexes: Synthesis, structure and analytical application in biological and environmental samples as anion selective sensors

A [{hydrotris(3-phenyl-5-methyl-1-pyrazolyl)borate}(3-phenyl-5-methyl-pyrazole) nickel chloride] [Tp^Ph,MeNi(Cl)Pz^Ph,MeH] (I) has been synthesized and explored as ionophores for the preparation of a poly (vinyl chloride) (PVC) membrane sensor for azide and thiocyanate anions. The compounds [Tp^Ph,MeNi(N₃)Pz^Ph,MeH] (II) and [Tp^Ph,MeNi(SCN)Pz^Ph,MeH] (III) were characterized by their crystal structures and proved to be bonded as monodentate through nitrogen atom of azide and thiocyanate anion. Potentiometric investigations also indicate high affinity of this receptor for thiocyanate and azide ions. PVC based membranes of I using as hexadecyltrimethylammonium bromide (HTAB) cation discriminator and o-nitrophenyloctyl ether (o-NPOE), dibutylphthalate (DBP), acetophenone (AP) and tributylphosphate (TBP) as plasticizing solvent mediators were prepared and investigated as SCN⁻ and N₃⁻ selective sensors. The best performance was shown by the membrane of thiocyanate with composition (w/w) of (I) (7%):PVC (31%):DBP (60%):HTAB (2%). This sensor works well over a wide concentration range 5.3 × 10⁻⁷ to 1.0 × 10⁻² M with Nernstian compliance (59.2 mV decade⁻¹ of activity) within pH range 2.5-9.0 with a response time of 11 s and showed good selectivity for thiocyanate ion over a number of anions. The sensor exhibits adequate life (3 months) and could be used successfully for the determination of thiocyanate content in human urine, saliva and river water samples. While the membrane of [Tp^Ph,MeNi(Cl)Pz^Ph,MeH] ionophore with composition (I) (6%):HTAB (4%):PVC (31%):TBP (59%) showed highest sensitivity and widest linear range for azide ion. These sensors exhibit the maximum working concentration range of 8.1 × 10⁻⁶ to 1.0 × 10⁻² M with Nernstian slope of 59.3 mV decade⁻¹ of activity. It can be applied for the monitoring of the azide ions concentration in aqueous black tea and orange juice samples.     

Novel potentiometric and optical silver ion-selective sensors with subnanomolar detection limits

Ten Ag⁺-selective ionophores have been characterized in terms of their potentiometric selectivities and complex formation constants in solvent polymeric membranes. The compounds with π-coordination show much weaker interactions than those with thioether or thiocarbamate groups as the coordinating sites. Long-term studies with the best ionophores show that the lower detection limit of the best Ag⁺ sensors can be maintained in the subnanomolar range for at least 1 month. The best ionophores have also been characterized in fluorescent microspheres. The so far best lower detection limits of 3 × 10⁻¹¹ M (potentiometrically) and 2 × 10⁻¹¹ M Ag⁺ (optically) are found with bridged thiacalixarenes.     

Substituent effect on anthracene-based bisboronic acid glucose sensors

Earlier we communicated an anthracene-based bisboronic acid sensor for glucose. Aimed at understanding the substituent effect, we have introduced various functional groups, such as the cyano, nitro, and fluoro group on the boronic acid moiety of this glucose sensor. Fluorescent binding studies indicated that the cyano-substituted sensor (4a) has the highest affinity (K 2540 M⁻¹) for glucose, but the lowest selectivity (three-fold over fructose); the fluoro-substituted compound (4c) shows the lowest affinity (630 M⁻¹) and a modest selectivity (15-fold over fructose); and the unsubstituted one (1a) shows the highest selectivity over fructose (43-fold) and a modest affinity (1472 M⁻¹).     

