Benoit Simard

Clusters of Superparamagnetic Iron Oxide Nanoparticles Encapsulated in a Hydrogel: A Particle Architecture Generating a Synergistic Enhancement of the T2 Relaxation

Clusters of iron oxide nanoparticles encapsulated in a pH-responsive hydrogel are synthesized and studied for their ability to alter the T(2)-relaxivity of protons. Encapsulation of the clusters with the hydrophilic coating is shown to enhance the transverse relaxation rate by up to 85% compared to clusters with no coating. With the use of pH-sensitive hydrogel, difficulties inherent in comparing particle samples are eliminated and a clear increase in relaxivity as the coating swells is demonstrated. Agreement with Monte Carlo simulations indicates that the lower diffusivity of water inside the coating and near the particle surface leads to the enhancement. This demonstration of a surface-active particle structure opens new possibilities in using similar structures for nanoparticle-based diagnostics using magnetic resonance imaging.

Large-scale production of single-walled carbon nanotubes by induction thermal plasma

High quality single-walled carbon nanotubes (SWNT) have been synthesized at large scales by the method of direct evaporation of carbon black and metallic catalyst mixtures, using induction thermal plasma technology. The processing system consists mainly of an RF plasma torch, which generates a plasma jet of extremely high temperature (~15 000 K), with a high energy density and abundance of reactive species (ions and neutrals). With the present reactor system, it has been demonstrated that carbon soot product which contains approximately 40 wt% of SWNT can be continuously synthesized at the high production rate of ~100 g h−1. The processing parameters involved have been examined closely in order to evaluate their individual influences on SWNT synthesis. The results have shown that the quality and purity of the SWNT produced are critically affected by the grade of carbon black, the plasma gas composition and the metallic catalyst employed. Theoretical calculations, including thermodynamic and two-dimensional thermal flow analyses, have also been performed to determine the optimal process environment most suitable for SWNT synthesis and to obtain a better understanding of the effects of process parameters. Finally, product comparisons have been made against other reference materials using Raman spectroscopy, which has shown that the quality of thermal plasma-grown SWNT is superior to that of arc discharge-grown SWNT and approaches the quality of laser-grown SWNT. This result confirms that the induction thermal plasma technology developed in this work is one of the most promising methods for the production of high quality SWNT at large scales for commercial uses.

The bond length of silver dimer

Abstract The spectroscopy of the A–X system of disilver in a supersonic jet has been studied at 120 MHz resolution. The lowest rotational levels were observed and an unequivocal J-numbering was established for the first time. The following bond lengths were derived: ro(X, 107Ag109Ag)=2.53350 (48)A, re(A). The ground state bond length is compared with previous experimental and ab initio determinations.

High resolution study of the (0, 0) and (1, 1) bands of the A0u+-X0g+ system of Au2

Abstract The spectra of the (0, 0) and (1, 1) bands of the A 0 u + - X 0 g + system of digold have been recorded at sub-Doppler resoltuion in a supersonic molecular beam apparatus employing laser vaporization. The rotational structures have been fully resolved from the origin and up, making the J -numbering unequivocal. The analysis confirms the results of a previous rotational analysis of Doppler-limited high temperature spectra of the (3, 0) and (2, 0) bands. The combination of data from both studies leads to improved molecular constants.

The cell labeling efficacy, cytotoxicity and relaxivity of copper-activated MRI/PET imaging contrast agents.

A new class of nanoparticle-based dual-modality positron emission tomography/magnetic resonance imaging (PET/MRI) contrast agents has been developed. The probe consists of a superparamagnetic iron oxide (SPIO) or manganese oxide core coated with 3,4-dihydroxy-D,L-phenylalanine (DL-DOPA). The chelator 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) was conjugated to DOPA termini. The DOTA modified nanoparticles allow chelation of copper for PET imaging. These surface functionalized nanoparticle-based probes have been characterized by various analytical techniques. The cell-labeling efficacy, cytotoxicity and relaxivity of these nanoparticles have been evaluated and compared with the same properties of one of the most commonly utilized MRI contrast agents, Feridex(®). Evidently, this new nanoparticle has a great potential for use in cell tracking with MRI and PET in the absence of transfecting agent. It is noteworthy that there is a sharp increase in r(2) relaxivity of these nanoparticles on coordination with Cu(2+) ions. Thus these iron oxide nanoparticles can also be explored as the smart magnetic resonance (MR) sensor for the detection of micromolar changes in copper concentration for neurodegenerative diseases such as Alzheimers disease, Menkes and Wilsons diseases, amyotrophic lateral sclerosis and prion diseases.

Photoionization spectroscopy of dichromium and dimolybdenum: Ionization potentials and bond energies

Photoionization spectroscopy has been used to probe molecular beams of laser-vaporized chromium (Cr2) and molybdenum (Mo2) dimers. Two-color photoionization efficiency spectroscopy has been used to determine the adiabatic ionization potential (IP) of Cr2 and Mo2 to be 56 449±8 cm−1 and 56 042±8 cm−1, respectively. The IP of Cr2 is combined with the IP of Cr [54 575.6±0.3 cm−1, Huber et al., Proc. R. Soc. London, Ser. A 342, 431 (1975)] and the bond energy of Cr2+ [10 200±500 cm−1, Su et al., Chem. Phys. Lett. 201, 199 (1993)] to yield a bond energy of 12 400±500 cm−1 for Cr2. One-color resonant two-photon ionization (R2PI) spectroscopy has been employed to probe the molybdenum dimer molecule in the energy region where its dissociation should occur. The dissociation limit has been ascribed to the threshold observed at 36 100±80 cm−1. This value is combined with the IP of Mo [57 204.3±0.3 cm−1, Rayner et al., J. Opt. Soc. Am. B 4, 900 (1987)] and Mo2 to yield a bond energy of 37 260±80 cm−1 for Mo2+.

