Periodic emission of droplets from an oscillating electrified meniscus of a low-viscosity, highly conductive liquid

The generation of identical droplets of controllable size in the micrometer range is a problem of much interest owing to the numerous technological applications of such droplets. This work reports an investigation of the regime of periodic emission of droplets from an electrified oscillating meniscus of a liquid of low viscosity and high electrical conductivity attached to the end of a capillary tube, which may be used to produce droplets more than ten times smaller than the diameter of the tube. To attain this periodic microdripping regime, termed axial spray mode II by Juraschek and Röllgen [R. Juraschek and F. W. Röllgen, Int. J. Mass Spectrom. 177, 1 (1998)], liquid is continuously supplied through the tube at a given constant flow rate, while a dc voltage is applied between the tube and a nearby counter electrode. The resulting electric field induces a stress at the surface of the liquid that stretches the meniscus until, in certain ranges of voltage and flow rate, it develops a ligament that eventually detaches, forming a single droplet, in a process that repeats itself periodically. While it is being stretched, the ligament develops a conical tip that emits ultrafine droplets, but the total mass emitted is practically contained in the main droplet. In the parametrical domain studied, we find that the process depends on two main dimensionless parameters, the flow rate nondimensionalized with the diameter of the tube and the capillary time, q, and the electric Bond number BE, which is a nondimensional measure of the square of the applied voltage. The meniscus oscillation frequency made nondimensional with the capillary time, f, is of order unity for very small flow rates and tends to decrease as the inverse of the square root of q for larger values of this parameter. The product of the meniscus mean volume times the oscillation frequency is nearly constant. The characteristic length and width of the liquid ligament immediately before its detachment approximately scale as powers of the flow rate and depend only weakly on the applied voltage. The diameter of the main droplets nondimensionalized with the diameter of the tube satisfies dd≈(6/π)1/3(q/f)1/3, from mass conservation, while the electric charge of these droplets is about 1/4 of the Rayleigh charge. At the minimum flow rate compatible with the periodic regimen, the dimensionless diameter of the droplets is smaller than one-tenth, which presents a way to use electrohydrodynamic atomization to generate droplets of highly conducting liquids in the micron-size range, in marked contrast with the cone-jet electrospray whose typical droplet size is in the nanometric regime for these liquids. In contrast with other microdripping regimes where the mass is emitted upon the periodic formation of a narrow capillary jet, the present regime gives one single droplet per oscillation, except for the almost massless fine aerosol emitted in the form of an electrospray.

Desenvolvimento e validação de métodos para a determinação de agrotóxicos em água e solo das áreas de recarga de Aquífero Guarani, na região das nascentes do Rio Araguaia, MT/GO.

Abstract: The area near the Araguaia River, between Goiás and Mato Grosso States, is the location of a portion of the recharging of the Guarani Aquifer, which is one of the world¿s largest aquifer systems and an important source of drinking water. This reservoir could be threatened by the widespread use of pesticides in maize and soybean cultivation in this area. Thus, this work developed analytical methods for the determination of imazethapyr, nicosulfuron, imazaquin, carbofuran, atrazine, linuron, clorimuronethyl and diflubenzuron, pesticides used in maize and soybean cultivation. Pesticide separation, identification and quantification were performed using High-Performance Liquid Chromatography with Diode Array Detection (HPLC-DAD) and Liquid Chromatography-Electrospray Ionization Tandem Mass Spectrometry (LC-ESI-MS/MS). Solid Phase Extraction (SPE) with C18 sorbents was optimized for sample extraction from water. Soil samples were extracted by mechanical shaking, sonication or microwave-assisted extraction with industrial and home microwave ovens. Methods were validated resulting in limits of quantification (LOQ) for the pesticides in water in the range of 0.015-0.1 ng mL, using SPE-HPLC-DAD, and 0.01 ng mL using LC-ESI-MS/MS. LOQ of 1 ng mL for all pesticides in soil were achieved using the home microwave oven and LC-ESI-MS/MS. Recoveries for pesticides with all methods were in the range 70-120 %. Relative standard deviations for repeatability and intermediate precision were less than 15 %. SPEHPLC- DAD and LC-ESI-MS/MS were employed for the analysis of samples of water from the recharge area and most of the pesticides were detected at concentrations below the minimum residue limit (MRL) of 0.1 ng mL established by the European Community. The home microwave oven and LC-ESI-MS/MS were used for the analysis of soil samples from two other regions of Brazil and the pesticides were not detected in these samples. Adsorption and desorption parameters were determined for imazethapyr, imazaquin, nicosulfuron and chlorimuron-ethyl, indicating that these pesticides have little affinity for the soil of the region of the Guarani Aquifer recharge, and show significant leaching potential, according to the ground water ubiquity score (GUS index) for these pesticides.

