A novel polyazacyclophane hexa-amine (1) has been designed, synthesized and characterized by X-ray crystallography, 1H NMR and fluorescence spectroscopy. 1 has the structural shape and disposition of charges complementary to the major groove of B-DNA. Acid dissociation constants for the protonated 1 were pKa1(D) = 4.8 and pKa2(D) = 8.5. Equilibrium constants for the binding of 1 to ctDNA and T4 DNA were 1.2 × 105 and 1.8 × 106, respectively.

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionNEXTParticipation of Two Carboxyl Groups in Phosphodiester Hydrolysis. 1. Hydrolysis of Bis(2-carboxyphenyl) Phosphate J. Am. Chem. Soc. 1995, 117, 12064−12069Thomas C. Bruice, Andrei Blaskó, and Mark E. PetyakCite this: J. Am. Chem. Soc. 1996, 118, 12, 3071Publication Date (Web):March 27, 1996Publication History Published online27 March 1996Published inissue 1 January 1996https://pubs.acs.org/doi/10.1021/ja9654037https://doi.org/10.1021/ja9654037correctionACS PublicationsCopyright © 1996 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views252Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (31 KB) Get e-Alertsclose Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHydrolysis of a Phosphate Diester by Simultaneous Carboxylate and Carboxyl Group Participation in a Rigid System with Kinetically Unfavorable Rotamers Frozen OutThomas C. Bruice, Andrei Blasko, Ramesh D. Arasasingham, Jang-Seob Kim, and Mark E. PetyakCite this: J. Am. Chem. Soc. 1995, 117, 12, 3639–3640Publication Date (Print):March 1, 1995Publication History Published online1 May 2002Published inissue 1 March 1995https://doi.org/10.1021/ja00117a044Request reuse permissionsArticle Views73Altmetric-Citations5LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (777 KB) Get e-Alertsclose Get e-Alerts

The energies of rotamer conformations of bis(2-carboxyphenyl) phosphate (2), where one o-carboxy group is ionized and the other is not, have been determined by semiempirical (SAM1, AM1/SM2.1) calculations in order to approximate the probability of the presence of conformations in which the o-CO2- is in position to act as a nucleophile toward phosphorus and the o-CO2H function can hydrogen bond to prostereogenic oxygens of the -(PO2-)(conformer B) or leaving phenoxide oxygen (conformer A). With simulated water phase, conformer B appears to be at the global energy minima and conformer A is somewhat less stable. The kinetics and the mechanism of hydrolysis of bis(2-carboxyphenyl) phosphate (2) have been elucidated by use of H-1 and P-31 NMR spectroscopy in acetonitrile/water 95:5 and D2O at pD up to 5.0 (39 degrees C). The hydrolysis of 2 is initiated by nucleophilic attack of the o-CO2- upon phosphate phosphorus resulting in the elimination of salicylic acid to provide salicyloyl cyclic phosphate (3) with a rate constant of 1-5 x 10(-3) s(-1) and 3 converts to salicyl monophosphate with rate constants varying between 1 and 5 x 10(-4) s(-1). The rapidity of the formation of 3 from 2 suggests the importance of both o-CO2- and o-CO2H participation {a subject of the following manuscript}.