Bioorthogonal Labeling, Bioimaging, and Photocytotoxicity Studies of Phosphorescent Ruthenium(II) Polypyridine Dibenzocyclooctyne Complexes.

The synthesis, characterization, photophysics, lipophilicity, and cellular properties of new phosphorescent ruthenium(II) polypyridine complexes functionalized with a dibenzocyclooctyne (DIBO) or amine moiety [Ru(N^N)2 (L)](PF6 )2 are reported (L=4-(13-N-(3,4:7,8-dibenzocyclooctyne-5-oxycarbonyl) amino-4,7,10-trioxa-tridecanyl-aminocarbonyl-oxy-methyl)-4'-methyl-2,2'-bipyridine bpy-DIBO, N^N=2,2'-bipyridine bpy (1 a), 1,10-phenanthroline phen (2 a); L=4-(13-amino-4,7,10-trioxa-tridecanylaminocarbonyl-oxy-methyl)-4'-methyl-2,2'-bipyridine bpy-NH2 , N^N=bpy (1 b), phen (2 b)). The strain-promoted alkyne-azide cycloaddition (SPAAC) reaction of the DIBO complexes 1 a and 2 a with benzyl azide were studied. Also, the DIBO complexes 1 a and 2 a can selectively label N-azidoglycans located on the surface of CHO-K1 and A549 cells that were pretreated with 1,3,4,6-tetra-O-acetyl-N-azidoacetyl-D-mannosamine (Ac4 ManNAz). Additionally, the intracellular trafficking and localization of these biomolecules were monitored using laser-scanning confocal microscopy. Interestingly, the biolabeling and cellular uptake efficiency of the DIBO complexes 1 a and 2 a were cell-line dependent, as revealed by flow cytometry and ICP-MS. Furthermore, the complexes showed good biocompatibility toward the Ac4 ManNAz-pretreated cells in the dark, but exhibited photoinduced cytotoxicity due to the generation of singlet oxygen.

Highly efficient multiphoton-absorbing quadrupolar oligomers for frequency upconversion.

Two series of quadrupolar diphenylamino-endcapped oligofluorenes, PhN-OF(n)-NPh (n=2-5) and PhN-OF(n)-TAZ-OF(n)-NPh (n=1-4), which have an electron-withdrawing 1,2,4-triazole (TAZ) moiety as central core, with D-π-A-π-D structural motif (D=donor, A=acceptor), have been synthesized by palladium-catalyzed Suzuki cross-coupling of 9,9-dibutyl-7-(diphenylamino)-2-fluorenylboronic acid and the corresponding (1,2,4-triazole-based) aryl halide as key step. On pumping with infrared femtosecond lasers, these oligomers showed very strong multiphoton-excited blue photoluminescence. These D-π-D and D-π-A-π-D quadrupolar oligofluorenes exhibit superior three-photon absorption properties compared to the respective D-π-A counterparts with a highest three-photon absorption cross-section (σ(3)) of up to 2.72×10(-77) cm(6) s(2) . Despite the comparable linear and multiphoton absorption properties of the two types of quadrupolar oligomers PhN-OF(n)-NPh and PhN-OF(n)-TAZ-OF(n)-NPh, only the former exhibit remarkably intense and highly efficient multiphoton-excited frequency-upconverted deep blue lasing, which gives rise to record high lasing efficiency of 0.097% and very narrow of full width at half-maximum of the lasing spectra. Our findings suggest that quadrupolar-type molecules/oligomers are superior for multiphoton excited frequency upconverted lasing to their dipolar counterparts and also provide important guidelines to design highly efficient three-photon absorption molecules for photoluminescence and lasing applications.

Cyanines as new fluorescent probes for DNA detection and two-photon excited bioimaging.

A series of cyanine fluorophores based on fused aromatics as an electron donor for DNA sensing and two-photon bioimaging were synthesized, among which the carbazole-based biscyanine exhibits high sensitivity and efficiency as a fluorescent light-up probe for dsDNA, which shows selective binding toward the AT-rich regions. The synergetic effect of the bischromophoric skeleton gives a several-fold enhancement in a two-photon absorption cross-section as well as a 25- to 100-fold enhancement in two-photon excited fluorescence upon dsDNA binding.

Non-coplanar 9,9-diphenyl-substituted oligofluorenes with large two-photon absorption enhancement.

The non-coplanar substituted phenyl rings at the 9-position of a fluorenyl unit can be involved in pi-electron delocalization in which the resulting oligofluorenes exhibit a very large enhancement of two-photon absorption cross sections up to 2559 GM at 710 nm.

Fluorene-based pi-conjugated oligomers for efficient three-photon excited photoluminescence and lasing.

A novel series of diphenylamino- and 1,2,4-triazole-end-capped, fluorene-based, pi-conjugated oligomers that includes extended oligofluorenes and oligothienylfluorenes has been synthesized by means of the palladium-catalyzed Suzuki cross-coupling of 9,9-dibutyl-7-(diphenylamino)-2-fluorenylboronic acid and the corresponding 1,2,4,-triazole-based aryl halide as a key step. It was demonstrated that efficient two- and three-photon excited photoluminescence and lasing in the blue region are obtained by pumping near-infrared femtosecond lasers on these materials. Although the absorption and emission maxima of the highly fluorescent and extended oligofluorenes reach a saturation limit, there exists an effective conjugation length for an optimum three-photon absorption cross section in the homologous oligofluorene series. On the other hand, the multiphoton excited emission spectrum and lasing wavelength can easily be modified or tuned by an incorporation of thienyl unit(s) into the fluorene-based pi-conjugated core with which exceptionally large three-photon absorption cross sections up to 3.59 x 10(-77) cm6 s2 in the femtosecond regime have been obtained, thereby highlighting the potential of this series of photonic materials. The optimized full width at half-maximum of the cavityless three-photon upconverted blue lasing spectra are sharply narrowed to approximately 6 nm with an efficiency of up to 0.013%.

Efficient three-photon excited deep blue photoluminescence and lasing of diphenylamino and 1,2,4-triazole endcapped oligofluorenes.

A novel homologues series of diphenylamino and 1,2,4-triazole endcapped pi-conjugated oligofluorenes has been synthesized using palladium-catalyzed Suzuki cross-coupling of 9,9-dibutyl-7-(diphenylamino)-2-fluorenylboronic acid, and 1,2,4,-triazole-substituted oligofluorenyl halide was used as a key step. Efficient two- and three-photon excited photoluminescence and lasing were obtained by pumping with near-infrared femto-second lasers. The three-photon absorption cross-section enhances significantly up to 2.48 x 10(-78) cm(6) s(2) in the femtosecond regime with the length of the conjugation system. The emission is in the deep blue region and the best full width half-maximum (fwhm) of the three-photon lasing is narrower than 6 nm which is the narrowest ever reported. It was also shown that the nonlinear optics (NLO) effect increased parabolically with the conjugation length but without changing the emission wavelength. This demonstrates that varying the conjugation length is a very effective way to tailor an OF-based NLO device for deep blue application. Our findings open a new avenue to design highly efficient multiphoton absorption molecules for photoluminescence and lasing as well as provide a novel series of organic molecules that can be used in NLO applications and fundamental study.