Sharing the salt bowl : counterion identity drives N-alkyl resorcinarene affinity for pyrophosphate in water
Twum, K., Iraj Sadraei, S., Feder, J., Taimoory, S. M., Rissanen, K., Trant, J. F., & Beyeh, N. K. (2022). Sharing the salt bowl : counterion identity drives N-alkyl resorcinarene affinity for pyrophosphate in water. Organic Chemistry Frontiers, 9(5), 1267-1275. https://doi.org/10.1039/D1QO01877A
Published inOrganic Chemistry Frontiers
© 2022 the Partner Organisations
N-Alkyl ammonium resorcinarene chloride receptors, NARX4, have been shown to act as high-sensitivity detectors of pyrophosphate (PPi), a biomarker of disease, in aqueous media through the chloride-to-PPi exchange [NAR(Cl)4 to NARPPi]. The nature of the anion of the macrocyclic NARX4 (X = Cl−, Br−, triflate OTf−) receptor greatly influences the PPi-affinity in aqueous media. The binding affinity for [NAR (Cl)4] is 3.61 × 105 M−1, while the NAR (Br)4 and NAR (OTf)4 show stronger binding of 5.30 × 105 M−1, and 6.10 × 105 M−1, respectively. The effects of upper rim ammonium cation, –N+H2R substituents (R = 3-hydroxypropyl, cyclohexyl, benzyl, or napththalen-1-ylmethyl), of the macrocyclic resorcinarene hosts have also been evaluated. The highest affinity was obtained using 3-hydroxypropyl groups due to the additional hydrogen bonds and the naphthyl upper-rim group that provides a larger hydrophobic surface area and favorable stacking interaction (i.e., π–π and CH–π). We note that two PPi molecules can bind to the more selective receptors through an additional interaction with the lower rim hydroxyls, making the resorcinarene a divalent binder. Comparing PPi with other phosphate anions (PO43−, AMP, ADP, and ATP) shows that the receptors are more selective for PPi due to the size and charge complementarity. Experimental (1H, 31P NMR, and isothermal titration calorimetry), and computational analyses support the reported trends for PPi selectivity even in highly competing aqueous media. ...
PublisherRoyal Society of Chemistry (RSC)
Publication in research information system
MetadataShow full item record
Additional information about fundingThe authors gratefully acknowledge financial support from the Provost Graduate Research Scholarship (KT, JF), Oakland University, MI, USA, and the University of Windsor, ON, Canada. This work was made possible by the facilities of the Shared Hierarchical Academic Research Computing Network (SHARCNET: http://www.sharcnet.ca) and Compute/Calcul Canada. This work was funded in part by the Natural Sciences and Engineering Research Council of Canada (Grant # 2018-06338 to JFT), the Windsor Cancer Centre Foundation Seeds4Hope Seed Grant Funding Program (Grant # 2017-03 to JFT), and an Ontario Early Researcher Award (Grant # ER18-14-114 to JFT). ...
Showing items with similar title or keywords.
Halogen bonding and host-guest chemistry between N-alkylammonium resorcinarene halides, diiodoperfluorobutane and neutral guests Pan, Fangfang; Dashti, Mohadeseh; Reynolds, Michael R.; Rissanen, Kari; Trant, John F.; Beyeh, Ngong Kodiah (Beilstein : Institut zur Foerderung der Chemischen Wissenschaften, 2019)Single crystal X-ray structures of halogen-bonded assemblies formed between host N-hexylammonium resorcinarene bromide (1) or N-cyclohexylammonium resorcinarene chloride (2), and 1,4-diiodooctafluorobutane and accompanying ...
Pan, Fangfang; Chen, Yingchun; Li, Siyu; Jiang, Minzhi; Rissanen, Kari (Wiley - VCH Verlag GmbH & Co. KGaA, 2019)Co-crystallizing iodine with a simple dicationic salt (1,8- diammoniumoctane chloride) results in the clathration of the iodine (I2) molecules inside trigonal and hexagonal helical channels of the crystal lattice with ...
Carlsson, Anna-Carin C.; Mehmeti, Krenare; Uhrbom, Martin; Karim, Alavi; Bedin, Michele; Puttreddy, Rakesh; Kleinmaier, Roland; Neverov, Alexei A.; Nekoueishahraki, Bijan; Gräfenstein, Jürgen; Rissanen, Kari; Erdélyi, Máté (American Chemical Society, 2016)We have investigated the influence of electron density on the three-center [N–I–N]+ halogen bond. A series of [bis(pyridine)iodine]+ and [1,2-bis((pyridine-2-ylethynyl)benzene)iodine]+ BF4– complexes substituted with ...
Inclusion complexes of Cethyl-2-methylresorcinarene and pyridine N-oxides: breaking the C–I⋯−O–N+ halogen bond by host–guest complexation Puttreddy, Rakesh; Beyeh, Ngong Kodiah; Rissanen, Kari (Royal Society of Chemistry, 2016)C ethyl-2-Methylresorcinarene forms host–guest complexes with aromatic N-oxides through multiple intra- and intermolecular hydrogen bonds and C–H⋯π interactions. The host shows conformational flexibility to accommodate ...
Aakeroy, Christer B.; Bryce, David L.; Desiraju, Gautam R.; Frontera, Antonio; Legon, Anthony C.; Nicotra, Francesco; Rissanen, Kari; Scheiner, Steve; Terraneo, Giancarlo; Metrangolo, Pierangelo; Resnati, Giuseppe (De Gruyter, 2019)This recommendation proposes a definition for the term “chalcogen bond”; it is recommended the term is used to designate the specific subset of inter- and intramolecular interactions formed by chalcogen atoms wherein the ...