Modeling Tomato Ripening Based on Carotenoid Raman Spectroscopy: Experimental Versus Kinetic Model.

This work reports on a combined experimental and theoretical investigation on the carotenoid Raman signal in several tomato fruits during their postharvest time evolution and ripening. Both resonant (180°) backscattering and polarized (90°) Raman scattering were used to monitor the most prominent bands of carotenoid (lycopene and ß-carotene) evolution in different tomato varieties. Relevant findings of the present investigations were that while the depolarization ratio of the ν1 band hardly changed with time, the Raman ν1 band intensity did change showing a similar pattern for all tomatoes investigated. Indeed, all cases investigated revealed a rise of the carotenoid signal coincident with the onset of the turning stage of the fruit ripening, a pronounced maximum of the Raman signal followed by a post-maximum decline at the red ripening stage. A kinetic model has been developed to describe the time evolution of the observed Raman signatures based on the rate coefficient of the carotenoid synthesis and the time evolution of the scattering coefficient of the fruit. The model describes satisfactorily the tomato evolution through the distinct ripening stages providing new insight on the assessment of the postharvest fruit control and quality.

Radio-frequency ion deflector for mass separation.

Electrostatic cylindrical deflectors act as energy analyzer for ion beams. In this article, we present that by imposing of a radio-frequency modulation on the deflecting electric field, the ion transmission becomes mass dependent. By the choice of the appropriate frequency, amplitude, and phase, the deflector can be used as mass filter. The basic concept of the new instrument as well as simple mathematic relations are described. These calculations and further numerical simulations show that a mass sensitivity is achievable. Furthermore, we demonstrate the proof-of-principle in experimental measurements, compare the results to those of from a 1 m linear time-of-flight spectrometer, and comment on the mass resolution of the method. Finally, some potential applications are indicated.

Linear Polarized Transmission Resonance Raman Studies in Fruits: Experimental Versus Model Calculations.

A linear polarized transmission resonance Raman spectroscopic technique was developed to measure the depolarization ratio of different ß-carotene Raman bands in carrot roots and mangos. Basically, this optical property was measured as a function of the vegetal tissue thickness and fruit postharvest lifetime. In general, the depolarization ratio increases as the sample optical thickness does and decreases as the fruit postharvest lifetime increases. In addition, a previous theoretical model was extended by considering the light state of polarization to obtain the depolarization ratio as a function of the sample absorption and scattering coefficient. It was shown how the reported theoretical model is able to satisfactorily describe the fruit optical parameter dependence on both the sample thickness and its postharvest time. Finally, the advantages and limitations of the present technique and theoretical mode are discussed.

Transmission resonance Raman spectroscopy: experimental results versus theoretical model calculations.

A laser spectroscopic technique is described that combines transmission and resonance-enhanced Raman inelastic scattering together with low laser power (< 30 mW) and good spatial resolution (< 200 µm) as operational features. The monitoring of the transmitted inelastic scattering provides an increased signal-to-noise ratio because the low fluorescence background and, on the other hand, the resonant character of the laser excitation, leads to enhanced analytical sensitivity. The spectroscopic technique was applied to investigate the carotenoid content (specifically the ß-carotene concentration) of distinct samples that included fruits, reaching a detection limit of the order of hundreds of picograms in solid samples, which is below the level needed for typical food control analysis. Additional features of the present development are direct sampling, noninvasive character, and fast analysis that is not time consuming. From a theoretical point of view, a model for the Raman signal dependence on the sample thickness is also presented. Essentially, the model considers the sample to be homogeneous and describes the underlying physics using only three parameters: the Raman cross-section, the laser-radiation attenuation cross-section, and the Raman signal attenuation cross-section. The model was applied successfully to describe the sample-size dependence of the Raman signal in both ß-carotene standards and carrot roots. The present technique could be useful for direct, fast, and nondestructive investigations in food quality control and analytical or physiological studies of animal and human tissues.

Spectroscopy and kinetics of tyrosinase catalyzed trans-resveratrol oxidation.

The spectroscopy and kinetics of the tyrosinase catalyzed trans-resveratrol oxidation were investigated by measuring both UV-vis absorption spectra over the 200-500 nm range and Raman spectra over the 600-1800 cm(-1) region. Room temperature UV-vis absorption spectra, as a function of time, showed the presence of two isosbestic points located at λ(1) = 270 nm and λ(2) = 345.5 nm delimiting two different regions: the reactant region around 300 nm, where the absorption decreased with time, and the product region over the low wavelength (λ < 260 nm) and high wavelength (λ > 390 nm) wavelength zone in which the absorption increased with time until, in both cases, constant values were achieved. A first-order kinetics was deduced with a rate coefficient of k(1) = (0.10 ± 0.001) min(-1), which turned out to be independent of substrate concentration over the 50-5 µM range; a feature that was rationalized by invoking the limiting case of the Michaelis-Menten scheme appropriate for substrate concentration much lower than the respective Michaelis constant. The observation of the distinct resonance enhanced Raman lines, specifically those peaking at 830 cm(-1), 753 cm(-1), and 642 cm(-1) together with their time evolution, permitted us to gain insight into some crucial features and steps of the catalytic reaction. Namely, that the formation of the so-called trans-resveratrol and tyrosinase (S)P complex with its O-O bridge plays a crucial role in the first steps of this enzymatic reaction and that the hydroxylation of the ortho C-H bond of the trans-resveratrol OH group occurs after O-O bond cleavage in the tyrosinase active site. The present study makes clear that a class of potential inhibitors of tyrosinase can be found in compounds able to bind the two Cu (II) ions of the enzyme bidentate form.