Five-order-of-magnitude reduction of the triplet lifetimes of N-heterocycles by complexation to a trinuclear mercury complex

The complexation of N-methylcarbazole and N-methylindole by trimeric perfluoro-o-phenylene mercury (1), which can be readily observed in CH2Cl2 solution, leads to the formation of [1.N-methylindole] (2) and [1.N-methylcarbazole] (3) as solid adducts. The solid-state photoluminescence spectra of these adducts show intense emission bands attributed to monomer phosphorescence of N-methylindole and N-methylcarbazole, respectively, with microsecond lifetimes. Remarkably, the triplet lifetimes of the heterocycles in 2 and 3 are shortened by 5 orders of magnitude when compared to those of the free heterocycles. These results are rationalized by invoking the combined external and internal spin-orbit coupling perturbation provided by the mercury and nitrogen atoms.     

Biogenic Silver Nanoparticles from Iris tuberosa as Potential Preservative in Cosmetic Products

Biogenic-silver nanoparticles emerge as new nanosilver platforms that allow us to obtain silver nanoparticles via “green chemistry”. In our study, biogenic-silver nanoparticles were obtained from Iris tuberosa leaf extract. Nanoparticles were characterized by a UV-vis spectroscopy, dynamical light scattering technique. The transmission electron microscope revealed spheric and irregular nanoparticles with 5 to 50 nm in diameter. Antimicrobial properties were evaluated against typical microbial contaminants found in cosmetic products, showing high antimicrobial properties. Furthermore, natural moisturizing cream was formulated with biogenic-silver nanoparticles to evaluate the preservative efficiency through a challenge test, indicating its promising use as preservative in cosmetics.     

Improving accuracy and precision of strain analysis by energy-filtered nanobeam electron diffraction

This article deals with uncertainty in the analysis of strain in silicon nanoscale structures and devices using nanobeam electron diffraction (NBED). Specimen and instrument related errors and instabilities and their effects on NBED analysis are addressed using a nanopatterned ultrathin strained silicon layer directly on oxide as a model system. We demonstrate that zero-loss filtering significantly improves the NBED precision by decreasing the diffuse background in the diffraction patterns. To minimize the systematic deviations the acquired data were verified through a reliability test and then calibrated. Furthermore, the effect of strain relaxation by specimen preparation using a FIB is estimated by comparing profiles, which were acquired by analyzing slices of strained structures in a 220-nm-thick region of the sample (invasive preparation) and the entire strained nanostructures, which are embedded in a thicker region of the same sample (noninvasive preparation). Together with the random deviation, the corresponding systematic shift results in a total deviation of ～1 × 10(-3) for NBED analyses, which is employed to estimate the measurement uncertainty in the thinner sample region. In contrast, the strain in the thick sample region is not affected by the preparation; the systematic shift reduces to a minimum, which improves the total deviation by ～50%.     

Synthesis, structural characterization, and properties of chromium(III) complexes containing amidinato ligands and eta2-pyrazolato, eta(2)-1,2,4-triazolato, or eta1-tetrazolato ligands

Treatment of anhydrous chromium(III) chloride with 2 or 3 equivalents of 1,3-di-tert-butylacetamidinatolithium or 1,3-diisopropylacetamidinatolithium in tetrahydrofuran at ambient temperature afforded Cr(tBuNC(CH3)NtBu)2(Cl)(THF) and Cr(iPrNC(CH3)NiPr)3 in 78% and 65% yields, respectively. Treatment of Cr(tBuNC(CH3)NtBu)2(Cl)(THF) with the potassium salts derived from pyrazoles and 1,2,4-triazoles afforded Cr(tBuNC(CH3)NtBu)2(X), where X=3,5-disubstituted pyrazolato or 3,5-disubstituted 1,2,4-triazolato ligands, in 65-70% yields. X-Ray crystal structure analyses of Cr(tBuNC(CH3)NtBu)2(Me2pz) (Me2pz=3,5-dimethylpyrazolato) and Cr(tBuNC(CH3)NtBu)2(Me2trz) (Me2trz=3,5-dimethyl-1,2,4-triazolato) revealed eta2-coordination of the Me2pz and Me2trz ligands. Treatment of Cr(tBuNC(CH3)NtBu)2(Cl)(THF) with trifluoromethyltetrazolatosodium (NaCF3tetz) in the presence of 4-tert-butylpyridine afforded Cr(tBuNC(CH3)NtBu)2(CF3tetz)(4-tBupy) in 30% yield. An X-ray crystal structure determination showed eta1-coordination of the tetrazolato ligand through the 2-nitrogen atom. The complexes Cr(iPrNC(CH3)NiPr)3 and Cr(tBuNC(CH3)NtBu)2(X) are volatile and sublime with <1% residue between 120 and 165 degrees C at 0.05 Torr. In addition, these complexes are thermally stable at >300 degrees C under an inert atmosphere such as nitrogen or argon. Due to the good volatility and high thermal stability, these new compounds are promising precursors for the growth of chromium-containing thin films using atomic layer deposition.     

