A minimization method for the sum of a convex function and a continuously differentiable function

This paper presents a method for finding the minimum for a class of nonconvex and nondifferentiable functions consisting of the sum of a convex function and a continuously differentiable function. The algorithm is a descent method which generates successive search directions by solving successive convex subproblems. The algorithm is shown to converge to a critical point.The authors wish to express their appreciation to the referees for their careful review and helpful comments.     

Measurement and modeling of work function changes during low energy cesium sputtering

In this paper, a H-terminated silicon wafer was bombarded by low energy cesium ions during ToF-SIMS analysis and work function variations of the target were measured for different analysis conditions. This measurement was performed by measuring the shift of the secondary ions energy distributions with a reflectron type analyzer. At first, the silicon’s work function change was found to be −2.3 eV during 500 eV Cs⁺ bombardment at 45°. This effect is due to the creation of a dipolar layer at the surface of the silicon by the implanted cesium. Then the work function variation was measured at 300 eV for varying cesium surface concentrations. The work function was found to decrease monotonously with the increasing cesium surface concentration, as during cesium adsorption experiments. The results were modeled following three different approaches and the value of the effective polarizability α of cesium was found to be equal to 1.9 × 10⁻³⁹ C m²/V. Finally, the effect of the bombardment energy on the work function variation was studied for beams with energies ranging from 250 to 2000 eV. The effective polarizability of cesium was found to increase with increasing Cs beam energy.     

D abstraction by H at a D-saturated Ru(0 0 1) surface

D abstraction (ABS) by H at Ru(0 0 1) surfaces initially saturated with D adatoms has been investigated using in situ mass spectrometry. HD and D₂ desorption rates are measured at various surface temperatures T as a function of H exposure time. Yield of D₂ desorption increases with T, while that of HD is little affected. Analyzing the measured rate curves, HD and D₂ desorption orders are evaluated to be 1.7 ± 0.1 and 2.5 ± 0.1, respectively, with respect to D coverage θ_D. To pursue the origin of the derived non-integral reaction orders the rate curves are further analyzed with the rate equations constructed to involve several ABS channels. Consequently, we find that the HD desorption is mainly governed by a second-order rate law in θ_D rather than the conventional hot atom-mediated ABS reaction even when it is corrected to include an isotope effect on ABS. We argue that such second-order ABS kinetics becomes important when the H atoms in excited state of chemisorption have energetically relaxed to some extent, and thereby tend to reside at, e.g. hexagonal closed packed hollow sites, interacting with nearby adatoms. On the other hand, the D₂ rate curves can be fit with third-order kinetics, consistent with the Langmuir-Hinshelwood mechanism in a super-saturation state. The isotope effect plays an essential role in the ABS reaction of D abstraction by H which competes with H abstraction by H as D adatoms are replaced by H atoms.     

Determination of Tetracyclines in Milk,Eggs and Honey Using in-situ Ionic Liquid Based Dispersive Liquid–Liquid Microextraction

In this study, in-situ ionic liquid based dispersive liquid?liquid microextraction method for enrichment of tetracyclines before liquid chromatographic analysis has been improved. A 1-benzyl-3- methylimidazolium chloride was used as an ionic liquid. To increase extraction efficiency, some optimization parameters (amount of ammonium hexafluorophoshate, extraction time, centrifugation time, ratio of ionic liquid/salt) were investigated. At optimized conditions, enrichment factors of four tetracycline antibiotics (tetracycline, chlortetracycline, methacycline, doxycycline) were between 25 and 98. The residues of tetracyclines were not found in the studied real samples. For the accuracy of the method, the concentration of 50 and 250 μg/L of standard tetracycline mixture solutions were spiked to the blank real milk, honey and egg samples and the percentage recoveries were obtained in the range of 75.8–109.7%.     

Synthesis of subphthalocyanines as probes for the accessibility of silica nanochannels

The synthesis of a new subphthalocyanine is reported. Its structural and photophysical properties are ideal for probing the accessibility of arrays of silica nanochannels.     

Determination of Folic Acid by CE in Various Cultivated Variety of Lentils

A simple extraction and determination method for folic acid (FA) in lentil samples was developed employing capillary electrophoresis. The analysis was performed in a 75 μm ID fused silica capillary using a running buffer of 10 mM sodium borate (10%, v/v, methanol, pH 9) at +18 kV and a detection wavelength at 200 nm. Methylparaben was used as the internal standard. FA signal response was linear in the range between 1.2 × 10^?5 and 4.8 × 10^?5 M. Limit of detection (inter-day) was determined at 6.12 × 10^?7 M (3.3 σs^?1). The amount of FA found in green, red and mignon lentils was found to range between 0.408 and 0.742 mg g^?1.     

