•Extensive fragmentation, no molecular ion in GC–MS analysis of synthetic cathinones.•Improved molecular ion intensity and more informative fragmentation using cold EI.•Potential for improved ...identification of cathinones using MS/MS of molecular ion
Gas chromatography–mass spectrometry is currently among the methods of choice for the analysis of synthetic cathinones. However, these analytes are extremely labile, and classical electron ionization (EI) results in excessive and relatively uninformative fragmentation, yielding little to no molecular ions. Cold EI reduces the internal energy of the analytes by expansion of supersonic molecular beams prior to their ionization, leading to improved molecular ion information. In this study, classical and cold EI were compared for the analysis of synthetic cathinones. We demonstrated that cold electron ionization produced enhanced molecular ion intensity for most of the bath salts considered, as well as more informative fragmentation. Principal component analysis showed that cold EI mass spectra are more discriminative than those obtained by classical EI. MS/MS can offer improved confidence in synthetic cathinone identification even in cases where the relative intensity of the molecular ion is very low in MS spectra.
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Depending on the spraying conditions and fluid properties, a variety of electrospray regimes exists. Here we explore the changes in ion production that accompany the transitions among the three axial ...spraying modes, the burst mode, the pulsating Taylor cone mode, and the cone-jet mode. Spray current oscillation and phase Doppler anemometry measurements, fast imaging of the electrified meniscus, and mass spectrometry are utilized to study the formation, size, velocity, and chemical composition of droplets produced in the three modes. High-speed images indicate that the primary droplets are produced by varicose waves and lateral kink instabilities on the liquid jet emerging from the Taylor cone, whereas secondary droplets are formed by fission. Dramatic changes in the droplet size distributions result from the various production and breakup mechanisms observed at different emitter voltages and liquid flow rates. We demonstrate that droplet fission can be facilitated by space charge effects along the liquid jet and in the plume. Compared to the other two regimes, a significantly enhanced signal-to-noise ratio, a lower degree of analyte oxidation, and milder fragmentation are observed for the cone-jet mode.
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Electrospray ionization mass spectrometry (ESI-MS) at flow rates below ~10 nL/min has been only sporadically explored because of difficulty in reproducibly fabricating emitters that can operate at ...lower flow rates. Here we demonstrate narrow orifice chemically etched emitters for stable electrospray at flow rates as low as 400 pL/min. Depending on the analyte concentration, we observe two types of MS signal response as a function of flow rate. At low concentrations, an optimum flow rate is observed slightly above 1 nL/min, whereas the signal decreases monotonically with decreasing flow rates at higher concentrations. For example, consumption of 500 zmol of sample yielded signal-to-noise ratios ~10 for some peptides. In spite of lower MS signal, the ion utilization efficiency increases exponentially with decreasing flow rate in all cases. Significant variations in ionization efficiency were observed within this flow rate range for an equimolar mixture of peptide, indicating that ionization efficiency is an analyte-dependent characteristic for the present experimental conditions. Mass-limited samples benefit strongly from the use of low flow rates and avoiding unnecessary sample dilution. These findings have important implications for the analysis of trace biological samples.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NUK, OBVAL, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
To provide an objective measure of the correlation between the internal energy content of ions generated by matrix-assisted laser desorption/ionization (MALDI) and the matrix properties, a series of ...well-characterized benzyl-substituted benzylpyridinium salts were used as thermometer molecules (TMs). To determine the internal energy variations of analyte ions, the survival yields of TM molecular ions were measured in three different matrixes, α-cyano-4-hydroxycinnamic acid (CHCA), 3,5-dimethoxy-4-hydroxycinnamic acid (sinapinic acid, SA), and 2,5-dihydroxybenzoic acid (DHB). Statistical analysis of extensive survival yield data indicated that there were discernible differences among the studied matrixes. The experimental survival yields of the TM ions were used to calculate the unimolecular decomposition rate coefficient. Corresponding theoretical reaction rate coefficients were calculated based on the Rice−Ramsperger−Kassel−Marcus (RRKM) theory for different internal energies of the TMs. The internal energies of the ions were obtained by projecting the experimental rate coefficient values onto the theoretical curves obtained by the RRKM calculations. Molecular ions of the analytes showed decreasing survival yields and consequently increasing internal energies in the three matrixes in the following order: CHCA, SA, and DHB with “cold”, “intermediate”, and “hot” characteristics, respectively. Qualitatively, this could be interpreted as a significant departure from earlier observations suggesting an opposite trend. The classification as hot and cold matrixes should be further qualified by accounting for the influence of laser pulse energy and the nature of the analyte. Higher laser pulse energy led to an elevated level of energy transferred to the analyte, which in turn resulted in a diminished survival yield of the analyte molecular ion. It is quite possible that the assignment of hot and cold reverses as the analyte or the laser energy changes. These findings can help predict the outcome of postsource decay experiments and clarify the concept of hot and cold matrixes in MALDI mass spectrometry.
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•Four types of seismic moment connections tested under column loss scenario.•Two full strength connections and two partial strength connections.•Finite element models validated against experimental ...data.•Three connections experienced large deflections prior to failure.•Partial strength connection requires strengthening to improve deformation capacity.
