Theoretical analysis of frontier orbitals,electronic transitions,and global reactivity descriptors of M(CO)4L2 type metal carbonyl complexes: a DFT/TDDFT study

Structural Chemistry - Metal carbonyl complexes, which have been known as effective catalysts since early days, find use in many fields both directly and indirectly. Although the use of metal...     

On classification of four-dimensional nilpotent Leibniz algebras

Leibniz algebras are certain generalization of Lie algebras. In this paper, we give the classification of four-dimensional non-Lie nilpotent Leibniz algebras. We use the canonical forms for the congruence classes of matrices of bilinear forms and some other techniques to obtain our result.     

Graphene oxide-octadecylsilane incorporated monolithic nano-columns with 50 μm id and 100 μm id for small molecule and protein separation by nano-liquid chromatography

In this study, graphene oxide-octadecylsilane incorporated monolithic nano-columns were developed for protein analysis by nano liquid chromatography (nano LC). The monolithic column with 100 μm id was first prepared by an in situ polymerization using ethylene dimethacrylate (EDMA), 3-chloro-2-hydroxypropylmethacrylate (HPMA-Cl), and methacryloyl graphene oxide nanoparticles (MGONPs). MGONPs were synthesized by the treatment of 3-(trimethoxysilyl)propylmethacrylate (TMSPM) and GO. Tetrahydrofuran (THF) and dodecanol were used as the porogenic solvent. The resulting column was functionalized by dimethyloctadecylch lorosilane (DODCS) for the enhancement of hydrophobicity. The functionalization greatly improved the baseline separation of hydrophobic compounds such as polyaromatic hydrocarbons (PAHs). The optimized monolith with respect to total polymerization mixture was characterized by using Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) X-ray diffraction (XRD) and chromatographic analyses. The blank monoliths without functionalization exhibited poor separation while a good separation performance of MGONPs functionalized monoliths was achieved. The monolith with 100 μm id was evaluated in protein separation in nano LC using RNase A, Cytochrome C, Lysozyme, Trypsin, and Ca isozyme II as the test proteins. It was shown that protein separation mechanism was based on large π-system of GO and hydrophobicity of the monolithic structure. Theoretical plates number up to 57 600 plates were achieved. The nano-column with 50 μm id was also prepared using the same polymerization mixture under the same chemical conditions. These nano-columns were employed for protein separation by nano LC, and the dependence of both nano-column performance on the internal diameter was also discussed.     

5-HT1A Serotonergic, α-Adrenergic and Opioidergic Receptors Mediate the Analgesic Efficacy of Vortioxetine in Mice

Vortioxetine is a multimodal antidepressant drug that affects several brain neurochemicals and has the potential to induce various pharmacological effects on the central nervous system. Therefore, we investigated the centrally mediated analgesic efficacy of this drug and the mechanisms underlying this effect. Analgesic activity of vortioxetine (5, 10 and 20 mg/kg, p.o.) was examined by tail-clip, tail-immersion and hot-plate tests. Motor performance of animals was evaluated using Rota-rod device. Time course measurements (30–180 min) showed that vortioxetine (10 and 20 mg/kg) administrations significantly increased the response latency, percent maximum possible effect and area under the curve values in all of the nociceptive tests. These data pointed out the analgesic effect of vortioxetine on central pathways carrying acute thermal and mechanical nociceptive stimuli. Vortioxetine did not alter the motor coordination of mice indicating that the analgesic activity of this drug was specific. In mechanistic studies, pre-treatments with p-chlorophenylalanine (serotonin-synthesis inhibitor), NAN-190 (serotonin 5-HT_1A receptor antagonist), α-methyl-para-tyrosine (catecholamine-synthesis inhibitor), phentolamine (non-selective α-adrenoceptor blocker), and naloxone (non-selective opioid receptor blocker) antagonised the vortioxetine-induced analgesia. Obtained findings indicated that vortioxetine-induced analgesia is mediated by 5-HT_1A serotonergic, α-adrenergic and opioidergic receptors, and contributions of central serotonergic and catecholaminergic neurotransmissions are critical for this effect.     

Delay equations with fluctuating delay related to the regenerative chatter

The mathematical models representing machine tool chatter dynamics have been cast as differential equations with delay. In this paper, non-linear delay differential equations with periodic delays which model the machine tool chatter with continuously modulated spindle speed are studied. The explicit time-dependent delay terms, due to spindle speed modulation, are replaced by state-dependent delay terms by augmenting the original equations. The augmented system of equations is autonomous and has two pairs of pure imaginary eigenvalues without resonance. The reduced bifurcation equation is obtained by making use of Lyapunov-Schmidt Reduction method. By using the reduced bifurcation equations, the periodic solutions are determined to analyze the tool motion. Analytical results show both modest increase of stability and existence of periodic solutions near the new stability boundary.     

