Gd2O3-mesoporous silica/gold nanoshells: A potential dual T1/T2 contrast agent for MRI-guided localized near-IR photothermal therapy.

A promising clinical trial utilizing gold-silica core-shell nanostructures coated with polyethylene glycol (PEG) has been reported for near-infrared (NIR) photothermal therapy (PTT) of prostate cancer. The next critical step for PTT is the visualization of therapeutically relevant nanoshell (NS) concentrations at the tumor site. Here we report the synthesis of PEGylated Gd2O3-mesoporous silica/gold core/shell NSs (Gd2O3-MS NSs) with NIR photothermal properties that also supply sufficient MRI contrast to be visualized at therapeutic doses (≥108 NSs per milliliter). The nanoparticles have r1 relaxivities more than three times larger than those of conventional T1 contrast agents, requiring less concentration of Gd3+ to observe an equivalent signal enhancement in T1-weighted MR images. Furthermore, Gd2O3-MS NS nanoparticles have r2 relaxivities comparable to those of existing T2 contrast agents, observed in agarose phantoms. This highly unusual combination of simultaneous T1 and T2 contrast allows for MRI enhancement through different approaches. As a rudimentary example, we demonstrate T1/T2 ratio MR images with sixfold contrast signal enhancement relative to its T1 MRI and induced temperature increases of 20 to 55 °C under clinical illumination conditions. These nanoparticles facilitate MRI-guided PTT while providing real-time temperature feedback through thermal MRI mapping.

(n,m)-Specific Absorption Cross Sections of Single-Walled Carbon Nanotubes Measured by Variance Spectroscopy.

A new method based on variance spectroscopy has enabled the determination of absolute absorption cross sections for the first electronic transition of 12 (n,m) structural species of semiconducting single-walled carbon nanotubes (SWCNTs). Spectrally resolved measurements of fluorescence variance in dilute bulk samples provided particle number concentrations of specific SWCNT species. These values were converted to carbon concentrations and correlated with resonant components in the absorbance spectrum to deduce (n,m)-specific absorption cross sections (absorptivities) for nanotubes ranging in diameter from 0.69 to 1.03 nm. The measured cross sections per atom tend to vary inversely with nanotube diameter and are slightly greater for structures of mod 1 type than for mod 2. Directly measured and extrapolated values are now available to support quantitative analysis of SWCNT samples through absorption spectroscopy.

High precision fractionator for use with density gradient ultracentrifugation.

The recent application of density gradient ultracentrifugation (DGU) for structural sorting of single-walled carbon nanotube samples has created a need for highly selective extraction of closely spaced layers formed in the centrifuged tube. We describe a novel computer-controlled device designed for this purpose. Through the use of fine needles, systematic needle motions, and slow flow rates, multiple sample layers can be aspirated under program control with minimal cross contamination between layers. The fractionator's performance is illustrated with DGU-sorted samples of single-walled carbon nanotubes.

Plasmonic gadolinium oxide nanomatryoshkas: bifunctional magnetic resonance imaging enhancers for photothermal cancer therapy.

Nanoparticle-assisted laser-induced photothermal therapy (PTT) is a promising method for cancer treatment; yet, visualization of nanoparticle uptake and photothermal response remain a critical challenge. Here, we report a magnetic resonance imaging-active nanomatryoshka (Gd2O3-NM), a multilayered (Au core/Gd2O3 shell/Au shell) sub-100 nm nanoparticle capable of combining T1 MRI contrast with PTT. This bifunctional nanoparticle demonstrates an r1 of 1.28 × 108 mM-1 s-1, an MRI contrast enhancement per nanoparticle sufficient for T1 imaging in addition to tumor ablation. Gd2O3-NM also shows excellent stability in an acidic environment, retaining 99% of the internal Gd(3). This report details the synthesis and characterization of a promising system for combined theranostic nanoparticle tracking and PTT.

Skewness Analysis in Variance Spectroscopy Measures Nanoparticle Individualization.

An important enabling step in nanoparticle studies is the sorting of heterogeneous mixtures to prepare structurally homogeneous samples. It is also necessary to detect and monitor aggregation of the individual nanoparticles. Although variance spectroscopy provides a simple optical method for finding low concentrations of heteroaggregates in samples such as single-walled carbon nanotube dispersions, it cannot detect the homoaggregates that are relevant for well-sorted samples. Here we demonstrate that variance spectral data can be further analyzed to find third moments of intensity distributions (skewness), which reveal the presence of emissive homoaggregates. Using experimental measurements on variously processed nanotube dispersions, we deduce a simple numerical standard for recognizing aggregation in the highly sorted samples that are increasingly available to nanoscience researchers.

Resonance Raman Optical Activity Spectra of Single-Walled Carbon Nanotube Enantiomers.

We present experimental Raman optical activity (ROA) spectra of enantio-enriched single-walled carbon nanotubes (SWCNTs). Enantiomeric samples of (6,5) SWCNTs were prepared using nonlinear density gradient ultracentrifugation (DGU). Upon excitation at 2.33 eV, remarkably strong G-band signals are obtained due to strong resonance enhancement with the E22(S) transition of (6,5) SWCNTs. Enhancement allows measuring the vibrational optical activity (VOA) at unusually low concentrations. The obtained results are in good agreement with the single-excited-state theory (SES). To our knowledge, these are the first experimental VOA spectra of SWCNTs.