Determination of hopane biomarkers in Arabian crude oils by gas chromatography-tandem mass spectrometry

Gas chromatography-mass spectrometry with the mass spectrometer operated in the tandem mode at a constant accelerating voltage was used to analyse for triterpanes in Arabian crude oils. Specific molecular parent-daughter ion pairs were selected for quantitative measurements owing to their metastable transitions in the first field-free region. More accurate relative distribution ratios of hydrocarbon biomarkers were determined by this sequential gating technique than by the conventional diagnostic daughter ion mass fragmentogram in common GC-MS. The data and spectra obtained from MS-MS operation may serve as unique “fingerprints” for these regional crudes     

Flow injection chemiluminescence determination of hydrazine by oxidation with chlorinated isocyanurates

A rapid and sensitive flow injection chemiluminescence (CL) method is described for the determination of hydrazine based on the CL generated during its reaction with either sodium dichloroisocyanurate (SDCC) or trichloroisocyanuric acid (TCCA) in alkaline medium. The emission intensity is greatly enhanced if dichlorofluorescein (DCF) as sensitizer is present in the reaction medium. The presence of citrate prevents the precipitation of some cations in the reaction medium and also causes an enhancement in emission intensity. The effect of analytical and flow injection variables on these CL systems and determination of hydrazine are discussed. The optimum parameters for the determination of hydrazine were studied and were found to be the following: SDCC and TCCA both 1x10(-3) M; NaOH, 2x10(-1) M; DCF, 5x10(-6) M; citrate, 1x10(-3) M and flow rate, 3.8 ml min(-1). The optimized method yielded 3sigma detection limits of 2x10(-7) and 3x10(-7) M for hydrazine with SDCC and TCCA oxidants, respectively. The method is simple, fast, sensitive, and precise and was applied to the determination of hydrazine in water samples.     

Kinetic studies on the solvolysis and axial ligand substitutions of bis-triphenylphosphine(cyclohexane-1,2-dione-dioximato)ruthenium(II) in non-aqueous solvents

Kinetic studies of ligand substitutions of the six-coordinated Ru^II pseudo-macrocyclic complex [Ru(CHDH)₂- (PPh₃)₂] (CHDH=cyclohexanedione-dioximato) have been spectrophotometrically investigated in a variety of solvents and at 70, 80, 85 and 90°C. The reactions studied are of the form:[(PPh₃)Ru(CHDH)₂(PPh₃)] + L =[(PPh₃)Ru(CHDH)₂L] + PPH₃ where L is imidazole, pyridine, piperidine or thiophene or a solvent molecule (PhCl, PhMe, MeCN, DMSO or DMF). The solvolysis reactions with chlorobenzene and toluene proceed to an equilibrium position favoring the bis-triphenylphosphine complex. All other reactions proceed to completion. From a mechanistic point of view the reactions were found to proceed through the formation of a five coordinate intermediate that possesses little or no discriminating ability towards the incoming nucleophiles. The rate data were thus interpreted in terms of a dissociative (D) or dissociative interchange (Id) mechanism. Activation parameters H and S are reported. Preliminary studies on the solvatochromic behavior of [Ru(CHDH)₂(PPh₃)₂] and the corresponding mixed complexes are discussed.     

Synthesis of 1,2,3-thiadiazolo[4,5-d] pyridazines,A new heterocyclic ring system

A method was developed for the synthesis of 5-carbethoxy-4-formyl-1,2,3-thiadiazole (I), its isomer (II); 5-benzoyl-4-formyl-1,2,3-thiadiazole (III), and its isomer (IV). It was demonstrated that although compounds I, III and IV with hydrazine gave 7H-1,2,3-thiadiazolo[4,5-d]-pyridazin-7-one (XXII), 7-phenyl-1,2,3-thiadiazolo[4,5-d]pyridazine (XXIII) and 4-phenyl-1,2,3-thiadiazolo[4,5-d]pyridazine (XXV), respectively; however, compound I gave its corresponding hydrazone (XXIV).     

Inhibition of Pb-Leaching from Lead Crystal Glass by Coating with Films Prepared by the Sol-Gel Method

The chemical durability of lead glass tumblers (24% PbO) in a 4% (v/v) acetic acid solution before and after coating with sol-gel derived SiO2 films was assessed to determine the extent of reduction in Pb-leaching that can be achieved. It was found that by coating the internal surface of the glass tumblers with 1 ml of 10% TEOS solutions at 100°C and densifying the coating formed at 500°C for 1 h, it was possible to reduce Pb-leaching to about one quarter of that of the uncoated glass.     