Size and charge effects on the binding of CO to late transition metal clusters

We report on the size and charge dependence of the C-O stretching frequency, nu(CO), in complexes of CO with gas phase anionic, neutral, and cationic cobalt clusters (Co(n)CO(-0+)), anionic, neutral, and cationic rhodium clusters (Rh(n)CO(-0+)), and cationic nickel clusters (Ni(n)CO(+)) for n up to 37. We develop models, based on the established vibrational spectroscopy of organometallic carbonyl compounds, to understand how cluster size and charge relate to nu(CO) in these complexes. The dominating factor is the available electron density for backdonation from the metal to the CO pi* orbital. Electrostatic effects play a significant but minor role. For the charged clusters, the size trends are related to the dilution of the charge density at the binding site on the cluster as n increases. At large n, nu(CO) approaches asymptotes that are not the same as found for nu(CO) on the single crystal metal surfaces, reflecting differences between binding sites on medium sized clusters and the more highly coordinated metal surface sites.

RESONANT TWO PHOTON IONIZATION SPECTROSCOPY OF THE MOLECULES V2, VNB AND NB2

Resonant two photon ionization (R2PI) spectroscopy was used to obtain detailed spectroscopic information on the neutral and cation ground states of the jet‐cooled molecules V2, VNb, and Nb2. By recording photoionization efficiency (PIE) spectra, their adiabatic ionization potentials were determined to be 51 269(5) cm−1 (V2), 51 554(10) cm−1 (VNb), and 51 359(10) cm−1 (Nb2). In VNb, we used different ionization routes to determine that the splitting between the Ω=0 and Ω=1 spin–orbit components of the X 3Σ− ground state was 230(3) cm−1. In the case of V2 and VNb, two thresholds were observed in the PIE spectra recorded via Ω=1 intermediate states. We were thus able to assign the ground states of V+2 and VNb+ as having 4Σ− symmetry, with second‐order spin–orbit splittings of 20(3) and 82(3) cm−1, respectively. A simple model was applied to calculate the locations of the 1Σ+ and 2Σ+ states which are responsible for the second‐order spin–orbit splitting of the neutral and cation ground states, respectively. O...

Electronic spectroscopy of the niobium dimer molecule: Experimental and theoretical results

Rotationally resolved electronic spectra of the niobium dimer molecule are reported for the first time. The molecules were produced by laser vaporization of a niobium target rod and cooled in a helium supersonic expansion. The molecular beam containing niobium dimer molecules was interrogated in the range 400–900 nm using a pulsed dye laser to excite fluorescence. Numerous Ω=0←Ω=0 and Ω=1←Ω=1 vibronic transitions were discovered in the region 630–720 nm and investigated at 200 MHz resolution using the cw output of a single mode ring dye laser. The principal features were classified into five Ω=0←Ω=0 systems originating from a common lower state of 0+g symmetry, and three Ω=1←Ω=1 systems originating from a common lower state of 1g symmetry. The two lower states were assigned as the Ω=0 and Ω=1 spin–orbit components of the X 3Σ−g ground state, which is derived from the electron configuration 1π4u1σ2g2σ2g1δ2g. The two spin–orbit components are split by several hundred cm−1 due to a strong, second‐order isoco...

Hydrogen-Catalyzed, Pilot-Scale Production of Small-Diameter Boron Nitride Nanotubes and Their Macroscopic Assemblies

Boron nitride nanotubes (BNNTs) exhibit a range of properties that are as compelling as those of carbon nanotubes (CNTs); however, very low production volumes have prevented the science and technology of BNNTs from evolving at even a fraction of the pace of CNTs. Here we report the high-yield production of small-diameter BNNTs from pure hexagonal boron nitride powder in an induction thermal plasma process. Few-walled, highly crystalline small-diameter BNNTs (∼5 nm) are produced exclusively and at an unprecedentedly high rate approaching 20 g/h, without the need for metal catalysts. An exceptionally high cooling rate (∼10(5) K/s) in the induction plasma provides a strong driving force for the abundant nucleation of small-sized B droplets, which are known as effective precursors for small-diameter BNNTs. It is also found that the addition of hydrogen to the reactant gases is crucial for achieving such high-quality, high-yield growth of BNNTs. In the plasma process, hydrogen inhibits the formation of N2 from N radicals and promotes the creation of B-N-H intermediate species, which provide faster chemical pathways to the re-formation of a h-BN-like phase in comparison to nitridation from N2. We also demonstrate the fabrication of macroscopic BNNT assemblies such as yarns, sheets, buckypapers, and transparent thin films at large scales. These findings represent a seminal milestone toward the exploitation of BNNTs in real-world applications.