Synthesis and Spectroscopic Properties of S-,O-Substituted Naphthoquinone Dyes

New S-,O-substituted naphthoquinone compounds (3a, 4b, 6, 7c, 9d, 10, 12, 13c, 14d, 15) were synthesized via vinilic substitution. 2,3-Dichloro-1,4-naphthoquinone gave 3a and 4b with 4,4′-thiobisbenzenethiol, respectively. Compounds 6 and 7c were obtained from the reaction of 2,3-dichloro-1,4-naphthoquinone with cyclohexylmercaptane. The compounds 9d and 10 were prepared from the reaction of 2,3-dichloro-1,4-naphthoquinone with 6-mercapto-1-hexanol. Compounds 12, 13c, 14d, and 15 were synthesized from the reaction of 2,3-dichloro-1,4-naphthoquinone with 1,6-hexanedithiol. Their structures were characterized by micro analysis, FT-IR, ¹H NMR, ¹³C NMR, MS, UV-Vis, and fluorescence spectroscopy.     

Emission of Toxic HCN During NOx Removal by Ammonia SCR in the Exhaust of Lean‐Burn Natural Gas Engines

Reducing greenhouse gas and pollutant emissions is one of the most stringent priorities of our society to minimize their dramatic effects on health and environment. Natural gas (NG) engines, in particular at lean conditions, emit less CO₂ in comparison to combustion engines operated with liquid fuels but NG engines still require emission control devices for NO_x removal. Using state‐of‐the‐art technologies for selective catalytic reduction (SCR) of NO_x with NH₃, we evaluated the interplay of the reducing agent NH₃ and formaldehyde, which is always present in the exhaust of NG engines. Our results show that a significant amount of highly toxic hydrogen cyanide (HCN) is formed. All catalysts tested partially convert formaldehyde to HCOOH and CO. Additionally, they form secondary emissions of HCN due to catalytic reactions of formaldehyde and its oxidation intermediates with NH₃. With the present components of the exhaust gas aftertreatment system the HCN emissions are not efficiently converted to non‐polluting gases. The development of more advanced catalyst formulations with improved oxidation activity is mandatory to solve this novel critical issue.     

NMR investigations of molecular motions inp-n-hexyloxybenzylidene-p′-n-propylaniline

Proton spin-lattice relaxation times,T ₁, have been measured in the smectic phases, S _G ² , S _G ¹ and S_A, and in the nematic phase of HxBPA, in the temperature range, 220K<T<360 K. In the S _G ¹ and S _G ² phases,T ₁ has been measured at 15 and 40 MHz. The (S _G ¹ →S _G ² ) and (S _G ² →S _G ¹ ) transitions are clearly seen as discontinuities inT ₁. The former transition is seen to be due to possible freezing or change of hydrocarbon chain motions of the molecule. Our data in the S _G ¹ phase have been fitted to a model in which anisotropic rotational diffusion of the end hydrocarbon chains as also that of the rigid part of the molecule are considered. In the nematic phase, at 351 K, the observed behaviour ofT ₁, measured in the frequency range, 5 to 40 MHz, agrees well with the theoretical predictions of Uklejaet al and Freed, who take into account long range collective order fluctuations and local reorientations. Using these theories, the correlation time for short range reorientations has been calculated from our results to be 4.3 × 10⁻¹⁰ and 1.1 × 10⁻⁹ s respectively.     

Synthesis, spectral, thermal and biological studies of Co(III) and binuclear Ni(II) complexes with a novel amine-imine-oxime ligand

Two different metal complexes of [Co(HL)(L)(Ac)₂]·4H₂O (I) and [Ni₂(L)₂(Ac)₂]·4H₂O (II), have been synthesized with newly prepared amine-imine-oxime ligand [HL = 3-(4′-aminobiphenyl-4-ylimino)-butan-2-one oxime, Ac = CH₃COO⁻]. This ligand HL was prepared by the condensation of diacetylmonoxime with benzidine. The structure of the ligand and complexes have been proposed by elemental analyses, IR, ¹H, and ¹³C NMR, electronic spectra, magnetic susceptibility measurements, mass spectra, molar conductivity and thermo gravimetric analysis. The molar conductance measurements of the complexes in DMF solution correspond to non electrolytic nature for the complexes. Octahedral and tetrahedral geometries have been determined to the complexes of Co(III) and binuclear Ni(II) respectively. The ligand and its metal complexes were tested in vitro for their biological effects. Their activities against two gram-positive (Bacillus subtilis and Staphylococcus aureus) and one fungal specie (Candida albicans) were found. They were inactive against tested gram negative bacteria. The text was submitted by authors in English.     

Finding transition pathways using the string method with swarms of trajectories

An approach to find transition pathways in complex systems is presented. The method, which is related to the string method in collective variables of Maragliano et al. (J. Chem. Phys. 2006, 125, 024106), is conceptually simple and straightforward to implement. It consists of refining a putative transition path in the multidimensional space supported by a set of collective variables using the average dynamic drift of those variables. This drift is estimated on-the-fly via swarms of short unbiased trajectories started at different points along the path. Successive iterations of this algorithm, which can be naturally distributed over many computer nodes with negligible interprocessor communication, refine an initial trial path toward the most probable transition path (MPTP) between two stable basins. The method is first tested by determining the pathway for the C7eq to C7ax transition in an all-atom model of the alanine dipeptide in vacuum, which has been studied previously with the string method in collective variables. A transition path is found with a committor distribution peaked at 1/2 near the free energy maximum, in accord with previous results. Last, the method is applied to the allosteric conformational change in the nitrogen regulatory protein C (NtrC), represented here with a two-state elastic network model. Even though more than 550 collective variables are used to describe the conformational change, the path converges rapidly. Again, the committor distribution is found to be peaked around 1/2 near the free energy maximum between the two stable states, confirming that a genuine transition state has been localized in this complex multidimensional system.     

