Publications and Posters
Below is a list of publications and posters involving Desorption
Electrospray Ionization (DESI) and Omni Spray™ Ion Sources.
Publications:
Clozapine Distribution in Rat Brain and Lung: A Comparison of Imaging by DESI-MS vs. LC-MS/MS Analysis of Homogenates
Justin M. Wiseman1, Candice Kissinger2, Demian R. Ifa3, Yongxin Zhu2, James Burleigh2, Simon Katner2, Candace Rohde2, R. Graham Cooks3
1. Prosolia, Inc., Indianapolis, IN USA
2. Bioanalytical Systems Inc. West Lafayette, IN USA
3. Purdue University, Department of Chemistry, West Lafayette, IN USA
Drug distribution studies in tissue are normally carried out using HPLC MS analysis of the homogenized tissue. In this poster, DESI imaging is used for the detection and imaging of the distribution and Clozapine from intact tissue and compares these results to those generated via HPLC MS.
Takats, Z.; Wiseman, J. M.; Gologan, B.; Cooks, R. G., Mass Spectrometry
Sampling Under Ambient Conditions with Desorption Electrospray Ionization.
Science 2004, 306, 471-473.
Abstract: A new method of desorption ionization
is described and applied to the ionization of various compounds,
including peptides and proteins present on metal, polymer, and
mineral surfaces. Desorption electrospray ionization (DESI) is
carried out by directing electrosprayed charged droplets and ions
of solvent onto the surface to be analyzed. The resulting mass
spectra are similar to normal ESI mass spectra in that they show
mainly singly or multiply charged molecular ions of the analytes.
Changes in the solution that is sprayed can be used to selectively
ionize particular compounds, including those in biological matrices.
In vivo analysis is demonstrated.
Takats, Z.; Wiseman, J. M.; Cooks, R. G., Ambient Mass Spectrometry
using Desorption Electrospray Ionization (DESI): Instrumentation,
Mechanisms and Applications in Forensics, Chemistry, and Biology.
J. Mass Spectrom. 2005, 40, (10), 1261-1275.
Abstract: DESI was used for small and large
molecules, in situ analysis, and high-throughput analyses.
Evidence is provided for both aheterogeneous charge-transfer
mechanism and a droplet pick-upmechanism of ionization. The speed,
lackof the need for sample preparation, selectivity,
and sensitivity of DESI are all demonstrated and discussed.Instrumentation
is also discussed. Forensic applications as well as emerging areas
of application including tissue imaging are given emphasis.
Takats, Z.; Cotte-Rodriguez, I.; Talaty, N.; Chen, H.; Cooks, R.
G., Direct, Trace Level Detection of Explosives on Ambient Surfaces
by Desorption Electrospray Ionization Mass spectrometry. Chem.
Comm. 2005, 15, 1950-1952.
Abstract: DESI is used to detect trace amounts of
explosives present on a variety of ambient surfaces in 5-second
analysis times without any sample preparation.
Talaty, N.; Takats, Z.; Cooks, R. G., Rapid in situ Detection of
Alkaloids in Plant Tissue Under Ambient Conditions using Desorption
Electrospray Ionization. Analyst 2005,
130, (12), 1624-1633.
Abstract: DESI was applied to the in situ detection
ofalkaloids in the tissue of poison hemlock (Conium maculatum),
jimsonweed (Datura stramonium)and deadly nightshade (Atropa
belladonna). All the previously reported alkaloids have been detected
in C. maculatum, while fifteen out of nineteen known alkaloids
for D. stramonium and the principal alkaloids of A. belladonna
were also identified. Quantitative precision of DESI is compared
with conventional electrospray ionization mass spectrometry (after
sample workup) and the RSD values for the same set of 25 dicotyledonous
C. maculatum seeds (one half of each seed analyzed by ESI and
the other by DESI) are 9.8% and 5.2%, respectively.
Cotte-Rodriguez, I.; Takáts, Z.; Talaty, N. N.; Chen, H.;
Cooks, R. G., Desorption Electrospray Ionization of Explosives on
Surfaces: Sensitivity and Selectivity Enhancement by Reactive Desorption
Electrospray Ionization. Anal. Chem. 2005,
77, (21), 6755-6764.
