Thermodynamic Investigation of the Micellization and the Adsorption of Short Perfluoroalkylated Diols via Fluorescence Spectroscopy and Tensiometry

The micellization and adsorption of two short chain perfluorodiols 3,3,4,4,5,5,6,6,6-nonafluorohexane-1,2-diol (nFHD) and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1,2-diol (tFOD) are examined from a thermodynamic point of view as a function of temperature and methanol content. The microenvironment of the fluorinated aggregates is evaluated by the fluorescence probe method using pyrene and a molecular rotor 1,1-dicyano-4-p-dimethylaminophenyl)-1,3-butadiene (DMAPhC). The formation of micellar aggregates being evidenced, the results are discussed in terms of the polarity and of the cohesion behavior of the micellar aggregates by taking into account the methanol (MeOH) effect. The critical micellization concentrations thus determined are compared with those given by surface tension measurements. Micellar and adsorption thermodynamic parameters such as Gibbs free energies, enthalpies, and entropies are determined together with the surface areas. The results are compared with literature data and discussed. A model for describing the adsorption process of the fluorinated compounds upon the influence of methanol is finally proposed. Copyright 2001 Academic Press.     

Paired hydrogen bonds in the hydrogen halide homodimer (HI)2

The HI homodimer was found to have structural and vibrational properties unlike any other previously studied (HX)(2) system, with X = F, Cl, and Br. The infrared spectrum of (HI)(2) is also observed to be distinctly different from the other members of the series. In addition, the interaction energy of the (HI)(2) dimer has been calculated using the coupled-cluster with singles, doubles, and perturbative triples [CCSD(T)] level of theory. A four-dimensional morphed intermolecular potential has been generated and then morphed using available near infrared and submillimeter spectroscopic data recorded in supersonic jet expansions. The morphed potential is found to have a single global minimum with a symmetric structure having C(2h) symmetry. The equilibrium dissociation energy is found to be 359 cm(-1) with the geometry in Jacobi coordinates of R(e) = 4.35 A?, θ(1) = 43°, θ(2) = 137°, and φ = 180°. The infrared spectrum is characterized by pairs of excited vibrational states resulting from the coupling of the two HI stretching modes. A qualitative model using a quadratic approximation has been fitted to obtain an estimate of this coupling. Furthermore, a morphed intermolecular potential for the vibrationally excited system was also obtained that gives a quantitative estimate of the shift in the potential due to the excitation. The submillimeter analysis is consistent with a ground state having its highest probability as a paired hydrogen bond configuration with R(0) = 4.56372(1) A? and an average angle θ=cos(-1)((1/2)) = 46.40(1)° (between the diatom center of mass∕center of mass axis and direction of each component hydrogen iodide molecule). On monodeuteration, however, the ground state is predicted to undergo an anomalous structural isotope change to an L-shaped HI-DI structure with highest probability at R(0) = 4.51 A?, θ(1) = 83°, θ(2) = 177°, and φ = 180°. These results provide a test for large scale ab initio calculations and have implications for the interpretation of photoinduced chemistry and other properties of the dimer.     

Synthesis and pharmacological evaluation of N-substituted 4,6-diaryl-3-pyridazinones as analgesic, antiinflammatory and antipyretic agents

The synthesis and the pharmacological evaluation of 19 new 4,6-diaryl-3-pyridazinones are reported. All compounds were screened for analgesic, antiinflammatory and antipyretic activities. Introduction of an arylpiperazinomethyl moiety in the 2-position of the pyridazinone ring resulted in the most potent activities. Compounds 2a, 2b, 2h and 2i exhibited a higher analgesic activity than did aspirin or noramidopyrine in the hot plate test.     

Ab initio and experimental studies of the large-amplitude motion in BF2OH

The ground state rotational spectrum of BF2OH was measured under high resolution by microwave Fourier transform spectroscopy (FTMW), and the small torsional splitting could be resolved for several lines. This splitting was analyzed using a phenomenological model previously developed for HNO3 [Coudert and Perrin, J. Mol. Spectrosc. 1995, 172, 352] and with the help of the geometries of the stationary points calculated ab initio. The torsional splitting was also calculated using the results of the calculations for the ground vibrational state, for the excited OH torsional states 91 and 92, and for the excited BOH bending state 41, and a satisfactory agreement with available experimental data was found.     