Temporal context and conditional associative learning

Background  

We investigated how temporal context affects the learning of arbitrary visuo-motor associations. Human observers viewed highly distinguishable, fractal objects and learned to choose for each object the one motor response (of four) that was rewarded. Some objects were consistently preceded by specific other objects, while other objects lacked this task-irrelevant but predictive context.     

Phases hexagonales colonnaires thermotrope et lyotrope : défauts observés par cryofracture et caractère anomal du thermotrope

Electron microscopy observations of replicas of freeze-fractured samples of two columnar hexagonal phases of different nature (a lyotropic one, the inverse AOT in water; a thermotropic one, ) yield very different results: most defects at microscopic scales are screw dislocations in the lyotropic phase, longitudinal edge dislocations in the thermotropic phase. A possible way to interpret these differences is as follows: in the lyotropic the Lamé coefficients and μ and the bend modulus K₃ would not display any anomaly compared to expected values; in the thermotropic the shear modulus μ would be ten times smaller than the compressibility modulus , while K₃ would still be comparable to (but larger than) the bend modulus of a small molecules liquid crystal. We present an elementary theoretical model of the latter case which could explain the anomalous measurements of K₃ and of the longitudinal compressibility (Ref. [#!ref10!#]) without contradicting more recent measurements of (Refs. [#!ref17!#,#!ref22!#]). Essentially, the hexagonal phase would be a phase with defects (longitudinal dislocations) akin to an hexatic phase but with some differences. Re?u : 26 mai 1997 / Révisé : 20 Janvier 1998 / Accepté : 27 avril 1998     

Analysis of Argan Oil Adulteration Using Infrared Spectroscopy

The determination of argan oil adulteration by other vegetable oils is a real analytical challenge. The authentication of argan oil needs fast and simple analytical techniques for quality control and testing. This study focuses on the detection and quantification of argan oil adulteration with different edible oils, using midinfrared spectroscopy with chemometrics. Chemometric treatment of MIR spectra has been assessed for the classification and quantification of argan oil adulteration with sunflower or soybean oils. The potential of MID spectroscopy combined with partial least squares regression (PLS) as a rapid analytical technique for the quantitative determination of adulterants in argan oil has been demonstrated. A PLS model has been established to predict the concentration of soybean and sunflower oil as adulterants in the calibration range between 0% and 30% (w/w) in argan oil with good prediction performances in the external validation.     

A spinorial characterization of hyperspheres

Let M be a compact orientable n-dimensional hypersurface, with nowhere vanishing mean curvature H, immersed in a Riemannian spin manifold ${\overline{M}}$ admitting a non trivial parallel spinor field. Then the first eigenvalue ${\lambda_1(D_{M}^{H})}$ (with the lowest absolute value) of the Dirac operator ${D_{M}^{H}}$ corresponding to the conformal metric ${\langle\;,\;\rangle^{H}=H^{2}\,\langle\;,\;\rangle}$ , where ${\langle\;,\;\rangle}$ is the induced metric on M, satisfies ${\left|\lambda_1(D_{M}^{H})\right|\le \frac{n}{2}}$ . By applying the Bourguignon-Gauduchon first variational formula, we obtain a necessary condition for ${\left|\lambda_1(D_{M}^{H})\right|=\frac{n}{2}}$ . As a consequence, we prove that round hyperspheres are the only hypersurfaces of the Euclidean space satisfying the equality in the Bär inequality $$\lambda_1(D_{M})^{2}\le \frac{n^{2}}{4{vol}(M)}\int_{M} H^{2}\, dV,$$ where D _M stands now for the Dirac operator of the induced metric.     

Realization and characterization of flexible supercapacitors based on doped graphene electrodes

Journal of Solid State Electrochemistry - High energy consumption leads to the development of various energy types. As a result, the storage of these different types of energy becomes a key issue....