An Enzyme‐free H2O2 Sensor Based on Poly(2‐Aminophenylbenzimidazole)/Gold Nanoparticles Coated Pencil Graphite Electrode

A poly(2‐aminophenylbenzimidazole)/gold nanoparticles (P2AB/AuNPs) coated disposable pencil graphite electrode (PGE) was fabricated as an enzyme‐free sensor for the H₂O₂ determination. P2AB/AuNPs and P2AB were successfully synthesized electrochemically on PGE in acetonitrile for the first time. The coatings were characterized by scanning electron microscopy, X‐ray diffraction spectroscopy, Energy‐dispersive X‐ray spectroscopy, Surface‐enhanced Raman spectroscopy, and UV‐Vis spectroscopy. AuNPs interacted with P2AB as carrier enhances the electrocatalytic activity towards reduction of H₂O₂. The analytical performance was evaluated in a 100 mM phosphate buffer solution at pH 6.5 by amperometry. The steady state current vs. H₂O₂ concentration is linear in the range of 0.06 to 100 mM (R²=0.992) with a limit of detection 3.67×10^?5 M at ?0.8 V vs. SCE and no interference is caused by ascorbic acid, dopamine, uric acid, and glucose. The examination for the sensitive determination of H₂O₂ was conducted in commercially available hair oxidant solution. The results demonstrate that P2AB/AuNPs/PGE has potential applications as a sensing material for quantitative determination of H₂O₂.     

Intermolecular interactions in nitrogen-containing aromatic systems

π–π and CH···N interactions are vital in biological systems. In this study, stacking and hydrogen-bonded interactions in pyrazine and triazine dimers were investigated by density functional theory combined with symmetry-adapted perturbation theory (DFT-SAPT) and counterpoise (CP)-corrected supermolecular MP2, SCS-MP2, B3LYP-D and CCSD(T) calculations. All interaction energies were computed using the optimized structures at the CP-corrected SCS/aug-cc-pVDZ level, which gave 1–2 kJ/mol lower interaction energies than the ones computed at the MP2 level. For both dimers, doubly hydrogen-bonded and cross-(displaced) stacked orientations were found to be the lowest energy ones. The reference CCSD(T) calculations favored the former structure in both dimer systems, whereas MP2 and SCS-MP2 located the latter as the lowest energy isomer. In particular, the former was found to be lower in energy than the latter by 2.28 and 1.01 kJ/mol at the CCSD(T)/aug-cc-pVDZ level for pyrazine and triazine, respectively. B3LYP-D produced interaction energies in agreement with the CCSD(T) at the equilibrium geometries, but it overestimates them at the short range and underestimates at the long intermonomer separations. Furthermore, it tends to give smaller equilibrium distances compared to the CCSD(T). DFT-SAPT method was in a good agreement with the reference CCSD(T) calculations. This suggests that DFT-SAPT can be employed to compute the full potential energy surface of these dimers. Moreover, DFT-SAPT calculations showed that the electrostatic and dispersion contributions are the most important energy components stabilizing these dimers. The present study aims to show which theoretical method is the most promising one for the investigation of intermolecular interactions dominated by π–π and CH···N. Therefore, the findings obtained in this study can be used to unravel the structures of nucleic acid bases and other systems stabilized by π–π and CH···N interactions.     

Simple high-performance liquid chromatographic method for determination of atropine and obidoxime in a parenteral injection device

Atropine and obidoxime in a parenteral injection device are determined by simple HPLC method simultaneously without any pretreatment at 228 nm. The relative standard deviations (R.S.D.) were below 1.6% for the compounds. The correlation coefficient was greater than 0.999 for both compounds in the calibration range. The recoveries at 5 mg/L concentration averaged as 95% for atropine and 102% for obidoxime. The uncertainty of the measurements for atropine and obidoxime was 2.8% and 2.4%, respectively.     

Azocalixarenes. 6: Synthesis, complexation, extraction and thermal behaviour of four new azocalix[4]arenes

Four new azocalix[4]arenes {5,11,17,23-tetrakis[(2-hydroxy-5-tert-butylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (1), 5,11,17,23-tetrakis[(2-hydroxy-5-nitro phenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (2), 5,11,17,23-tetrakis[(2-amino-5-carboxylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (3) and 5,11,17,23-tetrakis[(1-amino-2-hydroxy-4-sulfonicacidnapthylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (4)} have been synthesized from p-tert-butylphenol, p-nitrophenol, p-aminobenzoic acid and 1-amino-2-hydroxy-4-sulphonic acid by diazo coupling reaction with p-aminocalix[4]arene. The resulting ligands (1–4) were treated with three transition metal salts (e.g., CuCl₂·2H₂O, NiCl₂·6H₂O or CoCl₂·6H₂O). Cu(II), Ni(II) and Co(II) complexes of the azocalix[4]arene derivatives were obtained and characterized by UV-vis, IR, ¹H-NMR spectroscopic techniques and elemental analysis. All the complexes have a metal:ligand ratio of 2:1. The Cu(II) and Ni(II) complexes of azocalix[4]arenes are square-planar, while the Co(II) complexes of azocalix[4]arenes are octahedral with water molecules as axial ligands. The solvent extraction of various transition metal cations from the aqueous phase to the organic phase was carried out by using azocalix[4]arenes (1–4). It was found that, azocalix[4]arenes 1, 2 and 3 examined selectivity for transition metal cations such as Ag⁺, Hg⁺ and Hg²⁺. In addition, the thermal stability of metal:azocalix[4]arene complexes were also reported. Dedicated to Prof. Dr. Mustafa Yılmaz on the occasion of his 50th birthday