Molecular sensors anions

Anions play key roles in chemical and biological processes. Many anions act as nucleophiles, bases, redox agents or phase transfer catalysts. Most enzymes bind anions as either substrates or cofactors. The chloride ion is of special interest because it is crucial in several phases of human biology and in disease regulation. Moreover, it is of great interest to detect anionic pollutants such as nitrates and phosphates in ground water. Design of selective anion molecular sensors with optical or electrochemical detection is thus of major interest, however it has received much less attention than molecular sensors for cations. 

The methods of anion detection based on fluorescence involve quenching, complex formation, redox reactions and substitution reactions (Fernandez-Gutierrez and Munoz de la Pena, 1985). This chapter will be restricted to anion molecular sensors based on collisional quenching (in general, they exhibit a poor selectivity) and on recognition by an anion receptor linked to a fluorophore (fluoroionophore). 

Kovalchuk A, Bricks JL, Reck G et al (2004) A charge transfer-type fluorescent molecular sensor that lights up in the visible upon hydrogen bond-assisted complexation of anions. Chem Commun 1946-1947... 

The design of fluorescent sensors is of major importance because of the high demand in analytical chemistry, clinical biochemistry, medicine, the environment, etc. Numerous chemical and biochemical analytes can be detected by fluorescence methods cations (H+, Li+, Na+, K+, Ca2+, Mg2+, Zn2+, Pb2+, Al3+, Cd2+, etc.), anions (halide ions, citrates, carboxylates, phosphates, ATP, etc.), neutral molecules (sugars, e.g. glucose, etc.) and gases (O2, CO2, NO, etc.). There is already a wide choice of fluorescent molecular sensors for particular applications and many of them are commercially available. However, there is still a need for sensors with improved selectivity and minimum perturbation of the microenvironment to be probed. Moreover, there is the potential for progress in the development of fluorescent sensors for biochemical analytes (amino acids, coenzymes, carbohydrates, nucleosides, nucleotides, etc.). 

Many fluorescent molecular sensors for halide ions (except F ) are based on collisional quenching of a dye. In particular, the determination of chloride anions in living cells is done according to this principle. Examples of halide ion sensors are given in Figure 10.29. 

The drawback of these molecular sensors is their lack of selectivity, as shown by the Stern-Volmer constants (Table 10.4). For instance A-l, 6-methoxy-N-(3-sulfopropyl)quinolinium (SPQ) is mainly used as a Cl -sensitive fluorescent indicator, but its fluorescence is also quenched by several other anions (I-, Br and SCN-, but not by NO ). 

In Chapter 10, fluorescent pH indicators and fluorescent molecular sensors for cations, anions and neutral molecules are described, with an emphasis on design principles in regard to selectivity. 

As cheaper and readily accessible alternatives to regular dendrimers, hyper-branched polymers are increasingly being used as catalyst platforms. Rainer Haag has been one of the leaders in this field. He and C. Hajji provide an overview of an area for which commercial applications are most likely. Finally, all of these catalysis-related topics are complemented by a review of metallo-dendritic exoreceptors for the redox recognition of oxo-anions and halides, written by D. Astruc. This field offers new perspectives both for catalytic transformation and the development of molecular sensors. 

The accepted by EPA potentiometric methods involve selective electrodes for fluorides, cyanides, nitrates, ammonia, and sulfides detection [20]. The potentiometric characteristics of the anion-selective sensors are strongly dependent on the anion receptor design and properties [25]. At this time, molecular recognition of anions by synthetic receptors is an expanding research area. 

Polyazamacrocycles (or azacrown ethers) attract a thorough and constant interest of the researchers due to their imique ability of selective complexation of various metals, organic and inorganic anions, and some polar moleeules. During the last decades himdreds of such compounds were synthesized, whieh eontain nitrogen, oxygen, and sulfur atoms [1], Many polyazamacrocycles can serve as molecular sensors due to their photochemical or redox properties, they contain aromatic moieties which can be present as substituents at nitrogen atoms or can be incorporated in the cycle. 

Among all Fe(II) spin crossover compounds known to date, the extensively studied polymeric [Fe(4-R-l,2,4-triazole)3](anion)2 systems (R=amino, alkyl, hydroxyalkyl) appear to have the greatest potential for technological applications, for example in molecular electronics [1, 24, 25] or as temperature sensors [24, 26]. This arises because of their near-ideal spin crossover characteristics pronounced thermochromism, transition temperatures near room temperature, and large thermal hysteresis [1, 24, 27]. 

The squaraine rotaxanes based on the macrocycle 16b exhibit intense NIR absorption and emission maxima, and it should be possible to develop them into molecular probes for many types of photonic and bioimaging applications. In contrast, the squaraine fluorescence intensity is greatly diminished when the dye is encapsulated with macrocycle 18. The fluorescence is restored when a suitable anionic guest is used to displace the squaraine dye from a pseudorotaxane complex, which indicates that the multicomponent system might be applicable as a fluorescent anion sensor. 

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