Ultra-low current electrospray ionization of chloroform solution for the analysis of perfluorinated sulfonic acids.

RATIONALE: Femtoamp and picoamp electrospray ionization (ESI) characteristics of a nonpolar solvent were explored. The direct ESI mass spectrometry analysis of chloroform extract solution enabled rapid analysis of perfluorinated sulfonic acid analytes in drinking water. METHODS: Neat chloroform solvent and extracts were directly used in a typical wire-in ESI setup using micrometer emitter tips. Ionization currents were measured with femtoamp sensitivity while ramping the spray voltage from 0 to -5000 V. Methanol was used as a comparison to illustrate the characteristics of electrospraying chloroform. The effects of spray voltage and inlet temperature were studied. A liquid-liquid extraction workflow was developed to analyze perfluorooctanoate sulfonate (PFOS) in drinking water using an ion-trap mass spectrometer. RESULTS: The ionization onset of chloroform solution was 41 ± 17 fA at 300 V. The ionization current gradually increased with voltage while remaining below 100 pA when using voltages up to -5000 V. The ion signal of PFOS was significantly enhanced to improve the limit of detection (LoD) to 25 ppt in chloroform. Coupled with a liquid-liquid extraction workflow, LoD of 0.38-5.1 ppt and a quantitation range of 5-400 ppt were achieved for perfluorinated sulfonic compounds in 1-ml water samples. CONCLUSIONS: Femtoamp and picoamp modes expand the solvent compatibility range of ESI and can enable quantitative analysis in parts per trillion (ppt) concentrations.

Gigaohm and Teraohm Resistors in Femtoamp and Picoamp Electrospray Ionization.

The femtoamp electrospray ionization (femtoESI) mode has been shown to exhibit unique characteristics that may facilitate ionization efficiency studies and experiments requiring low ion beam flux. Investigation of femtoESI was hindered by a tiny, applied voltage window of 10-100 V, beyond which ionization currents quickly jumped to nanoamps. This window was difficult to locate because the exact onset voltage fluctuates due to variations in ion source alignments. Large resistors (0.1-100 TΩ) in series effectively expanded the femtoESI applied voltage range, up to 1400 V. By swapping resistors, rapid alternation allows for the comparison of both ESI modes under the same alignment. In peptide mixtures, analytes with lower surface activity are suppressed in the nanoESI mode whereas the femtoESI mode shows signal enhancement of less surface-active species. For protein solutions, there is little change in the charge states generated but the femtoESI mode does show a decrease in the average charge state of protein peaks. Peptides and proteins analyzed in the femtoESI mode also tend to generate higher intensity sodiated peaks over protonated peaks at specific charge states compared with nanoESI mode operation.

Nested-channel for on-demand alternation between electrospray ionization regimes.

On-demand electrospray ionization from different liquid channels in the same emitter was realized using filamented capillary and gas phase charge supply. The solution sub-channel was formed when back-filling solution to the emitter tip by capillary action along the filament. Gas phase charge carriers were used to trigger electrospray ionization from the solution meniscus at the tip. The meniscus at the tip opening may be fully filled or partially empty to generate electrospray ionization in main-channel regime and sub-channel regime, respectively. For emitters with 4 µm tip opening, the two nested electrospray (nested-ESI) channels accommodated ESI flow rates ranging from 50 pL min-1 to 150 nL min-1. The platform enabled on-demand regime alternations within one sample run, in which the sub-channel regime generated smaller charged droplets. Ionization efficiencies for saccharides, glycopeptide, and proteins were enhanced in the sub-channel regime. Non-specific salt adducts were reduced and identified by regime alternation. Surprisingly, the sub-channel regime produced more uniform responses for a peptide mixture whose relative ionization efficiencies were insensitive to ESI conditions in previous picoelectrospray study. The nested channels also allowed effective washing of emitter tip for multiple sampling and analysis operations.

Activation of the jasmonic acid pathway by depletion of the hydroperoxide lyase OsHPL3 reveals crosstalk between the HPL and AOS branches of the oxylipin pathway in rice.

The allene oxide synthase (AOS) and hydroperoxide lyase (HPL) branches of the oxylipin pathway, which underlie the production of jasmonates and aldehydes, respectively, function in plant responses to a range of stresses. Regulatory crosstalk has been proposed to exist between these two signaling branches; however, there is no direct evidence of this. Here, we identified and characterized a jasmonic acid (JA) overproduction mutant, cea62, by screening a rice T-DNA insertion mutant library for lineages that constitutively express the AOS gene. Map-based cloning was used to identify the underlying gene as hydroperoxide lyase OsHPL3. HPL3 expression and the enzyme activity of its product, (E)-2-hexenal, were depleted in the cea62 mutant, which resulted in the dramatic overproduction of JA, the activation of JA signaling, and the emergence of the lesion mimic phenotype. A time-course analysis of lesion formation and of the induction of defense responsive genes in the cea62 mutant revealed that the activation of JA biosynthesis and signaling in cea62 was regulated in a developmental manner, as was OsHPL3 activity in the wild-type plant. Microarray analysis showed that the JA-governed defense response was greatly activated in cea62 and this plant exhibited enhanced resistance to the T1 strain of the bacterial blight pathogen Xanthomonasoryzaepvoryzae (Xoo). The wounding response was attenuated in cea62 plants during the early stages of development, but partially recovered when JA levels were elevated during the later stages. In contrast, the wounding response was not altered during the different developmental stages of wild-type plants. These findings suggest that these two branches of the oxylipin pathway exhibit crosstalk with regards to biosynthesis and signaling and cooperate with each other to function in diverse stress responses.

Facile synthesis of polyaniline "sunflowers" with arrays of oriented nanorods.

Polyaniline (PANI) "sunflowers" made of arrays of oriented nanorods were synthesized by chemical oxidative polymerization of aniline in the presence of cetyltrimethylammonium bromide (CTAB) and suitable concentration of HNO3 at about 0 degrees C (ice bath). The reaction conditions, such as the concentration of reagents and reaction temperature were systematically investigated and controlled on the preparation of PANI "sunflowers". The results also suggest that HNO3 probably plays a key role in forming PANI "sunflowers". A possible forming mechanism of the PANI nanostructures is offered.