Thermal analysis of smithsonite and hydrozincite

Thermogravimetric analysis of synthetic smithsonite and hydrozincite, two secondary minerals of zinc, was used to determine their relative thermal stability. Thermal decomposition of smithsonite occurs at 293°C and hydrozincite at 220°C showing that the carbonate mineral is more stable than the hydroxy-carbonate mineral hydrozincite. Hot stage Raman spectroscopy confirms the decomposition of smithsonite and hydrozincite by 300 and 250°C, respectively. Thermogravimetry shows that a small amount of hydrozincite is formed during the synthesis of smithsonite. No evidence is found for the separate loss of the carbonate and hydroxyl units from hydrozincite.     

One- and Two-Photon Fluorescence Anisotropy of Selected Fluorene Derivatives

The steady-state excitation anisotropy spectra of fluorene derivatives were measured in viscous solvents, under the one- and two-photon excitation, over a broad spectral range (UV–Visible). The orientation of their absorption transition moments for the first, S₀S₁, and second, S₀S₂, excited states were determined. It was shown experimentally that a decrease in the angle between S₀S₁and S₀S₂ transitions corresponded to an increased value of two-photon absorption (2PA) cross section for these molecules. Two-photon excitation anisotropy was nearly constant over the spectral region investigated (in contrast to one-photon excitation anisotropy spectra) and can be roughly explained by a simple model of 2PA based on the single intermediate state approximation. For comparison, the same trend in two-photon excitation anisotropy was observed for Rhodamine B inglycerol.     

Bisdioxaborine polymethines with large third-order nonlinearities for all-optical signal processing

Organic materials with large third-order nonlinearities in the near-infrared spectral regime are critical in the development of photonic devices to be utilized in all-optical signal processing. We have developed polymethine materials, specifically bisdioxaborine-terminated polymethine dyes, which possess large ultrafast third-order nonlinearities and low nonlinear loss all in the near-infrared spectral regime. An extended bisdioxaborine polymethine anion exhibited the largest value of gamma (third-order microscopic nonlinearity) at 1.3 mum (|gamma| = 5.7 x 10-32 esu) and showed no characteristics of symmetry breaking, unlike other polymethines of similar lengths. A neat film of this molecule maintained relatively low linear loss in the near-infrared and showed a large third-order macroscopic nonlinearity at 1.3 mum (|chi(3)| = 3.6 x 10-10 esu), with a temporal response of less than 8 ps. Furthermore, the real part of chi(3) was nearly an order-of-magnitude larger than the imaginary component. Consequently, this material exhibited good figures of merit for all-optical signal processing throughout the entire telecommunications band.     

Investigation of two-photon absorption properties in branched alkene and alkyne chromophores

Novel alkene and alkyne branched structures have been synthesized, and their two-photon absorption (2PA) properties are reported. This series of alkene and alkyne trimer systems tests the mechanistic approach for enhancing the 2PA process which is usually dictated by the pi-bridging, delocalization length, and corresponding charge transfer on the 2PA cross sections. The results suggest that alkene branched systems have higher 2PA cross sections. While steady-state absorption and emission measurements were not successful in predicting the observed trend of 2PA cross sections, time-resolved measurements have explained the trends observed. It was found that, upon photoexcitation, there is an ultrafast charge localization to an intramolecular charge-transfer (ICT) state, followed by the presence of a solvent and conformationally relaxed ICT state in these branched systems.     

Synthesis and vibrational spectroscopic characterisation of synthetic hydrozincite and smithsonite

Hydrozincite and smithsonite were synthesised by controlling the partial pressure of CO₂. Previous crystallographic studies concluded that the structure of hydrozincite was a simple one. However both Raman and infrared spectroscopy show that this conclusion is questionable. Multiple bands are observed in both the Raman and infrared spectra in the (CO₃)²⁻ antisymmetric stretching and bending regions of hydrozincite showing that the symmetry of the carbonate anion is reduced and in all probability the carbonate anions are not equivalent in the hydrozincite structure. Multiple OH stretching vibrations centred in both the Raman and infrared spectra show that the OH units in the hydrozincite structure are non-equivalent. The Raman spectrum of synthetic smithsonite is a simple spectrum characteristic of carbonate with Raman bands observed at 1408, 1092 and 730 cm⁻¹.     

