A new type of core-shell upconversion nanoparticles which can be effectively excited at 795 nm has been designed and synthesized through spatially confined doping of neodymium (Nd(3+)) ions. The use of Nd(3+) ions as sensitizers facilitates the energy transfer and photon upconversion of a series of lanthanide activators (Er(3+), Tm(3+), and Ho(3+)) at a biocompatible excitation wavelength (795 nm) and also significantly minimizes the overheating problem associated with conventional 980 nm excitation. Importantly, the core-shell design enabled high-concentration doping of Nd(3+) (~0 mol %) in the shell layer and thus markedly enhanced the upconversion emission from the activators, providing highly attractive luminescent biomarkers for bioimaging without autofluorescence and concern of overheating.

Plasmon enhancement of optical properties is both fundamentally important and appealing for many biological and photonic applications. Although metal-enhanced two-photon excitation fluorescence has been demonstrated in the solid substrates, there is no report on metal enhanced overall two-photon excitation fluorescence in the colloid system. Here we systematically investigated gold nanorod enhanced one- and two-photon excitation fluorescence of a porphyrin molecule, T790. The separation distance between the metal core and T790 was varied by adjusting the silica shell thickness from 13 to 42 nm. One- and two-photon excitation fluorescence intensities of T790 were found to strongly depend on the thickness of silica shell that separates gold nanorod and T790. The optimum one- and two-photon excitation fluorescence enhancement was found to occur at shell thicknesses of 34 and 20 nm, with enhancement factors of 2.1 and 11.8, respectively. Fluorescence lifetime of T790 steadily decreased as the shell thickness decreased. The observed two-photon excitation fluorescence enhancement is ascribed to a combination effect of local electric field amplification and competition between increased radiative and non-radiative decay rates. Core-shell nanoparticles that displayed enhanced two-photon excitation fluorescence were also found to exhibit significantly improved singlet oxygen generation capability under two-photon excitation. The applications of these nanoparticles as effective agents for two-photon cell imaging and nano-photosensitizers for two-photon photodynamic therapy with improved efficiency have also been demonstrated in HepG2 cancer cells. The combined advantages of enhanced two-photon excitation fluorescence and two-photon induced singlet oxygen generation make these core-shell nanoparticles as attractive agents for two-photon imaging guided two-photon photodynamic therapy.

Gold nanorods with three different aspect ratios were prepared and their dual capabilities for two-photon imaging and two-photon photodynamic therapy have been demonstrated. These gold nanorods exhibit large two-photon absorption action cross-sections, about two orders of magnitude larger than small organic molecules, which makes them suitable for two-photon imaging. They can also effectively generate singlet oxygen under two-photon excitation, significantly higher than traditional photosensitizers such as Rose Bengal and Indocyanine Green. Such high singlet oxygen generation capability under two-photon excitation was ascribed to their large two-photon absorption cross-sections. Polyvinylpyrrolidone (PVP) coated gold nanorods displayed excellent biocompatibility and high cellular uptake efficiency. The two-photon photodynamic therapy effect and two-photon fluorescence imaging properties of PVP coated gold nanorods have been successfully demonstrated on HeLa cells in vitro using fluorescence microscopy and indirect XTT assay method. These gold nanorods thus hold great promise for imaging guided two-photon photodynamic therapy for the treatment of various malignant tumors.

Aggregated metal nanoparticles have been known to display significantly enhanced two-photon photoluminescence (TPPL) compared to nonaggregated nanoparticles, which could be utilized to develop platforms for two-photon sensing and imaging applications. Here we have conducted single-particle spectroscopic studies on gold (Au) nanoparticle clusters of different sizes to understand the enhancement mechanisms and explore the limit of maximum achievable enhancement. Our studies show that the TPPL intensity of Au nanoparticle clusters significantly increases from monomer to trimer. The averaged intensity of the Au nanosphere dimers and linear trimers is ~7.8 × 10(3) and ~7.0 × 10(4) times that of Au nanosphere monomers, respectively. A highest enhancement of 1.2 × 10(5) folds was obtained for the linear trimer. The TPPL spectra of these single Au nanosphere clusters closely resemble their corresponding scattering spectra, suggesting strong correlation between their TPPL with plasmon resonance. The scattering spectra of dimers and linear trimers displayed cos(2) dependence on the detection polarization, while their TPPL displayed cos(4) dependence on the excitation polarization, which are very similar to Au nanorods. These results suggest that two-photon excitation of dimer and linear trimer is strongly coupled to their longitudinal plasmon resonance modes. These studies help to provide insight on fundamental understanding of the enhancement mechanisms as well as development of biomedical and photonic applications.

The microstructural evolution during low temperature ageing of two commercial purity alloys (Al-1.2Cu-1.2Mg-0.2Mn and Al-1.9Cu-1.6Mg-0.2Mn at.%) was investigated. The initial stage of hardening in these alloys is very rapid, with the alloys nearly doubling in hardness during 20 h ageing at room temperature. The microstructural evolution during this stage of hardening was investigated using differential scanning calorimetry (DSC), isothermal calorimetry and threedimensional atom probe analysis (3DAP). It is found that during the hardening a substantial exothermic heat evolution occurs and that the only microstructural change involves the formation of Cu-Mg co-clusters. The kinetics of cluster formation is analysed and the magnitude of the hardening is discussed on the basis of a model incorporating solid solution hardening and modulus hardening originating from the difference in modulus between Al and clusters.

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.

Cu(2)O-Au nanocomposites (NCs) with tunable coverage of Au were prepared by a facile method of mixing gold nanoparticles (Au NPs) with copper(I) oxide nanowires (Cu(2)O NWs) in various ratios. These Cu(2)O-Au NCs display tunable optical properties, and their photocatalytic properties were dependent on the coverage density of Au NPs. The photocatalytic activity of Cu(2)O-Au NCs was examined by photodegradation of methylene blue. The presence of Au NPs enhanced the photodegradation efficiency of Cu(2)O NCs. The photocatalytic efficiency of Cu(2)O-Au NCs initially increased with the increasing coverage density of Au NPs and then decreased as the surface of Cu(2)O became densely covered by Au NPs. The enhanced photocatalytic efficiency was ascribed to enhanced light absorption (by the surface plasmon resonance) and the electron sink effect of the Au NPs.