Polydopamine-Coated TiO2 Nanotubes for Selective Photocatalytic Oxidation of Benzyl Alcohol to Benzaldehyde Under Visible Light.

TiO2 nanotube arrays grown by anodization were coated with thin layers of polydopamine as visible light sensitizer. The PDA-coated TiO2 scaffolds were used as photocatalyst for selective oxidation of benzyl alcohol under monochromatic irradiation at 473 nm. Benzaldehyde was selectively formed and no by-products could be detected. A maximized reaction yield was obtained in O2-saturated acetonitrile. A mechanism is proposed that implies firstly the charge carrier generation in polydopamine as a consequence of visible light absorption. Secondly, photo-promoted electrons are injected in TiO2 conduction band, and subsequently transferred to dissolved O2 to form O*2- radicals. These radicals react with benzyl alcohol and lead to its selective dehydrogenation oxidation towards benzaldehyde.

VUV and soft x-ray ionization of a plant volatile: Vanillin (C8H8O3).

Plant volatiles are emitted by plants in response to several forms of stress, including interaction with energetic photons. In the present work, we discuss the interaction of extreme UV and soft X-ray photons with a plant volatile, vanillin. The single and double (multiple) ionization of the vanillin molecule have been studied for the first time using time-of-flight mass spectrometry and VUV and soft X-ray photons (synchrotron radiation, at 12.0 eV, 21.2 eV, 130 eV, 310 eV, 531 eV, and 550 eV). At 12.0 and 21.2 eV, only singly charged species are observed and the parent ion, C8H8O3 (+), is the dominant species. Energy differences for some selected fragments were calculated theoretically in this energy region. At 130 eV, direct double and triple ionization of the valence electrons may occur. The fragmentation increases and CHO(+) becomes one of the main cations in the mass spectrum. The molecular ion is still the dominant species, but other fragments, such as C6H5O(+), begin to present similar intensities. At 310 eV, C 1s electrons may be ionized and Auger processes give rise to dissociative doubly ionized cations. Ionization around the O 1s edge has been studied both at the 531 eV resonance and above the ionization edge. Resonant and normal Auger processes play a significant role in each case and a large fragmentation of the molecule is observed at both photon energies, with intense fragments such as CHO(+) and CH3 (+) being clearly observed. A near edge X-ray absorption fine structure spectrum of the vanillin molecule was obtained around the O 1s ionization threshold. In addition, the fragmentation of vanillin has also been studied using a fast beam of electrons (800 eV), for the sake of comparison.

UV absorption cross-sections of a series of dimethylbenzaldehydes.

The ultraviolet absorption cross-sections of 2,4-, 2,5-, 2,6-, 3,4- and 3,5- dimethylbenzaldehydes are reported in the wavelength range 240-320 nm. The measurements were carried out in the temperature range 318-363 K using two different experimental systems (D 2 lamp-monochromator and D 2 lamp-diode array). The absorption spectra of the five aldehydes have been found to exhibit relatively high absorption cross-sections in the region of the tropospheric interest with maxima around 290 nm. This work provides the first UV cross-section measurements for these aromatic aldehydes. The obtained cross-section values enable us to estimate the tropospheric photolysis lifetimes of these compounds. The results suggest that photolysis could be an important removal process for these species in the troposphere.

Development of an isothermal heat-conduction photocalorimeter.

Assessing photostability (particularly of pharmaceuticals) is of growing importance, but hampered by a lack of reliable, rapid experimental testing protocols and instrumentation. In particular, most approaches require irradiation of the sample separately from the analytical measurement, which increases both experimental complexity and the number of assumptions that must be made when calculating stability. One technique that may obviate this is photocalorimetry, principally because the reporter of change (heat) is measured directly as a sample is irradiated. Although not a new idea, the design challenges of photocalorimeters are complex, primarily because light power is being introduced to the calorimeter which can thus both saturate the amplifiers and swamp the response of the sample. Careful instrument design is thus paramount. The aim of this work was to develop a robust, compact, and easy to use photocalorimeter with the immediate focus of developing photostability assays for pharmaceuticals. The final instrument design, arrived at through a series of iterative design modifications, is based on a twin differential heat-conduction principle and achieves an average base line deflection of -0.04+/-0.11 microW with light irradiating the sample cell. The performance capabilities of the instrument were demonstrated using a model system; the photodegradation of 2-nitrobenzaldehyde in solution.

The stereoselectivity of the Paternò-Büchi reaction between tertiary 2-furylmethanol derivatives and aromatic carbonyl compounds: on the nature of the hydroxy directing effect.

The photochemical reaction of 1-(2-furyl)-1-phenylethanol with benzaldehyde gave a mixture of regioisomeric products. The adduct obtained on the more hindered side of the molecule was obtained with complete diastereoselectivity. The same substrate with benzophenone gave only one product with a diastereoisomeric excess of 48%. The reaction of 2-(2-furyl)-3,3-dimethylbutan-2-ol with benzaldehyde and benzophenone gave the corresponding adducts on the more hindered side of the molecule with diastereoisomeric excesses of 42 and 71%, respectively. These results, and also those obtained using 2-furylphenylmethanol with benzophenone and acetone (complete diastereoselectivity and absence of diastereoselectivity, respectively), were explained assuming the attack of the excited carbonyl compound on the same side as the hydroxy group, through the formation of a hydrogen bond or of a complex. This type of attack gave the biradical intermediate in preferential conformations. The relative energies of these conformers account for the observed diastereoselectivity.