Electrospray Plume Research Articles

Inferring ion cluster lifetimes from energy-resolved mass spectra of an EMI-BF4 electrospray plume

The fragmentation of ion clusters within the accelerating fields of ionic liquid ion sources (ILISs) is well documented and degrades ILIS performance and lifetime. Some of the most popular ILIS liquids, such as EMI-BF4 (1-Ethyl-3-methylimidazolium tetrafluoroborate) and EMI-Im (1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), emit clusters with lifetimes as low as ∼1 ns. Studies of fragmentation within the accelerating field typically rely on measuring the plume energy distribution averaged over all plume species and comparing those measurements with numerical simulations to estimate ion cluster lifetimes. Here, for the first time, we estimate EMI-BF4 cluster lifetimes by analyzing the energy distributions of individual plume species. We use this novel analysis method to estimate mean lifetimes of positive EMI-BF4 ion clusters from previously published experimental data. We find that the mean lifetime ranges from τ=3.7ns to τ=124ns for [EMI+][EMI-BF4] dimers and ranges from τ=1.5ns to τ=23ns for [EMI+][EMI-BF4]2 trimers. Fitting those data to an analytical fragmentation model, we estimate the binding energy and temperature as ΔGS0=0.49eV and T=394K for dimers and ΔGS0=0.40eV and T=365K for trimers. Comparing our results with previous studies supports the conclusion that clusters are emitted with a wide distribution of internal energies, contrary to the common assumption of single internal energy for each species.

QCM response to variable energy electrospray plume

This paper presents the frequency response of a 6 MHz quartz crystal microbalance (QCM) when bombarded by ionic liquid ion source electrospray plumes of various energies using EMI-BF4\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_4$$\\end{document}. Time of flight mass spectrometry (ToF-MS) measurements confirm ion mode emission from the single, externally wetted tungsten emitter ion source and a retarding potential analyzer (RPA) was used to record the energy profile of the plume. The frequency change of the QCM is positively correlated with plume energy, with the most energetic plume (1900 eV) yielding the largest (positive) frequency change, and the lowest energy (30 eV) yielding a decrease in frequency. These measurements indicate removal of material on the quartz crystal surface at high energies, and deposition of propellant at low energies. X-ray photoelectron spectroscopy (XPS) was used to measure the equivalent homogeneous composition of the surface of each quartz crystal, which revealed traces of propellant across all samples and showed greater deposition rates when exposed to a low energy plume.

Electrospray plume divergence: Background pressure influence

The influence of background pressure on electrospray plume evolution is observed by simulating the emission and propagation of an electrospray particle population into an electric field at a range of relevant background pressures. Differences in plume evolution from atmospheric pressure to one hundredth of atmospheric pressure are evident from plume characteristics such as (1) the overall domain of the resulting plumes and (2) the terminal angle at a downstream terminus of one standard deviation and three standard deviations of particle number density. Plume divergence and terminal angle are shown to correlate strongly with background pressure for pressures above which plume-background collision rates are significant, consistent with experimental observations of increased plume divergence with increased background pressure. The results suggest a simple expression for the pressure below which a system achieves minimum plume divergence: Pth=kT/7.7299σfld for a system of temperature T, background fluid molecules with cross-section σfl, and plume species of diameter d.

Electric Field-Modulated Electrospray Ionization Mass Spectrometry for Quantity Calibration and Mass Tracking.

