FD) and Liquid Injection Field Desorption Ionization (LIFDI

Field Ionization (FI), Field desorption (FD) and Liquid Injection Field Desorption Ionization (LIFDI)

H. Bernhard Linden Linden CMS GmbH [email protected] www.LIFDI.com 1  LINDEN CMS GmbH, 2012 Soft ionization by FI, FD and LIFDI

Introduction by mouth watering soft ionization spectra 1. General and theoretical overview 2. Various instruments – identical technique 3. Automated LIFDI 4. Improved FI intensity 5. LIFDI on FT-ICR instruments 6. LIFDI of air/moisture sensitive metal complexes 7. Orbitrap with ESI-LIFDI combination

2  LINDEN CMS GmbH, 2012 FI and FD are known for soft ionization of non-polar compounds, LIFDI outperforms other MS techniques for characterization of organometallics due to its softness and convenient handling

order of soft ionization References

Liquid injection field desorption/ionization of transition decomposition decreases : ESI > LIFDI metal fluoride complexes

Trevor A. Dransfield, Ruqia Nazir, Robin N. Perutz and “LIFDI ... gave the molecular ion peaks [M]+ as base peaks (100%) ... . Adrian C. Whitwood With ESI, the compounds showed decomposition.” J. Fluorine Chem. 131, 2010, 1213-1217

loss of CO decreases : MALDI > FAB > FD *) Analysis of ruthenium carbonyl–porphyrin complexes: a comparison of matrix-assisted laser desorption/ionisation “ruthenium carbonyl complexes exhibited time-of-flight, fast-atom bombardment and field desorption abundant carbon monoxide (CO) loss in MALDI-TOF-MS and still a mass spectrometry, measurable CO loss in FAB-MS. Only FD-MS yielded the molecular ion M. Frauenkron, A. Berkessel and J. H. Gross as the base peak of the spectra in all cases.” Eur. J. Mass Spectrom. 1997, 3, 427 - 438

“fragmentation decreases Comparison of electrospray mass spectrometry with other soft ionization techniques for the characterization of cationic along the series FAB > ESI > FD “ *) π-hydrocarbon organometallic complexes , L. A. P. Kane-Maguire, R. Kanitz and M. M. Sheil J. Organometallic Chem., 1995, 486, 1-2, 243-248

*) Note: LIFDI wasn’t invented in the 90-ies yet, but LIFDI and FD share the same soft ionization, only the sample supply is different. 3  LINDEN CMS GmbH, 2012 example for soft ionization

Mo(CO)4(Sb4Et4Pr2) sample of H.J. Breunig, University Bremen, Germany Et Et m/z = 897,8 Pr Sb assumed formula and structure Sb expected Mo(CO) 4 isotope pattern Sb Pr Sb

oily, very reactive matter Et Et • decomposition upon chromatography • no crystals for X-ray characterization • ambiguous NMR data • elemental analysis not confirming the MW all routinely used • ESI - ineffectual due to dry toluene as solvent techniques failed • MALDI - rather impossible under inert conditions • EI did not show meaningfull spectra

4  LINDEN CMS GmbH, 2012 the presence of a mixture with scrambling alkyl ligands caused the oily consistence + Mo(CO) [(Sb Et Pr )] elucidating why X-ray, NMR 4 4 (6-n) n and elemental analysis failed reactive, air sensitive oil with 1 ≤ n ≤ 6 Et Et

Pr Sb LIFDI showed Sb the note: loss of ligands does not occur at least expected + Mo(CO)4 not from M (n=2) isotope pattern Sb for n=1-6

no (n=2) Pr Sb loss of Et CO from Et no (n=2) loss of Et from (n=2) no (n=4) loss of Pr from (n=1) (n=3) (n=2) (n=6) (n=5)

Liquid Injection Field Desorption Ionization Mass Spectrometry of Cyclic Metal Carbonyl Complexes with Tetra-Antimony Ligands H. J. Breunig, H. B. Linden, O. Moldovan J. Am. Soc. Mass Spectrom., 2013, 24, 164-166 5  LINDEN CMS GmbH, 2012

X-ray data showed clearly all Ga atoms and C60H90Ni7Ga 6 all Cp* ligands but the Ni atoms were

initially ambiguous due to the impurity with 8 Ni atoms.