Identification of metabolites of kurarinone from Sophora flavescens Ait in rat urine by ultra-performance liquid chromatography with linear ion trap orbitrap mass spectrometry

Purpose: To study the in vivo metabolism of kurarinone, a lavandulyl flavanone which is a major constituent of Kushen and a marker compound with many biological activities, using ultra-performance liquid chromatography coupled with linear ion trap Orbitrap mass spectrometry (UPLC-LTQ-Orbitrap- MS). Methods: Six male Sprague-Dawley rats were randomly divided into two groups. First, kurarinone was suspended in 0.5 % carboxymethylcellulose sodium (CMC-Na) aqueous solution, and was given to rats (n = 3, 2 mL for each rat) orally at 50 mg/kg. A 2 mL aliquot of 0.5 % CMC-Na aqueous solution was administered to the rats in the control group. Next, urine samples were collected over 0-24 h after the oral administrations and all urine samples were pretreated by a solid phase extraction (SPE) method. Finally, all samples were analyzed by a UPLC-LTQ-Orbitrap mass spectrometry coupled with an electrospray ionization source (ESI) that was operated in the negative ionization mode. Results: A total of 11 metabolites, including the parent drug and 10 phase II metabolites in rat urine, were first detected and interpreted based on accurate mass measurement, fragment ions, and chromatographic retention times. The results were based on the assumption that kurarinone glucuronidation was the dominant metabolite that was excreted in rat urine. Conclusion: The results from this work indicate that kurarinone in vivo is typically transformed to nontoxic glucuronidation metabolites, and these findings may help to characterize the metabolic profile of kurarinone.

Postprandial plasma phospholipids in men are influenced by the source of dietary fat

BACKGROUND: Postprandial lipemia represents a risk factor for chronic diseases, including type 2 diabetes. Little is known about the effect of dietary fat on the plasma lipidome in the postprandial period. OBJECTIVE: The objective of this study was to assess the effect of dairy fat and soy oil on circulating postprandial lipids in men. METHODS: Men (40-60 y old, nonsmokers; n = 16) were randomly assigned in a crossover design to consume 2 breakfast meals of dairy-based or soy oil-based foods. The changes in the plasma lipidome during the 4-h postprandial period were analyzed with electrospray ionization tandem mass spectrometry and included 316 lipid species in 23 classes and subclasses, representing sphingolipids, phospholipids, glycerolipids, and sterols. RESULTS: Nonparametric Friedman tests showed significant changes in multiple plasma lipid classes, subclasses, and species in the postprandial period after both dairy and soy meals. No difference was found in triglyceridemia after each meal. However, 6 endogenous lipid classes increased after dairy but decreased after soy (P < 0.05), including ether-linked phospholipids and plasmalogens and sphingomyelin (not present in soy), dihexosylceramide, and GM3 ganglioside. Phosphatidylcholine and phosphatidylinositol were not affected by the soy meal but were significantly elevated after the dairy meal (8.3% and 16%, respectively; P < 0.05). CONCLUSIONS: The changes in postprandial plasma phospholipids in men relate to the diet composition and the relative size of the endogenous phospholipid pools. Despite similar lipemic responses as measured by changes in triglyceride concentrations, the differential responses to dairy and soy meals derived through lipidomic analysis of phospholipids suggest differences in the metabolism of soybean oil and dairy fat. The increased concentrations of plasmalogens, with potential antioxidant capacity, in the postprandial period after dairy but not soy meals may represent a further important difference in the response to these sources of fat. The trial was registered at www.anzctr.org.au as ACTRN12610000562077.

Blind column selection protocol for two-dimensional high performance liquid chromatography

The selection of two orthogonal columns for two-dimensional high performance liquid chromatography (LC×LC) separation of natural product extracts can be a labour intensive and time consuming process and in many cases is an entirely trial-and-error approach. This paper introduces a blind optimisation method for column selection of a black box of constituent components. A data processing pipeline, created in the open source application OpenMS®, was developed to map the components within the mixture of equal mass across a library of HPLC columns; LC×LC separation space utilisation was compared by measuring the fractional surface coverage, fcoverage. It was found that for a test mixture from an opium poppy (Papaver somniferum) extract, the combination of diphenyl and C18 stationary phases provided a predicted fcoverage of 0.48 and was matched with an actual usage of 0.43. OpenMS®, in conjunction with algorithms designed in house, have allowed for a significantly quicker selection of two orthogonal columns, which have been optimised for a LC×LC separation of crude extractions of plant material.

Different complexation behavior of P-functionalized ferrocene derivatives towards SnCl2 , SnCl4 and SnPh2 Cl2 : auto-ionization and redox-type reactions

The novel phosphonyl-substituted ferrocene derivatives [Fe(η(5) -Cp)(η(5) -C5 H3 {P(O)(O-iPr)2 }2 -1,2)] (Fc(1,2) ) and [Fe{η(5) -C5 H4 P(O)(O-iPr)2 }2 ] (Fc(1,1') ) react with SnCl2 , SnCl4 , and SnPh2 Cl2 , giving the corresponding complexes [(Fc(1,2) )2 SnCl][SnCl3 ] (1), [{(Fc(1,1') )SnCl2 }n ] (2), [(Fc(1,1') )SnCl4 ] (3), [{(Fc(1,1') )SnPh2 Cl2 }n ] (4), and [(Fc(1,2) )SnCl4 ] (5), respectively. The compounds are characterized by elemental analyses, (1) H, (13) C, (31) P, (119) Sn NMR and IR spectroscopy, (31) P and (119) Sn CP-MAS NMR spectroscopy, cyclovoltammetry, electrospray ionization mass spectrometry, and single-crystal as well as powder X-ray diffraction analyses. The experimental work is accompanied by DFT calculations, which help to shed light on the origin for the different reaction behavior of Fc(1,1') and Fc(1,2) towards tin(II) chloride.