Analyses conducted by electrospray ionization (ESI) mass spectrometry (MS) typically entail performing a number of preparatory steps, which include quantity calibration and mass calibration. Quantity calibration can be affected by signal noise, while mass calibration can be affected by instrumental drift if analyses are performed over an extended period of time. Here, we present two methods for achieving these calibrations using modulation of electrospray plume by alternating electric fields and demodulating the resulting MS ion currents. For this purpose, we use an ESI source fitted with three ring electrodes between the electrospray emitter and the mass spectrometer's inlet. One of these electrodes is supplied with a sine electric signal. Optionally, a nanoESI emitter is also placed between the ring electrodes and the mass spectrometer's orifice to supply calibrant ions. The ion currents, recorded with this setup, present wave-like features. In the first variant, using a triple quadrupole mass analyzer, the ion currents are subjected to data treatment by fast Fourier transform (FFT), and the resulting FFT magnitudes are correlated with analyte concentrations to produce a calibration plot. In the second variant, using a quadrupole time-of-flight mass analyzer, the mass spectra recorded at the analyte ion current maxima are mass-checked using the m/z value of the internal standard (injected via nanoESI emitter), which appears predominantly in the time intervals corresponding to the analyte ion current minima. The setup has been characterized using simulation software and optimized. Overall, the method enables the preparation of quantity calibration plots and monitoring (minor) m/z drifts during prolonged analyses.

High-Speed Schlieren Imaging of Vapor Formation in Electrospray Plume.

Previous mechanistic descriptions of electrosprays mostly focused on the dynamics of Taylor cones, initial droplets, and progeny droplets. However, vapor formation during droplet desolvation in an electrospray plume has not been discussed to a great extent. Here, we implement a double-pass on-axis schlieren high-speed imaging system to observe generation and propagation of vapors in an offline electrospray source under different conditions. Switching between turbulent and laminar vapor flow was observed for all of the scanned conditions, which may be attributed to randomly occurring disturbances in the sample flow inside the electrospray emitter. Calculation of mean vapor flow velocity and analysis of vapor flow patterns were performed using in-house developed image processing programs. Experiments performed at different electrospray voltages (0-6 kV), solvent flow rates (100-600 μL min-1), and methanol concentrations (50-100%), indicate only a weak dependency between electrospray voltage and mean vapor velocity, implying that the vapor is mostly neutral; thus, the vapor is not accelerated by electric field. On the other hand, electrospraying solutions of analytes (with mass 151 Da or 12 kDa) did not remarkably increase the overall vapor flow velocity. The source of vapor's velocity is attributed to the inertia of the electrospray droplets. Although there are some differences between a modern electrospray ionization (ESI) setup and the setup used in our experiment (e.g., using a higher flow rate and larger emitter), we believe the findings of our study can be projected to a modern ESI setup.

Moderate Signal Enhancement in Electrospray Ionization Mass Spectrometry by Focusing Electrospray Plume with a Dielectric Layer around the Mass Spectrometer's Orifice.

Electrospray ionization (ESI) is among the commonly used atmospheric pressure ionization techniques in mass spectrometry (MS). One of the drawbacks of ESI is the formation of divergent plumes composed of polydisperse microdroplets, which lead to low transmission efficiency. Here, we propose a new method to potentially improve the transmission efficiency of ESI, which does not require additional electrical components and complex interface modification. A dielectric plate-made of ceramic-was used in place of a regular metallic sampling cone. Due to the charge accumulation on the dielectric surface, the dielectric layer around the MS orifice distorts the electric field, focusing the charged electrospray cloud towards the MS inlet. The concept was first verified using charge measurement on the dielectric material surface and computational simulation; then, online experiments were carried out to demonstrate the potential of this method in MS applications. In the online experiment, signal enhancements were observed for dielectric plates with different geometries, distances of the electrospray needle axis from the MS inlet, and various compounds. For example, in the case of acetaminophen (15 μM), the signal enhancement was up to 1.82 times (plate B) using the default distance of the electrospray needle axis from the MS inlet (d = 1.5 mm) and 12.18 times (plate C) using a longer distance (d = 7 mm).