A monostyryl-boradiazaindacene (BODIPY) derivative as colorimetric and fluorescent probe for cyanide ions

We developed a novel boradiazaindacene derivative to detect cyanide ions in solution at micromolar concentrations. This structurally simple chemosensor displays a large decrease in emission intensity and a reversible color change from red to blue on contact with cyanide ions. Highly fluorescent polymeric films can be obtained by doping with the chemosensor. Such polymeric materials can be used for the sensing of the cyanide ions in polymer matrices.     

A parametric study on biphasic medium conditions for the enantioselective production of naproxen by <Emphasis Type="Italic">Candida rugosa</Emphasis> lipase

A parametric study to increase the enantioselectivity of Candida rugosa lipase (CRL) toward S-Naproxen production by the hydrolysis of racemic Naproxen methyl ester in an aqueous-organic biphasic batch system was carried out. Effects of organic solvent type, aqueous phase/organic solvent volume ratio, agitation rate, concentrations of the substrate and the enzyme, pH of the aqueous phase, and temperature on the en antiomeric excess for the product (ee_p), on the enantiomeric ratio (E) and on the conversion (x) were evaluated. Employing isooctane as the solvent resulted in higher ee_p, E, and x than those obtained in hexane, cyclohexane, and toluene. The higher the volume ratio of aqueous phase/organic solvent employed, the higher the conversion and enantioselectivity achieved. The increase in agitation rate increased the hydrolysis rate. Higher concentration of racemic Naproxen methyl ester than 10 mg/mL decreased both the conversion and enantioselectivity. The increase in crude CRL concentration resulted in enhancement of x, but the decrease of fee_p and E. Acidic pH led to higher conversion and enantioselectivity than the medium and alkaline pH values. A further increase in temperature to over 45°C decreased the conversion and enantioselectivity. The highest enantiomeric ratio achieved in the S-Naproxen production was E=171.1, with x=49.8% and ee_p=95.7%.     

Synthesis, characterization and structure effects on extractability and selectivity of N,N'-bis(salicylaldehydene)-1,4-bis-(m-aminophenoxy)butane towards some divalent cations

The extraction of copper(II), nickel(II) and cobalt(II) from the aqueous phase with N,N'-bis(salicylaldehydene)-1,4-bis-(m-aminophenoxy)butane (MAS), which was synthesized from 1,4-bis(m-aminophenoxy)butane and salicylaldehyde, was studied. Microanalytical data, elemental analysis, UV-visible 1H and 13C n.m.r. spectra and IR-spectra were used to confirm the structures. The extractability and selectivity of divalent cations were evaluated as a function of relationship between distribution ratio of the metal and pH or ligand concentration. Cu+2 showed the highest extractability and selectivity at pH 6.0, whereas Ni+2 and Co+2 showed at pH 9.2. The stoichiometries of the compounds formed were estimated to be CuL, CoL, NiL, where L is N,N'-bis(salicylaldehydene)-1,4-bis-(m-aminophenoxy)butane. It was concluded that MAS can effectively be used in solvent extraction of copper(II), nickel(II) and cobalt(II) from the aqeous phase to the organic phase.     

Magnetic line source diffraction by a conductive half-plane in an anisotropic plasma

An integral theory that is associated with the scattered fields is considered for the solution of H-polarized line source diffraction by a conductive half-plane, which is surrounded by an anisotropic plasma. As the anisotropy does not affect an E-polarized incident wave, only one polarization case is considered. The cold plasma medium is characterized by the dielectric tensor. The constant external magnetic field producing the anisotropy in a cold plasma is applied parallel to the edge of the half-plane. The total, scattered, and diffracted waves are derived in terms of the Fresnel functions. Therefore, finite magnitude values at the transition boundaries are obtained. The wave behaviours are investigated numerically for different quantities of the medium.     

Iterated local search for workforce scheduling and routing problems

The integration of scheduling workers to perform tasks with the traditional vehicle routing problem gives rise to the workforce scheduling and routing problems (WSRP). In the WSRP, a number of service technicians with different skills, and tasks at different locations with pre-defined time windows and skill requirements are given. It is required to find an assignment and ordering of technicians to tasks, where each task is performed within its time window by a technician with the required skill, for which the total cost of the routing is minimized. This paper describes an iterated local search (ILS) algorithm for the WSRP. The performance of the proposed algorithm is evaluated on benchmark instances against an off-the-shelf optimizer and an existing adaptive large neighbourhood search algorithm. The proposed ILS algorithm is also applied to solve the skill vehicle routing problem, which can be viewed as a special case of the WSRP. The computational results indicate that the proposed algorithm can produce high-quality solutions in short computation times.