+ [Ni78(GaCp*)(GaCp*)6]

Single-crystal X-ray crystallography

instrument: Waters LCT, Ruhr University Bochum, Germany sample: courtesy Prof. Dr. Roland A. Fischer, Ruhr University Bochum, Germany

LINDEN CMS GmbH 6 One of the reviewers C64H88N4Cr2 suggested the above structure and refused accepting the publication [{({iPr2(C6H3)}2nacnac)Cr}2(m-Ph)(m-H)] unless proving the presence of the hydride ligand of the lower structure + M by a shift of the mole peak upon H/D exchange by just 1 Da (mole peak intensities of 5% would be sufficient)

isotope pattern

calculated

measured

A Tale of Two Isomers: A Stable Phenyl Hydride and a High-Spin (S=3) Benzene Complex of Chromium WH Monillas, GPA Yap, and KH Theopold, Angew. Chem. Int. Ed. 2007, 46, 6692-6694

instrument: Waters GCT, industrial R&D lab, Ludwigshafen, Germany LINDEN CMS GmbH 7 LIFDI of Grubbs Hoveyda Catalyst

M+

C31H38Cl2N2ORu m/z 626.1405

calculated isotope pattern

measured isotope pattern

548,12

+ (M-C3H7Cl)

-HCl

instrument: Waters Q-TOF II, Humboldt University, Berlin, Germany LINDEN CMS GmbH 8 Broadband LIFDI-FT-ICR mass spectrum of polystyrene 1050

M+• peaks n

n=6 n=14

9 instrument: Bruker Apex with LIFDI-ESI combination source, University Heidelberg, Germany  LINDEN CMS GmbH, 2012 Diesel eicosane

nonadecane

heptadecane heneicosane

tricosane

tetradecane tetracosane

undecane heptacosane

instrument: Thermo Fisher MAT900, University of Vienna, Austria 10  LINDEN CMS GmbH, 2012 LIFDI of liquid Si 69

TIC at 12 kV: -5 bis-(3-triethoxysilylpropyl)polysulfide above 10 A

“organosilane coupling agent for production of silica reinforced rubber ” 11  LINDEN CMS GmbH, 2000 Bis(3-triethoxysilylpropyl)disulphide

M+ 163 237 429

H5C2 — O O — C2 H5

H5C2 — O — Si — (CH2)3 — S — S — (CH2)3 — Si — O — C2 H5

H5C2 — O O — C2 H5 237

instrument: MAT 95 sample: industrial R&D lab, Hanau, Germany 12  LINDEN CMS GmbH, 2006 doubly charged ions

KH Gunzelmann, HM Hutmacher, R Wolf, J Richert, BASF AG, German MS meeting 2005 Sample: Z. Tomovic, M. D. Watson, K. Müllen, Angew. Chem. Int. Ed. 2004, 43, 755-758 13  LINDEN CMS GmbH, 2006 Soft ionization by FI, FD and LIFDI

Introduction 1. General and theoretical overview 2. Various instruments – identical handling 3. Automated LIFDI 4. Improved FI intensity 5. LIFDI on FT-ICR instruments 6. LIFDI of air/moisture sensitive metal complexes 7. Orbitrap with ESI-LIFDI combination

