Comparative Study of Influence of Experimental Configuration on Densities of Active Species in the Early Afterglows of N2/(0–2.5%)H2 HF Flowing Plasmas

Afterglows of mixed gas of N₂ and H₂(0–2.5%) flowing microwave discharges in a 5 mm diameter tube connected to a 5 L reactor via a tube of 1.8 cm diameter and 50 cm long, have been studied using optical emission spectroscopy. The obtained results at the entrance of the afterglow tube of 1.8 cm diameter: Short time afterglow (SA), (10^–3 s) and inside the 5 L reactor: Long time afterglow (LA), (10^–2 s) were then compared. It was found that, in N₂ at 2 Torr, 0.5 slpm, the active specie density ratios had a constant value of 10^–2 for N/N₂, but decreased respectively from 10^–3 to 10^–4 for N₂ (X,v?>?13)/N₂ and from 10^–6 to 10^–8 for N⁺₂ /N₂. By directly connecting the discharge tube inside the 5 L reactor, the density increases by 10 for N₂ (X,v?>?13) and by 10² for N₂⁺ by changing the afterglow from LA(10^?2 s) to a SA(10^–3 s). Moreover and by adding 1% of H₂ to N₂, the N/N₂ and H/H₂ ratios had constant values of 1% and 0.2% respectively. The SA(10^–3 s) appeared to be more efficient for surface treatments than the LA (10^–2 s).

     

Comprehensive Characterization of the Self-Folding Cavitand Dynamics

The conformational equilibria and guest exchange process of a resorcin[4]arene derived self-folding cavitand receptor have been characterized in detail by molecular dynamics simulations (MD) and ¹H EXSY NMR experiments. A multi-timescale strategy for exploring the fluxional behaviour of this system has been constructed, exploiting conventional MD and accelerated MD (aMD) techniques. The use of aMD allows the reconstruction of the folding/unfolding process of the receptor by sampling high-energy barrier processes unattainable by conventional MD simulations. We obtained MD trajectories sampling events occurring at different timescales from ns to s: 1) rearrangement of the directional hydrogen bond seam stabilizing the receptor, 2) folding/unfolding of the structure transiting partially open intermediates, and 3) guest departure from different folding stages. Most remarkably, reweighing of the biased aMD simulations provided kinetic barriers that are in very good agreement with those determined experimentally by ¹H NMR. These results constitute the first comprehensive characterization of the complex dynamic features of cavitand receptors. Our approach emerges as a valuable rational design tool for synthetic host-guest systems     

Data fusion methodologies for food and beverage authentication and quality assessment – A review

The ever increasing interest of consumers for safety, authenticity and quality of food commodities has driven the attention towards the analytical techniques used for analyzing these commodities. In recent years, rapid and reliable sensor, spectroscopic and chromatographic techniques have emerged that, together with multivariate and multiway chemometrics, have improved the whole control process by reducing the time of analysis and providing more informative results. In this progression of more and better information, the combination (fusion) of outputs of different instrumental techniques has emerged as a means for increasing the reliability of classification or prediction of foodstuff specifications as compared to using a single analytical technique. Although promising results have been obtained in food and beverage authentication and quality assessment, the combination of data from several techniques is not straightforward and represents an important challenge for chemometricians. This review provides a general overview of data fusion strategies that have been used in the field of food and beverage authentication and quality assessment.     

Preparation of a new lightly cross-linked liquid crystalline polyamide by interfacial polymerization. Application to the obtainment of microcapsules with photo-triggered release

Microcapsules based on a new liquid crystalline lightly cross-linked polyamide, in which the state of order can be triggered by means of external stimuli, such as temperature and light, were prepared by interfacial polymerization. This polyamide exhibited a nematic phase up to 166 °C and it started to decompose at 340 °C; morphological variations of the film were observed by Scanning Electron Microscopy in correspondence to the clearing temperature; moreover, by continuous irradiation with UV light at room temperature, the polymer underwent E–Z photoisomerization. The prepared microcapsules contained either toluene, or concentrated solutions of naphthalene or β-carotene, as the core; in all cases, their outer surface appeared smooth and dense, while heterogeneities could be seen on the inner face. Capsule diameter lay in the range 30–120 μm, depending on the encapsulated material, with quite narrow size distributions. To the authors’ knowledge, this is the first example of microcapsules whose shell is completely constituted by a liquid crystalline lightly cross-linked polymer. Release experiments of β-carotene were performed in water and in tetrahydrofuran. β-Carotene release in water at 20 °C was strongly influenced by UV irradiation: in the absence of irradiation, it was practically negligible while, when microcapsules were submitted to continuous irradiation with UV light, β-carotene was quickly released and reached 100% release after 5 min. Preliminary experiments concerning the effect of temperature and of a swelling solvent, such as THF, on release, were also performed.     