Abstract: DESI is used for trace detection of several explosives
directly from a variety of surfaces without sample preparations
or pretreatments. Several complex matrices studies, absolute limits
of detection and quantification experiments were conducted, demonstrating
the power of DESI in in situ explosives detection.
Van Berkel, G. J.; Ford, M. J.; Deibel, M. A., Thin-Layer Chromatography
and Mass Spectrometry Coupled Using Desorption Electrospray Ionization.
Anal. Chem. 2005, 77, (5), 1207-1215.
Abstract: DESI is used for connecting thin-layer
chromatography (TLC) with mass spectrometry. Development lanes
were scanned by moving the TLC plate under computer control while
directing the stationary DESI emitter charged droplet plume at
the TLC plate surface. Mass spectral data were recorded in either
selected reaction monitoring mode or in full scan ion trap mode
using a hybrid triple quadrupole linear ion trap mass spectrometer.
Mixture of aspirin, acetaminophen, and caffeine from an
over-the-counter pain medication were separated on a normal-phase
silica gel plate.
Chen, H.; Talaty, N. N.; Takáts, Z.; Cooks, R. G., Desorption
Electrospray Ionization Mass Spectrometry for High Throughput Analysis
of Pharmaceutical Samples in the Ambient Environment. Anal.
Chem. 2005, 77, (21), 6915-6927.
Abstract: DESI is used for on-line high-throughput
monitoring of pharmaceutical samples in the ambient environment,
without prior sample preparation.Positive and negative
ion DESI are used to characterize the active ingredients in pharmaceutical
samples formulated as tablets, ointments, and liquids.A
variable-speed moving belt was built for high-throughput sampling
is used to provide rapid qualitative and semiquantitative information
on drug constituents in tablets.
Weston, D. J.; Bateman, R.; Wilson, I. D.; Wood, T. R.; Creaser,
C. S., Direct Analysis of Pharmaceutical Drug Formulations Using
Ion Mobility Spectrometry/Quadrupole-Time-of-Flight Mass Spectrometry
Combined with Desorption Electrospray Ionization. Anal. Chem.
2005, 77, (23), 7572-7580.
Abstract: A DESI/IMS/ToF-MS instrument is used for the analysis
of pharmaceutical drug formulations such as cream and skin patch.
Limits of detection and selectivity for active drug responses
over excipient responses were conducted demonstrating the potential
applicability of this novel method to pharmaceutical screening.
Williams, J. H.; Scrivens, J. H., Rapid Accurate Mass Desorption
Electrospray Ionisation Tandem Mass Spectrometry of Pharmaceutical
Samples. Rapid Commun. Mass Spectrom. 2005,
19, (24), 3643-3650.
Abstract: DESI has been successfully combined with
a hybrid quadrupole time-of-flight mass spectrometer to provide
mass spectra and product ion mass spectra of active ingredients
formulated in pharmaceutical tablets, gels and ointments. Accurate
mass data has been obtained from the DESI mass spectra and of
the product ion fragments of selected ions, greatly enhancing
the selectivity and information content of the experiment.
Wiseman, J. M.; Puolitaival, S. M.; Takats, Z.; Cooks, R. G.; Caprioli,
R. M., Mass Spectrometric Profiling of Intact Biological Tissue
by Using Desorption Electrospray Ionization. Angew. Chemie 2005,
44, (43), 7094-7097.
Abstract: DESI was used for tissues imaging under
ambient conditions with spot sizes of less than 1 mm, a topicwith
implications for basic biochemistry, as well aspathology,
food safety, and real-time diagnosis duringsurgery. DESI
allows the direct and rapidanalysis of intact biological
tissues, including wholeorgans. In addition to its sensitive
and specific molecular detection, DESI enables adequate secondary-ion
yields for chemical confirmationby tandem mass spectrometry.
Rubakhin, SS; Jurchen, JC; Monroe, EB; Sweedler, JV, Imaging mass
spectrometry: fundamentals and applications to drug discovery. Drug
Discovery Today 2005, 10 (12): 823-837
Abstract: Review on imaging mass spectrometry (IMS),
which underlines works previously performed with DESI.