14  LINDEN CMS GmbH, 2012 FI, FD and LIFDI share the soft ionization mechanism but differ in Fieldterms of Ionization analyte and sample supply IUPAC : „removal of electrons from any species acronym full name type of analyte and sample supply by interaction with a high electrical field “ IUPAC 12.3.1. Ionization nomenclature 1997 FI i ntroduced : FeldemissionField Ionization, E.W. Müller, Ergebnisse der exakten analyte, Naturwissenschaften , 27, 1953, 290 -360 on p. 359 in chapter “Othercontinuously applications of the fieldsupplied electron microscope via gas” inlet e.g. GC Mass Spectrometric Analysis of Ions from the Field Microscope, M.G . Inghram and R. Gomer, J. Chem. Phys., 22, 1954, 1279-80 vaccuum lock

FD Field Desorption dissolved solid analyte, discontinuously loaded to emitter surface of vacuum Field Desortion Mass Spectrometry: a Technique for the Study of Thermally Unstable Substances of Low Volatility, H.D . Beckey , Int.J.Mass Spectrom. Ion Phys., 2, 1969, 500-503

LIFDI Liquid Injection , liquid or dissolved solid analyte, Field Desorption supplied through capillary vaccuum lock Ionization of vacuum discontinuously or continuously Liquid Injection Field Desorption Ionization: a New Tool for Soft Ionization of Samples Including Air-Sensitive Catalysts and Non-Polar Hydrocarbons, H.B. Linden, Eur. J. Mass Spectrom. 10, 2004, 459-468 15  LINDEN CMS GmbH, 2012 FI/FD/LIFDI emitter

Beckey, H.D.; Hilt, E.; Schulten, H.R. High Temperature Activation of Emitters for Field Ionization and Field Desorption Spectrometry, J. Phys. E:Sci. Instrum. 1973, 6, 1043-1044

Linden, H.B.; Hilt, E.; Beckey, H.D. High-Rate Growth of Dendrites on Thin Wire Anodes for Field Desorption Mass Spectrometry, J. Phys. E:Sci. Instrum. 1978, 11, 1033-1036

Rabrenovic, M.; Ast, T.; Kramer, V. Alternative Organic Substances for Generation of Carbon Emitters for Field Desorption Mass Spectrometry, Int. J. Mass Spectrom. Ion Phys. 1981, 37, 297-307

graphite dendrites have large surface for adsorption of sample 4 and enhance the electrical field strength by a factor 10 16  LINDEN CMS GmbH, 2011 A potential difference of 104 V generates a field strength of several 1010 V/m

● ● (not to scale) ● ●

● 4 ~5 x 10 V/µm whisker tip ● ● ● V F = D ● ● 10 kV V ~5 V/µm * K 2 mm Fo= tip ro K tip = 2 / ln (2D/ r o) with D >> ro ~ 30nm

H.D .Beckey,Principles of Field Desorption counter and Field Ionization Mass Spectrometry; Pergamon Press: Oxford, 1977, p.82 electrode 17  LINDEN CMS GmbH, 2012 A potential difference of 104 V generates a field strength of several 1010 V/m

δ+ δ- - ● ● ● +• (not to scale) ● ● ● --10 261480 kV ● +20 V ● ● ● ● - ● ● the weakest bound electron ● ● whereas in EI is removed in FI, FD, LIFDI by bymaking 70 eV EI electrons ions with field ionization quantum mechanical tunneling anyinternal inner electron excess making ions without can beenergy removed internalhalf live excess of hydrogen energy ● 1.3x10–1 s at 0.5 *104 V µm–1 –10 4 –1 IE ~ 10 eV 1.6x10 s at 1.0 *10 V µm ● ● 2.0x10–16 s at 2.5 *104 V µm–1 ● ● H.D .Beckey,Principles of Field Desorption 18 IE << 10 eV and Field Ionization Mass Spectrometry;  LINDEN CMS GmbH, 2012 Pergamon Press: Oxford, 1977, p.4 FI LIFDI protocol protocol for volatile samples only for volatile and non-volatile, polar and nonpolar, reactive and non-reactive samples insert new emitter, insert new emitter, tune with acetone tune with acetone

inert inert flash emitter clean yes conditions heat emitter clean yes conditions (under feed back) required required ? ?

no no

admit dip LIFDI capillary acquire data acquire data sample gas in sample solution continuously (with EHC ramp) for 1-3 s

Coulor code: sample supply (highlighted green), data acquisition (bold blue) and cleaning the emitter (bold brown)

Steps with substantial risk to breaking the emitter wire are highlighted bold red.

