A New Pulsed Flow Modulation GC × GC–MS with Cold EI System and Its Application for Jet Fuel Analysis

We designed and operated a new system of pulsed flow modulation (PFM) two dimensional comprehensive gas chromatography (GC × GC) mass spectrometry (MS). This system is based on the combination of PFM–GC × GC with a quadrupole mass spectrometer of GC–MS via a supersonic molecular beams interface and its fly-through Cold EI ion source and applied this system for the analysis of JP8 jet fuel. PFM is a simple GC × GC modulator that does not consume cryogenic gases while providing tunable second GC × GC column injection time for enabling the use of quadrupole based mass spectrometry regardless its limited scanning speed. We analyzed JP8 jet fuel with our new PFM–GC × GC–MS with Cold EI system and found that as the second dimension GC elution time is increased the observed molecular ion mass is reduced. This unique observation that helped in improved sample compounds identification under co-elution conditions was enabled via having abundant molecular ions in Cold EI for all the fuel compounds. We named this type of analysis as PFM–GC × GC × MS. We found and discuss in this paper that PFM–GC × GC–MS with Cold EI combines improved separation of GC × GC with Cold EI benefits of tailing-free ultra-fast ion source response time and enhanced molecular ions and mass spectral isomer and isotope information for the provision of increased sample identification information.

     

Study of Aqueous Biomolecules with Magnetic Flux Using Density,Viscosity, and Surface Tension Probe at 304.15 K

Doses of 0.0150 weber m^?2 magnetic flux for 30 minutes are given to four series of biomolecules in aqueous medium, densities (ρ), viscosities (η), and surface tension (γ) were measured at 304.15 K. The vitamins and carbohydrates decrease densities and viscosities and the difference of density from magnet to aqueous solution in order of dextrose (? 0.00025 kg m^?3) > fructose (? 0.00021 kg m^?3) = B6 (? 0.00021 kg m^?3) > starch (? 0.00018 kg m^?3) > B1 (? 0.0018 kg m^?3), while viscosity in order of starch (? 0.0044 kg m^?1s^?1) > fructose (? 0.0037 kg m^?1s^?1) > B1(? 0.0018 kg m^?1s^?1) > dextrose (? 0.0016 kg m^?1s^?1) > B6 (? 0.0012 kg m^?1s^?1). The surface tension also decreases in vitamin and carbohydrate. The proteins show increase in ρ, η, and γ value hence casein decrease the density and viscosity. The glutamine show increase in density and surface tension while decrease in viscosity and vice versa to alanine. These orders of the data indicate the intermolecular force between water and bimolecules in magnetic flux.     

Solid-phase extraction and field-amplified sample injection–capillary zone electrophoresis for the analysis of benzophenone UV filters in environmental water samples

A field-amplified sample injection–capillary zone electrophoresis (FASI-CZE) method for the analysis of benzophenone (BP) UV filters in environmental water samples was developed, allowing the separation of all compounds in less than 8 min. A 9- to 25-fold sensitivity enhancement was obtained with FASI-CZE, achieving limits of detection down to 21–59 μg/L for most of the analyzed BPs, with acceptable run-to-run and day-to-day precisions (relative standard deviations lower than 17 %). In order to remove water sample salinity and to enhance FASI sensitivity, an off-line solid-phase extraction (SPE) procedure using a Strata X polymeric reversed-phase sorbent was used and afforded recoveries up to 72–90 % for most BPs. With the combination of off-line SPE and FASI-CZE, limits of detection in the range 0.06–0.6 μg/L in a river water matrix, representing a 2,400- to 6,500-fold enhancement, were obtained. Method performance was evaluated by quantifying a blank river water sample spiked at 1 μg/L. For a 95 % confidence level, no statistical differences were observed between found concentrations and spiked concentrations (probability at the confidence level, p value, of 0.60), showing that the proposed off-line SPE-FASI-CZE method is suitable for the analysis of BP UV filters in environmental water samples at low microgram per liter levels. The method was successfully applied to the analysis of BPs in river water samples collected up- and downstream of industrialized and urban areas, and in some drinking water samples.     