A systematic investigation into a novel method for preparing carbon fibre–carbon nanotube hybrid structures

By electrospraying solvent dispersed carbon nanotubes (CNTs) with a binder onto carbon fibre (CF), hybrid structures, with an end aim to improve interfacial bonding in composites, were formed. The electrospray parameters controlling the modification of the CNT morphologies were studied. High-speed camera observations found applied voltage was critical for determining spray mode development. Electric field simulations revealed a concentrated electric field region around each fibre. Both voltage and distance played an important role in determining the CNT morphology by mediating anchoring strength and electric field force. The forming mechanism investigation of different surface morphologies suggested that binder with appropriate wetness gives freedom to the CNTs, allowing them to orientate radially from the CF surface. Linear density (LD) measurements and thermogravimetric analysis revealed that a 10 min coating increased the LD of a single CF filament by up to 31.7% while a 1 h treatment increased fibre bundle mass by 1%.

Interfacial characterization and reinforcing mechanism of novel carbon nanotube – carbon fibre hybrid composites

Carbon nanotube (CNT) deposition onto carbon fibre resulting in hybrid surface structures with various morphologies were successfully carried out using electrospray technique. In terms of tensile testing and Weibull analysis this process did not degrade fibre mechanical properties. When incorporated into composites, the interfacial shear strength (IFSS), as measured by single fibre fragmentation testing, increased by up to 124%. Experimental work was carried out to develop a deeper understanding of the interfacial reinforcing mechanism. Contact angle measurements demonstrated that the CNT deposition resulted in good wettability by the resin. Significant increases in roughness, friction and surface area were also found after CNT deposition, especially for the sample prepared using the parameter of 20 kV/10 cm at 100 °C. Surface energy analysis revealed that an increase in the dispersive surface energy due to the CNTs likely contributed to the improvement of interaction between fibre and matrix. Fractographic analysis revealed that the length of fibre pull-out and the size of cracks between the fibre and matrix were markedly decreased in the hybrid CNT surface structure, indicating that the stress transfer and interfacial shear strength have been improved. Finally, the potential for further improvement in interfacial composite properties by this approach was assessed.

High-performance liquid chromatography (HPLC) and high-performance liquid chromatography mass spectrometry (HPLC/MS) for the analysis of date rape drugs

The drugs studied in this work have been reportedly used to commit drug-facilitated sexual assault (DFSA), commonly known as "date rape". Detection of the drugs was performed using high-performance liquid chromatography with ultraviolet detection (HPLC/UV) and identified with high performance-liquid chromatography mass spectrometry (HPLC/MS) using selected ion monitoring (SIM). The objective of this study was to develop a single HPLC method for the simultaneous detection, identification and quantitation of these drugs. The following drugs were simultaneously analyzed: Gamma-hydroxybutyrate (GHB), scopolamine, lysergic acid diethylamide, ketamine, flunitrazepam, and diphenhydramine. The results showed increased sensitivity with electrospray (ES) ionization versus atmospheric pressure chemical ionization (APCI) using HPLC/MS. HPLC/ES/MS was approximately six times more sensitive than HPLC/APCI/MS and about fifty times more sensitive than HPLC/UV. A limit of detection (LOD) of 100 ppb was achieved for drug analysis using this method. The average linear regression coefficient of correlation squared (r2) was 0.933 for HPLC/UV and 0.998 for HPLC/ES/MS. The detection limits achieved by this method allowed for the detection of drug dosages used in beverage tampering. This method can be used to screen beverages suspected of drug tampering. The results of this study demonstrated that solid phase microextraction (SPME) did not improve sensitivity as an extraction technique when compared to direct injections of the drug standards.

Determination of Extracellular Molecules Produced by Vibrio Harveyi Using MS/MS

Quorum sensing (QS) is a process that allows bacteria to sense the population density of cells around them by communicating with each other via autoinducer molecules. This cross-communication is crucial in the regulation of bacterial processes such as bioluminescence, virulence, and biofilm formation. Previous research by Milburn and Makemson on Vibrio harveyi suggested that in addition of the known biosynthesis of three well-characterized autoinducers, dozens of unknown molecules are also produced and released to the environment by V. harveyi. This study was performed using electrospray tandem mass spectrometry with the purpose of detection and characterization of the extracellular molecules produced by V. harveyi, and assessment of their relationship to QS. A total of 11 molecules were characterized, from which three could be related to QS. These findings provide a glimpse of the nature of novel secondary metabolites produced by V. harveyi and provide the groundwork for further research.