19  LINDEN CMS GmbH, 2012

FD protocol

insert new emitter, for non-volatile samples only tune with acetone

withdraw FD probe fit FD probe to for reactive samples for non-reactive samples from ion source glove box interface

close isolation valve FD probe open valves vent vacuum lock needs of interface interface to

glove box remove FD probe insert FD probe from mass spec into glove box

heat emitter apply sample by inert syringe or dipping clean yes conditions required withdraw FD probe ? from glove box no

drip sample close valves solution on emitter of interface Coulor code: acquire data with EHC ramp insert FD probe remove FD probe sample supply (highlighted into vacuum lock with interface

from glove box green) pump vacuum lock, data acquisition (bold blue) open isolation valve fit FD probe with interface cleaning the emitter (bold to vacuum lock push FD probe brown) fully in Steps with substantial risk open interface valve to breaking the emitter wire tune ion optics again are highlighted bold red.

20  LINDEN CMS GmbH, 2012 Soft ionization by FI, FD and LIFDI

Introduction 1. Historical and theoretical overview 2. Various instruments – identical technique 3. Automated LIFDI 4. Improved FI intensity 5. LIFDI on FT-ICR instruments 6. LIFDI of air/moisture sensitive metal complexes 7. Orbitrap with ESI-LIFDI combination

21  LINDEN CMS GmbH, 2012 FI / FD / LIFDI ion source

cathode (counter electrode) 10 kV anode (activated emitter)

potential of cathode and emitter

AutoSpec -2 kV JMS - 700 +8 kV

-5 kV DFS +5 kV

GCT -10 kV ≤ +0.1 kV LCT AccuTOF, FT-ICR Orbitrap fused silica capillary (LIFDI only) 22  LINDEN CMS GmbH, 2012 FI / FD / LIFDI emitter

1 µm graphite dendrites have large surface for adsorption of sample

23  LINDEN CMS GmbH, 2012 schematic tip of a dendrite

surface diffusion of gas phase 4 adsorbed molecules <1 x 10 V/µm molecules tip of + 60° desorption due to graphite dendrite - Coulomb repulsion field ionization + + + by electron tunneling - ● e + + from the molecules 8 x 104 V/µm whisker axis - into the tip + + e + ●+ macroscopic field strength 5 x 104 V/µm 10 kV/ 2 mm = 5 V/µm surface diffusion of adsorbed molecules desorbed ion of non-volatile molecule

according to H.D. Beckey, Principles of Field Ionization and Field Desorption, Pergamon Press 1977, page 52, Fig. 2.14

24  LINDEN CMS GmbH, 2012

ion emission at whisker tips

graphite whisker

emission cone with Ø13 µm tungsten opening angle 60° wire 60° only ions in cone with opening angle 1° can 60° be focused

1° source transmission 1° of only ca. 10-4 optical axis 1° 1°

25  LINDEN CMS GmbH, 2012 instrumental and handling details AccuTOF with FI/FD/LIFDI

JEOL TOF instrument at University Bochum, Germany

26  LINDEN CMS GmbH, 2012 GCT-Premier with FI / FD / LIFDI

Waters TOF instrument at University of York, England 27  LINDEN CMS GmbH, 2012 DFS with FI / FD / LIFDI

Thermo Fisher instrument at Academy of Sciences, Beijing, China 28  LINDEN CMS GmbH, 2012 LIFDI source for LCT / Q-TOF interchangeable LIFDI power supply with ESI source

isolation valve forevacuum USB camera toggle valve

ESI source LIFDI probe

Removing the ESI source and installing the LIFDI source (or vice versa) takes about 15 minutes from the end of venting up to the start of re-evacuating the instrument.