Effects of timber skidding on chemical characteristics of herbaceous cover, forest floor and topsoil on skidroad in an oak (Quercus petrea L.) forest

This paper examines the effects of timber harvesting by skidding on some soil properties (sand, silt, clay, pH, organic carbon, bulk density and compaction), herbaceous cover (unit mass) and forest floor (unit weight) properties. Also N (%), P, K, Na, Ca, Mg, Fe, Zn, Cu and Mn (ppm) were determined in all herbaceous cover, forest floor and two soil depth (0–5 cm and 5–10 cm) on skidroad of an oak (Quercus petrea L.) stand in Istanbul Belgrad Forest – Turkey. In this study, obtained results are; the forest floor and the herbaceous cover amount on the skidroad have been found considerably lower than undisturbed area. There were some crucial changes in the characteristics of the soil which has been investigated down to 10 cm depth. Soil bulk density was found quite high in the samples taken from the skidroad subject to compaction compared to the ones on the undisturbed area. Nevertheless, no important difference had been detected between the skidroad and the undisturbed area at both soil depths in terms of organic carbon contents. Moreover, the soil acidity (pH) values showed noteworthy differences in the analysis of soil samples taken from both soil depths on the skidroad and on the undisturbed area. Fe and Cu contents of herbaceous samples on skidroad were significantly higher than undisturbed area. Forest floor on skidroad had significantly higher K content, and significantly lower Zn, Mn and N content compared to undisturbed area. P, Fe, Zn and Mn contents were found significantly lower in 0–5 cm soil depth on skidroad than undisturbed area. In 5–10 cm soil depth, concentrations of N, P, Fe, Zn and Mn were significantly lower, while Mg and Cu contents were significantly higher than undisturbed area. Results indicate that long-term harvest using skidding techniques on these sites had adversely affected soil cation concentrations, physical soil conditions and mass of herbaceous cover and forest floor.     

The bi-objective Pollution-Routing Problem

The bi-objective Pollution-Routing Problem is an extension of the Pollution-Routing Problem (PRP) which consists of routing a number of vehicles to serve a set of customers, and determining their speed on each route segment. The two objective functions pertaining to minimization of fuel consumption and driving time are conflicting and are thus considered separately. This paper presents an adaptive large neighborhood search algorithm (ALNS), combined with a speed optimization procedure, to solve the bi-objective PRP. Using the ALNS as the search engine, four a posteriori methods, namely the weighting method, the weighting method with normalization, the epsilon-constraint method and a new hybrid method (HM), are tested using a scalarization of the two objective functions. The HM combines adaptive weighting with the epsilon-constraint method. To evaluate the effectiveness of the algorithm, new sets of instances based on real geographic data are generated, and a library of bi-criteria PRP instances is compiled. Results of extensive computational experiments with the four methods are presented and compared with one another by means of the hypervolume and epsilon indicators. The results show that HM is highly effective in finding good-quality non-dominated solutions on PRP instances with 100 nodes.     

Effect of local variations of the laminar flame speed on the global finger-flame acceleration scenario

Numerous formulations describing the dynamics and morphology of corrugated flames, including the scenarios of flame acceleration, are based on a “geometrical consideration”, where the wrinkled-to-planar flame velocities ratio, S_w /S_L , is evaluated as the scaled flame surface area, while the entire combustion chemistry is immersed into the planar flame speed S_L , which is assumed to be constant. However, S_L may experience noticeable spatial/temporal variations in practice, in particular, due to pressure/temperature variations as well as non-uniform distribution of the equivalence ratio and/or that of combustible or inert dust impurities. The present work initiates the systematic study of the impact of the local S_L -variations on the global flame evolution scenario. The variations are assumed to be imposed externally, in a manner being a free functional of the formulation. Specifically, the linear, parabolic and hyperbolic spatial S_L -distributions are incorporated into the formulations of finger flame acceleration in pipes, and they are compared to the case of constant S_L . Both two-dimensional channels and cylindrical tubes are considered. The conditions promoting or moderating flame acceleration are identified, and the revisited equations for the flame shape, velocity and acceleration rate are obtained for various S_L -distributions. The theoretical findings are validated by the computational simulations of the reacting flow equations, with agreement between the theory and modelling demonstrated.