Droplet-gas interactions in nanoelectrospray multiphase flow

Electrospray (ES) is production of a charged droplet plume that transits from an electrically biased supply capillary to a counter electrode under the influence of an electric field. Drag interactions with the surrounding gas decelerate the droplets while transferring the momentum from droplets to accelerate the surrounding gas, resulting in an induced gas flow. This work seeks to characterize the structure of the resulting gas jet and identify the key mechanisms defining the flow structure. The phenomenon of gas jets produced by momentum transfer from nano-electrospray (nES) plumes is explored with schlieren visualization, thermal anemometry, and numerical simulations. Schlieren visualization experiments provide information on the flow structure in support of simulation predictions, and the hot thermistor anemometry measurements of gas velocities outside the spray demonstrate quantitatively validated simulation results. The study reveals the formation of a moderately high velocity coaxial gas jet within the nES plume and provides insight into the overall flow structure of the induced flow. The multiphase electrohydrodynamic simulations enable numerical experimentation to explore the fundamental physics of coupled droplet-gas transport and the resulting flow structure. The simulations, confirmed by the experiments, reveal gas jetting induced by nES with a narrow (sub hundred micrometers in diameter) core originating from the nES liquid-jet breakup region and a surrounding larger-in-extent zone (several hundred micrometers in diameter) of lower velocity gas flow within the electrospray plume. This behavior is due to nES ejecting a stream of droplets from the tip of a narrow liquid cone-jet, where the combined effect of many small droplets transferring momentum to a confined region of gas yields a narrow but high-velocity gas stream. The micro-jets produced by nES have practical utility for mass spectrometry, 3D printing and fabrication, and thermal management.

Rapid Droplet Sampling Interface for Low-Volume, High-Throughput Mass Spectrometry Analysis.

Here, we present a rapid droplet sampling interface (RDSI) electrospray ionization mass spectrometry (ESI-MS) system as a high-throughput, low-volume, noncontact, and minimal-carryover approach for characterization of liquids. Liquid characterization was achieved by combining droplet ejection with an open-face microflow capillary with a 2.5 μL/min continuous flow of carrier solvent. Through this implementation, single 0.3 nL droplets containing the analyte effectively mix with 4-8 nL of carrier solvent and create a combined electrospray plume. The carrier solvent continuously cleaned the system, eliminating carryover. A sampling rate of 5 Hz was achieved for droplets containing 1 μM propranolol or 5 μM leu-enkephalin with each droplet fully baseline-resolved (138 ± 32 ms baseline-to-baseline). Using a SCIEX API4000 mass spectrometer, a lower limit of quantification (LLOQ) of propranolol was 15 nM, corresponding to 1.16 fg of propranolol in the droplet, and was linear across 3 orders of magnitude. Quantitation could be achieved by adding an isotopically labeled internal standard, as done in conventional ESI. Signal transients were faster than the acquisition speed of the mass spectrometer, resulting in artificially high reproducibility of 15-30% RSD droplet-to-droplet. Analyte-solvent mixing ratios could be controlled by adjusting droplet positioning along the open-face capillary with an optimal position about 0.4 mm from the tip end. The range of analyte coverage was exemplified by measures of peptides and drugs in methanol, water, and buffer solutions. In a comparison to the Open Port Sampling Interface (OPSI) implemented on the same system, the RDSI had 78× greater sensitivity, 6× greater throughput and used significantly less carrier solvent.

Formation and fragmentation of 2-hydroxyethylhydrazinium nitrate (HEHN) cluster ions: a combined electrospray ionization mass spectrometry, molecular dynamics and reaction potential surface study.

