Exploring the Binding Ability of Phenanthroline-Based Polyammonium Receptors for Anions: Hints for Design of Selective Chemosensors for Nucleotides

• Published in: Journal of organic chemistry Vol. 74; no. 19; pp. 7349 - 7363
• Main Authors: Bazzicalupi, Carla, Bencini, Andrea, Biagini, Silvia, Faggi, Enrico, Meini, Stefano, Giorgi, Claudia, Spepi, Alessio, Valtancoli, Barbara
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 02.10.2009; Amer Chemical Soc
• Subjects: Aliphatic compounds; Analytical chemistry; Anions - chemistry; Binding Sites; Carbohydrates. Nucleosides and nucleotides; Chemistry; Chemistry, Organic; Exact sciences and technology; Fluorescent Dyes - chemistry; General, instrumentation; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Hydrogen Bonding; Nucleosides, nucleotides and oligonucleotides; Nucleotides - chemistry; Organic chemistry; Phenanthrolines - chemical synthesis; Phenanthrolines - chemistry; Physical Sciences; Preparations and properties; Quaternary Ammonium Compounds - chemical synthesis; Quaternary Ammonium Compounds - chemistry; Science & Technology; Static Electricity; ATP RECOGNITION; COMPLEX; FLUORESCENT CHEMOSENSORS; MOLECULAR RECOGNITION; CRYSTAL-STRUCTURE; LUMINESCENCE PROPERTIES; COORDINATION; SENSOR; SUPRAMOLECULAR CHEMISTRY; PROTONATED FORMS; Water; Purine derivatives; GTP; Nitrogen heterocycle; Fluorescence; Electron transfer; Molecular interaction; NMR spectrometry; Selectivity; Phosphorus Organic compounds; Macrocycle; Hydrogen 1; Anions; Force field method; Phosphorus 31; Cyclophane; Chemical synthesis; Acid medium; Ribonucleotide; Biological receptor; Purine nucleotide; Polyamine; Aliphatic compound; Theoretical study; Purine base; Chemical sensor; Nucleic base; Photoinduction; Pi-System; Ammonium compound; Biogenic amine; Potentiometric method; Nucleotide; Organic phosphate; Pyrimidine derivatives; Protonation; Fluorescent compound; ATP; Hydrogen bond; Crystalline structure
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo901423m

The synthesis of receptor 2,6,10,14,18-pentaaza[20]-21,34-phenanthrolinophane (L1), containing a pentaamine chain linking the 2,9 positions of a phenanthroline unit, is reported. The protonation features of L1 and of receptor 2,6,10,14,18,22-hexaaza[23]-24,37-phenanthrolinophane (L2) have been studied by means of potentiometric, 1H NMR, and spectrofluorimetric measurements; this study points out that the fluorescent emission of both receptors depends on the protonation state of the polyamine chain. In fact, the receptors are emissive only at neutral or acidic pH values, where all the aliphatic amine groups are protonated. Potentiometric titrations show that L2 is able to bind selectively ATP over TTP, CTP, and GTP. This selectivity is lost in the case of L1. 1H and 31P NMR measurements and molecular mechanics calculations show that the phosphate chains of nucleotides give strong electrostatic and hydrogen-bonding interactions with the ammonium groups of the protonated receptors, while the nucleobases interact either via π-stacking with phenanthroline or via hydrogen bonding with the ammonium groups. Of note, MM calculations suggest that all nucleotides interact in an inclusive fashion. In fact, in all adducts the phosphate chain is enclosed within the receptor cavities. This structural feature is confirmed by the crystal structure of the [(H6L2)2(TTP)2(H2O)2]4+ adduct. Fluorescence emission measurements at different pH values show that L2 is also able to ratiometrically sense ATP in a narrow pH range, thanks to emission quenching due to a photoinduced electron transfer (PET) process from an amine group of the receptor to the excited phenanthroline.