Cottingham, K.; Thinking outside the MS box. Analytical
Chemistry 2005, 17A
Abstract: Brief introduction on the DESI technology.
Hopfgartner, G; Varesio, E; New approaches for quantitative analysis
in biological fluids using mass spectrometric detection; TRAC-Trends
In Analytical Chemistry 2005, 24 (7): 583-589
Abstract: Review on quantitative analysis with mass spectrometric
detection with presentation of new ionization techniques, such
as desorption electrospray ionization.
Cooks, R. G.; Wiseman, J.; Takats, z.; Puolitaival,
S. ; Caprioli, R.; Desorption electrospray ionization (DESI); Molecular
& Cellular Proteomics 2005, 4 (8): S455-S455
Abstract: General review on the power of DESI and its applications
in metabolomics and biomolecular sensing.
Kauppila, T. J.; Wiseman, J. M.; Ketola, R. A.; Kotiaho, T.; Cooks,
R. G.; Kostiainen, R., Desorption Electrospray Ionization Mass Spectrometry
for the Analysis of Pharmaceuticals and Metabolites. Rapid Commun.
Mass Spectrom. 2006, 20, (3), 387-392.
Abstract: The performance of DESI in the analysis
of a group of pharmaceuticals and their glucuronic acid conjugates
is reported. In addition to the type of surface, spray solution
flow rate and the distance of the sprayer tip from the surface
were also found to have significant effects on the signal intensity.
Analytes with basic groups efficiently formed the corresponding
protonated molecules in the positive ion mode, whereas acidic
analytes, such as the glucuronic acid conjugates, formed intense
signals due to the deprotonated molecules in the negative ion
mode. Ionization of neutral compounds was less efficient and in
many cases it was achieved through adduct formation with simple
anions or cations.
Leuthold, L. A.; Mandscheff, J.; Fathi, M.; Giroud, C.; Augsburger,
M.; Varesio, E.; Hopfgartner, G., Desorption Electrospray Ionization
Mass Spectrometry: Direct Toxicological Screening and Analysis of
Illicit Ecstasy Tablets. Rapid Commun. Mass Spectrom. 2006,
20, (2), 103-110.
Abstract: DESI was used as a simple and
rapid way to analyze drug tablets and powders without sample preparation..
Twenty-one commercial drugs as well as some illicit Ecstasy tablets
and powders were analyzed. MS spectra almost exclusively showed
the protonated or deprotonated ion of the drug after directing
the pneumatically assisted electrospray onto the tablet’s
surface.With some tablets, inhomogeneity of the surface
resulted in different spectra depending on the spot analyzed,
thus showing that DESI could be used for imaging. With MS/MS spectra
library comparison or exact mass measurements, this technique
could become very powerful for the rapid analysis of unknown tablets
and shows the great potential of desorption techniques as an alternative
to solution-based analysis.
Rodriguez-Cruz, S. E., Rapid Analysis of Controlled Substances
Using Desorption Electrospray Ionization Mass Spectrometry. Rapid
Commun. Mass Spectrom. 2006, 20, (1), 53-60.
Abstract: Results from the ambient sampling
of licit and illicit tablets demonstrate the ability of the DESI
technique to detect the main active ingredient(s) or controlled
substance(s), even in the presence of other higher-concentration
components. Full-scan mass spectrometry data provide preliminaryidentification
by molecular weight determination, while rapid analysis using
the tandem massspectrometry (MS/MS) mode provides fragmentation
data which, when compared to the laboratory-generated
ESI-MS/MS spectral library, provide structural information and
final identificationof the active ingredient(s). The
consecutive analysis of tablets containing different active componentsindicates
there is no cross-contamination or interference from tablet to
tablet, demonstratingthe reliability of the DESI technique
for rapid sampling. Active ingredientshave been detected
for tablets in which the active component represents less than
1% of thetotal tablet weight, demonstrating the sensitivity
of the technique.
Cotte-Rodriguez, I.; Chen, H.; Cooks, R. G., Rapid Trace Detection
of Triacetone Triperoxide (TATP) by Complexation Reactions During
Desorption Electrospray Ionization. Chem. Comm. 2006,
9, 953-955.
