High-order nonlinearity of silica-gold nanoshells in chloroform at 1560 nm.

The nonlinear response of silica--gold nanoshells (SGNs) in chloroform was studied using laser pulses of 65 fs at 1560 nm. The experiments were performed using the thermally managed Z--scan technique that allows measurements of the electronic contribution for the nonlinear response, free from thermal influence. The results were analyzed using an analytical approach based on the quasi--static approximation that allowed extraction of the nonlinear susceptibility of a SGN from the data. High third--order susceptibility, χsh((3)) = - 1.5 x 10(-11) m(2)/V(2), approximately four orders of magnitude larger than for gold nanospheres in the visible, and large fifth--order susceptibility, χsh((5)) = - 1.4 x 10(-24) m(4)/V(4), were obtained. The present results offers new perspectives for nonlinear plasmonics in the near--infrared.

Theoretical and experimental studies of the photoluminescent properties of the coordination polymer [Eu(DPA)(HDPA)(H2O)2].4H2O.

We report on the hydrothermal synthesis of the [Eu(DPA)(HDPA)(H(2)O)(2)].4H(2)O lanthanide-organic framework (where H2DPA stands for pyridine-2,6-dicarboxylic acid), its full structural characterization including single-crystal X-ray diffraction and vibrational spectroscopy studies, plus detailed investigations on the experimental and predicted (using the Sparkle/PM3 model) photophysical luminescent properties. We demonstrate that the Sparkle/PM3 model arises as a valid and efficient alternative to the simulation and prediction of the photoluminescent properties of lanthanide-organic frameworks when compared with methods traditionally used. Crystallographic investigations showed that the material is composed of neutral one-dimensional coordination polymers infinity(1)[Eu(DPA)(HDPA)(H(2)O)(2)] which are interconnected via a series of hydrogen bonding interactions involving the water molecules (both coordinated and located in the interstitial spaces of the structure). In particular, connections between bilayer arrangements of infinity(1)[Eu(DPA)(HDPA)(H(2)O)(2)] are assured by a centrosymmetric hexameric water cluster. The presence of this large number of O-H oscillators intensifies the vibronic coupling with water molecules and, as a consequence, increases the number of nonradiative decay pathways controlling the relaxation process, ultimately considerably reducing the quantum efficiency (eta = 12.7%). The intensity parameters (Omega(2), Omega(4), and Omega(6)) were first calculated by using both the X-ray and the Sparkle/PM3 structures and were then used to calculate the rates of energy transfer (W(ET)) and back-transfer (W(BT)). Intensity parameters were used to predict the radiative decay rate. The calculated quantum yield obtained from the X-ray and Sparkle/PM3 structures (both of about 12.5%) are in good agreement with the experimental value (12.0 +/- 5%). These results clearly attest for the efficacy of the theoretical models employed in all calculations and create open new interesting possibilities for the design in silico of novel and highly efficient lanthanide-organic frameworks.

Plasmonic labeling of subcellular compartments in cancer cells: multiplexing with fine-tuned gold and silver nanoshells.

Fine-tuned gold and silver nanoshells were produced via an entirely reformulated synthesis. The new method yielded ultramonodisperse samples, with polydispersity indexes (PI) as low as 0.02 and narrow extinction bands suited for multiplex analysis. A library of nanoshell samples with localized surface plasmon resonances (LSPR) spanning across the visible range was synthesized. Hyperspectral analysis revealed that the average scattering spectrum of 100 nanoshells matched closely to the spectrum of a single nanoshell, indicating an unprecedented low level of nanoparticle-to-nanoparticle variation for this type of system. A cell labeling experiment, targeting different subcellular compartments in MCF-7 human breast cancer cells, demonstrated that these monodisperse nanoparticles can be used as a multiplex platform for single cell analysis at the intracellular and extracellular level. Antibody-coated gold nanoshells targeted the plasma membrane, while silver nanoshells coated with a nuclear localization signal (NLS) targeted the nuclear membrane. A fluorescence counterstaining experiment, as well as single cell hyperspectral microscopy showed the excellent selectivity and specificity of each type of nanoparticle for its designed subcellular compartment. A time-lapse photodegradation experiment confirmed the enhanced stability of the nanoshells over fluorescent labeling and their capabilities for long-term live cell imaging.