Municipal Solid Waste Landfill Leachate Treatment and Electricity Production Using Microbial Fuel Cells

Microbial fuel cells were designed and operated to treat landfill leachate while simultaneously producing electricity. Two designs were tested in batch cycles using landfill leachate as a substrate without inoculation (908 to 3,200 mg/L chemical oxygen demand (COD)): Circle (934 mL) and large-scale microbial fuel cells (MFC) (18.3 L). A total of seven cycles were completed for the Circle MFC and two cycles for the larger-scale MFC. Maximum power densities of 24 to 31 mW/m² (653 to 824 mW/m³) were achieved using the Circle MFC, and a maximum voltage of 635 mV was produced using the larger-scale MFC. In the Circle MFC, COD, biological oxygen demand (BOD), total organic carbon (TOC), and ammonia were removed at an average of 16%, 62%, 23%, and 20%, respectively. The larger-scale MFC achieved an average of 74% BOD removal, 27% TOC removal, and 25% ammonia reduction while operating over 52 days. Analysis of the microbial characteristics of the leachate indicates that there might be both supportive and inhibiting bacteria in landfill leachate for operation of an MFC. Issues related to scale-up and heterogeneity of a mixed substrate remain.     

Preparation of Water-in-Diesel Fuel Nanoemulsions Using High-Energy Emulsification Method and a Study of Some of Their Surface Active Properties

In this work, formations of water-in-diesel fuel nanoemulsions using water/mixed nonionic surfactant/diesel fuel system has been studied. The high-energy emulsification method was used to form three emulsions using different water contents: 5, 10, and 14% (v/v) namely; E1, E2, and E3, respectively. These nanoemulsions were stabilized with emulsifiers having different hydrophilic lipophilic balance (HLB), namely, Span 80 (HLB = 4.3), Emarol 85 (HLB = 11), and their mixture (SE) with HLB = 10. The effect of water on the droplet size formation has been investigated. The interfacial tension and thermodynamic properties of the individual and emulsifiers blends have been studied. The interfacial tension (γ) measurements at 30°C were used to determine the critical micelle concentration (CMC) and surface active properties of these emulsifiers. The water droplet sizes were measured by dynamic light scattering (DLS). From the obtained data, it was found that mean sizes between 19.3 and 39 nm were obtained depending on the water content and concentration of blend emulsifiers (SE). Also, the results show that the interfacial tension (γ) gives minimum value (10.85 mN/m) for SE comparing with individual emulsifier (17.13 and 12.77 mN/m) for Span 80 and Emarol 85, respectively. The visual inspection by transmission electron microscopy showed that the obtained results support the data obtained by dynamic light scattering.     

Ambient Species Density and Gas Temperature Radial Profiles Derived from a Schlieren Technique in a Low-Frequency Non-thermal Oxygen Plasma Jet

A quantitative interpretation of the schlieren technique applied to a non-thermal atmospheric-pressure oxygen plasma jet driven at low-frequency (50 Hz) is reported. The jet was operated in the turbulent regime with a hole-diameter based Reynolds number of 13,800. The technique coupled to a simplified kinetic model of the jet effluent region allowed deriving the temporally-averaged values of the gas temperature of the jet by processing the gray-level contrast values of digital schlieren images. The penetration of the ambient air into the jet due to turbulent diffusion was taken into account. The calibration of the optical system was obtained by fitting the sensitivity parameter so that the oxygen fraction at the nozzle exit was unity. The radial profiles of the contrast in the discharge off case were quite symmetric on the whole outflow, but with the discharge on, relatively strong departures from the symmetry were evident in the near field. The time-averaged gas temperature of the jet was relatively high, with a maximum departure of about 55 K from the room temperature; as can be expected owing to the operating molecular gas. The uncertainty in the temperature measurements was within 6 K, primarily derived from errors associated to the Abel inversion procedure. The results showed an increase in the gas temperature of about 8 K close to the nozzle exit; thus suggesting that some fast-gas heating (with a heating rate ~0.3 K/μs) still occurs in the near field of the outflow.     

