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Surface-enhanced Raman scattering (SERS) is a powerful and sensitive technique for the detection of fingerprint sig-nals of molecules and for the investigation of a series of surface chemical reactions. Many studies introduced quantita-tive applications of SERS in various fields and several SERS methods have been implemented for each specific applica- tion, ranging in performance characteristics, analytes used, instruments, and analytical matrices. In general, very few methods have been validated according to international guidelines. As a consequence, the application of SERS in high-ly- regulated environments is still considered risky and the perception of a poorly reproducible and insufficiently robust analytical technique has persistently retarded its routine implementation. Collaborative trials are a type of interlabora-tory study (ILS) frequently performed to ascertain the quality of a single analytical method. The idea of an ILS of quan- tification with SERS arose within the framework of Working Group 1 (WG1) of the COST Action BM1401 Ra-man4Clinics32 in an effort to overcome the problematic perception of quantitative SERS methods. Here we report the first interlaboratory SERS study ever conducted, involving 15 laboratories and 41 researchers. In this study we tried to define a methodology to assess the reproducibility and trueness of a quantitative SERS method, and to compare differ- ent methods. In our opinion, this is a first important step toward a “standardization” process of SERS protocols, not proposed by a single laboratory but by a larger community.

Anisotropic gold nanostructures are attracting attention due to the strong correlation between their shape and the localized surface plasmon resonances, which allows tuning their optical responses ...

The active targeting strategy has emerged as a promising approach to achieve selectivity in nanobiotechnology applications. Peptides are particularly suited as targeting moieties because the multiv...

Nanoclusters with plasmonic and magnetic properties are obtained with naked gold (AuNP) and iron oxide nanoparticles (FeOxNP) separately synthesized by laser ablation in water and simply assembled by using their opposite surface charges. Controlling the amount of AuNP and FeOxNP, we obtained nanoclusters with both good surface-enhanced resonance Raman scattering (SERRS) signals and superparamagnetic properties. Nanoclusters are incubated with murine macrophage cells which, after mixing with other macrophages, can be magnetically guided in solution by sorting them in less than 10 min. SERRS signals, observed at the single cell level, were recorded for the sorted macrophages, showing that the nanoclusters are active also in a biological environment and allow the identification of the incubated macrophage cells.

Single layer boron-doped graphene layers have been grown on polycrystalline copper foils by chemical vapor deposition using methane and diborane as carbon and boron sources, respectively. Any attempt to deposit doped layers in one-step has been fruitless, the reason being the formation of very reactive boron species as a consequence of diborane decomposition on the Cu surface, which leads to disordered nonstoichiometric carbides. However, a two-step procedure has been optimized: as a first step, the surface is seeded with pure graphene islands, while the boron source is activated only in a second stage. In this case, the nonstochiometric boron carbides formed on the bare copper areas between preseeded graphene patches can be exploited to easily release boron, which diffuses from the peripheral areas inward of graphene islands. The effective substitutional doping (of the order of about 1%) has been demonstrated by Raman and photoemission experiments. The electronic properties of doped layers have been char...

Photochromic molecules are part of a large class of materials in which light stimulus not only induces a color variation but also affects other physicochemical properties. However, the change of bulk electrical properties (e.g., electrical conductivity) via light excitation remains difficult to control because the intrinsically switchable molecules may lose their functionality when wired with conductive electrodes. In contrast with previous work based on single molecules, here we demonstrate a facile and accessible “wet-chemical” method to produce light-induced electrical switching. The electrical conductivity of a photochromic blend composed of diarylethene polymer and single-walled carbon nanotubes (SWNTs) is reversibly tuned according with UV–vis excitation. The devices present good thermal stability and remarkable fatigue resistance under ambient conditions. Supported by electrical and spectroscopic evidence, we show that the intertube electrical coupling, mediated by the light-induced electrocyclizat...