Electron inventory, kinetic assignment (E(n)), structure, and bonding of nitrogenase turnover intermediates with C2H2 and CO

Improved 1H ENDOR data from the S(EPR1) intermediate formed during turnover of the nitrogenase alpha-195Gln MoFe protein with C2(1,2)H2 in (1,2)H2O buffers, taken in context with the recent study of the intermediate formed from propargyl alcohol, indicate that S(EPR1) is a product complex, likely with C2H4 bound as a ferracycle to a single Fe of the FeMo-cofactor active site. 35 GHz CW and Mims pulsed 57Fe ENDOR of 57Fe-enriched S(EPR1) cofactor indicates that it exhibits the same valencies as those of the CO-bound cofactor of the lo-CO intermediate formed during turnover with CO, [Mo4+, Fe3+, Fe6(2+), S9(2-)(d43)](+1), reduced by m = 2 electrons relative to the resting-state cofactor. Consideration of 57Fe hyperfine coupling in S(EPR1) and lo-CO leads to a picture in which CO bridges two Fe of lo-CO, while the C2H4 of S(EPR1) binds to one of these. To correlate these and other intermediates with Lowe-Thorneley (LT) kinetic schemes for substrate reduction, we introduce the concept of an "electron inventory". It partitions the number of electrons a MoFe protein intermediate has accepted from the Fe protein (n) into the number transmitted to the substrate (s), the number that remain on the intermediate cofactor (m), and the additional number delivered to the cofactor from the P clusters (p): n = m + s - p (with p = 0 here). The cofactors of lo-CO and S(EPR1) both are reduced by m = 2 electrons, but the intermediates are not at the same LT reduction stage (E(n)): (n = 2; m = 2, s = 0) for lo-CO; (n = 4; s = 2, m = 2) for S(EPR1). This is the first proposed correlation of an LT E(n) kinetic state with a well-defined chemical state of the enzyme.     

Dioxaborine- and indole-terminated polymethines: effects of bridge substitution on absorption spectra and third-order polarizabilities

Cyanine-like dyes are promising candidates for third-order nonlinear optical (NLO) applications such as all-optical switching. Here, we examine the consequences for linear and nonlinear optical properties of varying substituents on the central methine unit of bis(dioxaborine)-terminated anionic pentamethines and bis(indole)-terminated cationic heptamethines. The variation in absorption maxima and electrochemical potentials with structure can generally be rationalized using the Dewar-Knott rules, providing that mesomeric and inductive electron-withdrawal and donation are explicitly considered. In the case of nitro- and (dioxaborinyl)vinyl-substituted bis(dioxaborine) pentamethines, the low-energy transitions are significantly broadened, consistent with (1)H NMR spectra indicating deviation from cyanine-like geometry. Real and imaginary parts of the third-order polarizabilities, Re(γ) and Im(γ), were measured at 1.3 μm. The values of Im(γ) indicate that the values of Re(γ) are significantly resonantly enhanced, while the positive value of Re(γ) found for a nitro-substituted dioxaborine example is atypical for a symmetrical polymethine and suggests that a two-state treatment is inadequate. The relevance of these results to chromophore design for third-order NLO applications is discussed.     

Examining the use of a time-varying loudness algorithm for quantifying characteristics of nonlinearly propagated noise (L)

A previous letter by Gee et al. [J. Acoust. Soc. Am. 121, EL1-EL7 (2007)] revealed likely shortcomings in using common, stationary (long-term) spectrum-based measures to quantify the perception of nonlinearly propagated noise. Here, the Glasberg and Moore [J. Audio Eng. Soc. 50, 331-342 (2002)] algorithm for time-varying loudness is investigated. Their short-term loudness, when applied to a shock-containing broadband signal and a phase-randomized signal with equivalent long-term spectrum, does not show a significant difference in loudness between the signals. Further analysis and discussion focus on the possible utility of the instantaneous loudness and the need for additional investigation in this area.