A new LIFDI-ESI combination source for this TOF will allow changing from one ionization technique to the other LIFDI capillary LIFDI emitter without venting the instrument .

Waters LCT instrument at University Bochum 29  LINDEN CMS GmbH, 2012 LIFDI sample dosing

under ambient or inert conditions

bottle can be sealed or open

30  LINDEN CMS GmbH, 2012 immerse capillary for 1-3 s

aspirating a plug of solution

20 mm length equal 40 nl

at capillary of 50 µm i.d.

travel time: ca. 10 s

31  LINDEN CMS GmbH, 2012 entire LIFDI cycle in real time

1. injection and evaporation (at 2x10-4 mbar in ca. 25 s)

2. voltages switched-on (wire is pulled away from capillary and thermally expanded with raising temperature)

3. desorption (at some 10-6 mbar in 60 s)

4. voltages switched-off (wire cools down and goes back to the former position)

HV+/HV- dipping and EHC 1-3s evaporation on fractionated desorption with increasing temperature/heating current t=0 t=25s t=50s t=1:25 HV+/HV- 32  LINDEN CMS GmbH, 2012 ready for next injection: go to 1. and EHC off injection and desorption of PEG 600

Total Ion

HV and Chromatogram dip HV and EHC off EHC on 60 mA parameters of emitter heating 0 mA ready for next sample supply sample supply current (EHC) and high voltage (HV)

+ (Mn+Na)

+ n=19 n=12 (Mn+K) + (Mn+H) LIFDI-spectrum

Instrument and sample: courtesy of AMD Intectra, Harpstedt, Germany 33  LINDEN CMS GmbH, 2012 33 injections/desorptions in 60 minutes

ion chromatogram of repetitive 4s injections of 3s reserpine 2s 1s cappilary dipped for 1-4 s 10 dips in 15 minutes

extended T I C peak

HV and 60 mA EHC on superimposed HV and EHC EHC off LIFDI- 0mA parameters

spectrum of reserpine

34  LINDEN CMS GmbH, 2012 Soft ionization by FI, FD and LIFDI

Introduction 1. Why is FI/FD/LIFDI very soft? 2. Various instruments – identical handling 3. Automated LIFDI 4. Improved FI intensity 5. LIFDI on FT-ICR instruments 6. LIFDI of air/moisture sensitive metal complexes 7. Orbitrap with ESI-LIFDI combination

35  LINDEN CMS GmbH, 2012 Automated LIFDI

Poster at German MS conference 2005 in Rostock (left, details below, copy available from the authors) Jens Griep-Raming1 and H. Bernhard Linden2 1) Thermo-Fisher Bremen, Germany 2) Linden CMS, Leeste, Germany.

Automated Liquid Injection Field Desorption Ionization for Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, DF Smith, TM Schaub, RP Rodgers, CL Hendrickson, and Alan G. Marshall, Anal. Chem. 2008, 80, 7379–7382

Characterization of Athabasca Bitumen Heavy Vacuum Gas Oil Distillation Cuts by Negative/Posi- tive Electrospray Ionization and Automated Liquid Injection Field Desorption Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, DF. Smith, P Rahimi, A Teclemariam, RP Rodgers, and AG Marshall, Energy & Fuels 2008, 22, 3118–3125

36  LINDEN CMS GmbH, 2012 Fully Automated LIFDI MS for High Throughput Screening of Compounds with Various Polarity J. Griep-Raming and H.B. Linden, German MS conference poster, Rostock, 2005

CCTV

LIFDI probe

LIFDI capillary

GC PAL autosampler

37  LINDEN CMS GmbH, 2012 Fully Automated LIFDI MS for High Throughput Screening of Compounds with Various Polarity J. Griep-Raming and H.B. Linden, German MS conference poster, Rostock, 2005

Schematic of the autosampler loading mechanism: The plunger of the syringe is removed. The LIFDI capillary is fed through the syringe and the beveled needle. The capillary is moved up/down with the lever which normally moves the plunger.

