Nitrite-selective sensors

Absorbance of a nitrite selective sensor membrane Experimental (o) and theoretical ( ) (composed of ETH 2439, NI 1, and PTTFPB in calibration plots plasticized PVC) exposed to different concentrations of nitrite... 

Although the ISEs based on cobyrinates have good selectivity for nitrite over several anions, they also respond to salicylate and thiocyanate. To eliminate this interference, the nitrite-selective electrode based on ionophore 2 was placed behind a microporous gas-permeable membrane (GPM) in a nitrogen oxide gas-sensor mode (75). NOx was generated from nitrite in the sample at pH 1.7 and, after crossing the GPM, was trapped as nitrite by an internal solution that was buffered at pH 5.5 (0.100 M MES-NaOH, pH 5.5, containing 0.100 M NaCl). The internal solution was "sandwiched" between the nitrite-selective electrode and the GPM. 

Figure 6 shows the selectivity behavior of this NOx gas sensor. The sensor had a sub-Nernstian response toward nitrite, with slopes in the range of -45 to -50 mV/decade. Further, the response observed with salicylate and thiocyanate was diminished substantially, as compared to that obtained with the original nitrite-selective electrode (Figure 3). In addition, the gas sensor described here does not suffer interferences from nitrate, bicarbonate, acetate, benzoate, or chloride. These excellent selectivity properties of the sensor are a combination of the selectivity characteristics of the nitrite-selective electrode and the additional discrimination provided by the GPM.

V. Biagiotti, F. Valentini, E. Tamburri, M.L. Terranova, D. Moscone and G. Palleschi, Synthesis and characterization of polymeric films and nanotubule nets used to assemble selective sensors for nitrite detection in drinking water. Sens. Actuat. B, 122, 236-242 (2007). 

In order to improve the practical application of potentiometric sensors, much effort must be devoted to developing membrane materials whose selectivity deviates fi-om the Hofmeister series. Chloride- and nitrite-selective electrodes based on lipophylic vitamin B12 derivatives have been reported by Simon.xhese electrodes were the first anion-selective electrodes of which selectivity sequence did not obey the Hofmeister series. Since then, a number of anion-selective liquid-membrane electrodes have been developed using a variety of hosts metallocenes, diphosphonium dication salts, diquartemary ammonium dication salts, bisthiourea derivatives, metalloporphyrins, lipophylic macrocyclic polyamines, cytosine-dependent triamine and metallophtalocyamines. " " Among this large variety of compounds studied, the metalloporphyrins seem to be the most promising for the preparation of effective ion-selective potentiometric sensors. " - ... 

Metalloporphyrins, one carbon larger but structurally analogous to the corrin ring of vitamin B12, exhibited unique anion ionophore properties when incorporated into a polymer membrane. Mn(III), Co(III), Ru(II), and Sn(IV) porphyrin-based ion-selective sensors exhibit high selectivity for thiocyanate, nitrite/thiocyanate, thiocyanate and siicylate, respectively. doo-io7,i 10-114 nature of the... 

One of the pitfalls of microbial sensors, viz. their low selectivity, can be overcome by combining cells with an immobilized enzyme. Thus, creatinine deaminase (CDA, EC 3.5.4.21) hydrolyses creatinine to N-methylhydantoin and ammonium ion, the ammonia produced being successively oxidized to nitrite and nitrate ion by nitrifying bacteria. These bacteria have not yet been characterized but are known to be a mixed culture of Nitrosomonas sp. and Nitrobacter sp. The reaction sequence involved is as follows ... 

In potentiometric sensors, an electrical potential between the working electrode and a reference electrode is measured at zero current conditions in a solution containing ions that exchange with the surface. The first potentiometric MIP sensor was prepared in 1992 by Vinokurov (1992). The substrate-selective polyaniline electrode was electrosynthesized with polypyrrole, polyaniline, and aniline-p-aminophenol copolymers. The development of an MIP-based potentiometric sensor was reported in 1995 by Hutchins and Bachas (1995). This potentiometric sensor has high selectivity for nitrite with a low detection limit of (2 + l)x 10 M (Fig. 15.10). 

In addition to the summary registration of nitrifiable substances, it is also possible to quantify N-compounds selectively by using microbial sensors. Microbial sensors for the monitoring of ammonium ions, ammonia, nitrite, nitrate and urea have been described (see Table 9). Nitrifiers are generally used, but not only (see also Sect. 3.2.4). 

The sensor did not respond to volatile compounds such as acetic acid, ethyl alcohol, and amines (diethylamine, propylamine, and butylamine) or to nonvolatile nutrients such as glucose, amino acids, and metal ions (potassium and sodium ions). Therefore, the selectivity of this microbial sensor was satisfactory in the presence of these different substances. The current output of the sensor was almost constant for more than 21 days and 400 assays. The microbial sensor can be used to assay sodium nitrite for a long period. In the same experiments the concentration of sodium nitrite was determined by both the sensor proposed and the conventional method (dime-thyl-a-naphtylamine method). A good correlation was obtained between the sodium nitrite concentrations determined by the two methods (correlation coefficient 0.99). 

Other early work in this field included the use of tetrakis(p-aminophenyl)-porphyrin (Fig. 7a), which was electrodeposited onto glassy carbon and showed a near-Nernstian response to iodide [76]. Electrodeposited methylthiophene-methylpyrrole copolymer was deposited and shown to give a near-Nernstian response to bromide [77]. Pyrrole-3-boronate (Fig. 7b) could be deposited to give films with a good response and marked selectivity to fluoride [78]. A cobalt aminophthalocyanine could also be electropolymerised to give a good sensor for nitrite [79] or sulphide ion [80]. 

As earlier reported for electrochemical sensing, often the active chromo-phore will be dispersed in a polymeric matrix. For example, Mohr and Wolfbeis reported a nitrate sensor [121] where the active chromophore is a rhodamine B dye which had been modified with an octadecyl side chain to render it hydrophobic and prevent leaching. The dye was dispersed in a plasticised PVC membrane containing a hydrophobic anion carrier (tridodecylmethylammo-nium chloride). On exposure to nitrate, the fluorescence of the dye increased. This membrane, however, only displayed Hofmeister-type selectivity and was also affected by pH. Replacing the quaternary ammonium anion carrier with a palladium phospine chloride carrier led to selectivity for nitrite [ 122], probably due to a preferential interaction between Pd and nitrite ion. 

Figure 6. Selectivity pattern of the NOx gas sensor. The sensor was exposed to 0.010 M H2SO4 containing the following anions nitrite (1), salicylate (2), thiocyanate (3), benzoate (4), nitrate (5), chloride (6), bicarbonate (7), acetate (8). (Adapted from ref. 15.)...

More recently, in the determination of cyanide with a metallic silver-wire electrode Frenzel ei al.[38] have shown that relatively non-selective potentiometric sensors may be used to make selective determinations by enhancing the selectivity using gas-diffusion separations. Potential interferences from sulfide, sulfite and nitrite which may form interfering gaseous species were removed by a pre-oxidation with permanganate and dichromate. 

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