A novel uranyl membrane sensor with potentiometric anionic response

A novel potentiometric uranyl membrane sensor with a divalent anionic response is developed, characterized and used for determination of uranyl ion. The sensor incorporates triethylenetetramine (TETA) as an ionophore in poly(vinyl chloride) matrix membrane (PVC) plasticized with o-nitrophenyloctyl ether (o-NPOE). In strong sulphate test solutions, UO₂²⁺ ion forms a highly stable [UO₂(SO₄)₂]²⁻ anion, extractable in TETA as {(2TETAH)²⁺ [UO₂(SO₄)₂]²⁻} complex. Formation of the complex is confirmed and characterized by elemental analysis, mass spectrometry and infrared spectrometry. Sensor based on this system displays at pH 2.5-3.8 a linear response over the concentration range of 1.0 × 10⁻¹-3.5 × 10⁻⁵ mol l⁻¹ uranium with a near-Nernstian calibration slope of −26.5 ± 0.3 mV decade⁻¹. The lower limit of detection is ∼5 μg ml⁻¹, the lifetime is 12 weeks and negligible interferences are caused by most common cations. Validation of the assay method reveals excellent performance characteristics in terms of sensitivity, selectivity, fast response and potential stability. The sensor is used for the determination of 0.01-7.09 wt% uranium in naturally occurring and certified ore samples. The results show an average recovery of 97.6% and compare fairly well with data obtained using X-ray fluorescence technique.     

Design and evaluation of a thorium (IV) selective optode

A novel optical sensor has been proposed for sensitive determination of thorium (IV) ion in aqueous solutions. The thorium sensing membrane was prepared by incorporating 4-(p-nitrophenyl azo)-pyrocatechol (NAP) as ionophore in the plasticized PVC membrane containing tributyl phosphate (TBP) as plasticizer. The membrane responds to thorium ion by changing color reversibly from yellow to red-brown in glycine buffer solution at pH 3.5. The proposed sensor displays a linear range of 8.66 × 10⁻⁶-2.00 × 10⁻⁴ M with a limit of detection of 6 × 10⁻⁶ M. The response time of the optode was about 8.8-12.5 min, depending on the concentration of Th (IV) ions. The selectivity of optode to Th (IV) ions in glycine buffer is good. The sensor can readily be regenerated by exposure to a solution mixture of sodium fluoride and 5-sulfosalicylic acid (dihydrate) (0.01 M each). The optode is fully reversible. The proposed optode was applied to the determination of thorium (IV) in environmental water samples.     

Imaging fiber microarray fluorescent ion sensors based on bulk optode microspheres

Optical imaging fibers with micrometer-sized wells were used as a sensing platform for the development of microarray optical ion sensors based on selective bulk extraction principles established earlier for optodes. Uniform 10 μm sized microspheres based on plasticized poly(vinyl chloride) containing various combinations of ionophores, fluoroionophores and lipophilic ion-exchangers were prepared for the detection of sodium, potassium, calcium and chloride, and deposited onto the wells of etched fiber bundles. Specifically, sodium sensing particles were based on tert-butylcalix[4]arene tetraacetic acid tetraethylester, potassium particles on 2-dodecyl-2-methyl-1,3-propanediyl bis[N-[5′-nitro(benzo-15-crown-5)-4′-yl]carbamate] (BME-44), calcium particles on an acrylic derivative of ETH 129 (AU-1) covalently attached to a methacrylic polymer, and chloride particles based on the anticrown ionophore [9]mercuracarborand-3 (MC-3). The fluorescence emission characteristics of individual microspheres were observed from the backside of the fibers and were found to selectively and rapidly change as a function of the sample composition. The optical characteristics of the particles were found to be comparable to that of corresponding thin optode films and particles deposited onto microscope glass slides. The measuring ranges (logarithmic molar concentrations) at pH 7.0 were found as −3 to 0 for sodium, −3.5 to −0.5 for potassium, −7 to −2 for calcium, and −5 to 0.5 for chloride. Selectivities were determined over other common electrolytes and found to be sufficient for physiological applications. The simultaneous deposition of sodium and chloride sensing particles was successfully performed, demonstrating that such microarray sensors are capable of simultaneously sensing multiple analytes. This technology is compatible with other microsphere-based fluorescent sensing principles, forming a promising total analysis platform for a variety of applications.     

A cerium(III) selective polyvinyl chloride membrane sensor based on a Schiff base complex of N,N'-bis[2-(salicylideneamino)ethyl]ethane-1,2-diamine

A polyvinyl chloride (PVC) based membrane sensor for cerium ions was prepared by employing N,N′-bis[2-(salicylideneamino)ethyl]ethane-1,2-diamine as an ionophore, oleic acid (OA) as anion excluder and o-nitrophenyloctyl ether (o-NPOE) as plasticizer. The plasticized membrane sensor exhibits a Nernstian response for Ce(III) ions over a wide concentration range (1.41 × 10⁻⁷ to 1.0 × 10⁻² M) with a limit of detection as low as 8.91 × 10⁻⁸ M. It has a fast response time (<10 s) and can be used for 4 months. The sensor revealed a very good selectivity with respect to common alkali, alkaline earth and heavy metal ions. The response of the proposed sensor is independent of pH between 3.0 and 8.0. It was used as an indicator electrode in potentiometric titration of fluoride, carbonate and oxalate anions and determination of cerium in simulated mixtures.     

