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111.
112.
Milhazes N Martins P Uriarte E Garrido J Calheiros R Marques MP Borges F 《Analytica chimica acta》2007,596(2):231-241
A complete physicochemical characterisation of MDMA and its synthetic precursors MDA, 3,4-methylenedioxybenzaldehyde (piperonal) and 3,4-methylenedioxy-β-methyl-β-nitrostyrene was carried out through voltammetric assays and Raman spectroscopy combined with theoretical (DFT) calculations. The former provided important analytical redox data, concluding that the oxidative mechanism of the N-demethylation of MDMA involves the removal of an electron from the amino-nitrogen atom, leading to the formation of a primary amine and an aldehyde. The vibrational spectroscopic experiments enable to afford a rapid and reliable detection of this type of compounds, since they yield characteristic spectral patterns that lead to an unequivocal identification.Moreover, the rational synthesis of the drug of abuse 3,4-methylenedioxymethamphetamine (MDMA or “ecstasy”) from one of its most relevant precursors 3,4-methylene-dioxyamphetamine (MDA), is reported. In addition, several approaches for the N-methylation of MDA, a limiting synthetic step, were attempted and the overall yields compared. 相似文献
113.
The influence of lattice water in the magnetic properties of spin-crossover [Fe(bpp)2]X2.nH2O salts [bpp = 2,6-bis(pyrazol-3-yl)pyridine] is well-documented. In most cases, it stabilizes the low-spin state compared to the anhydrous compound. In other cases, it is rather the contrary. Unraveling this mystery implies the study of the microscopic changes that accompany the loss of water. This might be difficult from an experimental point of view. Our strategy is to focus on some salts that undergo a nonreversible dehydration-hydration process without loss of crystallinity. By comparison of the structural and magnetic properties of original and rehydrated samples, several rules concerning the role of water at the microscopic level can be deduced. This paper reports on the crystal structure, thermal studies, and magnetic properties of [Fe(bpp)2][Cr(bpy)(ox)2]2.2H2O (1), [Fe(bpp)2][Cr(phen)(ox)2]2.0.5H2O.0.5MeOH (2), and [Fe(bpp)2][Cr(phen)(ox)2]2.5.5H2O.2.5MeOH (3). Salt 1 contains both high-spin (HS) and low-spin (LS) Fe2+ cations in a 1:1 ratio. Dehydration yields the anhydrous spin-crossover compound with T1/2 downward arrow = 353 K and T1/2 upward arrow = 369 K. Rehydration affords the dihydrate [Fe(bpp)2][Cr(bpy)(ox)2]2.2H2O (1r) with 100% HS Fe2+ sites. Salt 2 also contains both HS and LS Fe2+ cations in a 1:1 ratio. Dehydration yields the anhydrous spin-crossover compound with T1/2 downward arrow = 343 K and T1/2 upward arrow = 348 K. Rehydration affords [Fe(bpp)2][Cr(phen)(ox)2]2.0.5H2O (2r) with 72% Fe2+ sites in the LS configuration. The structural, magnetic, and thermal properties of these rehydrated compounds 1r and 2r are also discussed. Finally, 1 has been dehydrated and resolvated with MeOH to give [Fe(bpp)2][Cr(bpy)(ox)2]2.MeOH (1s) with 33% HS Fe2+ sites. The influence of the guest solvent in the Fe2+ spin state can anticipate the future applications of these compounds in solvent sensing. 相似文献
114.
Clemente-León M Ito T Yashiro H Yamase T Coronado E 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):4042-4047
Langmuir monolayers and LB films of the ring-shaped mixed-valence polyoxomolybdate [Mo142O429H10(H2O)49(CH3CO2)5(CH3CH2CO2)](30-) (Mo142) dissolved in the aqueous subphase have been successfully fabricated by using the adsorption properties of a DODA monolayer. Infrared and ultraviolet-visible spectroscopy of the LB films indicates that Mo142 and DODA molecules are incorporated within these LB films. X-ray reflectivity experiments indicate that the LB films exhibit a well-defined lamellar structure formed by bilayers of DODA molecules alternating with monolayers of Mo142. Using behenic acid-modified hydrophobic quartz substrate is critical for the formation of the well-defined lamellar structure. From the values of the periodicity obtained by these experiments it is clear that the Mo142 clusters lie flat along the charged organic layers. AFM images also showed the flat and homogeneous films on the quartz substrates treated with behenic acid. Cyclic voltammograms of Mo142-LB films deposited on ITO substrates showed quasi-reversible oxidation/reduction waves with positive shift of the potential compared to the case of solution. 相似文献
115.