Design of Clayware Separator-Electrode Assembly for Treatment of Wastewater in Microbial Fuel Cells

Performance of six different microbial fuel cells (MFCs) made from baked clayware, having 450 ml effective anodic chamber volume, was evaluated, with different configurations of separator electrode assemblies, to study the feasibility of bioelectricity generation and high-strength wastewater treatment in a single-chambered mediator-less air-cathode MFC. Superior performance of an air-cathode MFC (ACMFC) with carbon coating on both sides of the separator was observed over an aqueous cathode MFC, resulting in a maximum volumetric power of 4.38 W m^?3 and chemical oxygen demand (COD) removal efficiency of more than 90 % in a batch cycle of 4 days. Hydrophilic polymer polyvinyl alcohol (PVA) was successfully used as a binder. The problem of salt deposition and fouling of cathode could be minimized by using a sock net current collector, replacing the usual stainless steel wire. However, electrolyte loss due to evaporation is a problem that needs to be resolved for better performance of an ACMFC.     

Effects of humidity and temperature on the electrochemical activities of H2/O2 PEMFCs using hybrid membrane electrolytes

Electrochemical characteristics of single cell performances at various humidity conditions and constant temperatures of 40?100 °C using membrane electrode assemblies (MEAs) were studied. The MEAs consist of alternative proton-conducting hybrid membrane electrolyte and noble Pt/C catalyst for the H₂/O₂ proton exchange membrane fuel cells (PEMFCs). The function of humidity on the cell performances was investigated at larger current density values of 501 mA cm^?2 and constant cell temperatures of 80 and 90 °C and the relative humidity of 100 %. The power density value of 400 mW cm^?2 was obtained when the same MEA at similar operating conditions was used. The effects of temperature on the single cell performances were investigated at various temperature ranges of 40–100 °C and constant relative humidity of 50, 70, and 100 %. The maximum current density and power density values of about 600 mA cm^?2 and 160 mW cm^?2, respectively, were obtained at 90 °C with 100 % RH. The results were compared with the reported results of Nafion membrane and similar hybrid membranes operating at low temperatures for H₂/O₂ fuel cells. Finally, the results provided an alternative proton-conducting electrolyte as promising candidate for low/intermediate temperature operating H₂/O₂ fuel cells.     

Synthesis and characterization poly(ϵ-caprolactone-b-ethylene glycol-b-ϵ-caprolactone) ABA type block copolymers via “Click” chemistry and ring-opening polymerization

Synthesis of poly(?-caprolactone-b-ethylene glycol-b-?-caprolactone) ABA type block copolymer by “click” chemistry and ring-opening polymerization (ROP) was reported by using propargyl polyethylene glycol (propargyl-PEG) and terminally azido poly(?-caprolactone) ester (PCL-N₃). For this purpose, primarily propargyl-PEG was synthesized by using reaction of PEGs (3000 Da, 2000 Da, 1500 Da, 1000 Da, 600 Da ve 400 Da) and propargyl chloride. 3-azido-1-propanol was obtained by using chemical interaction of 3-chloro-1-propanol and sodium azide. Synthesis of PCL-N₃ was carried out by means of ROP of ?-caprolactone and 3-azido-1-propanol. Finally, poly(?-caprolactone-b-ethylene glycol-b-?-caprolactone) ABA type block copolymers were synthesized by using PCL-N₃ and propargyl-PEG. The primary parameters such as concentration, time, and temperature that influenced the reactions were assessed. The product characterization was achieved using NMR, FT-IR, GPC, elemental analysis, and fractional precipitation [non-solvent (petroleum ether-mL)/solvent (THF-mL)] techniques.     

Corrosion Inhibition Efficiency in Relation to Micellar Interaction Parameters of Cationic/Nonionic Surfactant Mixtures for Carbon Steel Pipelines in 1 M HCl Solution