38  LINDEN CMS GmbH, 2012 Fully Automated LIFDI MS for High Throughput Screening of Compounds with Various Polarity J. Griep-Raming and H.B. Linden, German MS conference poster, Rostock, 2005

Bis-(3-triethoxysilylpropyl)polysulfide

“The“The spectrum (of PEG 1000) is indistinguishable from a spectrum obtained in manual sample loading mode. It has been obtained on an overnight run, run, during during which which 30 30 samples samples were measured. The samples have been of different chemical origin, covering various compound classes such as hydrocarbons, polymers, steroids, fatty acid esters, and many more.”

39  LINDEN CMS GmbH, 2012 Soft ionization by FI, FD and LIFDI

Introduction 1. Why is FI/FD/LIFDI very soft? 2. Various instruments – identical handling 3. Automated LIFDI 4. Improved FI intensity of gases 5. LIFDI on FT-ICR instruments 6. LIFDI of air/moisture sensitive metal complexes 7. Orbitrap with ESI-LIFDI combination

40  LINDEN CMS GmbH, 2012 tuning by FI with acetone supplied through LIFDI capillary

gives saturated signal at normal multiplier voltage of 350 V multiplier voltage had to be reduced to 250 V for tuning purpose

acetone supplied through reference gas inlet gives signal at normal multiplier voltage of 350 V not higher than 1 V

courtesy of Kim Wickström, Neste Oil Oy, Finland; instrument: ProSpec 41  LINDEN CMS GmbH, 2012 Sample gas is released between the whiskers schematically: R 60 m

sample gas

L 3.5mm instead of being blown into V= R²L the entire ion source.  40 nl

42  LINDEN CMS GmbH, 2012 LIFDI gives high intensity FI signals (through 50 µm id capillary at ca. 8 x 10-6 mbar source pressure )

43  LINDEN CMS GmbH, 2012 . . . as compared to usual FI sensitivity (through reference gas inlet at ca. 4 x 10-5 mbar source pressure )

44  LINDEN CMS GmbH, 2012 FI

gas supply for tuning

or for FI from headspace

45  LINDEN CMS GmbH, 2012 FI of Me2Sb-SbMe2 from headspace under ineret conditions

measured calculated instrument: MAT 900, industrial R&D lab, Leverkusen, Germany sample: courtesy Prof. Dr. Breunig, University Bremen, Germany 46  LINDEN CMS GmbH, 2012 Soft ionization by FI, FD and LIFDI

47  LINDEN CMS GmbH, 2012 9.4 T FT-ICR MS

at University of Florida, Tallahassee, USA

with LIFDI probe and

FDF-700 power supply providing high voltage emitter heating current total ion current EHC-TIC-feedback

courtesy of Tanner M Schaub, University of Florida, Tallahassee, USA 48  LINDEN CMS GmbH, 2012 Petroleomics with LIFDI

PittCon Award lecture of Alan G. Marshall, New Orleans 2003

49  LINDEN CMS GmbH, 2012 Single Scan Broadband 650 Unique Elemental FD FT-ICR Mass Composition Assignments Spectrum Ave. m/Δm50% = 442,000

Moderate Maturity Internal Calibration RMS Crude Oil Error: 85 ppb (20 Alkylbenzenes) No FD emitter heat applied Assignment RMS Error (n=650): 192 ppb

Tanner M Schaub, Theses 2004

50 250 300 350 400 m/z 450 500 550 600 Improved Resolving Power Using He Gas Pulse – Single Scan

M+• ions containing a 13C atom can be distinguished from (M+H)+ ions C3 vs. SH4 0.0034 Da (∆m =0.00447)

