Poly(methyl methacrylate) as an Environmentally Responsive Capping Material for Aluminum Nanoparticles.

We present an investigation of the photochemistry of aluminum nanoparticles (Al NPs) capped with poly(methyl methacrylate) (PMMA). Powder X-ray diffraction and Fourier transform infrared spectroscopy with total attenuated reflection confirm the presence of crystalline aluminum cores and the PMMA cap and allow us to confirm the latter's photodegradation upon exposure to UV light. The PMMA-Al NPs were also characterized by differential scanning calorimetry coupled with thermogravimetric analysis to study the thermal profiles for polymer combustion and metal oxidation exotherms. Transmission electron microscopy confirms that the Al NPs, around 36 nm in diameter, are embedded in the PMMA matrix. Following UV irradiation, the PMMA-Al NPs react considerably faster with alkaline solutions, compared with unphotolyzed samples. Photoactivation of the nanocomposite induces partial decomposition of the PMMA capping layer, exposing the underlying reactive metal cores to the surrounding environment and accelerating its redox reactivity. Photolysis times of 1, 6, 24, and 52 h were investigated to establish a minimum UV exposure time for the activation of the PMMA-Al NPs toward hydrolytic hydrogen gas generation.

Metal and Metal Carbide Nanoparticle Synthesis Using Electrical Explosion of Wires Coupled with Epoxide Polymerization Capping.

In this study, metal-containing nanoparticles (NPs) were produced using electrical explosion of wires (EEW) in organic solvents. The explosion chamber was constructed from Teflon to withstand the shockwave, allow growth and reaction of the incipient NPs in various organic solvents containing dissolved ligands, and allow a constant flow of argon to maintain an inert environment. A survey of different transition d-block metals was conducted with metals from groups 4-8, affording metal carbide NPs, while metals from groups 9-12 gave elemental metallic NPs. Tungsten carbide phase WC1-x, which has not been previously isolated as a single-phase material, was exclusively formed during EEW. We used polymerization initiation by electron-rich metallic nanoparticles (PIERMEN) as a capping technique for the nascent NPs with an alkyl epoxide employed as the monomers. Transmission electron microscopy showed spherical particles with the metallic core embedded in a polymer matrix with predominantly smaller particles (<50 nm), but also a broad size distribution with some larger particles (>100 nm). Powder X-ray diffraction (PXRD) was used to confirm the identity of the metallic NPs. The capping agents were characterized using ATR-FTIR spectroscopy. No evidence is observed for the formation of crystalline oxides during EEW for any metals used. Differential scanning calorimetry/thermal gravimetric analysis was used to study the NP's behavior upon heating under an air flow up to 800 °C with the product oxides characterized by PXRD. The bifurcation between metal-carbide NPs and metal NPs correlates with the enthalpy of formation of the product carbides. We observed PIERMEN capping of elemental metal NPs only when the metal has negative standard electrode potentials (relative to a bis(biphenyl) chromium(I)/(0) reference electrode).

Aluminum nanoparticles capped by polymerization of alkyl-substituted epoxides: ratio-dependent stability and particle size.

We report here on the polymerization of epoxide monomers on incipient aluminum nanoparticle cores and the effects of changing the epoxide-capping precursor and the metallic monomer ratio on the resultant stability and particle size of passivated and capped aluminum nanoparticles. When altering the ratio of aluminum to cap monomer precursor, nanoparticles capped with epoxydodecane, epoxyhexane, and epoxyisobutane show a clear decreasing trend in stability with decreasing alkane substituent length. The nanoparticle core size was unaffected by cap ratio or composition. PXRD (powder X-ray diffraction) and DSC/TGA (differential scanning calorimetry/thermal gravimetric analysis) confirm the presence of successfully passivated face-centered cubic (fcc) aluminum nanoparticles. We also report preliminary results from ATR-FTIR (attenuated total reflectance-Fourier transform infrared), (13)C CPMAS (cross-polarization/magic-angle spinning), and (27)Al MAS solid-state NMR (nuclear magnetic resonance) measurements. The most stable aluminum nanoparticle-polyether core-shell nanoparticles are found at an Al:monomer mole ratio of 10:1 with an active Al(0) content of 94%.

A metallacarborane redox mediator for an enzyme-immobilized chitosan-modified bioanode.

We describe here the first report of a metallacarborane complex as a redox mediator in a functioning biofuel cell. Specifically, we have prepared a water-soluble salt of the complex anion [commo-3,3'-Fe-(closo-2,1-C(2)B(9)H(11))(2)](-) and employed it as a redox mediator for glucose oxidation using chitosan/multiwalled carbon nanotube-modified electrodes comprising immobilized glucose oxidase. Experiments have indicated an increased amperometric response to glucose feeding, providing the complex mediator was initially supplied in the phosphate buffer electrolyte solution. Cathodic peak currents increased to a maximum of 1.24mA/cm(2) up to the saturating threshold concentration of glucose, indicating a significant degree of metallacarborane-enzyme communication and supporting the notion of a proposed metallacarborane redox mediator in biofuel cells. Upon incorporation of the mediator by anion exchange in the chitosan with the enzyme prior to measurement, however, an attenuated response to glucose feeding was detected, despite efforts to use different tactics to cast such films on the electrode such as a bilayer scheme. It is believed that the uptake of significant quantities of the metallacarborane into the chitosan is sponsoring a gross change in the microstructure of the biopolymer. This is supported by SEM imaging of the metallacarborane-modified chitosan, which revealed a remarkable transformation of the biopolymer scaffold.

