The products of thermal decomposition of iron nitrate nonahydrate doped into poly(vinylidene difluoride) are examined using Mössbauer spectroscopy. Very little of the expected nitrogen dioxide product is observed, which is attributed to Fe catalysis of the decomposition of NO. The active site of the catalysis is shown to be Fe(OH) in the polymer matrix, which is, unexpectedly, reduced to Fe(OH).
View Article and Find Full Text PDFPoly(vinylidene difluoride) (PVDF) doped with transition metal nitrate hydrates are cast into thin films giving a high β-phase content. Analysis of the thermal behavior of the doped PVDF shows that the decomposition of the metal (II) nitrate hydrates to metal (II) oxides is catalyzed by the PVDF, as evidenced by reduction in the decomposition temperature by as much as 170 °C compared to the pure metal salts. In contrast, there is little to no apparent catalysis for the decomposition of the metal (III) nitrate hydrates.
View Article and Find Full Text PDFThe morphology of sub-micron poly(methyl methacrylate) films coated to glass supports by spin coating from toluene is examined using surface profilometry. Wrinkled surfaces with local quasi-sinusoidal periodicity were seen on the surfaces of films with thicknesses of larger than 75 nm. The surface wrinkles had large aspect ratios with wavelengths in the tens of microns and amplitudes in the tens of nanometers.
View Article and Find Full Text PDFThin films of three differently charged xanthene dyes: rhodamine 6G (Rh6G, cationic), fluorescein 27 (F27, neutral), and disodium fluorescein (DSF, anionic) were cast onto a polystyrene (PS) coated glass substrate to investigate ion-π interactions. Absorbance spectroscopy was used to determine the aggregation state of the dyes on the PS surface. Deconvolution of the spectra of films revealed multiple peaks for all dyes assigned to isolated monomers, aggregates, and complexes between the dye and the polymer substrate.
View Article and Find Full Text PDFIn water rhodamine 6G (Rh6G) tends to form aggregates at higher concentrations while in ethanol the aggregation is minimal. The extent of aggregation can be controlled by changing the water to ethanol ratio. In ethanol the absorption spectra have a low energy peak and a higher energy shoulder, which are assigned to the S π-π* transition and vibronic side band, respectively, of Rh6G monomers.
View Article and Find Full Text PDFRhodamine 6G is spin-cast onto gold surfaces and the reflectance, emission, excitation, and SERS spectra are reported. Electron microscopy shows that the particle sizes of the gold are uniform for all preparations. Reflection spectra demonstrate the spectroscopic signature for Rh6G aggregates for thicker films and that the gold plasmon band shifts due to the refractive index change on the surface.
View Article and Find Full Text PDFThe spectral response of ultrathin films of rhodamine 6G (Rh6G) cast onto polyvinylidenefluoride (PVDF) coated glass slides is studied to investigate a perceived fluorescence emission enhancement. Varying the thickness of the Rh6G layer (submonolayer to multiple layers) on the PVDF layer revealed the existence of multiple Rh6G species on the surface, similar to previous reports on glass. Excitation spectra show that J-type excitons are not responsible for an emission enhancement.
View Article and Find Full Text PDFThe reaction of trinitrotoluene (TNT) with bases has been investigated by NMR and visible spectroscopy methods. Hydroxide ion was found to react in one of two ways, either by deprotonation of the methyl group or by nucleophilic attack on the aromatic ring to form a σ adduct. The rate of each mode of reaction depends upon the polarity of the solvent.
View Article and Find Full Text PDFMetal Enhanced Fluorescence (MEF) typically produces enhancement factors of 10 to 50. By using a polymer layer as the dielectric spacer enhancements as high as 1,600 can be observed. The effect occurs with a variety of different polymers and substrates, all of which act to trap light in the dielectric layer.
View Article and Find Full Text PDFTrinitrobenzene (TNB) and trinitrotoluene (TNT) react in N,N-dimethylformamide (DMF) to form multiple species in solution. Despite structural similarities, electronic spectra show that the reactivity is different for TNB and TNT. In addition to reaction with the DMF solvent, residual water in nominally dry DMF generates sufficient hydroxide for reaction with TNB and TNT.
View Article and Find Full Text PDFPhotovoltaic devices based on single-walled carbon nanotubes (SWNTs) and n-silicon heterojunctions have been fabricated by a spray deposition process. We provide direct evidence that nanotubes serve as an active photosensing material involved directly in the photon absorption process as well as contributing to charge separation, transport and collection. The characteristic band of the SWNT band in the photoconductivity spectrum matches the S(11) absorption band of semiconducting SWNTs of 7,6 chirality.
View Article and Find Full Text PDFMesoporous silicon (PSi) microcavities (MC) based on one-dimensional photonic crystals have been studied as optical sensors for relative humidity (RH). Oxidized PSi modified the structure of the MC such that the spectral position of the MC resonance peak depended on the humidity. A spectral shift of the MC resonance peak of up to 6 nm to longer wavelengths was observed as the RH increased from 20% to 85%.
View Article and Find Full Text PDFThe addition of some small molecules can red shift UV-Visible absorption and quench the fluorescence of poly(3-octadecylthiophene).
View Article and Find Full Text PDFA bilayer composite of single walled carbon nanotubes (SWNTs) deposited onto Nafion exhibits substantial mechanical motion upon exposure to visible or near-infrared light. The magnitude of the actuation parallels the absorption spectrum of the SWNTs in the near-infrared, but the actuation diminishes in the visible and disappears in the UV portions of the spectrum. In the near-infrared region, the photoactuation is linear with respect to the light intensity.
View Article and Find Full Text PDF[graph: see text] The electrochemical, structural, and spectroscopic properties of bis(phosphine imide)s have been investigated. p-Phenylenebis(phosphine imide)s Ar3PNC6H4NPAr3 (1a-d) have two reversible single-electron oxidations. The first oxidation potentials can be varied from -0.
View Article and Find Full Text PDFAn actuating system composed of nafion ionomeric polymer coated with single-walled carbon nanotubes electrodes was studied as an electromechanical actuator. The actuator gives a sizable mechanical response to low voltages (turn-on voltage of approximately 2.5 V) under open-air conditions, i.
View Article and Find Full Text PDFChem Commun (Camb)
March 2004
Poly[3-(oligoethylene oxide)-4-methylthiophene] is doped by HCl in aqueous solution in the absence of oxygen and undergoes dramatic solvatochromism in water-ethanol mixtures.
View Article and Find Full Text PDFA series of [Ru(bpy)(2)](2+) complexes linked by a controlled number of azine units (one to seven) were synthesized and studied in the solution phase. Polymers and dimer model compounds were examined by cyclic voltammetry and IR, NMR, and visible-NIR spectroscopies. The NMR spectra and the cyclic voltammograms indicated that the Ru(2+) sites influenced the main chain properties at least 15 A from the metal site.
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