File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Systematic studies on photoluminescence of oligo(arylene-ethynylene)s: Tunability of excited states and derivatization as luminescent labeling probes for proteins

TitleSystematic studies on photoluminescence of oligo(arylene-ethynylene)s: Tunability of excited states and derivatization as luminescent labeling probes for proteins
Authors
Keywordsπ-Conjugation
Fluorescence
Oligo(phenylene-ethynylene)
Protein-labeling
Solvatochromism
Issue Date2006
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.eurjoc.org
Citation
European Journal Of Organic Chemistry, 2006 n. 14, p. 3125-3139 How to Cite?
AbstractFunctionalized oligo(phenylene-ethynylene)s (OPEs) with different conjugation lengths, p-X(C 6H 4C≡C) nSiMe 3 (n = 1-4; X = NH 2, NMe 2, H) were synthesized by Sonogashira coupling of (phenylene-ethynylene)s and 1-iodo-4-(trimethylsilylethynyl)benzene, followed by desilylation of the p-substituted (trimethylsilylethynyl)benzenes with potassium hydroxide. The photoluminescent properties for the OPE series with different chain lengths and their solvatochromic responses were examined. The absorption maxima were red-shifted with increasing numbers of -(C 6H 4C≡C)- units (n), and a linear plot of the absorption energy maxima vs. 1/n was obtained for each series. The emission spectra in dichloromethane showed a broad and structureless band, the energies of which (in wavenumbers) also fit linearly with 1/n. Both the absorption and emission wavelength maxima of the NH 2- and NMe 2-substituted OPEs exhibited significant solvent dependence, whereas the parent OPEs (X = H) showed only minor shifts of the λ max values in different solvents. Substituent effects upon the photoluminescent characteristics of the OPEs and the tunability of the excited states were examined with the p-X(C 6H 4C≡C) nSiMe 3 (n = 2, 3; X = NH 2, NMe 2, H, SMe, OMe, OH, and F) series. The H- and F-substituted counterparts exhibited high-energy vibronically structured emissions attributed to the 3(ππ*) excited states of the (arylene-ethynylene) backbone. For compounds bearing NH 2 and NMe 2 groups, a broad red-shifted emission with a remarkable Stokes shift from the respective absorption maximum was observed, which can be assigned to an n → π* transition. The n → π* assignment was supported by MO calculations on the model compounds p-X(C 6H 4C≡C) 2SiH 3 (X = NH 2, H). Functionalization of the oligo(arylene-ethynylene)s with the N-hydroxysuccinimidyl (NHS) moiety enabled covalent attachment of the fluorophore to HSA protein molecules. A series of fluorescent labels, namely p-X(C 6H 4C≡C) n-C 6H 4NHS, (n = 1, X = NH 2, NMe 2, SMe, OMe, OH, F; n = 2, X = NH 2, NMe 2) and p-Me 2NC 6H 4C≡C(C 4H 2S)-C≡CC 6H 4NHS were synthesized, and their conjugates with HSA (human serum albumin) were characterized by MALDI-TOF mass spectrometry, UV/Vis absorption spectroscopy, and gel electrophoresis. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
Persistent Identifierhttp://hdl.handle.net/10722/69683
ISSN
2015 Impact Factor: 3.068
2015 SCImago Journal Rankings: 1.245
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorZhi, YGen_HK
dc.contributor.authorLai, SWen_HK
dc.contributor.authorChan, QKWen_HK
dc.contributor.authorLaw, YCen_HK
dc.contributor.authorTong, GSMen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:15:54Z-
dc.date.available2010-09-06T06:15:54Z-
dc.date.issued2006en_HK
dc.identifier.citationEuropean Journal Of Organic Chemistry, 2006 n. 14, p. 3125-3139en_HK
dc.identifier.issn1434-193Xen_HK
dc.identifier.urihttp://hdl.handle.net/10722/69683-
