{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21404"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21404","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Part I. Molecular tweezers: Role of preorganization and synthetic progress toward a water soluble tweezer. Part II. Progress towards an empirical approach to carbohydrate recognition","abstract":"Part I. Three molecular tweezers have been synthesized to determine the role of preorganization in the host-guest complexation of these systems. The synthesis of these tweezers was accomplished by the reaction of their respective dibromo-pyrylium salts with an absolute ethanol/aqueous ammonium hydroxide solution followed by a lithium/halogen exchange and addition of dimethoxyacridone chromophores. Tweezers 11-13 have zero, one, and two additional degrees of free rotation, respectively, which lessens the enforced syn cofacial orientation of the diacridine chromophores and the overall rigidity of the system. $\\sp1$H NMR binding studies indicate an increase in the association constant (K$\\sb{a}$) with the increase in rigidity. The effects of increasing rigidity are additive with $\\rm\\Delta\\Delta G\\sp\\circ\\sb{13\\to11}=2\\Delta\\Delta G\\sp\\circ\\sb{13\\to12}$ = 1.8 kcal$\\cdot$mol$\\sp{-1}$. Thus, the enforced syn orientation of 11 provides no special benefit other than its role in preorganizing the host.","abstract_html":"Part I. Three molecular tweezers have been synthesized to determine the role of preorganization in the host-guest complexation of these systems. The synthesis of these tweezers was accomplished by the reaction of their respective dibromo-pyrylium salts with an absolute ethanol/aqueous ammonium hydroxide solution followed by a lithium/halogen exchange and addition of dimethoxyacridone chromophores. Tweezers 11-13 have zero, one, and two additional degrees of free rotation, respectively, which lessens the enforced syn cofacial orientation of the diacridine chromophores and the overall rigidity of the system. $\\sp1$H NMR binding studies indicate an increase in the association constant (K$\\sb{a}$) with the increase in rigidity. The effects of increasing rigidity are additive with $\\rm\\Delta\\Delta G\\sp\\circ\\sb{13\\to11}=2\\Delta\\Delta G\\sp\\circ\\sb{13\\to12}$ = 1.8 kcal$\\cdot$mol$\\sp{-1}$. Thus, the enforced syn orientation of 11 provides no special benefit other than its role in preorganizing the host.","abstract_has_math":true,"creators":["Baloga, Monica Helaine"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Zimmerman, Steven C."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:07:41Z","date_published":"2011-05-07T13:07:41Z","updated_at":"2026-07-22T22:25:17Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":["Copyright 1995 Baloga, Monica Helaine"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9543524","(UMI)AAI9543524"],"render_values":[{"text":"AAI9543524","href":null,"code":true},{"text":"(UMI)AAI9543524","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21404","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Zimmerman, Steven C."]},{"key":"dc:creator","label":"Author","values":["Baloga, Monica Helaine"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:07:41Z","10000-01-01","1995"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Organic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1995 Baloga, Monica Helaine"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9543524","(UMI)AAI9543524","http://hdl.handle.net/2142/21404"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Part I. Three molecular tweezers have been synthesized to determine the role of preorganization in the host-guest complexation of these systems. The synthesis of these tweezers was accomplished by the reaction of their respective dibromo-pyrylium salts with an absolute ethanol/aqueous ammonium hydroxide solution followed by a lithium/halogen exchange and addition of dimethoxyacridone chromophores. Tweezers 11-13 have zero, one, and two additional degrees of free rotation, respectively, which lessens the enforced syn cofacial orientation of the diacridine chromophores and the overall rigidity of the system. $\\sp1$H NMR binding studies indicate an increase in the association constant (K$\\sb{a}$) with the increase in rigidity. The effects of increasing rigidity are additive with $\\rm\\Delta\\Delta G\\sp\\circ\\sb{13\\to11}=2\\Delta\\Delta G\\sp\\circ\\sb{13\\to12}$ = 1.8 kcal$\\cdot$mol$\\sp{-1}$. Thus, the enforced syn orientation of 11 provides no special benefit other than its role in preorganizing the host.","In addition, progress towards the synthesis of a water soluble molecular tweezer containing unsubstituted phenanthridinium chromophores is described.","Part II. Several classes of guest molecules present a complex three dimensional array of hydrogen bond donor and acceptor groups. In such cases a more empirical approach to host design may be most effective. We describe a rapid synthesis of bis(amidonaphthyridine) receptors by Friedlander condensations using various diketone precursors (i.e. 1,3-diacetyl benzene and 1,1$\\sp\\prime$-diacetyl ferrocene) and 2,6-diaminopyridine-3-carboxaldehyde (36). Complexation studies are reported including HPLC analysis of these receptors on glucose-bonded stationary phases.","Made available in DSpace on 2011-05-07T13:07:41Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9543524.pdf: 4117709 bytes, checksum: 368e4a0881b891c4e568f71acdadbed6 (MD5) Previous issue date: 1995","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:50:33Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:23:06-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Part I. Molecular tweezers: Role of preorganization and synthetic progress toward a water soluble tweezer. Part II. Progress towards an empirical approach to carbohydrate recognition"]}]}],"canonical_facts":{"dc:contributor":["Zimmerman, Steven C."],"dc:creator":["Baloga, Monica Helaine"],"dc:date":["2011-05-07T13:07:41Z","10000-01-01","1995"],"dc:description":["Part I. Three molecular tweezers have been synthesized to determine the role of preorganization in the host-guest complexation of these systems. The synthesis of these tweezers was accomplished by the reaction of their respective dibromo-pyrylium salts with an absolute ethanol/aqueous ammonium hydroxide solution followed by a lithium/halogen exchange and addition of dimethoxyacridone chromophores. Tweezers 11-13 have zero, one, and two additional degrees of free rotation, respectively, which lessens the enforced syn cofacial orientation of the diacridine chromophores and the overall rigidity of the system. $\\sp1$H NMR binding studies indicate an increase in the association constant (K$\\sb{a}$) with the increase in rigidity. The effects of increasing rigidity are additive with $\\rm\\Delta\\Delta G\\sp\\circ\\sb{13\\to11}=2\\Delta\\Delta G\\sp\\circ\\sb{13\\to12}$ = 1.8 kcal$\\cdot$mol$\\sp{-1}$. Thus, the enforced syn orientation of 11 provides no special benefit other than its role in preorganizing the host.","In addition, progress towards the synthesis of a water soluble molecular tweezer containing unsubstituted phenanthridinium chromophores is described.","Part II. Several classes of guest molecules present a complex three dimensional array of hydrogen bond donor and acceptor groups. In such cases a more empirical approach to host design may be most effective. We describe a rapid synthesis of bis(amidonaphthyridine) receptors by Friedlander condensations using various diketone precursors (i.e. 1,3-diacetyl benzene and 1,1$\\sp\\prime$-diacetyl ferrocene) and 2,6-diaminopyridine-3-carboxaldehyde (36). Complexation studies are reported including HPLC analysis of these receptors on glucose-bonded stationary phases.","Made available in DSpace on 2011-05-07T13:07:41Z (GMT). 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Progress towards an empirical approach to carbohydrate recognition"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:17Z"}