{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/31671"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/31671","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"Self-Assembled Monolayers As Models For Silica","abstract":"The reaction of hydroquinone and 1,12-dibromododecane affords 4-(12-bromo-dodecyloxy)phenol (4, 7% yield). The alkyl bromide (4) was converted to the corresponding thiol with thiourea to afford 4-(12-mercaptododecyloxy)phenol (1) in 52% yield. The reaction of t-butyllithium with 4-bromoanisole followed by reaction with 1-12-dibromododecane affords a mixture of 4-bromoanisole, 1,12-dibromododecane ,and 4-(12-bromododecyl)-anisole (6). Silica gel chromatography resulted in an inseperable mixture of 4-bromoanisole and (6). Reaction of the mixture with BBr3 afforded 4-(12-bromododecyl)phenol (7) in 34% yield. The alkyl bromide (7) was converted to the corresponding thiol with thiourea to afford 4-(12-mercaptododecyl)phenol (2) in 9% yield. Reduction of 16-mercaptohexadecanoic acid with BH3â hTHF afforded 16-mercaptohexadecanol (3) in 53% yield. All new compounds were characterized by ¹H NMR, ¹³C NMR, transmission IR, HRMS, and, where possible, elemental microanalysis. Self-assembled monolayers (SAMs) on gold were prepared using thiols 1, 2, and 3. SAMs were characterized using reflectance-absorbance infrared spectroscopy (RAIRS). Diagnostic vibrational modes were assigned by comparing RAIRS spectra to normal mode frequencies and intensities calculated using DFT methods at the 6-31G* level using commercial software. Water droplet goiniometry found contact angles of 52o, 53o, and 64o for SAMs prepared from 1, 2, and 3, respectively. SAMs of 1 and 2 were found to be hydrophilic. When SAMs prepared from 1, 2, and 3 were silylated with phenyldimethylchlorosilane, the resulting contact angles were 78o, 74o, and 75o respectively. A significant increase in contact angles for silylated SAMs of 1 and 2 indicated facile silanization of the surface hydroxides. RAIRS spectra were also obtained for the functionalized SAMs. Silylated SAMs prepared from 1, 2, and 3 are currently under investigation as models for silica-immobilized metallocene olefin polymerization catalysts.","abstract_html":"The reaction of hydroquinone and 1,12-dibromododecane affords 4-(12-bromo-dodecyloxy)phenol (4, 7% yield). The alkyl bromide (4) was converted to the corresponding thiol with thiourea to afford 4-(12-mercaptododecyloxy)phenol (1) in 52% yield. The reaction of t-butyllithium with 4-bromoanisole followed by reaction with 1-12-dibromododecane affords a mixture of 4-bromoanisole, 1,12-dibromododecane ,and 4-(12-bromododecyl)-anisole (6). Silica gel chromatography resulted in an inseperable mixture of 4-bromoanisole and (6). Reaction of the mixture with BBr3 afforded 4-(12-bromododecyl)phenol (7) in 34% yield. The alkyl bromide (7) was converted to the corresponding thiol with thiourea to afford 4-(12-mercaptododecyl)phenol (2) in 9% yield. Reduction of 16-mercaptohexadecanoic acid with BH3â hTHF afforded 16-mercaptohexadecanol (3) in 53% yield. All new compounds were characterized by ¹H NMR, ¹³C NMR, transmission IR, HRMS, and, where possible, elemental microanalysis. Self-assembled monolayers (SAMs) on gold were prepared using thiols 1, 2, and 3. SAMs were characterized using reflectance-absorbance infrared spectroscopy (RAIRS). Diagnostic vibrational modes were assigned by comparing RAIRS spectra to normal mode frequencies and intensities calculated using DFT methods at the 6-31G* level using commercial software. Water droplet goiniometry found contact angles of 52o, 53o, and 64o for SAMs prepared from 1, 2, and 3, respectively. SAMs of 1 and 2 were found to be hydrophilic. When SAMs prepared from 1, 2, and 3 were silylated with phenyldimethylchlorosilane, the resulting contact angles were 78o, 74o, and 75o respectively. A significant increase in contact angles for silylated SAMs of 1 and 2 indicated facile silanization of the surface hydroxides. RAIRS spectra were also obtained for the functionalized SAMs. Silylated SAMs prepared from 1, 2, and 3 are currently under investigation as models for silica-immobilized metallocene olefin polymerization catalysts.","abstract_has_math":false,"creators":["Cavadas, Francisco T."],"institution":"Virginia Tech","degree_name":"Master of Science","degree_level":"masters","degree_discipline":"Chemistry","degree_department":"Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":["Deck, Paul A.","Anderson, Mark R."],"committee_members":["Hanson, Brian E."],"year":2001,"date_issued":"2001-08-15","date_published":"2001-08-15","updated_at":"2026-07-22T22:19:24Z","subjects":["silica","Self-Assembled monolayers"],"languages":[],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-04102002-103407"],"render_values":[{"text":"etd-04102002-103407","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10919/31671","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.committeechair","label":"Committee Chair","values":["Deck, Paul A.","Anderson, Mark R."]},{"key":"dc:contributor.committeemember","label":"Committee Member","values":["Hanson, Brian E."]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Cavadas, Francisco T."