Photoelectron Spectroscopy of Isolated Multiply Negatively Charged Oligonucleotides

Weber, J. Mathias; Ioffe, Ilya N.; Berndt, K.; Löffler, Daniel; Friеdrich, J.; Ehrler, Oli T.; Danell, Allison S.; Parks, Joel H.; Kappes, Manfred M.

doi:10.1021/ja049736c

Cited by 47 publications

(63 citation statements)

References 41 publications

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“…[4][5][6]32,33 The Kappes group successfully integrated an ESI source to a RT hexapole ion trap and a magnetic-bottle PES analyzer for the studies of MCAs. [38][39][40] One of the limitations of the first ESI-PES apparatus was the lack of ion temperature control because the Paul trap was operated at room temperature. Molecular ions, in particular complex MCAs or weakly bounded anions, could carry substantial internal energies even at RT.…”

Section: Experimental Methodsmentioning

confidence: 99%

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

Wang

2015

The Journal of Chemical Physics

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Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.

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Section: Experimental Methodsmentioning

confidence: 99%

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

Wang

2015

The Journal of Chemical Physics

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Section: Experimental Methodsmentioning

confidence: 99%

“…[75][76][77][78][79][80] The coupling of ESI with PES allowed MCAs to be spectroscopically characterized for the first time. [4][5][6][32][33][34][35][36][37][38][39][40] When an electron is detached from a MCA, it experiences a short-range attraction by the nuclei and a long-range repulsion from the negatively charged residual ion, resulting in the socalled RCB (Fig. 2(a)).…”

Section: Photoelectron Imaging Of Multiply-charged Anions: the Imentioning

confidence: 99%

A multi-agent quantum Monte Carlo model for charge transport: Application to organic field-effect transistors

Bauer

Jäger

Jordan

et al. 2015

The Journal of Chemical Physics

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We have developed a multi-agent quantum Monte Carlo model to describe the spatial dynamics of multiple majority charge carriers during conduction of electric current in the channel of organic field-effect transistors. The charge carriers are treated by a neglect of diatomic differential overlap Hamiltonian using a lattice of hydrogen-like basis functions. The local ionization energy and local electron affinity defined previously map the bulk structure of the transistor channel to external potentials for the simulations of electron- and hole-conduction, respectively. The model is designed without a specific charge-transport mechanism like hopping- or band-transport in mind and does not arbitrarily localize charge. An electrode model allows dynamic injection and depletion of charge carriers according to source-drain voltage. The field-effect is modeled by using the source-gate voltage in a Metropolis-like acceptance criterion. Although the current cannot be calculated because the simulations have no time axis, using the number of Monte Carlo moves as pseudo-time gives results that resemble experimental I/V curves.

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“…The EA values of the hexa-dA anions are expected to decrease with the increase of absolute charge due to the destabilizing electrostatic field [65,66]. Indeed, recent photo-electron spectroscopy studies by Kappes and coworkers on (A 5 Ϫ4H) 4Ϫ demonstrate the fourth vertical electron affinity to be 0.11 eV (the adiabatic electron affinity was reported to be slightly negative) [65,66].…”

Section: Qualitative Trends In Product Partitioningmentioning

confidence: 99%

“…Indeed, recent photo-electron spectroscopy studies by Kappes and coworkers on (A 5 Ϫ4H) 4Ϫ demonstrate the fourth vertical electron affinity to be 0.11 eV (the adiabatic electron affinity was reported to be slightly negative) [65,66]. Hence the EA values of the hexa-dA charge states studied here can be expected to be small for the (A 6 Ϫ3H) 3Ϫ species and to decrease or even be negative for the (A 6 Ϫ4H) 4Ϫ and (A 6 Ϫ5H) 5Ϫ species.…”

Section: Qualitative Trends In Product Partitioningmentioning

confidence: 99%

Gas-phase ion/ion reactions of transition metal complex cations with multiply charged oligodeoxynucleotide anions

Barlow

Hodges

Xia

et al. 2008

J. Am. Soc. Mass Spectrom.

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Multiply deprotonated hexadeoxyadenylate anions, (A 6 ϪnH) nϪ , where n ϭ 3-5, have been subjected to reaction with a range of divalent transition-metal complex cations in the gas phase. The cations studied included the bis-and tris-1,10-phenanthroline complexes of Cu II , Fe II , and Co II , as well as the tris-1,10-phenanthroline complex of Ru II . In addition, the hexadeoxyadenylate anions were subjected to reaction with the singly charged Fe III and Co III N,N=-ethylenebis(salicylideneiminato) complexes. The major competing reaction channels are electron-transfer from the oligodeoxynucleotide anion to the cation, the formation of a complex between the anion and cation, and the incorporation of the transition-metal into the oligodeoxynucleotide. The latter process proceeds via the anion/cation complex and involves displacement of the ligand(s) in the transition-metal complex by the oligodeoxynucleotide. Competition between the various reaction channels is governed by the identity of the transition-metal cation, the coordination environment of the metal complex, and the oligodeoxynucleotide charge state. In the case of the divalent metal phenanthroline complexes, competition between electron-transfer and metal ion incorporation is particularly sensitive to the coordination number of the reagent metal complexes. Both electron-transfer and metal ion incorporation occur to significant extents with the bis-phenanthroline ions, whereas the trisphenanthroline ions react predominantly by metal ion incorporation. To our knowledge this work reports the first observations of the gas-phase incorporation of multivalent transition-metal cations into oligodeoxynucleotide anions and represents a means for the selective incorporation of transition-metal counter-ions into gaseous oligodeoxynucleotides. [6 -8] have allowed the formation of gas-phase ions of biopolymers, including oligodeoxynucleotides (ODNs), making these ions amenable to study by mass spectrometry. Like peptides and proteins, ODNs are amphoteric, [9] allowing formation of either positively or negatively charged ions. Formation of negatively charged oligonucleotides is quite facile using ESI and, as a result, negatively charged ODN ions have been the most widely studied [9]. Oligodeoxynucleotide ions with bound metals formed by MALDI or ESI, especially those containing transition metals, have shown fragmentation behavior, which is distinct and complementary to that of ions devoid of metals [6 -8].The study of the interaction of transition metals with DNA is of critical importance, given the variety of roles such interactions fulfill. Transition-metal complexes display nuclease activity and consequently complexes such as (methidium-propyl-EDTA)iron(II) have been utilized as footprinting agents [10]. Ruthenium(II) complexes have been extensively examined as spectroscopic probes of local DNA structure [11,12]. The mechanism of action of the chemotherapeutic agent cisplatin involves binding to DNA to prevent replication [13][14][15]. Mass spectrometry has been u...

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Photoelectron Spectroscopy of Isolated Multiply Negatively Charged Oligonucleotides

Cited by 47 publications

References 41 publications

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

A multi-agent quantum Monte Carlo model for charge transport: Application to organic field-effect transistors

Gas-phase ion/ion reactions of transition metal complex cations with multiply charged oligodeoxynucleotide anions

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