No Gas Pulse m/m50%= 250,000 Gas Pulse

Tanner M Schaub, Theses 2004

485.46 485.48 485.5 51 m/z continuous flow LIFDI

75 nl/min

Øi 10 µm 15 mA EHC +10V / -10 kV

20 s/scan i.e. 25 nl/scan

Continuous Flow Sample Introduction for Field Desorption/Ionization Mass Spectrometry, T.M. Schaub, H.B. Linden, C.L. Hendrickson, A.G. Marshall, Rapid Commun. Mass Spectrom. 18 (14), 1641-1644 (2004)

52  LINDEN CMS GmbH, 2012 Tanner M Schaub, Theses 2004

53 Fig. 6 from: Schaub et al., Anal.Chem., 2005, 77, 1317-1324 n= 28 n= 32 The storage time in the accumulation hexapole of n= 36 FT-ICR instruments is ca. n= 24 106 times longer than the n=40 entire flight time of TOF or sector instruments.

fragments with n= 21 22 23 25 26 27 29 30 31 33 34 35 37 38 39 The presence even of He in the accumulation octopole entails collision induced dissociation (CID) of fragile intact molecular ions sacrificing soft ionization.

54  LINDEN CMS GmbH, 2012 New Emitter Used Emitter – 30 crude oil applications Loss of sensitivity is not observed after 30 crude oil samples. Tanner M Schaub, Florida State University, Tallahassee, Theses 2004 55 Soft ionization by FI, FD and LIFDI

56  LINDEN CMS GmbH, 2012 M+ (M-O )+ The Q-TOF II must 2 not have any Argon in the accumulation hexapole: Ar would prevent the molecular ions from being detected due to collision induced dissociation. (see next slide)

C22H39O2N2F4P2Rh

 LINDEN CMS GmbH, 2012

instrument:: Waters Q-TOF II, Humboldt University Berlin, Germany C22H39O2N2F4P2Rh with Ar in collision hexapole

Note: m/z 604 This is CID but not MS/MS

(RhC F N)+ 5 4 (note the intensity of 2x103 as + compared to (M-O2) that of the next slide) - tBuNC

- tBu+H

- C5F4N

- PEt3

instrument:: Waters Q-TOF II, Humboldt University Berlin, Germany

LINDEN CMS GmbH 58 + MS/MS on the (M-O2) ion

+ 20 eV (M-O2) collision m/z 604 is isolated by energy the quad and excited for CID by 20 eV. The fragments are analyzed by the TOF

+ tBuNC (M-O ) + 2 (RhC5NF4) - C5F4N (tBu-H)

PEt3

instrument:: Waters Q-TOF II, Humboldt University Berlin, Germany

LINDEN CMS GmbH 59 M+ C H Fe O P S MW 878 45 36 2 4 2 2 (M - CO)+ at 35 mA emitter heating current

Ph4C2H2P2 m/z 396.1

 LINDEN CMS GmbH, 2012

instrument:: Waters GCT Premier, University of Illinois, Urbana-Champaign, USA M+

C H Fe O P S MW 878 45 36 2 4 2 2 (M - CO)+ at 50 mA emitter heating current (M - 2CO)+ thermal fragments can appear

536 (M - 3CO)+

- Ph2C3H4S2 m/z 258

+ Ph4C2H2P2 m/z 396.1

- Fe2CO

m/z 139,9  LINDEN CMS GmbH, 2012

instrument:: Waters GCT Premier, University of Illinois, Urbana-Champaign, USA

LIFDI Spectrum under inert conditions 2 of [- -(cis-Me3SiCH 2Bi)2 ][W(CO)5]2

+ [M-W(CO)5]