New potentiometric sensors for creatinine

Three main types of creatinine potentiometric membrane sensors are described. They are based on the use of dibenzo-30-crown-10 (DB30C10) with potassium tetrakis(p-chlorophenyl)borate type (I), dibenzo-30-crown-10 alone type (II), and potassium tetrakis(p-chlorophenyl)borate alone type (III), incorporating in poly(vinyl chloride) matrix membrane plasticized with either o-nitrophenyl octyl ether or dioctylphthalate. The sensors are used for quantification of creatinine after soaking the membranes in 0.1 M creatinine solution for 2 days. The sensors show almost the same potentiometric response characteristics. Sensor type (I) exhibits Nernstian responses over a concentration range of 5.0 × 10⁻⁵ mol l⁻¹-1.0 × 10⁻² mol l⁻¹ creatinine with cationic slopes of 59.5 ± 0.1 and 60 ± 0.2 mV decade⁻¹ and detection limits of 1.1 × 10⁻⁵ mol l⁻¹ and 8 × 10⁻⁶ mol l⁻¹ creatinine, over the pH range of 3.5-6.5 and 3.5-7.0, for o-NPOE and DOP solvent mediators, respectively. Sensor type (II) displays Nernstian responses over a concentration range of 6.0 × 10⁻⁵ mol l⁻¹-1.0 × 10⁻² mol l⁻¹ creatinine with cationic slopes of 60.0 ± 0.1 and 65.0 ± 0.2 mV decade⁻¹ and detection limits of 1.5 × 10⁻⁵ mol l⁻¹ and 1.4 × 10⁻⁵ mol l⁻¹ creatinine over the pH range of 2.6-6.2 and 2.5-6.0, for o-NPOE and DOP solvent mediators, respectively. Sensor type (III) shows Nernstian responses over a concentration range of 7.0 × 10⁻⁵ mol l⁻¹-1.0 × 10⁻² mol l⁻¹ creatinine with cationic slopes of 60 ± 0.1 and 62.0 ± 0.2 mV decade⁻¹ and detection limits of 2.7 × 10⁻⁵ mol l⁻¹ and 2.0 × 10⁻⁵ mol l⁻¹ creatinine over the pH range of 2.5-6.0, for o-NPOE and DOP solvent mediators, respectively. The response times of the sensors for 10⁻³ mol l⁻¹ creatinine solution are instantaneous (4-10 s). The sensors show long-term stability with life span of ∼6 months. The sensors are used for determination of serum creatinine of rats (Rattus Norvigicus) with mean R.S.D. of 2.62%, and the results agreed well with the Jaffe kinetic method.     

A highly selective thallium(I) electrode based on a thia substituted macrocyclic ionophore

A new highly Tl(I)-selective PVC membrane electrode based on tetrathia macrocycle 6,7: 14,15-dibenzo-5,8,13,16-tetraoxo-1,4,9,12-tetrathiacyclohexadecane [Bz₂O₄(16)aneS₄] (I) as membrane carrier, o-nitrophenyloctyl ether (o-NPOE) as solvent mediator and potassium tetrakis(p-chlorophenyl)borate (KTpClPB) as lipophilic additive has been developed. The best performance was given by the membrane of macrocycle (I) with composition 3:120:1.5:50 (I:o-NPOE:KTpClPB:PVC). This electrode exhibits a Nernstian response to Tl(I) ions in the concentration range 1.0 × 10⁻¹-2.23 × 10⁻⁶ M with a slope of 58.2 mV/decade of concentration and a detection limit of 1.58 × 10⁻⁶ M. The response time of the sensor is 12 s and can be used over a period of 4 months with good reproducibility. The proposed electrode revealed good selectivity over a wide variety of other cations including alkali, alkaline earth, heavy and transition metals. The electrode works well over a pH range of 3.2-11.5 and in partially non-aqueous medium with up to 30% organic content. The sensor was also used as an indicator electrode in potentiometric titration of Tl(I) ions with KI solution.