Transient photothermal spectra of plasmonic nanobubbles

The photothermal efficacy of near-infrared gold nanoparticles (NP), nanoshells, and nanorods was studied under pulsed high-energy optical excitation in plasmonic nanobubble (PNB) mode as a function of the wavelength and duration of the excitation laser pulse. PNBs, transient vapor nanobubbles, were generated around individual and clustered overheated NPs in water and living cells. Transient PNBs showed two photothermal features not previously observed for NPs: the narrowing of the spectral peaks to 1 nm and the strong dependence of the photothermal efficacy upon the duration of the laser pulse. Narrow red-shifted (relative to those of NPs) near-infrared spectral peaks were observed for 70 ps excitation laser pulses, while longer sub- and nanosecond pulses completely suppressed near-infrared peaks and blue shifted the PNB generation to the visual range. Thus, PNBs can provide superior spectral selectivity over gold NPs under specific optical excitation conditions.     

Effect of the cooling rate on dimerization of C60(•-) in fullerene salt (DMI+)2·(C60(•-))·{Cd(Et2NCS2)2I-}

The salt (DMI(+))(2)·(C(60)(?-))·{Cd(Et(2)NCS(2))(2)I(-)} (1) containing fullerene radical anions, the anions of cadmium diethyldithiocarbamate iodide, and N,N'-dimethylimidazolium cations was obtained. Fullerenes are monomeric in 1 at 250 K and form three-dimensional packing in which each fullerene has nearly tetrahedral surroundings from neighboring fullerenes. Fullerenes with a shorter interfullerene center-to-center distance of 10.031(2) ? form spiral chains arranged along the lattice c axis. The convolution consists of four fullerene molecules. Dimerization realized in 1 within the spiral chains below 135 K manifests a strong dependence on the cooling rate. The "frozen" monomeric phase was obtained upon instant quenching of 1. This phase is stable below 95 K for a long time but slowly converted to the dimeric phase at T > 95 K. It exhibits a weak antiferromagnetic interaction of spins below 95 K (the Weiss temperature is -4 K), which results in the splitting of the electron paramagnetic resonance (EPR) signal into two components below 10 K. A disordered phase containing both C(60)(?-) monomers and singly bonded (C(60)(-))(2) dimers with approximately 0.5/0.5 occupancies is formed at an intermediate cooling rate (for 20 min). The position of each fullerene in this phase is split into three positions slightly shifted relative to each other. The central position corresponds to nonbonded fullerenes with interfullerene center-to-center distances of 9.94-10.00 ?. Two other positions are coincided to dimeric fullerenes formed with the right and left fullerene neighbors within the spiral chain. This intermediate phase is paramagnetic with nearly zero Weiss temperature due to isolation of C(60)(?-) by diamagnetic species and exhibits a strongly asymmetric EPR signal below 20 K. A diamagnetic phase containing ordered singly bonded (C(60)(-))(2) dimers can be obtained only upon slow cooling of the crystal for 6 h.     

Probing platinum degradation in polymer electrolyte membrane fuel cells by synchrotron X-ray microscopy

Synchrotron-based scanning transmission X-ray spectromicroscopy (STXM) was used to characterize the local chemical environment at and around the platinum particles in the membrane (PTIM) which form in operationally tested (end-of-life, EOL) catalyst coated membranes (CCMs) of polymer electrolyte membrane fuel cells (PEM-FC). The band of metallic Pt particles in operationally tested CCM membranes was imaged using transmission electron microscopy (TEM). The cathode catalyst layer in the beginning-of-life (BOL) CCMs was fabricated using commercially available catalysts created from Pt precursors with and without nitrogen containing ligands. The surface composition of these catalyst powders was measured by X-ray Photoelectron Spectroscopy (XPS). The local chemical environment of the PTIM in EOL CCMs was found to be directly related to the Pt precursor used in CCM fabrication. STXM chemical mapping at the N 1s edge revealed a characteristic spectrum at and around the dendritic Pt particles in CCMs fabricated with nitrogen containing Pt-precursors. This N 1s spectrum was identical to that of the cathode and different from the membrane. For CCM samples fabricated without nitrogen containing Pt-precursors the N 1s spectrum at the Pt particles was indistinguishable from that of the adjacent membrane. We interpret these observations to indicate that nitrogenous ligands in the nitrogen containing precursors, or decomposition product(s) from that source, are transported together with the dissolved Pt from the cathode into the membrane as a result of the catalyst degradation process. This places constraints on possible mechanisms for the PTIM band formation process.     

Metal-free inorganic ligands for colloidal nanocrystals: S2-, HS-, Se2-, HSe-, Te2-, HTe-, TeS3(2-), OH-, and NH2- as surface ligands

All-inorganic colloidal nanocrystals were synthesized by replacing organic capping ligands on chemically synthesized nanocrystals with metal-free inorganic ions such as S(2-), HS(-), Se(2-), HSe(-), Te(2-), HTe(-), TeS(3)(2-), OH(-) and NH(2)(-). These simple ligands adhered to the NC surface and provided colloidal stability in polar solvents. The versatility of such ligand exchange has been demonstrated for various semiconductor and metal nanocrystals of different size and shape. We showed that the key aspects of Pearson's hard and soft acids and bases (HSAB) principle, originally developed for metal coordination compounds, can be applied to the bonding of molecular species to the nanocrystal surface. The use of small inorganic ligands instead of traditional ligands with long hydrocarbon tails facilitated the charge transport between individual nanocrystals and opened up interesting opportunities for device integration of colloidal nanostructures.     

Perfectly dissolved boron nitride nanotubes due to polymer wrapping

We report for the first time that boron nitride nanotubes (BNNTs) may be dissolved in organic solvents by wrapping them with a polymer. Transmission electron microscopy and cathodoluminescence studies indicate the strong pi-pi interactions between BNNTs and the polymer. A band gap ranging from 5.2 to 5.5 eV was documented for the BNNTs independent of their geometrical characteristics by using ultraviolet-visible absorption experiments on composite films and thin BNNT films prepared from solutions.     

CdSe and CdSe/CdS nanorod solids

We demonstrate the self-organization of CdSe nanorods into nematic, smectic, and crystalline solids. Layered colloidal crystals of CdSe nanorods grow by slow destabilization of a nanocrystal solution upon allowing the diffusion of a nonsolvent into the colloidal solution of nanocrystals. The colloidal crystals of nanorods show characteristic birefringence, which we assign to specific spherulite-like texture of each nanorod assembly. To demonstrate the general character of nanorod self-assembly technique, CdSe/CdS heterostructure nanorods were organized into highly luminescent superlattices.     

Structural Analogy Method in Studies of Adamantanes

The potential of the structural analogy method in the topological studies of adamantane derivatives and analogs is demonstrated. The topological and structural characteristics of these compounds are calculated. Chromatographic retention indices were determined experimentally. Correlations between the topological indices and the physicochemical and chromatographic characteristics are investigated.