The 2-hydroxyethylhydrazinium nitrate ([HOCH2CH2NH2NH2]+NO3-, HEHN) ionic liquid has the potential to power both electric and chemical thrusters and provide a wider range of specific impulse needs. To characterize its capabilities as an electrospray propellant, we report the formation of HEHN cluster ions in positive electrospray ionization (ESI) and their collision-induced dissociation. The experiment was carried out using ESI guided-ion beam mass spectrometry which mimics an electrospray thruster in terms of ion emission, injection into a vacuum and fragmentation in space. Measurements include compositions of primary ions in the electrospray plume and their individual dissociation product ion cross sections and threshold energies. The results were interpreted in light of theoretical modeling. To determine cluster structures that are comprised of [HE + H]+ and NO3- constituents, classical mechanics simulations were used to create initial guesses; and for clusters that are formed by reactions between ionic constituents, quasi-classical direct dynamics trajectory simulations were used to mimic covalent bond formation and structures. All candidate structures were subject to density functional theory optimization, from which global minimum structures were identified and used for construction of reaction potential energy surface. The comparison between experimental values and calculated dissociation thermodynamics was used to verify the structures for the emitted species [(HEHN)nHE + H]+, [(HEHN)n(HE)2 + H]+, [(HE)n+1 + H]+ and [(HE)nC2H4OH]+ (n = 0-2), of which [(HE)1-2 + H]+ dominates. Due to the protic nature of HEHN, cluster fragmentation can be rationalized by proton transfer-mediated elimination of HNO3, HE and HE·HNO3, and the latter two become dominant in larger clusters. [(HE)2 + H]+ and [(HE)nC2H4OH]+ contain H-bonded water and consequently are featured by water elimination in fragmentation. These findings help to evaluate ion formation and fragmentation efficiencies and their impacts on electrospray propulsion.

High angle mass flux of an electrospray plume

High-resolution mass flux measurements of an electrospray plume are reported at high (>30^{circ }) angles, which are relevant to direct impingement of downstream electrodes. Interrogation of the plume edge greatly reduces uncertainty in electrospray device lifetime estimation related to mass flux to electrode surfaces. An angularly-actuated Thermoelectric Quartz Crystal Microbalance (TQCM) provides resolution down to sim2 pg cm^{-2} s^{-1}, allowing the highest resolution mass flux measurements of an electrospray plume to be reported herein. In-situ microscopy of the electrospray meniscus revealed changes to the electrode lines-of-sight of approximately 2°–3° due to the increasing meniscus tip height with beam current. Using the TQCM measurements and previous QCM results, a data-driven model is proposed for estimating electrode impingement as a function of beam current and aperture line-of-sight, which quantitatively captures the rapid increase in mass flux at higher beam currents or at low angles. The results show it is possible to guarantee negligible electrode impingement within a specified range of throttle levels.

Recent Advances in Single-Cell Metabolomics Based on Mass Spectrometry

Recent Advances in Single-Cell Metabolomics Based on Mass Spectrometry

Electrospray plume evolution: Influence of drag

The University of California, Los Angeles (UCLA) Plasma, Energy, & Space Propulsion Laboratory (PESPL) presents the Discrete Electrospray Lagrangian Interaction (DELI) Model for simulating the evolution of electrospray plumes. This publication describes the DELI Model, verification of its Coulomb collision module, model validation with atmospheric plume data, and novel comparisons of simulated plumes evolved with different fractions of the drag force. DELI Model results reproduce experimentally-observed droplet clustering events that yield plume expansion as a result of Coulomb repulsion. Furthermore, the presented comparison of identical emitted species evolved to steady state with different fractions of applied drag force demonstrates decreased mean droplet velocity and increased plume expansion with increased drag force. Publication results serve as a useful tool in examining electrospray plume evolution in atmospheric and vacuum regimes.

Erratum: “Ion-induced charge emission from unpolished surfaces bombarded by an [Emim][BF4] electrospray plume” [J. Appl. Phys. 131, 243302 (2022)

Erratum: “Ion-induced charge emission from unpolished surfaces bombarded by an [Emim][BF4] electrospray plume” [J. Appl. Phys. 131, 243302 (2022)

Ion-induced charge emission from unpolished surfaces bombarded by an [Emim][BF4] electrospray plume

Experiments were conducted at the University of Illinois at Urbana Champaign Electric Propulsion Laboratory to study the ion-induced secondary charge emission from surfaces bombarded by an [Emim][BF4] electrospray plume. The surfaces were unpolished and had oxide and hydrocarbon layers typical of as-received materials used in electrospray experiments. The effect of changing the bias from −85 to +85 V on the target collecting current from the electrospray plume was measured. These data are used to calculate the yield of positive and negative charged species emission from the target due to bombarding cations and anions. The yields of positive charges per incident cation (γcation+), negative charges per incident cation (γcation−), positive charges per incident anion (γanion+), and negative charges per incident anion (γanion−) are measured for eight different industrial materials commonly used in electrospray diagnostics or thruster and spacecraft construction. These yields range from 0 to 1.3 charges per incident ion over a range of emitter voltages from 1.5 to 2.9 kV and largely display linearly increasing trends with increasing emitter voltage. Over this emitter voltage range, γcation+ ranges from 0 to 0.55, γcation− ranges from 0 to 0.75, γanion+ ranges from 0 to 0.4, and γanion− ranges from 0.3 to 1.3. The data show for the first time positive and negative charges being emitted due to both cation and anion bombardment and suggest that secondary ions sputtered from the surface are important to the secondary charge emission behavior in electrospray plumes.

Multiscale modeling of electrospray ion emission

A multi-scale approach to electrospray ion source modeling has been developed. The evolution of a single-emitter electrospray plume in a pure ionic regime is simulated with a combination of electrohydrodynamic fluids and n-body particle modeling. Simulations are performed for the ionic liquid, EMI-BF4, firing in a positive pure-ion mode. The metastable nature of ion clusters is captured using an ion fragmentation model informed by molecular dynamics simulations and experimental data. Results are generated for three operating points (120, 324, and 440 nA) and are used to predict performance relevant properties, such as the divergence angle and the extractor surface impingement rate. Comparisons to experimental data recorded at similar operating points are provided.

Comparison of computational algorithms for simulating an electrospray plume with a n-body approach

In order to better evaluate the trade-offs between different simulation options for an electrospray thruster plume, we have developed a multi-scale n-body code to compute the evolution of a single emitter electrospray plume in the pure ionic regime. The electrostatic force computations in the simulation are captured through the use of three different computational algorithms with various degrees of approximation. The results of the simulations for a simple test case are compared in terms of computational speed and accuracy. The test case utilizes a single operating point (323nA) for a stable meniscus solution for the ionic liquid EMI-BF4 firing in the positive pure ion mode. Complex species and probabilistic fragmentation processes are neglected. An overview is provided of the trade-off between accuracy and computational speed for the three algorithms in the context of simulating the electrostatic interactions between particles. For a large number of particles, the faster algorithms show a significant reduction in computational time while maintaining a high level of accuracy with a proper choice of tuning parameters.

In-Line Dopant Generation for Atmospheric Pressure Ionization Mass Spectrometry.

A concentric trace gas permeation tube that diffuses chemical reagents to a central carrier gas stream is used to drive chemical reaction pathways and influence gas-phase chemistry for a variety of atmospheric pressure ionization sources for mass spectrometry. Tunable permeation through the reservoir-jacketed polymer membrane is triggered by the heated gas moving through the tube, evaporating the dopant into a sheath dry gas or into a sample stream in room air without diluting the analyte concentration. The permeator is used to add dopants to an electrospray plume for analyte ion charge reduction and to perform hydrogen-deuterium exchange on biomolecules in different spray conditions. Dopants are also added to atmospheric pressure chemical ionization to favor the ionization of select components of diesel fuel. Atmospheric pressure photoionization is performed with the permeation tube in line with tubing transporting sample headspace to an enclosed discharge lamp. Toluene dopant from the permeator increases the proton transfer and charge exchange signal from clove oil and mothballs many times without exposing the laboratory to reagent fumes. Water permeation is also used to humidify the sample gas stream.