Local mode behavior in H(2)Te

A high-resolution spectrum of hydrogen telluride (H(2)Te) was recorded in the 4050-7000 cm(-1) region. Two bands could be observed at 4900 and 5980 cm(-1) and were assigned as the (20(+/-),1) <-- (00(+),0) and (30(+/-),0) <-- (00(+),0) bands, respectively. Rotational transitions of the two bands were assigned for the most abundant H(2) (130)Te and H(2) (128)Te isotopic species. Line position analyses were carried out to investigate a possible local mode behavior. For the first time we found in H(2)Te strong experimental evidence for such a behavior for the higher-lying band as its two upper vibrational states are only 0.027 and 0.032 cm(-1) apart for the H(2) (130)Te and H(2) (128)Te isotopic species, respectively.     

Electric Arc Fluctuations in DC Plasma Spray Torch

Direct current plasma torches for plasma spraying applications generate electric arc instabilities. The resulting fluctuations of input electrical power hamper a proper control of heat and momentum transfers to materials for coating deposition. This paper gives an overview of major issues about arc instabilities in conventional DC plasma torches. Evidences of arc fluctuations and their consequences on plasma properties and on material treatments are illustrated. Driving forces applied to the arc creating its motion are described and emphasis is put on the restrike mode that depends on the arc reattachment and the boundary layer properties around the arc column. Besides the arc root shown as a key region of instability, the Helmholtz oscillation is also described and accounts for the whole plasma torch domain that can generate pressure fluctuations coupled with voltage ones.     

Predicting mixture coadsorption in soft porous crystals: experimental and theoretical Study of CO2/CH4 in MIL-53(Al)

We present a synergistic experimental and theoretical study of CO(2)/CH(4) mixture coadsorption in breathing metal-organic framework MIL-53(Al). Mixture adsorption experiments were performed and their results were analyzed by comparing them to predictions made from pure-component adsorption data using the Osmotic Framework Adsorption Solution Theory (OFAST). This analytical model, fully validated for the first time, was then used to predict coadsorption properties as a function of temperature, pressure, and mixture composition. The phase diagrams obtained show a surprising non-monotonic behavior.     

Out-of-plane Testing Procedure for Inverse Identification Purpose: Application in Sheet Metal Plasticity

Many recent works in inverse identification of constitutive parameters have pointed to the need of tests which exhibit heterogeneous strain paths. The present study details a new testing procedure based on out-of-plane motion capture by Stereo-Image Correlation (SIC). With the original test proposed hereby, a unique sample is deformed on a tensile machine along two perpendicular tensile directions, two perpendicular shear directions and one expansion area. The choice of the sample shape is discussed along with the stereo imaging device, 3D reconstruction and measurement uncertainties. The test sample is made from a sheet of commercially pure titanium. A Finite-Element updating inverse method is applied in order to identify six parameters of an anisotropic plastic constitutive model. Results show that this new testing procedure allows every constitutive parameter of the model to be identified from one and only one test.     

A Computational and Experimental Approach Linking Disorder,High‐Pressure Behavior,and Mechanical Properties in UiO Frameworks

Whilst many metal–organic frameworks possess the chemical stability needed to be used as functional materials, they often lack the physical strength required for industrial applications. Herein, we have investigated the mechanical properties of two UiO‐topology Zr‐MOFs, the planar UiO‐67 ([Zr₆O₄(OH)₄(bpdc)₆], bpdc: 4,4′‐biphenyl dicarboxylate) and UiO‐abdc ([Zr₆O₄(OH)₄(abdc)₆], abdc: 4,4′‐azobenzene dicarboxylate) by single‐crystal nanoindentation, high‐pressure X‐ray diffraction, density functional theory calculations, and first‐principles molecular dynamics. On increasing pressure, both UiO‐67 and UiO‐abdc were found to be incompressible when filled with methanol molecules within a diamond anvil cell. Stabilization in both cases is attributed to dynamical linker disorder. The diazo‐linker of UiO‐abdc possesses local site disorder, which, in conjunction with its longer nature, also decreases the capacity of the framework to compress and stabilizes it against direct compression, compared to UiO‐67, characterized by a large elastic modulus. The use of non‐linear linkers in the synthesis of UiO‐MOFs therefore creates MOFs that have more rigid mechanical properties over a larger pressure range.