Turing Instabilities at Hopf Bifurcation

Turing–Hopf instabilities for reaction-diffusion systems provide spatially inhomogeneous time-periodic patterns of chemical concentrations. In this paper we suggest a way for deriving asymptotic expansions to the limit cycle solutions due to a Hopf bifurcation in two-dimensional reaction systems and we use them to build convenient normal modes for the analysis of Turing instabilities of the limit cycle. They extend the Fourier modes for the steady state in the classical Turing approach, as they include time-periodic fluctuations induced by the limit cycle. Diffusive instabilities can be properly considered because of the non-catastrophic loss of stability that the steady state shows while the limit cycle appears. Moreover, we shall see that instabilities may appear even though the diffusion coefficients are equal. The obtained normal modes suggest that there are two possible ways, one weak and the other strong, in which the limit cycle generates oscillatory Turing instabilities near a Turing–Hopf bifurcation point. In the first case slight oscillations superpose over a dominant steady inhomogeneous pattern. In the second, the unstable modes show an intermittent switching between complementary spatial patterns, producing the effect known as twinkling patterns.     

Persistent spectral hole-burning in a -doped aluminosilicate glass from 8 to 295 K: Study of the burning and refilling kinetics, and of optical dephasing

High-temperature persistent spectral hole-burning (PSHB), up to room temperature, has been observed in a Eu ³⁺ -doped aluminosilicate glass using a high peak-power nanosecond dye laser. Spontaneous refilling as well as thermal cycling measurements show that at least two mechanisms, a fast and a slow one, are involved in our sample. We suggest that the fast or “easy” component may correspond to a non-photochemical local rearrangement of the host or to photoreduction of the Eu ³⁺ ions and that the second one leading to very stable photoproducts may correspond to transfer of an electron over a sizable distance through a several-step process. The mechanisms we suggest agree with light-induced hole refilling measurements. Line broadening mechanisms are discussed and the temperature-dependent part of the homogeneous width and of the spectral shift is interpreted in terms of a two-phonon (Raman) process involving pseudo-local phonons. Received 28 July 1999     

Temporal evolution of radionuclides in sludge from wastewater treatment plants

22 sludge samples were analyzed from three municipal wastewater treatment plants to assess both the occurrence and the temporal behavior of radioactivity during 8 sampling campaigns carried out over the period 2007–2009. As regards natural gamma emitters radionuclides from the natural ²³⁸U series (such as ²³⁴Th, ²¹⁴Pb, ²¹⁴Bi, ²¹⁰Pb) and the ²³²Th series (such as ²²⁸Ac, ²¹²Pb, ²¹²Bi and ²⁰⁸Tl) and other natural gamma emitters such as ⁷Be, ²¹⁰Pb_u or ⁴⁰K were measured. In the case of man-made radionuclides small amounts of ¹³⁷Cs were found, while significant amounts of ¹³¹I were detected in some samples. Correlations were found between radionuclides with the same origin. No seasonal variation for the ²³⁸U and ²³²Th series was found in the studied period but ⁷Be and ²¹⁰Pb_u showed seasonal variation that was explained by the monthly rainfall. The internal and external hazard indices were calculated and the results indicate that the radiological characteristics of the sludge do not present a significant radiological risk and make them suitable for future applications.     

Modulating the Photochemistry of Bipyridylic Compounds by Symmetric Substitutions

A quantum electronic study of the effect of substituents on (2,2′‐bipyridyl)‐3,3′‐diol and (2,2′‐bipyridyl)‐3,3′‐diamine is presented. A large difference in the photochemical behavior between the original and the substituted selected systems is expected. For the sake of simplicity, the study is restricted to the symmetrically bi‐substituted compounds: fluorine, the more electronegative atom and thus a strong σ‐acceptor but also a weak π‐donor group, and NO₂, a strong π‐acceptor substituent. Among the large set of compounds studied, two receive special attention: 5,5′‐dinitro‐(2,2′‐bipyridyl)‐3,3′‐diamine and 6,6′‐difluoro‐(2,2′‐bipyridyl)‐3,3′‐diol. While in the former case the nitro substitution transforms (2,2′‐bipyridyl)‐3,3′‐diamine, previously suggested to behave as a photomemory material, into a simple fluorescent species, the latter substitution turns (2,2′‐bipyridyl)‐3,3′‐diol into a fresh new candidate for a photomemory device.