VSCF in internal coordinates and the calculation of anharmonic torsional mode transitions

The vibrational self-consistent field (VSCF) method assumes separability in normal modes in its usual version. However, the method fails in cases such as soft torsional modes which are better treated by angular variables. We develop VSCF equations based on the assumption of wave function separability in internal coordinates. To test the method, simple illustrative applications to small systems are provided: trans-HONO, cis-HONO, H₂S₂, and H₂O₂. The code directly uses points from ab initio calculations, and the method proves to be accurate for all types of transitions. For typical torsional transitions, the error in the computed frequency is smaller than that of VSCF in normal coordinates. The wave functions for the torsional mode are compared with the corresponding normal mode wave functions. The differences are substantial. The results are encouraging for extension of the model for large polyatomic systems. Work along these lines is in progress.     

Determination of pesticide residues in peaches by using gas chromatography and mass spectrometric detection

ABSTRACT

A multi-residue method using selected ion monitoring mode GC-MSD has been developed for the quantitative analysis of 30 widely used pesticides in fresh peaches produced in Swat Malakand, Pakistan. The planned methodology involved a sample extraction procedure using liquid-liquid partition with acetonitrile followed by a clean-up step based on solid-phase extraction (SPE). Method validation was performed in accordance with European Union guidelines. The European Union criteria (recovery 70–120%, RSD <20%) were met for majority of pesticides. For most of the pesticides, signal-to-noise ratios were good and background-corrected mass spectra often contained sufficient diagnostic to enable identity and confirmation. The limits of quantification (LOQs) were in the range 0.01–1.0 mg/kg. The above method was successfully applied to the analysis of peach samples (n = 30) from the field. Pesticide concentration in real peach samples was compared with the maximum residue levels (MRLs). Pesticide residues were detected in 73% of the peach samples. Most frequent residues were metalaxyl, α-cypermethrin, azoxystrobin, dimethoate, tebuconazol, λ-cyhalothrin and spiromesifin in peach samples.     

Pump-limited, 203 W, single-frequency monolithic fiber amplifier based on laser gain competition

We present high power results of a Yb-doped fiber amplifier seeded with a combination of broad and single-frequency laser signals. This two-tone concept was used in conjunction with externally applied or intrinsically formed thermal gradients to demonstrate combined stimulated Brillouin scattering suppression in a copumped monolithic, polarization-maintaining (PM) fiber. Depending on the input parameters and the thermal gradient, the output power of the single-frequency signal ranged from 80 to 203?W with slope efficiencies from 70% to 80%. The 203?W amplifier was pump limited and is, to the best of our knowledge, the highest reported in the literature for monolithic, PM single-frequency fiber amplifiers.     

Tether-Directed Regioselective Synthesis of an Equatorialface Bisadduct of Azafullerene Using Cyclo-[2]-octylmalonate

Bisazafullerene (C₅₉N)₂ has been functionalized under aerobic conditions with cyclo-[2]-octylmalonate through a Mannich-type reaction, furnishing the corresponding monoadduct. A regioselective tether-directed Bingel cyclopropanation reaction was then carried out on the azafullerene core to yield a single bisadduct. Spectroscopic analysis of the formed bisadduct showed it to have a C₁ symmetrical structure, making it inherently chiral. Single-crystal X-ray analysis revealed the addition pattern of the azafullerene bisadduct to be equatorial_face. Examination of the optical properties showed the evolution of new absorption bands, which can be used as signatures for the characterization of equatorial_face bisadducts of C₅₉N. Finally, redox assays showed that the LUMO level of the equatorial_face bisadduct was increased compared to that of the parent (C₅₉N)₂.     

A probabilistic mechanical model for prediction of aggregates’ size distribution effect on concrete compressive strength

To predict aggregates’ size distribution effect on the concrete compressive strength, a probabilistic mechanical model is proposed. Within this model, a Voronoi tessellation of a set of non-overlapping and rigid spherical aggregates is used to describe the concrete microstructure. Moreover, aggregates’ diameters are defined as statistical variables and their size distribution function is identified to the experimental sieve curve. Then, an inter-aggregate failure criterion is proposed to describe the compressive-shear crushing of the hardened cement paste when concrete is subjected to uniaxial compression. Using a homogenization approach based on statistical homogenization and on geometrical simplifications, an analytical formula predicting the concrete compressive strength is obtained. This formula highlights the effects of cement paste strength and aggregates’ size distribution and volume fraction on the concrete compressive strength. According to the proposed model, increasing the concrete strength for the same cement paste and the same aggregates’ volume fraction is obtained by decreasing both aggregates’ maximum size and the percentage of coarse aggregates. Finally, the validity of the model has been discussed through a comparison with experimental results (15 concrete compressive strengths ranging between 46 and 106 MPa) taken from literature and showing a good agreement with the model predictions.     

Novel lanthanum sulfide–decorated zirconia nanohybrid for enhanced electrochemical oxygen evolution reaction

Journal of Solid State Electrochemistry - Metal sulfide and oxides have drawn interest as economical substitutes to noble metal catalysts due to their ability for oxygen evolution reaction (OER)...     

Facile synthesis of scheelite-type NdOsO4 directly grown on carbon cloth for oxygen evolution reaction

Journal of Solid State Electrochemistry - In the recent work, the scheelite-type ABO4&nbsp;compound (A = Nd and B = Os) is synthesized via a hydrothermal route directly...     

Complementary Site-Selective Halogenation of Nitrogen-Containing (Hetero)Aromatics with Superacids

Site-selective functionalization of arenes that is complementary to classical aromatic substitution reactions remains a long-standing quest in organic synthesis. Exploiting the generation of halenium ion through oxidative process and the protonation of the nitrogen containing function in HF/SbF₅, the chlorination and iodination of classically inert Csp²−H bonds of aromatic amines occurs. Furthermore, the superacid-promoted (poly)protonation of the molecules acts as a protection, favoring the late-stage selective halogenation of natural alkaloids and active pharmaceutical ingredients     

On the Generalization of Reissner Plate Theory to Laminated Plates,Part I: Theory

This is the first part of a two-part paper presenting the generalization of Reissner thick plate theory (Reissner in J. Math. Phys. 23:184–191, 1944) to laminated plates and its relation with the Bending-Gradient theory (Lebée and Sab in Int. J. Solids Struct. 48(20):2878–2888, 2011 and in Int. J. Solids Struct. 48(20):2889–2901, 2011). The original thick and homogeneous plate theory derived by Reissner (J. Math. Phys. 23:184–191, 1944) is based on the derivation of a statically compatible stress field and the application of the principle of minimum of complementary energy. The static variables of this model are the bending moment and the shear force. In the present paper, the rigorous extension of this theory to laminated plates is presented and leads to a new plate theory called Generalized-Reissner theory which involves the bending moment, its first and second gradients as static variables. When the plate is homogeneous or functionally graded, the original theory from Reissner is retrieved. In the second paper (Lebée and Sab, 2015), the Bending-Gradient theory is obtained from the Generalized-Reissner theory and comparison with an exact solution for the cylindrical bending of laminated plates is presented.     

The adsorption of quaternary ammonium salts at a mercury solution interface: Part II. Non-symmetrical quaternary ammonium salts

The adsorption of triethyl alkyl (and allyl) ammonium bromides on a mercury electrode has been investigated. The isotherms and values of the free energy of adsorption yield information on the mode of adsorption of the cations. The formation of partial bimolecular films on the surface of mercury by the cations studied has been described and a simple explanation put forward concerning the mechanism of destruction of these films.