We describe novel composite nanoparticles consisting of a gold-silver nanocage core and a mesoporous silica shell functionalized with the photodynamic sensitizer Yb-2,4-dimethoxyhematoporphyrin (Yb-HP). In addition to the long-wavelength plasmon resonance near 750-800 nm, the composite particles exhibited a 400-nm absorbance peak and two fluorescence peaks, near 580 and 630 nm, corresponding to bound Yb-HP. The fabricated nanocomposites generated singlet oxygen under 630-nm excitation and produced heat under laser irradiation at the plasmon resonance wavelength (750-800 nm). In particular, we observed enhanced killing of HeLa cells incubated with nanocomposites and irradiated by 630-nm light. Furthermore, an additional advantage of fabricated conjugates was an IR-luminescence band (900-1060 nm), originating from Yb(3+) ions of bound Yb-HP and located in the long-wavelength part of the tissue transparency window. This modality was used to control the accumulation and biodistribution of composite particles in mice bearing Ehrlich carcinoma tumors in a comparative study with intravenously injected free Yb-HP molecules. Thus, these multifunctional nanocomposites seem an attractive theranostic platform for simultaneous IR-luminescence diagnostic and photodynamic therapy owing to Yb-HP and for plasmonic photothermal therapy owing to Au-Ag nanocages.

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A wet-chemical approach is used to fabricate centimeter-scale gold nanoisland films (NIFs) with tunable morphology of islands and with strong electromagnetic coupling between them. The approach consists in a uniform seeding of small gold nanoparticles on a glass or silicon substrate, followed by controllable growth of the seeds into small nanoislands. A special technique for TEM sampling was developed to follow the gradual formation of larger-sized isolated nanoparticles, nanoislands of sintered overgrown seeds, and a complete gold layer with nanoscale cracks. The electromagnetic field distribution inside the fabricated NIFs was calculated by FDTD simulations applied to actual TEM images of the fabricated samples rather than to artificial models commonly used. SERS measurements with 1,4-aminothiophenol (ATP) molecules demonstrated the analytical enhancement factor about of 10(7) and the fundamental enhancement factor about of 10(8) for optimized substrates. These values were at least 1 order of magnitude higher than that for self-assembled arrays of gold nanostars and silver nanocubes. SERS spectra of independent samples demonstrated good sample-to-sample reproducibility in terms of the relative standard deviation (RSD) of the main peaks less than 20%. Additionally, Raman maps with 1 μm increment in X-Y directions of NIFs (800 spectral spots) demonstrated good point-to-point repeatability in the intensity of the main Raman vibration modes (RSD varied from 5% to 15% for 50 randomly selected points). A real-life application of the fabricated SERS substrates is exemplified by the detection of the thiram fungicide in apple peels within the 5-250 ppb linear detection range. Specifically, the NIF-based SERS technology detected thiram on apple peel down to level of 5 ng/cm(2).

Strategies for protein detection via surface-enhanced Raman spectroscopy (SERS) currently exploit the formation of randomly generated hot spots at the interfaces of metal colloidal nanoparticles, which are clustered together by intrusive chemical or physical processes in the presence of the target biomolecule. We propose a different approach based on selective and quantitative gathering of protein molecules at regular hot spots generated on the corners of individual silver nanocubes in aqueous medium at physiological pH. Here, the protein, while keeping its native configuration, experiences an intense local E-field, which boosts SERS efficiency and detection sensitivity. Uncontrolled signal fluctuations caused by variable molecular adsorption to different particle areas or inside clustered nanoparticles are circumvented. Advanced electron microscopy analyses and computational simulations outline a strategy relying on a site-selective mechanism with superior Raman signal enhancement, which offers the perspective of highly controlled and reproducible routine SERS detection of proteins.