The effect of the nature of the organic solvent on the gamma radiolysis of cholesteric esters

The relative efficiency of various chlorinated compounds as solvents for color transition temperatures lowering due to radiolysis is shown to be due to the C-Cl bond strength in the solvent.     

5d early-transition-metal corroles: a trioxo-bridged binuclear tungsten(VI) derivative

The synthesis and full characterization of the first tungsten corrole reveal that it is a binuclear trioxo-bridged complex of tungsten(VI), a coordination motif without precedence for tungsten chelated by other ligands.     

The different behavior of rutile and anatase nanoparticles in forming oxy radicals upon illumination with visible light: an EPR study

Photoexcited TiO(2) has been found to generate reactive oxygen species, yet the precise mechanism and chemical nature of the generated oxy species especially regarding the different crystal phases remain to be elucidated. Visible light-induced reactions of a suspension of titanium dioxide (TiO(2)) in water were investigated using electron paramagnetic resonance (EPR) coupled with the spin-trapping technique. Increased levels of both hydroxyl (˙OH) and superoxide anion (˙O(2)(-)) radicals were detected in TiO(2) rutile and anatase nanoparticles (50 nm). The intensity of signals assigned to the ˙OH and ˙O(2)(-) radicals was larger for the anatase phase than that originating from rutile. Moreover, illumination with visible (nonUV) light enhanced ˙O(2)(-) formation in the rutile phase. Singlet oxygen was not detected in water suspension of TiO(2) neither in rutile nor in anatase nanoparticles, but irradiation of the rutile phase with visible light revealed a signal, which could be attributed to singlet oxygen formation. The blue part of visible spectrum (400-500 nm) was found to be responsible for the light-induced ROS in TiO(2) nanoparticles. The characterization of the mechanism of visible light-induced oxy radicals formation by TiO(2) nanoparticles could contribute to its use as a sterilization agent.     

On the normalization of a mass spectrum for comparison of two spectra

It is indicated that for comparison of two mass-spectra the normalization of each ion current should be done such that each spectrum will form a unit vector, i.e., SigmaXi2 = 1, where Xi are the various components of the mass spectrum.     

Oxygen atom transfer reactions from isolated (oxo)manganese(V) corroles to sulfides

A series of five free-base corroles were metalated and brominated to form 10 manganese(III) corroles. Two of the free-base corroles and six manganese(III) corroles were analyzed by X-ray crystallography, including one complex that may be considered a transition-state analogue of oxygen atom transfer (OAT) from (oxo)manganese(V) to thioansisole. Oxidation by ozone allowed for isolation of the 10 corresponding (oxo)manganese(V) corroles, whose characterization by (1)H and (19)F NMR spectroscopy and electrochemistry revealed a low-spin and triply bound manganese-oxygen moiety. Mechanistic insight was obtained by investigating their reactivity regarding stoichiometric OAT to a series of p-thioanisoles, revealing a magnitude difference on the order of 5 between the β-pyrrole brominated (oxo)manganese(V) corroles relative to the nonbrominated analogues. The main conclusion is that the (oxo)manganese(V) corroles are legitimate OAT agents under conditions where proposed oxidant-coordinated reaction intermediates are irrelevant. Large negative Hammett ρ constants are obtained for the more reactive (oxo)manganese(V) corroles, consistent with expectation for such electrophilic species. The least reactive complexes display very little selectivity to the electron-richness of the sulfides, as well as a non-first-order dependence on the concentration of (oxo)manganese(V) corrole. This suggests that disproportionation of the original (oxo)manganese(V) corrole to (oxo)manganese(IV) and (oxo)manganese(VI) corroles, followed by substrate oxidation by the latter complex, gains importance when the direct OAT process becomes progressively less favorable.     

Ion mobility spectrometry: a personal retrospective

With a background in mass spectrometric studies of gas-phase ion chemistry the atmospheric pressure technology of ion mobility spectrometry (IMS) presented me with challenges and opportunities. Fundamental studies of the parameters that influence the mobility of ions in a low electric field yielded insights about the effects of temperature, drift gas composition and the conformation of ions on the collision cross section. The inadequacy of current rigid-sphere, polarization limit and hard-core models to predict the mobility of ions particularly at low temperature and in heavy drift gases, led to inclusion of additional terms to the hard-core model to account for these effects. These studies eventually resulted in the two monographs entitled “Ion Mobility Spectrometry” and “Ion Mobility Spectrometry –Second Edition” co-authored with Prof. Gary Eiceman and published by Taylor & Francis, CRC Press in 1994 and 2005, respectively. Novel applications for biological and medical applications were developed on the basis of measurement of biogenic amines by IMS, in particular the rapid, accurate and inexpensive diagnosis of vaginal infections.     

Biogenic amines in bread as indicators of spoilage

Elevated levels of biogenic amines (trimethylamine, putrescine and cadaverine), measured by ion mobility spectrometry (IMS) were found in a sample of “dark rye” bread that had a pungent odor but not in other bread samples. The odorless breads included three types of rye bread, whole wheat, pita bread and a baguette. Sample preparation was simple and consisted of extraction of the biogenic amines into water followed by filtering the solution. The biogenic amines were measured from a single drop (50 μL) of the extract solution. The progress of spoilage was also monitored in the odorous and odorless “dark rye”. Volatile trimethylamine, readily monitored by IMS, was the main compound responsible for the offensive odor in the spoilt bread. The samples were classified by an automatic algorithm as “fresh”, “intermediate” or “spoilt” on the basis of the total biogenic amine level. Thus, we report the development of a fast and objective method to distinguish between spoilt bread and bread that is suitable for consumption.     

Interlacing multiplexing techniques for optical morphological correlation

We propose a novel approach to implement nonlinear morphological correlation. Previous implementation was based on a time sequential approach that consists on displaying different binary image decomposition in a joint transform correlator adding each joint power spectra sequentially. A second Fourier transformation of the sum of joint power spectra gives the correlation output. In this paper, we propose to interlace the different binary images into one single distribution. Then, we introduce the distribution in a conventional joint transform correlator. The correlation output gives the morphological correlation at a specific location. The advantage is important considering that no sequential approach is needed anymore, so the necessary number of correlations is reduced. Optical implementation results are provided.