Acridino-Diaza-20-Crown-6 Ethers: New Macrocyclic Hosts for Optochemical Metal Ion Sensing

Acridino-diaza-20-crown-6 ether derivatives as new turn-on type fluorescent chemosensors with an excellent functionality and photophysical properties have been designed and synthesized for metal ion-selective optochemical sensing applications. Spectroscopic studies revealed that in an acetonitrile-based semi-aqueous medium, the sensor molecules exhibited a remarkable fluorescence enhancement with high sensitivity only toward Zn²⁺, Al³⁺ and Bi³⁺, among 23 different metal ions. Studies on complexation showed a great coordinating ability of logK > 4.7 with a 1:1 complex stoichiometry in each case. The detection limits were found to be from 59 nM to micromoles. The new ionophores enabled an optical response without being affected either by the pH in the range of 5.5–7.5, or the presence of various anions or competing metal ions. Varying the N-substituents of the new host-backbone provides diverse opportunities in both immobilization and practical applications without influencing the molecular recognition abilities.     

New Polymerizable Tetraaza Macrocycle Containing Two Acridine Units for Selective Fluorescence Sensing of Metal Ions

A new fluorescent bis(acridino)-macrocycle containing two allyl groups was synthesized and photophysically studied. Studies were carried out on metal ion recognition and selectivity-influencing effects including the determination of the relevant thermodynamic constants as logK and pK_a. The proposed sensor molecule is recommended for the development of Zn²⁺-selective optochemical analyzers based on covalently immobilized ionophores as it has a unique pH-independent metal ion recognition ability, which is not influenced by anions and other potentially occurring metal ions in biological samples.

     

Pyridino-18-crown-6 ether type chemosensors containing a benzothiazole fluorophore unit: Synthesis and enantiomeric recognition studies

Three new fluorescent enantiopure pyridino-18-crown-6 ethers containing a benzothiazole unit were prepared, and the enantiomeric discrimination of these sensor molecules toward the hydrogen perchlorate salts of 1-phenylethylamine, 1-(1-naphthyl)ethylamine, phenylglycine methyl ester and phenylalanine methyl ester was studied in acetonitrile by fluorescence spectroscopy. The ligands revealed appreciable or moderate selectivity toward the enantiomers of hydrogen perchlorate salts of 1-phenylethylamine, 1-(1-naphthyl)ethylamine and phenylglycine methyl ester.     

Covalently Immobilizable Tris(Pyridino)-Crown Ether for Separation of Amines Based on Their Degree of Substitution

A great number of biologically active compounds contain at least one amine function. Appropriate selectivity can only be accomplished in a few cases upon the substitution of these groups, thus functionalization of amines generally results in a mixture of them. The separation of these derivatives with very similar characteristics can only be performed on a preparative scale or by applying pre-optimized HPLC methods. A tris(pyridino)-crown ether was designed and synthetized for overcoming these limitations at a molecular level. It is demonstrated, that this selector molecule is able to distinguish protonated primary, secondary and tertiary amines by the formation of reversible complexes with different stabilities. This degree of substitution-specific molecular recognition of amines opens the door to develop separation processes primarily focusing on the purification of biologically active compounds in a nanomolar scale.