Breaking the Brightness Barrier: Design and Characterization of a Selected-Ion Fluorescence Measurement Setup with High Optical Detection Efficiency

Tiwari, Prince; Metternich, Jonas B.; Czar, Martin F.; Zenobi, Renato

doi:10.1021/jasms.0c00264

Cited by 21 publications

(49 citation statements)

References 37 publications

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“…Two anodized aluminum alloy tubes were also added to reduce chance of the diverging laser beam hitting the metal surface of the ICR cell. The optical background signal was reduced ∼5 times to the same level of QIT . The obtained fluorescence decay curve was fitted with an exponentially modified Gaussian (GaussMod).…”

Section: Resultsmentioning

confidence: 99%

“…The same experiment was repeated without ions in the ICR cell for background subtraction. The fluorescence lifetime experiments followed a similar protocol . Fluorescence spectra were recorded by commercial software (Solis version 4.3, Andor), fluorescence decay data were recorded by TimeHarp software, the mass spectrometric data (mass spectrum, chromatogram, transient, and instrumental conditions) were recorded by our new DAQ system, and all data were analyzed using OriginPro 2019.…”

Section: Methodsmentioning

confidence: 99%

“…The difficulties include low numbers of trapped ions and thus weak fluorescence, a high degree of photodissociation (PD), and the need to modify a mass spectrometer with an interface for optical excitation and detection (i.e., limited optical access) . Until now, mostly quadrupole ion traps (QITs, “Paul trap” and cylindrical) and linear ion traps (LTQs) have been modified for fluorescence experiments. ,,− Although QITs and LTQs have a higher throughput and sensitivity, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is superior in terms of m / z range, mass resolution, and extended trapping times. For example, the m / z range of a modern QIT is up to 4000 Th, while an FT-ICR MS usually offers more than 10,000 Th.…”

Section: Introductionmentioning

confidence: 99%

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Adapting a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer for Gas-Phase Fluorescence Spectroscopy Measurement of Trapped Biomolecular Ions

Metternich

Tiwari

et al. 2021

Anal. Chem.

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Gas-phase fluorescence spectroscopy is still in its infancy, which demands further instrumental developments. In this study, a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS), equipped with a lab-developed data acquisition system, was coupled to a tunable femtosecond laser and a state-of-the-art optical system for fluorescence studies of massselected ions. For excitation, a laser beam was focused (beam size < 1.0 mm) into the cylindrical ICR cell. A wire mesh replaced the back trapping plate, allowing ∼10% of the fluorescence emitted from trapped ions to be collected by a lens installed beside the wire mesh. The collected fluorescence light was then transmitted outside of the mass spectrometer via fiber optics. A novel accumulation during detection (ADD) scheme was developed to increase the duty cycle of gas-phase fluorescence spectroscopy experiments. With ADD, >90% duty cycle for mass spectrometry and fluorescence experiments could be achieved. This instrument was able to perform fluorescence experiments on various ions, from simple rhodamine dyes to large biomolecules (i.e., peptides and proteins) labeled with dyes of various optical properties. A fluorescence lifetime measurement of trapped rhodamine 6G cations was also performed, yielding a value of 5.97 ± 0.23 ns. This setup has a broad mass range and decent fluorescence spectroscopy performance (i.e., the emission spectrum of rhodamine 6G can be acquired with good S/N in a minute). Finally, this setup also allows more challenging gas-phase fluorescence spectroscopy experiments, for example, of low quantum yield fluorophores and large biomolecules in their native state that appear at high m/z, which may not be doable with quadrupole ion traps (QIT).

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Adapting a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer for Gas-Phase Fluorescence Spectroscopy Measurement of Trapped Biomolecular Ions

Metternich

Tiwari

et al. 2021

Anal. Chem.

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“…We recently developed an instrument in our lab that facilitates diverse fluorescence experiments with high fluorescence collection efficiency. [16] Fluorescence-based experiments like excitation and emission spectroscopy, lifetime measurements, and ion imaging of trapped ions can be performed with this setup. And the high fluorescence collection efficiency results from the large fluorescence collection solid angle that could be achieved with a lens placed very close to the ion cloud.…”

Section: Gas-phase Fluorescence Spectroscopy Of Biomolecular Ionsmentioning

confidence: 99%

“…periments. [11,[13][14][15][16] Fluorescence from trapped gaseous ions was first reported way back in 1981. [17] Fluorescence from trapped fluorescent dyes could only be obtained in the early 2000s.…”

Section: Gas-phase Fluorescence Spectroscopy Of Biomolecular Ionsmentioning

confidence: 99%

Fluorescence-based Techniques to Study the Structure and Dynamics of Mass-selected Biomolecular Ions

Tiwari

2021

Chimia

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Laser-induced fluorescence studies on mass-selected biomolecules are a promising route to understand their properties in the gas phase and probe their intrinsic properties in a solvent-free environment. Fluorescence has been used to investigate the conformation and dynamics of gaseous biomolecular ions. With Förster Resonance Energy Transfer (FRET), it is now possible to obtain sensitive intramolecular distance information from large biomolecules, like proteins, with high chemical specificity. With growing interest and applications, gas-phase fluorescence measurements can shed greater light on the characteristics of proteins in the gas phase. Compared to the solution phase measurements, gas-phase fluorescence can also help understand the influence of solvent interactions on the protein structure and function.

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Cryogenic Ion Fluorescence Spectroscopy: FRET in Rhodamine Homodimers and Heterodimers

Kjær,

Vu‐Phung,

Toft Lindkvist

et al. 2023

Chemistry A European J

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The internal electronic communication between two or more light‐absorbers is fundamental for energy‐transport processes, a field of large current interest. Here we have studied the intrinsic photophysics of homo‐ and heterodimers of rhodamine cations where just two methylene units bridge the dyes. Gas‐phase experiments were done on frozen molecular ions at cryogenic temperatures using the newly built LUNA2 mass spectroscopy setup in Aarhus. Both absorption (from fluorescence excitation) and dispersed‐fluorescence spectra were measured. In the gas phase, there is no dielectric screening from solvent molecules, and the effect of charges on transition energies is maximum. Indeed, bands are redshifted compared to those of monomer dyes due to the electric field that each dye senses from the other in a dimer. Importantly, also, as two chemically identical dyes in a homodimer do not experience the same field along the long axis, each dye has separate absorption. At low temperatures, it is therefore possible to selectively excite one dye. We find that fluorescence is dominantly from the dye with the lowest transition energy no matter which dye is photoexcited. Hence our work unequivocally demonstrates Förster Resonance Energy Transfer even in homodimers where one dye acts as donor and the other as acceptor.

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Breaking the Brightness Barrier: Design and Characterization of a Selected-Ion Fluorescence Measurement Setup with High Optical Detection Efficiency

Abstract: Breaking the brightness barrier: design and characterization of a selected-ion fluorescence measurement setup with high optical detection efficiency

Cited by 21 publications

References 37 publications

Adapting a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer for Gas-Phase Fluorescence Spectroscopy Measurement of Trapped Biomolecular Ions

Adapting a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer for Gas-Phase Fluorescence Spectroscopy Measurement of Trapped Biomolecular Ions

Fluorescence-based Techniques to Study the Structure and Dynamics of Mass-selected Biomolecular Ions

Cryogenic Ion Fluorescence Spectroscopy: FRET in Rhodamine Homodimers and Heterodimers

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