Controllable growth of chains and grids from polyoxomolybdate building blocks linked by silver(I) dimers

Molecular growth processes utilizing a beta-octamolybdate synthon and {Ag2} dimers are described and the directing influence of "encapsulating" cations and coordinating solvent is also demonstrated. The growth of two 1D chains, (nBu4N)2n[Ag2Mo8O26]n (1) and (nBu4N)2n[Ag2Mo8O26(CH3CN)2]n (2), is achieved when nBu4N+ ions are used, and the diameter of the chains can be expanded by the coordination of CH3CN solvent (2). The formation of a type of gridlike structure in which 1D chains are crossed-over each other in alternatively packed layers is achieved in DMSO as the solvent; DMSO acts as a linking group to give (nBu4N)2n[Ag2Mo8O26(dmso)2]n (3), which, similar to 1 and 2, still incorporates the Bu4N+ ions that exert an "encapsulating" influence. However, in (HDMF)n[Ag3(Mo8O26)(dmf)4]n (4) the relatively bulky Bu4N+ ions are exchanged for protonated DMF cations, thereby allowing the chains to condense to a 2D array. The building block concept is further enforced by the isolation of a "monomeric" unit (Ph4P)2[Ag2Mo8O26(dmso)4] (5), which is isolated when the Ph4P+ ions are so "encapsulating" as to prevent aggregation of the {Ag-Mo8-Ag} building blocks. The nature of the AgAg dimers in each of the compounds 1-4 is examined by DFT calculations and the interplay between these Ag-Ag interactions and the structure types is described.     

HPLC and GC Methods for Determination of Lubricants and Their Evaluation in Analysis of Real Samples of Polyethylene

High performance liquid chromatography (HPLC) and gas chromatography (GC) are introduced for analysis of polymer lubricants (stearamide, oleamide and erucamide). In the HPLC method, a reverse phase octadecylsilane (ODS) column along with acetonitrile/methanol (60:40) as a mobile phase were used. Detection of analytes was performed by a UV detector at 202 nm. The analysis time was less than 8 min. In the GC method, polar capillary column and flame ionization detector (FID) were used for separations and detection, respectively. The analysis time by GC was longer than HPLC and was about 30 min. Limits of detection, linear range and repeatability of both methods are similar, but determination of oleamide in real samples by HPLC method is difficult due to complexity of the initial part of HPLC chromatogram in polyethylene samples. That problem is not observed in the GC method. Detection limits in both methods for all analytes are lower than 0.003% which are much lower than the amount of lubricants in commercial polymers (0.05–0.2%).     

Supercritical carbon dioxide extraction of Mentha pulegium L. essential oil

The dependence of Mentha pulegium L. (pennyroyal) essential oil composition, obtained by supercritical carbon dioxide (SC-CO₂), with the following parameters: pressure, temperature, extraction time (dynamic), and modifier (methanol) was studied. The results were also compared with those obtained by conventional hydrodistillation method in laboratory conditions. Regarding the percentages of menthone (30.3%) and pulegone (52.0%), the optimum SFE results were obtained at the following experimental conditions: pressure=100 atm, T=35 °C, dynamic time=10 min, and V_modifier=0 μl. The results of hydrodistillation showed that the major components of M. pulegium L. were pulegone (37.8%), menthone (20.3%), and piperitenone (6.8%). The evaluation of the composition of each extract was performed by gas chromatography-mass spectrometry.     

Swarm intelligence-based hyper-heuristic for the vehicle routing problem with prioritized customers

The vehicle routing problem (VRP) is a combinatorial optimization management problem that seeks the optimal set of routes traversed by a vehicle to deliver products to customers. A recognized problem in this domain is to serve ‘prioritized’ customers in the shortest possible time where customers with known demands are supplied by one or several depots. This problem is known as the Vehicle Routing with Prioritized Customers (VRPC). The purpose of this work is to present and compare two artificial intelligence-based novel methods that minimize the traveling distance of vehicles when moving cargo to prioritized customers. Various studies have been conducted regarding this topic; nevertheless, up to now, few studies used the Cuckoo Search-based hyper-heuristic. This paper modifies a classical mathematical model that represents the VRPC, implements and tests an evolutionary Cuckoo Search-based hyper-heuristic, and then compares the results with those of our proposed modified version of the Clarke Wright (CW) algorithm. In this modified version, the CW algorithm serves all customers per their preassigned priorities while covering the needed working hours. The results indicate that the solution selected by the Cuckoo Search-based hyper-heuristic outperformed the modified Clarke Wright algorithm while taking into consideration the customers’ priority and demands and the vehicle capacity.

     

BSLPSDN: Base station location privacy via software-defined networking (SDN) in wireless sensor networks

Base station's location privacy in a wireless sensor network (WSN) is critical for information security and operational availability of the network. A key part of securing the base station from potential compromise is to secure the information about its physical location. This paper proposes a technique called base station location privacy via software-defined networking (SDN) in wireless sensor networks (BSLPSDN). The inspiration comes from the architecture of SDN, where the control plane is separated from the data plane, and where control plane decides the policy for the data plane. BSLPSDN uses three categories of nodes, namely, a main controller to instruct the overall operations, a dedicated node to buffer and forward data, and lastly, a common node to sense and forward the packet. We employ three kinds of nodes to collaborate and achieve stealth for the base station and thus protecting it against the traffic-analysis attacks. Different traits of the WSN including energy status and traffic density can actively be monitored by BSLPSDN, which positively affects the energy goals, expected life of the network, load on common nodes, and the possibility of creating diversion in the wake of an attack on the base station. We incorporated multiple experiments to analyze and evaluate the performance of our proposed algorithm. We use single controller with multiple sensor nodes and multiple controllers with multiple sensor nodes to show the level of anonymity of BS. Experiments show that providing BS anonymity via multiple controllers is the best method both in terms of energy and privacy.