Domenico Acierno Eugenio Amendola Simona Concilio Pio Iannelli Antonio Massa Paola Scarfato 《Macromolecular Symposia》2002,180(1):61-72
The use of the same thermoplastic polymer for both the matrix and the filler in the preparation of composites is very attractive, because such composites are in principle fully recyclable. Recently it has been reported the preparation of a mono-material composite (MMC) made of polypropylene to be used in automobile parts. In this work we report on the preparation and characterization of matrices for quasi MMC made of poly(ethylene terephthalate) (PET). Particularly we found PET copolymers containing isophthalate (IPA) units adequate to be used as matrix. 相似文献
116.
In a previous paper a general procedure for deriving stabilized finite element schemes for advective type problems based on invoking higher order balance laws over finite size domains was presented. This provides an expression for the element stabilization parameter in terms of the solution residual and its first derivatives in a kind of iterative or adaptative manner. Details of the application of this procedure to 1D and 2D advective–diffusive problems are given. Some examples of applications showing the potential of the new approach are presented. © 1997 John Wiley & Sons, Ltd. 相似文献
117.
Miguel Clemente-Len Hlne Soyer Eugenio Coronado Christophe Mingotaud Carlos J. Gmez-García Pierre Delhas 《Angewandte Chemie (International ed. in English)》1998,37(20):2842-2845
Magnetic Langmuir–Blodgett films containing well-organized monolayers of single-molecule magnets are reported. The single-molecule magnets in question are high-spin molecular clusters of the type [Mn12O12(carboxylate)16]. The structure of such multilayered inorganic–organic composites is depicted schematically in the figure. 相似文献
118.
Claudia Filoni Bahram Shirzadi Marco Menegazzo Eugenio Martinelli Corrado Di Natale Andrea Li Bassi Luca Magagnin Lamberto Du Gianlorenzo Bussetti 《Molecules (Basel, Switzerland)》2021,26(23)
Flexible and economic sensor devices are the focus of increasing interest for their potential and wide applications in medicine, food analysis, pollution, water quality, etc. In these areas, the possibility of using stable, reproducible, and pocket devices can simplify the acquisition of data. Among recent prototypes, sensors based on laser-induced graphene (LIGE) on Kapton represent a feasible choice. In particular, LIGE devices are also exploited as electrodes for sensing in liquids. Despite a characterization with electrochemical (EC) methods in the literature, a closer comparison with traditional graphite electrodes is still missing. In this study, we combine atomic force microscopy with an EC cell (EC-AFM) to study, in situ, electrode oxidation reactions when LIGE or other graphite samples are used as anodes inside an acid electrolyte. This investigation shows the quality and performance of the LIGE electrode with respect to other samples. Finally, an ex situ Raman spectroscopy analysis allows a detailed chemical analysis of the employed electrodes. 相似文献
119.
Recent attempts to recover the graviton propagator from spin foam models involve the use of a boundary quantum state peaked on a classical geometry. The question arises whether beyond the case of a single simplex this suffices for peaking the interior geometry in a semiclassical configuration. In this paper we explore this issue in the context of quantum Regge calculus with a general triangulation. Via a stationary phase approximation, we show that the boundary state succeeds in peaking the interior in the appropriate configuration, and that boundary correlations can be computed order by order in an asymptotic expansion. Further, we show that if we replace at each simplex the exponential of the Regge action by its cosine—as expected from the semiclassical limit of spin foam models—then the contribution from the sign-reversed terms is suppressed in the semiclassical regime and the results match those of conventional Regge calculus. 相似文献
120.
André Romero da Silva Natalia Mayumi Inada Daniel Rettori Mariana Ozello Baratti Anibal Eugenio Vercesi Renato Atilio Jorge 《Journal of photochemistry and photobiology. B, Biology》2009,94(2):101-112
In(III)-meso-tetraphenylporphyrin (InTPP) was encapsulated into nanoparticles (smaller than 200 nm) of poly(d,l-lactide-co-glycolide) (PLGA) using the emulsification–evaporation technique. The photodynamic efficacy of InTPP-loaded nanoparticles and its cellular uptake was investigated with LNCaP prostate tumour cells, in comparison with the free InTPP. The effects of incubation time (1–3 h), drug concentration (1.8–7.7 μmol/L) and incident light dose (15–45 J/cm2) with both encapsulated and free InTPP were studied. The type of cell death induced by the photochemical process using both encapsulated and free InTPP was also investigated. Cell viability was reduced more significantly with increasing values of these effects for InTPP-loaded nanoparticles than with the free drug. The cellular death induced by both encapsulated and free InTPP was preponderantly apoptotic. Confocal laser scanning microscopy data showed that the InTPP-loaded nanoparticles, as well free InTPP, were localized in the cells, and always in the perinuclear region. Encapsulated InTPP was measured by the intensity of fluorescence intensity of cell extracts and was three times more internalized into the cells than was the free InTPP. Electron paramagnetic resonance experiments corroborated the participation of singlet oxygen in the photocytotoxic effect of nanoparticles loaded with InTPP. 相似文献