Improving the Sensitivity of Mass Spectrometry by Using a New Sheath Flow Electrospray Emitter Array at Subambient Pressures (original) (raw)
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13C2-Ethanol, 13C6-glucose, and LC-MS grade water were purchased from Sigma-Aldrich (St. Louis, MO, USA), while acetone and 9-aminoacridine were from Acros (Geel, Belgium). The high-density micro-arrays for mass spectrometry (MAMS) with 100-µm recipient sites ...
Analytical Chemistry, 2008
An electrospray ionization mass spectrometry (ESI-MS) source and interface has been designed that enables efficient ion production and transmission in a 30 Torr pressure environment using solvents compatible with typical reversed-phase liquid chromatography (RPLC) separations. In this design, the electrospray emitter is located inside the mass spectrometer in the same region as an electrodynamic ion funnel. This avoids the use of a conductance limit ion inlet, as required by a conventional atmospheric pressure ESI source, and allows more efficient ion transmission to the mass analyzer. The new source, titled Subambient Pressure Ionization with Nanoelectrospray (SPIN), improves instrument sensitivity, increases the understanding of the electrospray process, and enables new electrospray interface designs. Performance of the SPIN source was evaluated by electrospraying standard solutions at 300 nL/min, and comparing results with those obtained from a standard atmospheric pressure ESI source that used a heated capillary inlet. The importance of desolvation was also investigated by electrospraying at different flow rates, which showed that the ion funnel provided an effective desolvation region to aid the creation of gas phase analyte ions. This initial study demonstrated a ∼ 5-fold improvement in sensitivity when the SPIN source was used compared to a standard atmospheric pressure ESI source.
Mass spectrometry …, 2005
A comprehensive evaluation and a thorough discussion of the fields of possible applications of the Direct-EI interface are described in this review. Direct-EI allows the direct introduction of the effluent from a capillary HPLC column into the electron ionization (EI) ion source of a mass spectrometer. Thanks to the reduced liquid intake and an in-source nebulizer, the interfacing process occurs smoothly and entirely into the ion source. No intermediate interfacing mechanisms of any sort are interposed between the column and the mass spectrometer, thus circumventing any undesired sample loss and minimizing the effort for instrument modification. Theoretically, any GC-MS system can be converted into an LC-MS for EI amenable compounds. Several parameters, crucial for a successful integration of liquid chromatography and mass spectrometry, have been considered in the evaluation of the functioning of such an interface: limit of detection, linearity of response, reproducibility, and chromatographic compatibility. Different mobile phases, also containing non-volatile buffers, were taken into account, demonstrating an outstanding separation flexibility. The entire set of experiments was carried out at different flow rates and temperatures of the ion source. The interface behavior was also tested in real world applications, with mixtures of pesticides, hormones, nitro-PAH, and endocrine-disrupting compounds, allowing picogram level detection and the possibility to record library-matchable, readily interpretable electron ionization mass spectra, for prompt compound characterization and confirmation. # 2005 Wiley Periodicals, Inc., Mass Spec Rev 24: [978][979][980][981][982][983][984][985][986][987][988][989] 2005
CHIMIA International Journal for Chemistry, 2009
The present work shows that the electrochemical properties of electrospray ionization (ESI) can be used to add functions to the process. As example, we show how the choice of the electrode material can be used to study interactions between metal ions and biomolecules in mass spectrometry (MS). In positive ionization MS, an electrospray device acts as anode, which implies oxidation reactions. Sacrificial electrodes (made of copper or zinc) are used to supply the electrospray current and to produce cations that are able to react on-line with compounds of interest. Thus, the interactions between copper ions and ligands or peptides were investigated by using a copper electrode. Another example is the in situ electrogeneration of a dinuclear zinc(ii) complex for the mass tagging of phosphopeptides when working with a zinc electrode. In order to perform these reactions on the same microchip, a dual-channel microsprayer was used, where one channel was dedicated to the tag electrogeneration and the other to the infusion of a phosphopeptides solution. Finally, this dual-channel microsprayer was used to study complexation at liquid-liquid interfaces in biphasic ESI-MS, such as thioether crowns and lead ions or peptides and phospholipids complexes. These examples illustrate the use of electrochemistry and on-chip reactions in ESI-MS analysis.