The effect of different nine molar mixed ratios of didecyl dimethyl ammonium chloride as a cationic surfactant and nonyl phenol ethoxylate (e.o. = 9) as a nonionic surfactant, on the inhibition behavior of carbon steel have been examined using the weight loss and the potensiodynamic methods. The results show that these mixed cationic/nonionic surfactant mixtures (II to X) can be used to inhibit the corrosion of steel pipelines in the petroleum acid job. The surface active properties of the used surfactant mixtures were calculated using the surface tension measurements and the critical micelle concentration (CMC) values. The micellar interaction parameters of the investigated mixtures were calculated using the data of CMC. From the corrosion results it was found that, the maximum synergistic effect was obtained by the mixtures VIII (30%C + 70%N) and IV (70%C + 30%N). They exhibited inhibition efficiency expressed by the rate of corrosion as 5.15 and 1.53 miles per year respectively, at 400 ppm. The positive synergistic behavior of these mixtures pronounced the better results than which obtained by the individual inhibitors (cationic or nonionic alone). At the same time the maximum micellar interaction parameter was obtained by the mixtures VIII and IV (?1.85 and ?1.80, respectively). These results justified the strong relationship between the corrosion inhibition efficiency and the micellar interaction parameters of the mixed surfactants which used as an organic corrosion inhibitors.     

Phospholipid/Polydiacetylene Vesicle-Based Colorimetric Assay for High-Throughput Screening of Bacteriocins and Halocins

Multi-phase anaerobic reactor for H₂ and CH₄ production from paperboard mill wastewater was studied. The reactor was operated at hydraulic retention times (HRTs) of 12, 18, 24, and 36 h, and organic loading rates (OLRs) of 2.2, 1.5, 1.1, and 0.75 kg chemical oxygen demand (COD)/m³ day, respectively. HRT of 12 h and OLR of 2.2 kg COD/m³ day provided maximum hydrogen yield of 42.76?±?14.5 ml/g COD_removed and volumetric substrate uptake rate (?rS) of 16.51?±?4.43 mg COD/L h. This corresponded to the highest soluble COD/total COD (SCOD/TCOD) ratio of 56.25?±?3.3 % and the maximum volatile fatty acid (VFA) yield (Y_VFA) of 0.21?±?0.03 g VFA/g COD, confirming that H₂ was mainly produced through SCOD conversion. The highest methane yield (18.78?±?3.8 ml/g COD_removed) and ?rS of 21.74?±?1.34 mgCOD/L h were achieved at an HRT of 36 h and OLR of 0.75 kg COD/m³ day. The maximum hydrogen production rate (HPR) and methane production rate (MPR) were achieved at carbon to nitrogen (C/N) ratio of 47.9 and 14.3, respectively. This implies the important effect of C/N ratio on the distinction between the dominant microorganism bioactivities responsible for H₂ and CH₄ production.     

Al-doped La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> as oxide anode for solid oxide fuel cells using dry C<Subscript>3</Subscript>H<Subscript>8</Subscript> fuel

Direct hydrocarbon type solid oxide fuel cells are attractive from simple gas feed process and also high energy conversion efficiency. In this study, La_0.5Sr_0.5MnO₃ (LSM55) perovskite oxide was studied as oxide anode for direct hydrocarbon type solid oxide fuel cell (SOFC). Although reasonable power density like 1 W/cm² and open circuit voltage (OCV) (1.1 V) at 1273 K was exhibited when H₂ was used as fuel, the power density as well as OCV of the cell using LSM55 for anode was significantly decreased when dry C₃H₈ was used for fuel. After power generation measurement, LSM55 phase was decomposed to MnO and La₂MnO₄. Effects of various dopants to Mn site in LSM55 were studied and it was found that partial substitution of Mn in LSM55 with other cation, especially transition metal, is effective for increasing maximum power density. In particular, reasonable high power density can be achieved on the cell using Ni-doped LSM55 for anode. On the other hand, Al substitution is effective for increasing stability against reduction and so, dopant effects of Al were studied in more details for dry C₃H₈ fuel. The power density as well as OCV increased with increasing Al content and the highest power density was achieved at x = 0.4 in La_0.5Sr_0.5Mn_1 ? x Al _x O₃. Among the examined composition, it was found that the cell using La_0.5Sr_0.5Mn_0.6Al_0.4O₃ anode shows the largest power density (0.2 W/cm²) at 1173 K and high OCV (1.01 V) against dry C₃H₈ fuel.     