Novel applications of single-walled carbon nanotubes (SWNT) rely on the development of new strategies to make them easier to handle without affecting their structural properties. In this work, we have selectively deposited Au nanoparticles (Au NP) on SWNT assisted by UV light irradiation. XPS analysis and UV-vis spectroscopy indicate that the deposition occurs at the defects generated after oxidation of the SWNT. By addition of n-dodecylthiol, the separation of oxidized tubes with Au NP (Au-ox-SWNT) from tubes devoid of Au NP (bare tubes, b-SWNT) was achieved. Raman and UV-vis-NIR spectra indicate that UV irradiation induces a faster nucleation of Au NP on metallic SWNT. This new technique can be useful for the preparation of nanohybrid composites with enhanced properties, as increased thermal stability, and to obtain purified SWNT.

Tetrakis-2,3-[5,6-di-(2-pyridyl)pyrazino]porphyrazinatopalladium(II) [Py 8TPyzPzPd] ( 1) and the corresponding pentapalladated species [(PdCl 2) 4Py 8TPyzPzPd] ( 2), dissolved (c approximately 10 (-5)-10 (-6) M) in preacidified dimethylformamide ([HCl] approximately 10 (-4) M), behave as potent photosensitizing agents for the production of singlet oxygen, (1)O 2, with Phi Delta values of 0.89 +/- 0.04 and 0.78 +/- 0.05, respectively. The related octacation [(2-Mepy) 8TPyzPzPd] (8+) ( 3), examined under similar experimental conditions, exhibits lower Phi Delta values, that is, 0.29 +/- 0.02 (as an iodide salt) and 0.32 +/- 0.02 (as a chloride salt). In view of the very high values of Phi Delta, the photophysics of complexes 1 and 2 has been studied by means of pump and probe experiments using ns laser pulses at 532 nm as excitation source. Both complexes behave like reverse saturable absorbers at 440 nm because of triplet excited-state absorption. The lifetimes of the triplet excited states are 65 and 96 ns for the penta- and mononuclear species, respectively. Fluorescence quantum yields (Phi f) are approximately 0.1% for both 1 and 2. Such low Phi f values for the two complexes are consistent with the high efficiency of triplet excited-state formation and the measured high yields of (1)O 2. Time-dependent density-functional theory (TDDFT) calculations of the lowest singlet and triplet excited states of the mono- and pentapalladated species help to rationalize the photophysical behavior and the relevant activity of the complexes as photosensitizers for the (1)O 2 ( (1)Delta g) generation.

Understanding and controlling the chemical reactivity of carbon nanotubes (CNTs) is a fundamental requisite to prepare novel nanoscopic structures with practical uses in materials applications. Here, we present a comprehensive microscopic and spectroscopic characterization of carbon nanotubes which have been chemically modified. Specifically, scanning tunneling microscopy ( STM) investigations of short-oxidized single-walled carbon nanotubes (SWNTs) functionalized with aliphatic chains via amide reaction reveal the presence of bright lumps both on the sidewalls and at the tips. The functionalization pattern is consistent with the oxidation reaction which mainly occurs at the nanotube tips. Thermogravimetric analysis (TGA), steady-state electronic absorption (UV-vis-NIR), and Raman spectroscopic studies confirm the STM observations.

We report a new approach that uses microwaves to rapidly functionalize carbon nanotubes by using 1,3-dipolar cycloaddition of aziridines, well-known precursors to azomethine ylides, in solvent-free conditions. The efficiency of our microwave-mediated protocol is confirmed by comparison to a similar protocol in classical conditions for the azomethine ylides in DMF. Under these latter conditions, the reaction proceeds in 5 days (against 1 h under microwave irradiation), and the functionalization degree is much lower, as confirmed by thermogravimetric analysis and Raman spectroscopy. With our procedure, we easily scale-up the reaction up to 250 mg of functionalized MWNT in 1 h. We also provide an indirect proof of the covalent sidewall functionalization of the tubes.