Abstract: DESI mass spectrometry is used for rapid, specific
and sensitive detection of trace amounts of the notorious explosive
TATP present on ambient surfaces by alkali metal complexation
in a simple spray technique.
Chen, H.; Cotte-Rodriguez, I.; Cooks, R. G., cis-Diol Functional
Group Recognition by Reactive Desorption Electrospray Ionization
(DESI). Chem. Comm. 2006, 6, 597-599.
Abstract: DESI is used for rapid, specific and sensitive
detection of trace amounts of the notorious explosive TATP present
on ambient surfaces by alkali metal complexation in a simple spray
technique.
Nefliu, M.; Venter, A.; Cooks, R. G., Desorption Electrospray Ionization
and Electrosonic Spray Ionization for Solid- and Solution-phase
Analysis of Industrial Ppolymers. Chem. Comm. 2006,
8, 888-890.
Abstract: DESI and electrosonic spray ionization
(ESSI), two new techniques, are used to measure average molecular
weights and molecular weight distributions of solid-phase and
solution-phase samples of the same polymers.
Chen, H; Cotte-Rodriguez, I; Cooks, RG; cis-diol functional group
recognition by reactive desorption electrospray ionization (DESI).
Chemical Communications 2006, (6): 597-599
Abstract: Heterogeneous reactions at a solution/solid interface
are utilized in an ambient mass spectrometry experiment with DESI
to recognize the cis-diol functionality by its selective complexation
reaction to form a cyclic boronate.
Cooks, R. G.; Ouyang, Z.; Takats, Z.; Wiseman, J. M.; Ambient Mass
Spectrometry. Science 2006, 311, 1566-1570.
Abstract: DESI extremelyrapid analysis
coupled with high sensitivity and high chemical specificity areadvantageously
applied to high-throughput metabolomics, explosives detection,
natural productsdiscovery, and biological tissue imaging,
among other applications. Future possible uses of DESI for in
vivo clinical analysis and its adaptation to portable mass spectrometers
are described.
Myung, S; Wiseman, JM; Valentine, SJ; Takats, Z; Cooks, RG; Clemmer;
Coupling desorption electrospray ionization with ion mobility/mass
spectrometry for analysis of protein structure: Evidence for desorption
of folded and denatured states. Journal Of Physical Chemistry
B 2006, 110 (10): 5045-5051
Abstract: DESI was coupled to an ion mobility time-of-flight
massspectrometer for the analysis of proteins. Analysis
of solid-phase horse heart cytochrome c and chicken eggwhite
lysozyme proteins with different DESI solvents and conditions
shows similar mass spectra and chargestate distributions
to those formed when using electrospray to analyze these proteins
in solution. The ionmobility data show evidence for compact
ion structures or elongated structures. The results suggest thatthe
DESI experiment is somewhat gentler than ESI and under appropriate
conditions, it is possible to preservestructural information
throughout the DESI process.
Wu, S; Zhang, K; Kaiser, NK; Bruce, JE; Incorporation of a flared
inlet capillary tube on a Fourier transform ion cyclotron resonance
mass spectrometer. Journal Of The American Society For Mass
Spectrometry 2006, 17 (6): 772-779
Abstract: Flared inlet capillary tubes have been coupled
with a Fourier transform ion cyclotron resonance (FT-ICR) mass
spectrometer to help the ion transmission from the atmospheric
pressure to the first vacuum region. We investigated different
types of atmospheric pressure ionization methods using flared
inlet tubes. For most of the ionization methods, such as ESI and
DESI, increased ion current transmitted from the atmospheric pressure
ion source to the first stage vacuum system was observed with
the use of our enhanced ion inlet designs. The corresponding ion
intensity detected on a FT-ICR mass spectrometer was also observed
to increase two- to fivefold using ESI or DESI with the flared
tube inlet. Moreover, increased spray tip positional tolerance
was observed with implementation of the flared inlet tube.
Mulligan, CC; Talaty, N; Cooks, RG; Desorption electrospray ionization
with a portable mass spectrometer: in situ analysis of ambient surfaces.