The beam-to-column connections of moment-resisting steel frames should exhibit capacities that allow them to transfer the forces that develop under normally expected loading conditions. However, when a column is lost owing to accidental loading, these conditions change, and the forces are redistributed to the adjacent beams and columns. In such cases, the connections must be capable of resisting the combined axial and flexural loads and allow for the redistribution of the loads, so that progressive collapse development is prevented. In this study, we investigated the performances of four types of beam-to-column connections, namely, the welded cover plate flange connection (CWP), the haunch end plate bolted connection (EPH), the reduced beam section welded connection (RBS), and the unstiffened extended end plate bolted connection (EP), against progressive collapse. Two span frames were constructed and tested under a central column removal scenario until failure. The results from the experimental tests were used to validate finite element models. The CWP, EPH, and RBS specimens showed good ductility, with the catenary action making a significant contribution to the ultimate load resistance. Further, the ultimate rotations of the beams were greater than the deformation limit given in the latest Unified Facilities Criteria guidelines for design of buildings to resist progressive collapse. Specimen EP showed the lowest ductility and ultimate load resistance, with the bolts in the rows under tension fracturing before the catenary action could develop. Further, the failure mode for specimen EP indicated that bolt strengthening is necessary for improving its progressive collapse resistance.
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8.
Solvated Ion Evaporation from Charged Water Nanodroplets Znamenskiy, Vasiliy; Marginean, Ioan; Vertes, Akos
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory,
09/2003, Volume:
107, Issue:
38
Journal Article
Peer reviewed
The behavior of electrified droplets in an atmospheric environment and the mechanism of ion formation in electrospray ionization are the subject of continuing debate. Experimental evidence to decide ...between the various models of ion formation (e.g., ion evaporation, Coulomb explosion, and charge residue model) is not readily available and is especially scarce for nanometer-sized droplets. Even the morphology, the structure, and the dynamics of aqueous nanodroplets containing ionic solutes are poorly understood. Classical molecular dynamics simulations were used to explore the effect of ions on the shape and structure of these droplets. We also followed the gas-phase formation of hydronium and glycine homologue ions from the disintegrating nanodroplets. Droplets up to 6.5 nm in diameter were studied using potentials for the peptides and water that accounted for their internal degrees of freedom. Validity testing of the model indicated good agreement between the calculated radial distribution functions for water and corresponding neutron diffraction data. The self-diffusion coefficients and the enthalpy of evaporation derived from the model also gave good agreement with the experimental values. Our results showed that the ions were distributed in concentric layers within the droplet. This is a departure from the expectation that ions inside the droplet follow a monotonic radial distribution close to the surface because of the Coulomb repulsion and/or hydrophobic forces. Due to the presence of ions in the droplet, both overall shape deformations and enhanced surface fluctuations were observed. Charge reduction at the Rayleigh limit proceeded through the formation of transient surface protrusions. For droplets containing ions, amplitude protrusions higher than in the case of pure water droplets developed. These protrusions served as the intermediate stage preceding ion ejection. The evaporated ions detached from the droplet with a solvation shell of approximately 10 water molecules per ion. Our data were coherent with the solvated ion evaporation model for droplets close to the Rayleigh limit. To the best of our knowledge, these are the first molecular dynamics calculations on realistic charged nanodroplets to give insight into their structure and fission dynamics.
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Spraying of liquids through an electrified meniscus has become a method of choice to produce ions from large biomolecules. Using mass spectrometry, the generated ions can be analyzed to provide ...detailed information on their composition and structure. This technique enables high-throughput protein analysis that is a prerequisite for answering the questions presented by proteomics. In this report, Taylor cone deformations are shown to play a central role in the mechanism of electrostatic spraying. Spontaneous spray current oscillations are known to exist in most electrospray regimes and affect the stream of ions introduced into the mass spectrometer. Fast time-lapse imaging of the Taylor cone throughout its evolution indicates the presence of a nodal line and standing waves on its surface. Four phases of the cone pulsation cycle (liquid accumulation, cone formation, ejection of a jet, relaxation) are established. Based on image analysis, apex velocities, curvatures, and opening angles are determined. During jet ejection, the apex velocity and the curvature exhibit singularities. Furthermore, the pulsation frequencies of the Taylor cone deformations are determined using Fourier analysis of light refraction measurements. The oscillation frequency of the electrospray current collected by the counter electrode shows close correlation to the cone deformations, providing the first direct evidence that links spray current oscillations to Taylor cone pulsation. Thus, monitoring the oscillation frequency throughout the spraying process and adjusting the spray parameters can be used to stabilize the spray. Furthermore, synchronizing the injection of ions in time-of-flight systems with the spontaneous spray oscillations may improve the signal-to-noise ratio in the collected mass spectra.
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A detailed characterization of a conventional low-flow electrospray ionization (ESI) source for mass spectrometry (MS) using solution compositions typical of reversed-phase liquid chromatography is ...reported. Contrary to conventional wisdom, the pulsating regime consistently provided better ESI-MS performance than the cone-jet regime for the interface and experimental conditions studied. This observation is supported by additional measurements showing that a conventional heated capillary interface affords more efficient sampling and transmission for the charged aerosol generated by a pulsating electrospray. The pulsating electrospray provided relatively constant MS signal intensities over a wide range of voltages, while the signal decreased slightly with increasing voltage for the cone-jet electrospray. The MS signal also decreased with increasing emitter−interface distance for both pulsating and cone-jet electrosprays due to the expansion of the charged aerosol plume. At flow rates below 100 nL/min, the MS signal increased with increasing flow rate due to increased number of gas-phase ions produced. At flow rates greater than 100 nL/min, the signal reached a plateau due to decreasing ionization efficiency at larger flow rates. These results suggest approaches for improving MS interface performance for low-flow (nano- to micro-) electrosprays.
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