Analysis of 'ARN' naphthenic acids by high temperature gas chromatography and high performance liquid chromatography

Examination by high temperature GC (HTGC) of the methyl esters of the so-called 'ARN' naphthenic acids from crude oils of North Sea UK, Norwegian Sea and West African oilfields revealed the distributions of resolved 4-8 ring C80 tetra acids and trace amounts of other acids. Whilst all three oils contained apparently the same major acids, the proportions of each differed, possibly reflecting the growth temperatures of the archaebacteria from which the acids are assumed to have originated. The structures of the 4, 5, 7 and 8 ring acids are tentatively assigned by comparison with the known 6 ring acid and related natural products and an HPLC method for the isolation of the individual acids is described. ESI-MS of individual acids isolated by preparative HPLC established the elution order of the 4-8 ring acids on the HPLC and HTGC systems and revealed the presence of previously unreported acids tentatively identified as C81 and C82 7 and 8 ring analogues.     

Liquid chromatography-inductively coupled plasma mass spectrometry.

The technique of coupling liquid chromatography to inductively plasma mass spectrometry (ICP-MS) is reviewed. A brief introduction to the ICP-MS instrument is given as well as methods to couple the two analytical instruments together. The various types of LC that have been used with ICP-MS detection are discussed and advantages over traditional methods of detection are highlighted, such as the improvements in sensitivity and selectivity. Several applications that have been described in the literature are reviewed. An outlook for the future of LC-ICP-MS, particularly with regard to elemental speciation is given.     

Sensitivity of in-Plane Strain Measurement to Calibration Parameter for out-of-Plane Specimen Rotations

In practice, out-of-plane motions usually are not avoidable during experiments. Since 2D–DIC measurements are vulnerable to parasitic deformations due to out-of-plane specimen motions, three-dimensional digital image correlation (StereoDIC or 3D–DIC) oftentimes is employed. The StereoDIC method is known to be capable of accurate deformation measurements for specimens subjected to general three-dimensional motions, including out-of-plane rotations and displacements. As a result, there has been limited study of the deformation measurements obtained when using StereoDIC to measure the displacement and strain fields for a specimen subjected only to out-of-plane rotation. To assess the accuracy of strain measurements obtained using stereovision systems and StereoDIC when a specimen undergoes appreciable out of plane rotation, rigid body out-of-plane rotation experiments are performed in the range ?40⁰?≤?θ?≤?40⁰ using a two-camera stereovision system. Results indicate that (a) for what would normally be considered “small angle” calibration processes, the measured normal strain in the foreshortened specimen direction due to specimen rotation increases in a non-linear manner with rotation angle, with measurement errors exceeding ±1400με and (b) for what would normally be considered “large angle” calibration processes, the magnitude of the errors in the strain are reduced to ±300με. To theoretically assess the effect of calibration parameters on the measurements, two separate analyses are performed. First, theoretical strains due to out-of-plane rigid body rotation are determined using a pinhole camera model to project a series of three-dimensional object points into the image plane using large angle calibration parameters and then re-project the corresponding sensor plane coordinates back into the plane using small angle calibration parameters. Secondly, the entire imaging process is also simulated in order to remove experimental error sources and to further validate the theory. Results from both approaches confirmed the same strain error trends as the experimental strain measurements, providing confidence that the source of the errors is the calibration process. Finally, variance based sensitivity analyses show that inaccuracy in the calibrated stereo angle parameter is the most significant factor affecting the accuracy of the measured strain.     

Identification of the Local Elasto-Plastic Behavior of FSW Welds Using the Virtual Fields Method

The present study focuses on the identification of the evolution of the local elasto-plastic properties of an Al 5456 FSW weld. To make the best use of the data collected using digital image correlation and to obtain an accurate identification of the evolution of the mechanical properties throughout the weld, an inverse procedure based on the Virtual Fields Method is proposed. Then, the strain-rate dependence of these properties is investigated by performing a set of tensile tests with a cross-head displacement speed evolving from 0.01 mm.s^???1 to 76 mm.s^???1. Identification of the evolution of the plastic properties throughout the weld with high spatial resolution has been achieved, and results from our study indicate that the plastic parameters in the center of the weld undergo a significant change even at low strain-rate (10 s^???1).     

Oligoether-strapped calix[4]pyrrole: an ion-pair receptor displaying cation-dependent chloride anion transport

A ditopic ion-pair receptor (1), which has tunable cation- and anion-binding sites, has been synthesized and characterized. Spectroscopic analyses provide support for the conclusion that receptor 1 binds fluoride and chloride anions strongly and forms stable 1:1 complexes ([1·F](-) and [1·Cl](-)) with appropriately chosen salts of these anions in acetonitrile. When the anion complexes of 1 were treated with alkali metal ions (Li(+), Na(+), K(+), Cs(+), as their perchlorate salts), ion-dependent interactions were observed that were found to depend on both the choice of added cation and the initially complexed anion. In the case of [1·F](-), no appreciable interaction with the K(+) ion was seen. On the other hand, when this complex was treated with Li(+) or Na(+) ions, decomplexation of the bound fluoride anion was observed. In contrast to what was seen with Li(+), Na(+), K(+), treating [1·F](-) with Cs(+) ions gave rise to a stable, host-separated ion-pair complex, [F·1·Cs], which contains the Cs(+) ion bound in the cup-like portion of the calix[4]pyrrole. Different complexation behavior was seen in the case of the chloride complex, [1·Cl](-). Here, no appreciable interaction was observed with Na(+) or K(+). In contrast, treating with Li(+) produces a tight ion-pair complex, [1·Li·Cl], in which the cation is bound to the crown moiety. In analogy to what was seen for [1·F](-), treatment of [1·Cl](-) with Cs(+) ions gives rise to a host-separated ion-pair complex, [Cl·1·Cs], in which the cation is bound to the cup of the calix[4]pyrrole. As inferred from liposomal model membrane transport studies, system 1 can act as an effective carrier for several chloride anion salts of Group 1 cations, operating through both symport (chloride+cation co-transport) and antiport (nitrate-for-chloride exchange) mechanisms. This transport behavior stands in contrast to what is seen for simple octamethylcalix[4]pyrrole, which acts as an effective carrier for cesium chloride but does not operates through a nitrate-for-chloride anion exchange mechanism.     

Optimization of HNO production from N,O-bis-acylated hydroxylamine derivatives

A wide range of N,O-bis-acylated hydroxylamine derivatives with chloro or arenesulfonyl leaving groups, and a related set of N-hydroxy-N-acylsulfonamides, have been synthesized and evaluated for nitroxyl (HNO) production. Mechanistic studies have revealed that the observed aqueous chemistry is more complicated than originally anticipated, and have been used to develop a new series of efficient HNO precursors (4u-4x, 7c-7d) with tunable half-lives.