Synthesis of jet fuel through the oligomerization of butenes on zeolite catalysts

In this study, the oligomerization of a butene mixture composed of 1-butene, cis-2-butene and trans-2-butene over several types of zeolites in a fixed-bed catalytic reactor at an elevated pressure was studied to produce hydrocarbons in the jet fuel range (C₈–C₁₆). Three types of zeolites, HZSM-5, Hβ and HY, were compared to evaluate the performance during the synthesis of jet fuel via the oligomerization of the aforementioned butene mixture. Compared to HY and Hβ, HZSM-5 showed a very stable butene conversion rate with high selectivity to jet-fuel-range hydrocarbon, which could be attributed to high resistance to coke resulting from the pore structure. HZSM-5 (50) shows the best quantitative conversion performance and yield for jet fuel for a time-on-stream of up to 6 h. It was also noted that the branched-to-linear hydrocarbon ratio reached 8.7 over the HZSM-5 (50) catalyst, which is beneficial to improve the cold properties of jet fuel. The present study reveals that HZSM-5 (50) is a potential catalyst for jet fuel synthesis through the oligomerization of butene mixture, exhibiting high stability and a high yield.     

Response Surface Methodology Based Optimization of β-Glucosidase Production from Pichia pastoris

The thermotolerant yeast Pichia etchellsii produces multiple cell bound β-glucosidases that can be used for synthesis of important alkyl- and aryl-glucosides. Present work focuses on enhancement of β-glucosidase I (BGLI) production in Pichia pastoris. In the first step, one-factor-at-a-time experimentation was used to investigate the effect of aeration, antifoam addition, casamino acid addition, medium pH, methanol concentration, and mixed feed components on BGLI production. Among these, initial medium pH, methanol concentration, and mixed feed in the induction phase were found to affect BGLI production. A 3.3-fold improvement in β-glucosidase expression was obtained at pH 7.5 as compared to pH 6.0 on induction with 1 % methanol. Addition of sorbitol, a non-repressing substrate, led to further enhancement in β-glucosidase production by 1.4-fold at pH 7.5. These factors were optimized with response surface methodology using Box–Behnken design. Empirical model obtained was used to define the optimum “operating space” for fermentation which was a pH of 7.5, methanol concentration of 1.29 %, and sorbitol concentration of 1.28 %. Interaction of pH and sorbitol had maximum effect leading to the production of 4,400 IU/L. The conditions were validated in a 3-L bioreactor with accumulation of 88 g/L biomass and 2,560 IU/L β-glucosidase activity.     

Chemical composition and α-amylase inhibitory activity of the essential oil from Sabina chinensis cv. Kaizuca leaves

Sabina chinensis cv. Kaizuca (SCK) is a variant of S. chinensis L. The essential oil from its leaves exhibited α-amylase inhibitory activity in vitro and the IC₅₀ value was 187.08 ± 0.56 μg/mL. Nineteen compounds were identified from this essential oil by gas chromatography–mass spectrometry (GC-MS) analysis. The major compounds identified were bornyl acetate (42.6%), elemol (20.5%), β-myrcene (13.7%) and β-linalool (4.0%). In order to study the reason of the α-amylase inhibitory activity of this essential oil, the identified compounds were docked with α-amylase by molecular docking individually. Among these compounds, γ-eudesmol exhibited the lowest binding energy (?6.73 kcal/mol), followed by α-copaen-11-ol (?6.66 kcal/mol), cubedol (?6.39 kcal/mol) and α-acorenol (?6.12 kcal/mol). The results indicated that these compounds were the active ingredients responsible for the α-amylase inhibitory activity of essential oil from SCK.     

GC–MS characterisation and biological activity of essential oils from different vegetative organs of Plectranthus barbatus and Plectranthus caninus cultivated in north Italy

Essential oils (EOs) from the roots, stems and leaves of Plectranthus barbatus (A) and Plectranthuscaninus (B), cultivated in north Italy, were obtained by steam distillation and chemically characterised by gas chromatography–mass spectrometry. The highest yields were obtained from roots (268.15 and 673.60 mg/kg from A and B), followed by leaves (64.34 and 26.65 mg/kg) and stems (19.76 and 18.63 mg/kg). A total of 128 structures were identified in A and 121 in B. Fe⁺⁺ chelating and antiradical activities (DPPH and ABTS) were evaluated: root and stem EOs showed the strongest activities, while EOs from leaves did not show relevant activities. All EOs were tested for their in vitro antimicrobial activity, showing optimal growth-inhibition in antibiogram (?>35 mm) and MIC tests (32–64 μg/mL) against Candida albicans, while EOs from leaves of both species showed a good activity (25 < ? < 34 mm, MIC 64–128 μg/mL) against Escherichia coli.     

