This review article summarizes the recent progress on surface plasmon-enhanced light harvesting and its applications toward enhanced photocatalysis, photodynamic therapy, chemical transformations and photovoltaics.

A facile method was used to prepare uniform Au NR/TiO2 and Au/Ag NR/TiO2 core-shell composite nanoparticles. Au/Ag NR/TiO2 nanoparticles were found to display significantly enhanced visible light photo-catalytic activity compared to Au NR/TiO2 and the commercially available TiO2 nanoparticles. The enhancement mechanism was ascribed to injection of hot electrons of photo-excited Au/Ag NRs to TiO2, which was confirmed by 633 nm laser induced reduction of silver ions on the surface of Au/Ag NR/TiO2 composite nanoparticles.

Gold (Au) nanoparticles that display strong two-photon photoluminescence (TPPL) are attractive contrast agents for noninvasive live cell/tissue imaging with deep penetration because of their excellent biocompatibility and low cytotoxicity. The TPPL properties of Au nanoparticles are strongly dependent on the particle shape. As chemically prepared nanoparticles are generally inhomogeneous, conventional ensemble-based TPPL measurements can only give averaged results of particles of different morphologies. Singleparticle spectroscopy can avoid the complication induced by the sample inhomogeneity in ensemble measurements and help to establish the morphology−property relationship. Here we have investigated the scattering spectra and TPPL properties of Au nanoparticles of different shapes on the single particle level and explored their potential applications in cancer cell imaging. Au nanoparticles of five different shapes (nanospheres, nanocubes, nanotriangles, nanorods, and nanobranches) with similar dimensions have been chosen for the study. The TPPL spectra of these Au nanoparticles were found to be strongly modulated by plasmon resonance. TPPL intensity increases in the order of nanospheres, nanocubes, nanotriangles, nanorods, and nanobranches. The averaged TPPL intensity of a single Au nanobranch is 47750 times that of a single Au nanosphere. Two-photon action cross sections of single Au NSs, Au NCs, Au NTs, Au NRs, and Au NBs were estimated to be ∼83, ∼500, ∼1.5 × 10 3 , ∼4.2 × 10 4 , and ∼4.0 × 10 6 GM, respectively. Laser-induced melting experiments on single Au nanobranches demonstrate that the tips played an important role in the observed strong TPPL. Application of these Au nanobranches as excellent two-photon imaging contrast agents has been demonstrated on HepG2 cancer cells.

Metal nanoparticles have potential applications as bioimaging and photosensitizing agents. Aggregation effects are generally believed to be adverse to their biomedical applications. Here we have studied the aggregation effects on two-photon induced photoluminescence and singlet oxygen generation of Au nanospheres and Au nanorods of two different aspect ratios. Aggregated Au nanospheres and short Au nanorods were found to display enhanced two-photon induced photoluminescence and singlet oxygen generation capabilities compared to the unaggregated ones. The two-photon photoluminescence of Au nanospheres and short Au nanorods were enhanced by up to 15.0- and 2.0-fold upon aggregation, and the corresponding two-photon induced singlet oxygen generation capabilities were enhanced by 8.3 and 1.8-fold, respectively. The two-photon induced photoluminescence and singlet oxygen generation of the aggregated long Au nanorods were found to be lower than the unaggregated ones. These results support that the change in their two-photon induced photoluminescence and singlet oxygen generation originate from aggregation modulated two-photon excitation efficiency. This finding is expected to foster more biomedical applications of metal nanoparticles as Au nanoparticles normally exist in an aggregated form in the biological environments. Considering their excellent biocompatibility, high inertness, ready conjugation, and easy preparation, Au nanoparticles are expected to find more applications in two-photon imaging and two-photon photodynamic therapy.

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Owing to their unique photo-physical properties, rare-earth ions-doped upconversion nanoparticles (UCNPs) have attracted extensive attention in recent years. UCNPs have many special merits, such as a long luminescence lifetime, narrow emission band widths, high quantum yields and low toxicity, which allows their potential applications in bio-medical field, biological luminescent labels and drug delivery carriers. Compared with traditional fluorescence labels exited by UV (ultraviolet), such as organic dyes and quantum dots, UCNPs can transfer near-infrared (NIR) light into visible light, which is commonly called upconversion luminescence (UCL). This paper reviews the recent advances of several typical synthesis methods of UCNPs in detail as well as the fabrication and optimization of the particle morphology, and the latest advances of UCNPs for multimode imaging, surface passivation and functionalization are also described.

PEG-SH-capped gold nanorods (Au NRs) well dispersed in various organic solvents have been prepared to study the solvent effects on the two-photon photoluminescence (TPPL) properties and ultrafast excitation dynamics of Au NRs. The TPPL intensities of Au NRs in different organic solvents including DMF, DEG, CH3OH, C2H5OH, CH3CN, DMSO, and THF were found to be significantly quenched compared to that of Au NRs in H2O. Ultrafast time-resolved transient absorption and pump-probe measurements have been performed on Au NRs in H2O, DMF, and DEG to understand the corresponding quenching mechanisms. Different from the excitation decay behaviors of Au NRs in H2O, an additional transient species was observed in Au NRs in DMF or DEG upon photoexcitation. This intermediate state is ascribed to the charge-separated species, which serves as direct evidence to support that the observed TPPL quenching in various organic solvents is due to electron transfer from electron-donating solvents to the excited Au NRs. The charge-transfer mechanism was further supported by the observation that the TPPL intensity of Au NRs in H2O was found to be quenched by nearly 5.0-fold in the presence of S(2-). These studies provide useful information on fundamental understanding of the TPPL properties as well as development of various potential biological applications of gold nanoparticles.

We have demonstrated that cysteine and glutathione induced edge-to-edge coupling of gold nanocubes (Au NCs) caused a band-selective enhancement of two-photon photoluminescence (TPPL). The photoluminescence intensity of the X-band of Au NCs was found to be enhanced up to 60-fold and 46-fold upon addition of cysteine and glutathione, respectively, while the intensity of L-band remained almost unchanged. This band-selective enhancement behavior is totally different from the previously observed aggregation enhanced TPPL of spherical metal nanoparticles (NPs). The band-selective enhancement was ascribed to preferential enhancement of the X-band emission through resonant coupling with longitudinal surface plasmon resonance (SPR) band of the Au NCs assembly. This phenomenon was utilized to develop a new two-photon fluorescence turn-on sensing platform for detection of cysteine and glutathione. This method displayed high sensitivity and excellent selectivity over the other 19 amino acids. Together with the advantage of deep tissue penetration and localized excitation of two-photon near-infrared excitation, this strategy has promising applications in in vivo biosensing and imaging.