M+

instrument: MAT 900, Bayer AG, Leverkusen, Germany sample: Prof. Dr. Breunig group, University Bremen, Germany 62 Balázs L, Breunig H J, Lork E, Angew. Chem. Int. Ed. 2002, 13, 2309-17  LINDEN CMS GmbH, 2012 Ru4H4(CO)12

isotope pattern

calculated

measured

instrument: GCT, Toyota, Nagoya, Japan sample: Prof. Dr J. Scott McIndoe, University of Victoria, CANADA N.J. Farrer and J.S. McIndoe, Encyclopedia of Mass Spectrometry, 6, 2007, 903-915 63  LINDEN CMS GmbH, 2012 loss of CO is neglegible in LIFDI Fe3(CO)12

M+ isotope pattern

calculated

measured

(M-CO) +

sample: Prof. Dr J. Scott McIndoe, University of Victoria, CANADA instrument:: Waters GCT Premier, industrial R&D lab, Nagoya, Japan 64  LINDEN CMS GmbH, 2012 loss of CO is loss of CO is dominant in EI neglegible in LIFDI Fe3(CO)12 comparison EI spectrum LIFDI spectrum

M+ CO+ (M-2CO)+

+ FeCO (M-CO)+

Fe+ M+ (M-CO) +

sample: Prof. Dr J. Scott McIndoe, University of Victoria, CANADA instrument:: Waters GCT Premier, industrial R&D lab, Nagoya, Japan 65  LINDEN CMS GmbH, 2012

+ calculated C20H30UCl2 + C20H30UCl2 measured

Cl U + C10H15UCl3 Cl

LIFDI MS of F-element complexes prepared at University of California, Irvine, according to: Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds P. J. Fagan, J. M. Manriquez, E. A. Maatta, A. M. Seyam, T. J. Marks, J. Am. Chem. Soc. 1981, 103, 6650-6667 66 instrument:: Waters GCT Premier, University of California, Irvine, USA  LINDEN CMS GmbH, 2012 66 Soft ionization by FI, FD and LIFDI

67  LINDEN CMS GmbH, 2012 LIFDI and ESI ion sources simultaneously installed on axis of an Exactive Orbitrap

LIFDI sample supply

The source of interest is switched on, the other one off. The ESI or LIFDI capillary and tune parameters are used ESI respectively for acquisition of ESI or LIFDI spectra. sample supply Exactive Orbitrap with LIFDI and ESI ion sources simultaneously installed on axis Mathias H. Linden, H. Bernhard Linden, Alexander Makarov, Mikhail Belov, Maciej Bromirksi, Carolin Sieck, Kei Murata, Zuolun Zhang and Todd B. Marder IMSC Poster, Geneva, Switzerland, August 24-29, 2014 68  LINDEN CMS GmbH, 2012 C54H34BF10NS2

M+

Exactive Orbitrap with LIFDI and ESI ion sources simultaneously installed on axis Mathias H. Linden, H. Bernhard Linden, Alexander Makarov, Mikhail Belov, Maciej Bromirksi, Carolin Sieck, Kei Murata, Zuolun Zhang and Todd B. Marder IMSC Poster, Geneva, Switzerland, August 24-29, 2014 69  LINDEN CMS GmbH, 2012 C51H59N2O6P2Rh

M+

70  LINDEN CMS GmbH, 2012 PEG 1500 LIFDI on Orbitrap

(M+Na)+

(M+2Na)2+

71  LINDEN CMS GmbH, 2000 PEG 1500 ESI on Orbitrap

(M+2Na)2+

(M+Na)+

72  LINDEN CMS GmbH, 2000 Conclusion

FI, FD and LIFDI share the same ionization mechanism.

LIFDI and FI keep the emitter in the ion source under vacuum all the time, FD removes the emitter from the ion source breaking vacuum for each sample.

The LIFDI and FI protocol is quick, safe, and easily accessible to automation and continuous operation.

LIFDI ionizes polar and non-polar, volatile and non-volatile, reactive and inert samples forming true molecular ions without matrix interference.

LIFDI offers high throughout and hyphenated techniques which are not accessible to FD.

73  LINDEN CMS GmbH, 2012