Chemical Communications 2006, (16): 1709-1711
Abstract: Desorption electrospray ionization (DESI) is implemented
on a portable mass spectrometer and used to demonstrate in situ
detection of active ingredients in pharmaceutical preparations,
alkaloids in plant tissues, explosives, chemical warfare agent
simulants and agricultural chemicals from a variety of surfaces;
air monitoring applications using DESI are also introduced.
D'Agostino, PA; Hancock, JR; Chenier, CL; Lepage, CRJ ; Liquid
chromatography electrospray tandem mass spectrometric and desorption
electrospray ionization tandem mass spectrometric analysis of chemical
warfare agents in office media typically collected during a forensic
investigation. Journal Of Chromatography A 2006,
1110 (1-2): 86-94
Abstract: An emerging technique, desorption
electrospray ionization (DESI-MS/MS), was investigated for the
direct determination of TEP, GB and GD sampled onto solid phase
microextraction (SPME) fibers exposed to spiked office media and
compared with traditional mass spectrometry ionizations. The spiked
chemical warfare agents were recovered with varying efficiencies
during this study, but in all cases sufficient chemical warfare
agent was recovered for mass spectrometric identification purposes.
Full high resolution mass spectra were acquired for all the chemical
warfare agents in the continuum mode, which typically resulted
in mass measurement errors of 0.001 Da or less.
Williams, J. P.; Patel, V. J.; Holland, R.; Scrivens, J. H. The
Use Of Recently Described Ionizsation Techniques For The Rapid Analysis
Of Some Common Drugs And Samples Of Biological Origin. Rapid
Commun. Mass Spectrom. 2006, 20, 1447-1456.
Abstract: Three ionisation techniques that require
no sample preparation or extraction prior to mass analysishave
been used for the rapid analysis of pharmaceutical tablets and
ointments. These methods were(i) the novel direct analysis
in real time (DART), (ii) DESI, and(iii) desorption atmospheric
pressure chemical ionisation (DAPCI). The performance of the three
techniques was investigated for a number of common drugs. Significant
differences between these approaches were observed. For compounds
of moderate to low polarity DAPCI produced moreeffective
ionisation. Accurate DESI and DAPCI tandem mass spectra were obtained
and these greatlyenhance the selectivity and information
content of the experiment.
Nefliu, M.; Venter, A.; Cooks, R. G., Moore, C. Enhanced Desorption
Ionization using Oxidizing Electrosprays. J Am Soc Mass Spectrom.
2006, 17, 1091–1095.
Abstract: A signal enhancement of two orders of magnitude
was achieved when reactive desorption electrospray ionization
(DESI) was used to investigate copper(II) dibutyl dithiocarbamate,Cu(II)(bu2dtc)2,
found in a specialized polymer. Cu(II) was oxidized to Cu(III)
during the DESI experiment by oxidants in the spray solvent. Such
oxidants could be present or formed during electrospray (e.g.,
O2) or deliberately added to the spray solvent (this approach
is called reactive DESI). When a strong oxidizing agent (e.g.,
iodine) was added to the spray solvent, the signal increased by
two orders of magnitude relative to the pure solvent spray. The
correlation between the standard reduction potential of the oxidant
and the signal intensity and signal to noise ratio of the product
ion for various reagents, was tested and discussed. The observed
DESI enhancements in rates of oxidation are not observed in homogeneous
solution. The major peaks in the collision induced dissociation
(CID) spectrum of the complex ion[Cu(III)(bu2dtc)2]+ were identified
using isotopic distributions and MS3 data.
Poster:
Lowe, T.; Boge, J. A.; Barker, P. J.; Blanksby, S. J. Characterization
Of Hindered Amine Light Stabilizers (HALS) In Polymer Coatings By
DESI, ESI And Tandem Mass Spectrometry. Presented at ASMS in
Seattle, 2006
Abstract: Analysis of HALS in polymers is traditionally
conducted using eitherelectron paramagnetic spectroscopy
(EPR) or chromatography. Inthis poster, various mass
spectrometric techniquesfor sensitive and rapid analysis
of HALS in polymers such as DESI and Omni-Spray have been successfully
applied.
Courtesy of Dr. Steve Blanksby and Troy Lowe
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