dc.description.abstractFunctionalized oligo(phenylene-ethynylene)s (OPEs) with different conjugation lengths, p-X(C 6H 4C≡C) nSiMe 3 (n = 1-4; X = NH 2, NMe 2, H) were synthesized by Sonogashira coupling of (phenylene-ethynylene)s and 1-iodo-4-(trimethylsilylethynyl)benzene, followed by desilylation of the p-substituted (trimethylsilylethynyl)benzenes with potassium hydroxide. The photoluminescent properties for the OPE series with different chain lengths and their solvatochromic responses were examined. The absorption maxima were red-shifted with increasing numbers of -(C 6H 4C≡C)- units (n), and a linear plot of the absorption energy maxima vs. 1/n was obtained for each series. The emission spectra in dichloromethane showed a broad and structureless band, the energies of which (in wavenumbers) also fit linearly with 1/n. Both the absorption and emission wavelength maxima of the NH 2- and NMe 2-substituted OPEs exhibited significant solvent dependence, whereas the parent OPEs (X = H) showed only minor shifts of the λ max values in different solvents. Substituent effects upon the photoluminescent characteristics of the OPEs and the tunability of the excited states were examined with the p-X(C 6H 4C≡C) nSiMe 3 (n = 2, 3; X = NH 2, NMe 2, H, SMe, OMe, OH, and F) series. The H- and F-substituted counterparts exhibited high-energy vibronically structured emissions attributed to the 3(ππ*) excited states of the (arylene-ethynylene) backbone. For compounds bearing NH 2 and NMe 2 groups, a broad red-shifted emission with a remarkable Stokes shift from the respective absorption maximum was observed, which can be assigned to an n → π* transition. The n → π* assignment was supported by MO calculations on the model compounds p-X(C 6H 4C≡C) 2SiH 3 (X = NH 2, H). Functionalization of the oligo(arylene-ethynylene)s with the N-hydroxysuccinimidyl (NHS) moiety enabled covalent attachment of the fluorophore to HSA protein molecules. A series of fluorescent labels, namely p-X(C 6H 4C≡C) n-C 6H 4NHS, (n = 1, X = NH 2, NMe 2, SMe, OMe, OH, F; n = 2, X = NH 2, NMe 2) and p-Me 2NC 6H 4C≡C(C 4H 2S)-C≡CC 6H 4NHS were synthesized, and their conjugates with HSA (human serum albumin) were characterized by MALDI-TOF mass spectrometry, UV/Vis absorption spectroscopy, and gel electrophoresis. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.en_HK
dc.languageengen_HK
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.eurjoc.orgen_HK
dc.relation.ispartofEuropean Journal of Organic Chemistryen_HK
dc.subjectπ-Conjugationen_HK
dc.subjectFluorescenceen_HK
dc.subjectOligo(phenylene-ethynylene)en_HK
dc.subjectProtein-labelingen_HK
dc.subjectSolvatochromismen_HK
dc.titleSystematic studies on photoluminescence of oligo(arylene-ethynylene)s: Tunability of excited states and derivatization as luminescent labeling probes for proteinsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1434-193X&volume=&spage=3125&epage=3139&date=2006&atitle=Systematic+Studies+on+Photoluminescence+of+Oligo(arylene-ethynylene)s:+Tunability+of+Excited+States,+and+Derivatization+as+Luminescent+Labeling+Probes+for+Proteinsen_HK
dc.identifier.emailTong, GSM:tongsm@hkucc.hku.hken_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityTong, GSM=rp00790en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/ejoc.200600103en_HK
dc.identifier.scopuseid_2-s2.0-33746075555en_HK
dc.identifier.hkuros118759en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33746075555&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.issue14en_HK
dc.identifier.spage3125en_HK
dc.identifier.epage3139en_HK
dc.identifier.isiWOS:000239314900012-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridZhi, YG=7004142893en_HK
dc.identifier.scopusauthoridLai, SW=55104882100en_HK
dc.identifier.scopusauthoridChan, QKW=14041210100en_HK
dc.identifier.scopusauthoridLaw, YC=14042155800en_HK
dc.identifier.scopusauthoridTong, GSM=7102328656en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats