Thermal energy distribution observed in electrospray ionization

Drahos, László; Heeren, Ron M. A.; Collette, Caroline; Pauw, Edwin De; Vékey, Károly

doi:10.1002/(sici)1096-9888(199912)34:12<1373::aid-jms907>3.0.co;2-#

Cited by 102 publications

(173 citation statements)

References 28 publications

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“…Earlier studies on the thermal energy distribution in ESI [53] revealed that the characteristic temperature of ions at the time of formation, assumed to be the temperature of the droplet, was 500 -600 K, much higher than the temperature of the ion source (300 -350 K). Such high temperatures may be acquired through friction of the fast-moving droplets with gas molecules in the interface, which overcompensates for the effect of evaporative cooling.…”

Section: Effects Of Desi and Essi Source Parameters On The Survival Ymentioning

confidence: 99%

“…Studies involving the effect of various instrumental parameters on the energetics of the ESI source have also been conducted, and they aimed at gaining a better understanding of the ionization mechanism and of the possibility of efficiently tuning the internal energy of the ions generated [49,[52][53][54]. It has been demonstrated that in ESI the shape of the P(E) curve corresponds approximately to a thermal energy distribution [53]. Characteristic temperatures have been calculated for a "cold" ion source (i.e., zero cone voltage) and for conditions corresponding to varying degrees of in-source ion activation.…”

Section: Esorption Electrospray Ionization (Desi) Is An Ambient Ionmentioning

confidence: 99%

“…The internal energy of ions generated through spray ionization techniques originates in the thermal energy of the droplets from which they emerge [53], and in the conversion of kinetic energy into internal energy in the course of collisions with the gas molecules in the atmospheric pressure interface. Earlier studies on the thermal energy distribution in ESI [53] revealed that the characteristic temperature of ions at the time of formation, assumed to be the temperature of the droplet, was 500 -600 K, much higher than the temperature of the ion source (300 -350 K).…”

Section: Effects Of Desi and Essi Source Parameters On The Survival Ymentioning

confidence: 99%

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Internal energy distributions in desorption electrospray ionization (DESI)

Nefliu

Smith

Venter

et al. 2008

J. Am. Soc. Mass Spectrom.

108

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The internal energy distributions of typical ions generated by desorption electrospray ionization (DESI) were measured using the "survival yield" method, and compared with corresponding data for electrospray ionization (ESI) and electrosonic spray ionization (ESSI). The results show that the three ionization methods produce populations of ions having internal energy distributions of similar shapes and mean values (1.7-1.9 eV) suggesting similar phenomena, at least in the later stages of the process leading from solvated droplets to gas-phase ions. These data on energetics are consistent with the view that DESI involves "droplet pick-up" (liquid-liquid extraction) followed by ESI-like desolvation and gas-phase ion formation. The effects of various experimental parameters on the degree of fragmentation of p-methoxy-benzylpyridinium ions were compared between DESI and ESSI. The results show similar trends in the survival yields as a function of the nebulizing gas pressure, solvent flow rate, and distance from the sprayer tip to the MS inlet. These observations are consistent with the mechanism noted above and they also enable the user to exercise control over the energetics of the DESI ionization process, through manipulation of external and internal ion source parameters. [1, 24, 29 -32], and explosives detection [4,8,[33][34][35][36][37]. Investigations into the fundamentals of the droplet dynamics and ionization mechanism have also been conducted through systematic measurements of the droplet size and velocity [38], computer simulations [39], surface charging effects [40], or more simply, by evaluating the mass spectra of various types of analytes in conjunction with variations in the experimental parameters [41]. These investigations suggested that the primary ionization mechanism in DESI is "droplet pick-up", i.e., extraction of the analyte into the droplet, followed by electrospray ionization (ESI)-like mechanism in which the progeny droplets are desolvated yielding ionized molecules. One of the arguments supporting this conclusion, the similarity between the ESI and DESI mass spectra, also implies that the two ion sources should generate populations of ions with similar internal energy distributions, P(E). It should be noted though, that the initial events in the two experiments are quite different, and recent simulations show that the process of formation of progeny droplets from the initial ϳ4 m droplets in DESI is not dependent on charge build-up as it is in ESI. These dissimilarities need not result in differences in the final internal energy (E) since the later processes occurring in the atmospheric pressure interface are probably the same for these two processes and, as we will show later, dominate the energetics of the process.Here we use the "survival yield" (SY) method [42] applied to a set of thermometer ions (benzylpyridinium cations) to judge internal energy deposition associated with soft ionization techniques [43] to measure and compare the internal energy distributions of the ions generated b...

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Section: Effects Of Desi and Essi Source Parameters On The Survival Ymentioning

confidence: 99%

Section: Esorption Electrospray Ionization (Desi) Is An Ambient Ionmentioning

confidence: 99%

Section: Effects Of Desi and Essi Source Parameters On The Survival Ymentioning

confidence: 99%

See 1 more Smart Citation

Internal energy distributions in desorption electrospray ionization (DESI)

Nefliu

Smith

Venter

et al. 2008

J. Am. Soc. Mass Spectrom.

108

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“…These two effects are strongly coupled and are expected to influence both internal energy deposition and S/N ratio. Drahos and colleagues have shown that for various instruments, including quadrupole and Fourier transform mass spectrometers operated at various ion source temperatures (25-150°C) the internal energy distribution of ESI ions can be approximated by Boltzmann distribution with different characteristic temperatures [38]. For capillary temperatures of 50 -75°C, Gabelica et al [34] showed that P(E) curves exhibit a low-energy tail, indicating the presence of partially solvated ions reaching the capillary-skimmer region of the mass spectrometer.…”

Section: Combined Influence Of Api Capillary Temperature and Air Amplmentioning

confidence: 99%

“…Shortening the droplet/ion residence time causes a reduction in evaporative cooling, and thus leads to a higher internal energy. The characteristic droplet temperature [38] increases with increasing droplet velocity, resulting in ions being ejected with higher internal energies. Interestingly, at low N 2 flow rates and high capillary temperatures, a region of high mean internal energy ESI ions is also observed.…”

Section: Combined Influence Of Api Capillary Temperature and Air Amplmentioning

confidence: 99%

Comparison of the internal energy deposition of venturi-assisted electrospray ionization and a venturi-assisted array of micromachined ultrasonic electrosprays (AMUSE)

Hampton

Silvestri

Forbes

et al. 2008

J. Am. Soc. Mass Spectrom.

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The internal energy deposition of a Venturi-assisted array of micromachined ultrasonic electrosprays (AMUSE), with and without the application of a DC charging potential, is compared with equivalent experiments for Venturi-assisted electrospray ionization (ESI) using the "survival yield" method on a series of para-substituted benzylpyridinium salts. Under conditions previously shown to provide maximum ion yields for standard compounds, the observed mean internal energies were nearly identical (1.93-2.01 eV). Operation of AMUSE without nitrogen flow to sustain the air amplifier focusing effect generated energetically colder ions with mean internal energies that were up to 39% lower than those for ESI. A balance between improved ion transfer, adequate desolvation, and favorable ion energetics was achieved by selection of optimum operational ranges for the parameters that most strongly influence the ion population: the air amplifier gas flow rate and API capillary temperature. Examination of the energy landscapes obtained for combinations of these parameters showed that a low internal energy region (:"S1.0 eV) was present at nitrogen flow rates between 2 and 4 L min-1 and capillary temperatures up to 250°C using ESI (9% of all parameter combinations tested). Using AMUSE, this region was present at nitrogen flow rates up to 2.5 L min-] and all capillary temperatures (13% of combinations tested). The signal-to-noise (SIN) ratio of the intact p-methylbenzylpyridinium ion obtained from a 5 p,M mixture of thermometer compounds using AMUSE at the extremes of the studied temperature range was at least fivefold higher than that of ESI, demonstrating the potential of AMUSE ionization as a soft method for the characterization of labile species by mass spectrometry. niques, there has been considerable activity toward the development of even "softer" methods, including atmospheric pressure-MALDI [5], sonic spray ionization (SSI) [6], electrosonic spray ionization (ESSI) [7], and cold spray ionization (CSI) [8], with the intent of exploring improved ways for detecting biological species such as peptides [9], proteins [10,11], noncovalent complexes [12], and nucleic acids [13].The Array of Micromachined UltraSonic Electrosprays (AMUSE) was invented by Fedorov and Degertekin for high throughput, multiplexed MS [14] and was first demonstrated on an MS system jointly by the Fedorov, Degertekin, and Fernandez groups [15]. In the AMUSE, the processes of droplet formation and DC droplet charging are decoupled. The application of a radio

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Gas phase thermal denaturation of an oligonucleotide duplex and its complexes with minor groove binders

Gabelica

Rosu

Houssier

et al. 2000

Rapid Commun. Mass Spectrom.

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Electrospray ionization with in-source collisionally induced dissociation has been used to probe the gas phase stability of an oligonucleotide duplex and its complexes with some minor groove binding drugs. On the basis of the arguments developed in detail by Drahos et al. (J. Mass Spectrom. 1999; 34:1373), this type of experiment can also be described as 'thermal denaturation in the gas phase'. We found that the gas phase denaturation curves were very similar to the solution phase denaturation curves determined by the traditional UV spectrophotometric method and, by analogy with the melting temperature T(m) which characterizes the stability in solution, we define a melting voltage V(m) to characterize the stability in the gas phase. A comparison of the T(m) and V(m) relative values suggests that the structure of the complexes is conserved during the electrospray process which transfers the ions from the solution to the gas phase.

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Thermal energy distribution observed in electrospray ionization

Cited by 102 publications

References 28 publications

Internal energy distributions in desorption electrospray ionization (DESI)

Internal energy distributions in desorption electrospray ionization (DESI)

Comparison of the internal energy deposition of venturi-assisted electrospray ionization and a venturi-assisted array of micromachined ultrasonic electrosprays (AMUSE)

Gas phase thermal denaturation of an oligonucleotide duplex and its complexes with minor groove binders

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