Ionization and transmission efficiency in an electrospray ionization—mass spectrometry interface
Journal of the American Society for Mass Spectrometry, 2007
The ionization and transmission efficiencies of an electrospray ionization (ESI) interface were investigated to advance the understanding of how these factors affect mass spectrometry (MS) sensitivity. In addition, the effects of the ES emitter distance to the inlet, solution flow rate, and inlet temperature were characterized. Quantitative measurements of ES current loss throughout the ESI interface were accomplished by electrically isolating the front surface of the interface from the inner wall of the heated inlet capillary, enabling losses on the two surfaces to be distinguished. In addition, the ES current lost to the front surface of the ESI interface was spatially profiled with a linear array of 340-m-diameter electrodes placed adjacent to the inlet capillary entrance. Current transmitted as gas-phase ions was differentiated from charged droplets and solvent clusters by measuring sensitivity with a single quadrupole mass spectrometer. The study revealed a large sampling efficiency into the inlet capillary (Ͼ90% at an emitter distance of 1 mm), a global rather than a local gas dynamic effect on the shape of the ES plume resulting from the gas flow conductance limit of the inlet capillary, a large (Ͼ80%) loss of analyte ions after transmission through the inlet arising from incomplete desolvation at a solution flow rate of 1.0 L/min, and a decrease in analyte ions peak intensity at lower temperatures, despite a large increase in ES current transmission efficiency. (J Am Soc Mass Spectrom 2007, 18, 1582-1590 E lectrospray ionization (ESI) has become a prominent ionization technique for a broad range of chemical and biological applications of mass spectrometry (MS) [1, 2] because of its ability to create intact, multiply charged gas-phase ions (from, e.g., biomolecules in solution) and its facile coupling with on-line separation techniques [such as liquid chromatography (LC)] [3-6]. The sensitivity of ESI-MS is largely determined by the effectiveness of producing gas-phase ions from analyte molecules in solution (ionization efficiency) and the ability to transfer the charged species from atmospheric pressure to the low-pressure region of the mass analyzer (transmission efficiency) [7-10].
ELECTROPHORESIS, 2005
Design, optimisation, and evaluation of a sheath flow interface for automated capillary electrophoresis-electrospray-mass spectrometry A sheath-flow capillary electrophoresis-mass spectrometry (CE-MS) system utilizing a fully integrated large-bore stainless-steel emitter electrode tapered at the end for micro-ionspray operation has been developed and evaluated. A separation capillary with an outer diameter of up to 360 mm was inserted into the electrode thus forming a void volume of less than 15 nL between the capillary end and the electrospray ionisation (ESI) tip. The sheath liquid, usually methanol-water (80:20) with 0.1% formic acid for positive ion mode or methanol for negative ion mode, was delivered at 0.5-1.0 mL/ min. Unlike previously reported CE-MS interfaces, the CE-MS probe was incorporated directly onto an Applied Biosystems/MDS SCIEX orthogonal-spray Turbo "V" ion source for ease of use and automatic operation. This integration enables fast and facile coupling and replacement of the separation capillary without interrupting the ion source configuration, and the sheath liquid supply. The reusable electrospray electrode was precisely fabricated and aligned with the length of the nebulizing gas tube for improved reproducibility. Automation was achieved through software control of both CE and tandem MS (MS/MS) for unattended batch sample analysis. The system was evaluated for attomole-to low femtomole-level profiling of model peptides and protein mixtures, bisphosphates, as well as antiviral nucleosidic drugs in cellular extracts.
Analytical Chemistry, 2012
Combining electrospray ionization (ESI) and solvent assisted inlet ionization (SAII) provides higher ion abundances over a wide range of concentrations for peptides and proteins than either ESI or SAII. In this method, a voltage is applied to a union connector linking tubing from a solvent delivery device and the fused silica capillary, used with SAII, inserted into a heated inlet tube of an Orbitrap Exactive mass spectrometer (MS). The union can be metal or polymeric and the voltage can be applied directly or contactless. Solution flow rates from less than a 1 μL min −1 to over 100 μL min −1 can be accommodated. It appears that the voltage is only necessary to provide charge separation in solution, and the hot MS inlet tube and the high velocity of gas through the tube linking atmospheric pressure and vacuum provides droplet formation. As little as 100 V produces an increase in ion abundance for certain compounds using this method relative to no voltage. Interestingly, the total ion current observed with SAII and this electrosprayed inlet ionization (ESII) method are very similar for weak acid solutions, but with voltage on, the ion abundance for peptides and proteins increase as much as 100-fold relative to other compounds in the solution being analyzed. Thus, switching between SAII (voltage off) and ESII (voltage on) provides a more complete picture of the solution contents than either method alone.