Surface Modification of Poly-ε-Caprolactone with an Atmospheric Pressure Plasma Jet

In this work, poly-ε-caprolactone samples are modified by an atmospheric pressure plasma jet in pure argon and argon/water vapour mixtures. In a first part of the paper, the chemical species present in the plasma jet are identified by optical emission spectroscopy and it was found that plasmas generated in argon/0.05 % water vapour mixtures show the highest emission intensity of OH (A–X) at 308 nm. In a subsequent section, plasma jet surface treatments in argon and argon/water vapour mixtures have been investigated using contact angle measurements and X-ray photoelectron spectroscopy. The polymer samples modified with the plasma jet show a significant decrease in water contact angle due to the incorporation of oxygen-containing groups, such as C–O, C=O and O–C=O. The most efficient oxygen inclusion was however found when 0.05 % of water vapour is added to the argon feeding gas, which correlates with the highest intensity of OH (X) radicals. By optimizing the OH (X) radical yield in the plasma jet, the highest polymer modification efficiency can thus be obtained.     

Preliminary investigation for the development of surrogate debris from nuclear detonations in marine-urban environments

The effect of ambient gas on measurements with microwave-assisted laser-induced plasma in microwave-assisted laser-induced breakdown spectroscopy (MA-LIBS) was studied with relevance for the analysis of nuclear fuel. A pelletized gadolinium oxide (Gd₂O₃) sample, which was used as a simulated nuclear fuel, was irradiated by a pulsed Nd:YAG laser (532 nm, 5 mJ) coupled with microwaves (2.45 GHz, 400 W) under various gases of air, Ar, and He. Microwaves can be effectively used to enhance laser-induced plasma emissions. The emission spectrums of Gd obtained by MA-LIBS in Ar and He gases are much better than those of the air case. Namely, the spectral lines can be clearly identified and are far from molecular bands. Furthermore, the emission intensity is highest with low background emissions. Linear calibration curves of Ca in the concentration range between 0 and 500 mg/kg as an impurity in Gd₂O₃ have been successfully obtained in all gases. The detection limits of Ca impurity in air, Ar and He gases were 2, 0.8 and 0.6 mg/kg, respectively, which are much lower than the required limits of Ca impurity in nuclear fuels.     

Neptunium estimation in the spent fuel dissolver solution by inductively coupled plasma-atomic emission spectroscopy

This paper deals with the optimization of experimental conditions for the estimation of Np in spent fuel dissolver solution using 2-thenoyltrifluoroacetone (HTTA) as extractant. The quantitative extraction of Np from the dissolver solution employing 0.5 M HTTA/xylene was followed by its estimation by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) after stripping it from the organic phase with 8 M HNO₃. The reliability of the method was checked by standard addition technique. The method is precise and accurate yielding Np analytical recovery of 99 ± 1%.     

Theoretical design and preparation of high thermal-stable jet fuel

A high thermal-stable jet fuel design method was developed using composition-properties relations and basic specification properties of jet fuel. Tannery diagrams were provided to visualize relationships among three main components (n-paraffins, iso-paraffins, cycloparaffins, or aromatics) with four major specification properties (density, flash point, freezing point, net heat of combustion) and thermal sta- bility. An optimum chemical composition was established to meet performance requirements: n-paraffins 25%-45%, iso-paraffins 15%-30%, cycloparaffins 30%-50%, and aromatics 5%. The thermal stability test on four fuel samples with and without optimal composition indicated that the thermal stabilities of fuel samples with optimal composition are higher than RP-3 jet fuel, and that the theoretical design method is a reliable method to screen the basic oil for the high thermal-stable jet fuel.