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2014-03-14T20:33:18Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2014-03-14T20:33:18Z","2012-06-22"]},{"key":"dc:date.issued","label":"Date","values":["2001-08-15"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Tech"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["masters"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Science"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Virginia Polytechnic Institute and State University"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["silica","Self-Assembled monolayers"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["In Copyright"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/vocab/InC/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-04102002-103407"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10919/31671"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The reaction of hydroquinone and 1,12-dibromododecane affords 4-(12-bromo-dodecyloxy)phenol (4, 7% yield). The alkyl bromide (4) was converted to the corresponding thiol with thiourea to afford 4-(12-mercaptododecyloxy)phenol (1) in 52% yield. The reaction of t-butyllithium with 4-bromoanisole followed by reaction with 1-12-dibromododecane affords a mixture of 4-bromoanisole, 1,12-dibromododecane ,and 4-(12-bromododecyl)-anisole (6). Silica gel chromatography resulted in an inseperable mixture of 4-bromoanisole and (6). Reaction of the mixture with BBr3 afforded 4-(12-bromododecyl)phenol (7) in 34% yield. The alkyl bromide (7) was converted to the corresponding thiol with thiourea to afford 4-(12-mercaptododecyl)phenol (2) in 9% yield. Reduction of 16-mercaptohexadecanoic acid with BH3â hTHF afforded 16-mercaptohexadecanol (3) in 53% yield. All new compounds were characterized by ¹H NMR, ¹³C NMR, transmission IR, HRMS, and, where possible, elemental microanalysis. Self-assembled monolayers (SAMs) on gold were prepared using thiols 1, 2, and 3. SAMs were characterized using reflectance-absorbance infrared spectroscopy (RAIRS). Diagnostic vibrational modes were assigned by comparing RAIRS spectra to normal mode frequencies and intensities calculated using DFT methods at the 6-31G* level using commercial software. Water droplet goiniometry found contact angles of 52o, 53o, and 64o for SAMs prepared from 1, 2, and 3, respectively. SAMs of 1 and 2 were found to be hydrophilic. When SAMs prepared from 1, 2, and 3 were silylated with phenyldimethylchlorosilane, the resulting contact angles were 78o, 74o, and 75o respectively. A significant increase in contact angles for silylated SAMs of 1 and 2 indicated facile silanization of the surface hydroxides. RAIRS spectra were also obtained for the functionalized SAMs. Silylated SAMs prepared from 1, 2, and 3 are currently under investigation as models for silica-immobilized metallocene olefin polymerization catalysts."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Master of Science"]},{"key":"dc:title","label":"Title","values":["Self-Assembled Monolayers As Models For Silica"]}]}],"canonical_facts":{"dc:contributor.committeechair":["Deck, Paul A.","Anderson, Mark R."],"dc:contributor.committeemember":["Hanson, Brian E."],"dc:contributor.department":["Chemistry"],"dc:creator":["Cavadas, Francisco T."],"dc:date.accessioned":["2014-03-14T20:33:18Z"],"dc:date.available":["2014-03-14T20:33:18Z","2012-06-22"],"dc:date.issued":["2001-08-15"],"dc:description.abstract":["The reaction of hydroquinone and 1,12-dibromododecane affords 4-(12-bromo-dodecyloxy)phenol (4, 7% yield). The alkyl bromide (4) was converted to the corresponding thiol with thiourea to afford 4-(12-mercaptododecyloxy)phenol (1) in 52% yield. The reaction of t-butyllithium with 4-bromoanisole followed by reaction with 1-12-dibromododecane affords a mixture of 4-bromoanisole, 1,12-dibromododecane ,and 4-(12-bromododecyl)-anisole (6). Silica gel chromatography resulted in an inseperable mixture of 4-bromoanisole and (6). Reaction of the mixture with BBr3 afforded 4-(12-bromododecyl)phenol (7) in 34% yield. The alkyl bromide (7) was converted to the corresponding thiol with thiourea to afford 4-(12-mercaptododecyl)phenol (2) in 9% yield. Reduction of 16-mercaptohexadecanoic acid with BH3â hTHF afforded 16-mercaptohexadecanol (3) in 53% yield. All new compounds were characterized by ¹H NMR, ¹³C NMR, transmission IR, HRMS, and, where possible, elemental microanalysis. Self-assembled monolayers (SAMs) on gold were prepared using thiols 1, 2, and 3. SAMs were characterized using reflectance-absorbance infrared spectroscopy (RAIRS). Diagnostic vibrational modes were assigned by comparing RAIRS spectra to normal mode frequencies and intensities calculated using DFT methods at the 6-31G* level using commercial software. Water droplet goiniometry found contact angles of 52o, 53o, and 64o for SAMs prepared from 1, 2, and 3, respectively. SAMs of 1 and 2 were found to be hydrophilic. When SAMs prepared from 1, 2, and 3 were silylated with phenyldimethylchlorosilane, the resulting contact angles were 78o, 74o, and 75o respectively. A significant increase in contact angles for silylated SAMs of 1 and 2 indicated facile silanization of the surface hydroxides. RAIRS spectra were also obtained for the functionalized SAMs. Silylated SAMs prepared from 1, 2, and 3 are currently under investigation as models for silica-immobilized metallocene olefin polymerization catalysts."],"dc:description.degree":["Master of Science"],"dc:identifier.other":["etd-04102002-103407"],"dc:identifier.uri":["http://hdl.handle.net/10919/31671"],"dc:publisher":["Virginia Tech"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:subject":["silica","Self-Assembled monolayers"],"dc:title":["Self-Assembled Monolayers As Models For Silica"],"dc:type":["Thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["masters"],"thesis:degree_name":["Master of Science"],"thesis:institution_name":["Virginia Polytechnic Institute and State University"]},"updated_at":"2026-07-22T22:19:24Z"}