Capping and passivation of aluminum nanoparticles using alkyl-substituted epoxides.

We report here on the synthesis and passivation of small (20-30 nm) aluminum nanoparticles using alkyl-substituted epoxides as capping agents. FTIR and 13C NMR spectroscopy indicate that the epoxides polymerize to form a polyether cap on the surfaces of the aluminum nanoparticles. Nanoparticles capped with epoxyhexane and epoxydodecane are stable in air, but particles capped with epoxyisobutane are pyrophoric. TEM images show spherical Al particles. Powder X-ray diffraction shows the presence of crystalline Al. Titrimetric analysis of the core-shell nanostructures in air reveals that 96% of the total aluminum present is active (unoxidized) aluminum.

Synthesis and characterization of srilankite nanowires.

We describe the synthesis and characterization of srilankite (Ti2ZrO6) nanowires. The nanowires are produced via hydrothermal synthesis with a TiO2/ZrO2 mixture under alkaline conditions. The zirconium titanate nanowires have median diameters of 60 nm and median lengths of 800 nm with the (022) axis along the length of the nanowire. Electron microscopy, energy dispersive X-ray spectroscopy, powder X-ray diffraction, and electron diffraction are used to characterize the phases and compare nanowires produced with varying molar ratios of Ti and Zr. Electron diffraction patterns produced from single nanowires show highly crystalline nanowires displaying a compositional-ordering superlattice structure with Zr concentrated in bands within the crystal structure. This is in contrast to naturally occurring bulk srilankite where Zr and Ti are randomly substituted within the crystal lattice. Streaking is observed in the electron diffraction patterns suggesting short-range ordering within the superlattice structure.

Dual fluorescence from an isonido ReIII rhenacarborane phosphine complex, [7,10-mu-H-7-CO-7,7-(PPh3)2-isonido-7,8,9-ReC2B7H9].

The complex [7,10-mu-H-7-CO-7,7-(PPh3)2-isonido-7,8,9-ReC2B7H9] has been synthesized by treatment of the complex salt [NHMe3][3,3-Cl2-3,3-(CO)2-closo-3,1,2-ReC2B9H11] with PPh3 in refluxing THF (tetrahydrofuran) and isolated as intensely colored orange-red microcrystals. Spectroscopic NMR and IR data have suggested that the product has a highly asymmetric structure with two inequivalent PPh3 ligands and a single CO ligand. Measurement of 11B NMR spectra in particular have indicated seven distinct boron vertexes, although the resulting cage degradation by removal of two BH vertexes was confirmed only following X-ray crystallographic analysis, which revealed the pentadecahedral isonido-7,8,9-ReC2B7 architecture. The 11B NMR resonances span an enormous chemical shift range (Deltadelta = 113), and this appears to be a direct consequence of the deshielding of the boron vertex directly opposite the quadrilateral |ReCCB| aperture. The new complex has been shown by electrochemical measurements to undergo a reversible one-electron oxidation. Digitally simulated cyclic voltammograms support a proposed square scheme (E(1/2) = 0.58, 0.69 V vs ferrocene) involving a reversible isonido-closo transition of the metallacarborane cage. Most unusually for a metallacarborane complex, ambient temperature solutions in CH2Cl2 and DMF have been shown to be intensely turquoise-blue fluorescent (lambda(em) = 442 nm, Phi = 0.012). Fluorescence spectroscopy measurements in MeTHF (2-methyltetrahydrofuran) glass at 77 K have indicated that the likely cause of such a broad emission is dual fluorescence (lambda(em) = 404, 505 nm), with both emissions displaying vibronic structure. Following excited-state lifetime decay analysis, the emissive behavior has been accredited to metal-perturbed 1IL states, with the lower energy emission arising from a slight geometric distortion of the initially excited complex.

Kinetic behavior of polymer-coated long-period-grating fiber-optic sensors.

A new method of analysis employing the time-dependent response of long-period-grating (LPG) fiber-optic sensors is introduced. The current kinetic approach allows analysis of the time-dependent wavelength shift of the sensor, in contrast to previous studies, in which the LPG sensing element has been operated in an equilibrium mode and modeled with Langmuir adsorption behavior. A detailed kinetic model presented is based on diffusion of the analyte through the outer protective membrane coating into the affinity coating, which is bound to the fiber cladding. A simpler phenomenological approach presented is based on measurement of the slope of the time-dependent response of the LPG sensor. We demonstrate the principles of the kinetic methods by employing a commercial Cu+2 sensor with a carboxymethylcellulose sensing element. The detailed mathematical model fits the time-dependent behavior well and provides a means of calibrating the concentration-dependent time response. In the current approach, copper concentrations below parts per 10(6) are reliably analyzed. The kinetic model allows early-time measurement for low concentrations of the analyte, where equilibration times are long. This kinetic model should be generally applicable to other affinity-coated LPG fiber-optic sensors.