Fluorescence-Based Detection of the Desolvation Process of Protein Ions Generated in an Aqueous Electrospray Plume.

A new experimental setup to study laser-induced fluorescence from analytes at different locations in an electrospray plume has been developed. The high fluorescence collection efficiency (∼2%) of the setup, along with a sensitive charge coupled device (CCD) detector, enabled the study of low ion concentrations (down to ∼fM) in the plume. The use of small electrospray tip inner diameters (<1 μm) facilitated the fast desolvation of gaseous protein ions in an aqueous electrospray plume. Fluorescence spectra were acquired from specific locations along the plume axis in different aqueous electrospray plumes with three different analytes: a rhodamine dye and two proteins (ubiquitin and apomyoglobin) labeled with rhodamine dyes. To confirm the presence of gaseous ions, pure gas-phase fluorescence spectra were acquired in the vacuum of a modified ion trap mass spectrometer. These spectra were used to fit to confirm the presence of gaseous species in the corresponding spectra obtained from the electrospray plume. This study shows that with small inner diameter spray capillaries, gaseous protein ions generated at atmospheric pressure in an electrospray plume can be detected with fluorescence-based techniques. Fluorescence measurements can be used to study their structure in the electrospray plume, and the dynamics as they transition from solution to the gas phase and in the early stages after desolvation from charged droplets. Other techniques can also be applied to further study gaseous biomolecular structures under ambient conditions immediately after desolvation.

Hydroxylammonium Nitrate Species in a Monopropellant Electrospray Plume

A mixture of 1-ethyl-3-methylimidazolium ethyl sulfate () and hydroxylammonium nitrate (HAN) is an energetic monopropellant potentially suitable in a multimode chemical-electric microtube-electrospray micropropulsion system. In this work, electrospray plume mass spectra are compared between the monopropellant mixture and neat . This comparison clearly indicates new and additional species present in the plume due to the addition of HAN. Mass spectra from 20 to were obtained over a variety of angles and flow rates from to in both cation and anion extraction modes. Mass spectra dependence on flow rate and angular orientation agree qualitatively well with literature. Results indicate the presence of HAN-based species in anion mode, but no HAN-based species in cation mode. Three of the four monomer species from the monopropellant are apparent in the plume; , , and are observed, whereas is noticeably absent. Results also show emission of both proton-transferred covalent forms of HAN: [HA-H] and . Swapping of anion and cation species between the constituents of the monopropellant mixture is also observed.

Microdroplet Fusion Chemistry for Charge State Reduction of Synthetic Polymers via Bipolar Dual Spray with Anionic Reagents.

Microdroplet fusion chemistry is an emerging area of analyte manipulation that utilizes the ion source region of a mass spectrometer to covalently derivatize or manipulate the charge state distribution. This technique utilizes two electrospray emitters in close proximity, where the droplets from each electrospray plume fuse and undergo the subsequent chemistry. In this study, microdroplet fusion chemistry via bipolar dual spray has demonstrated the ability to reduce the average charge state of polyethylene glycol (PEG) cations using anionic reagents. Bipolar dual spray was implemented on a commercial mass spectrometer with limited hardware modifications to the ion source. Reagents including ammonium hydroxide, formic acid, and lithium chloride showed dramatic shifts in the average charge state of PEG 3.8K cations (e.g., 5.0+ to 2.5+) along with the emergence of newly detected charge states. An organic base, tributylamine, had no effect on the charge state distribution of PEG 3.8K cations. These results were consistent with an ion-pairing mechanism, where reagent anions destabilized ammonium cation interactions with PEG 3.8K upon droplet fusion from the negative and positive emitters. Additional bipolar dual spray experiments with PEG 12.6K demonstrated the ability to transform uninterpretable mass information into distinct charge states ranging from [M+8NH4]+ to [M+3NH4]+. Overall, this study provides insight into the nature of dual spray chemistry and will aid future experimental design in microdroplet covalent chemistry.