5 research outputs found
The Gas-Phase Photophysics of Eosin Y and its Maleimide Conjugate
The use of the xanthene
family of dyes as fluorescent probes in
a wide range of applications has provided impetus for the studying
of their photophysical properties. In particular, recent advances
in gas-phase techniques such as FRET that utilize such chromophores
have placed a greater importance on the characterization of these
properties in the gas phase. Additionally, the use of synthetic linker
chains to graft the chromophores in a site-specific manner to their
target system is ubiquitous. There is, however, often limited information
on how the addition of such a linker chain may affect the photophysical
properties of the chromophores, which is of fundamental importance
for interpretation of experimental data reliant on grafted chromophores.
Here, we present data on the optical spectroscopy of different protonation
states of Eosin Y, a fluorescein derivative. We compare the photophysics
of Eosin Y to its maleimide conjugate, and to the thioether product
of the reaction of this conjugate with cysteamine. Comparison of the
mass spectra following laser irradiation shows that very different
relaxation takes place upon addition of the maleimide moiety but that
the photophysics of the bare chromophore are restored upon addition
of cysteamine. This radical change in the photophysics is interpreted
in terms of charge-transfer states, whose energy relative to the S<sub>1</sub> ā S<sub>0</sub> transition of the chromophore is dependent
on the conjugation of the maleimide moiety. We also show that the
shape of the absorption band is unchanged in the gas-phase as compared
to the solution-phase, showing a maximum with a shoulder toward the
blue, and examination of isotope distributions of the isolated ions
show that this shoulder cannot be due to the presence of dimers. Consideration
of the fluorescence emission spectrum allows a tentative assignment
of the shoulder to be due to a vibrational progression with a high
FranckāCondon factor
Visible and Ultraviolet Spectroscopy of Gas Phase Rhodamine 575 Cations
The visible and ultraviolet spectroscopy
of gas phase rhodamine
575 cations has been studied experimentally by action-spectroscopy
in a modified linear ion trap between 220 and 590 nm and by time-dependent
density functional theory (TDDFT) calculations. Three bands are observed
that can be assigned to the electronic transitions S<sub>0</sub> ā
S<sub>1</sub>, S<sub>0</sub> ā S<sub>3</sub>, and S<sub>0</sub> ā (S<sub>8</sub>,S<sub>9</sub>) according to the theoretical
prediction. While the agreement between theory and experiment is excellent
for the S<sub>3</sub> and S<sub>8</sub>/S<sub>9</sub> transitions,
a large shift in the value of the calculated S<sub>1</sub> transition
energy is observed. A theoretical analysis of thermochromism, potential
vibronic effects, andāqualitativelyāelectron correlation
revealed it is mainly the latter that is responsible for the failure
of TDDFT to accurately reproduce the S<sub>1</sub> transition energy,
and that a significant thermochromic shift is also present. Finally,
we investigated the nature of the excited states by analyzing the
excitations and discussed their different fragmentation behavior.
We hypothesize that different contributions of local versus charge
transfer excitations are responsible for 1-photon versus 2-photon
fragmentation observed experimentally
Single-Photon, Double Photodetachment of Nickel Phthalocyanine Tetrasulfonic Acid 4- Anions
Single-photon,
two-electron photodetachment from nickel phthalocyanine
tetrasulfonic acid tetra anions, [NiPc]<sup>4ā</sup>, was examined
in the gas-phase using a linear ion trap coupled to the DESIRS VUV
beamline of the SOLEIL Synchrotron. This system was chosen since it
has a low detachment energy, known charge localization, and well-defined
geometrical and electronic structures. A threshold for two-electron
loss is observed at 10.2 eV, around 1 eV lower than previously observed
double detachment thresholds on multiple charged protein anions. The
photodetachment energy of [NiPc]<sup>4ā</sup> has been previously
determined to be 3.5 eV and the photodetachment energy of [NiPc]<sup>3āā¢</sup> is determined in this work to be 4.3 eV.
The observed single photon double electron detachment threshold is
hence 5.9 eV higher than the energy required for sequential single
electron loss. Possible mechanisms are for double photodetachment
are discussed. These observations pave the way toward new, exciting
experiments for probing double photodetachment at relatively low energies,
including correlation measurements on emitted photoelectrons
Action-FRET: Probing the Molecular Conformation of Mass-Selected Gas-Phase Peptides with FoĢrster Resonance Energy Transfer Detected by Acceptor-Specific Fragmentation
The use of FoĢrster resonance
energy transfer (FRET) as a
probe of the structure of biological molecules through fluorescence
measurements in solution is well-attested. The transposition of this
technique to the gas phase is appealing since it opens the perspective
of combining the structural accuracy of FRET with the specificity
and selectivity of mass spectrometry (MS). Here, we report FRET results
on gas-phase polyalanine ions obtained by measuring FRET efficiency
through specific photofragmentation rather than fluorescence. The
structural sensitivity of the method was tested using commercially
available chromophores (QSY 7 and carboxyrhodamine 575) grafted on
a series of small, alanine-based peptides of differing sizes. The
photofragmentation of these systems was investigated through action
spectroscopy, and their conformations were probed using ion mobility
spectrometry (IMS) and Monte Carlo minimization (MCM) simulations.
We show that specific excitation of the donor chromophore results
in the observation of fragments that are specific to the electronic
excitation of the acceptor chromophore. This shows that energy transfer
took place between the two chromophores and hence that the action-FRET
technique can be used as a new and sensitive probe of the structure
of gas-phase biomolecules, which opens perspectives as a new tool
in structural biology
Gas-Phase Structural and Optical Properties of Homo- and Heterobimetallic Rhombic Dodecahedral Nanoclusters [Ag<sub>14ā<i>n</i></sub>Cu<sub><i>n</i></sub>(Cī¼C<i>t</i>Bu)<sub>12</sub>X]<sup>+</sup> (X = Cl and Br): Ion Mobility, VUV and UV Spectroscopy, and DFT Calculations
The
rhombic dodecahedral nanocluster [Ag<sub>14</sub>(Cī¼C<i>t</i>Bu)<sub>12</sub>Cl]<sup>+</sup>, which has been structurally
characterized using X-ray crystallography, was transferred to the
gas phase using electrospray ionization, where it was characterized
by ion mobility (IM), vacuum ultraviolet (VUV), and ultraviolet (UV)
spectroscopies in conjunction with DFT calculations. IM reveals a
single peak, and modeling of the collision cross-section with the
X-ray structure suggests that the cluster maintains its condensed
phase structure upon transfer to the gas phase. The VUV spectra exhibit
rich fragmentation, including: photoionization to give [Ag<sub>14</sub>(Cī¼C<i>t</i>Bu)<sub>12</sub>Cl]<sup>2+ā¢</sup> with an onset of 8.84 Ā± 0.08 eV; cluster fission fragmentation
via losses of (AgCī¼C<i>t</i>Bu)<sub><i>n</i></sub> and (AgCī¼C<i>t</i>Bu)<sub><i>n</i>ā1</sub>(AgCl); and via reductive elimination of (<i>t</i>BuCī¼C)<sub>2</sub>. Apart from channels associated
with photoionization, similar fragment ions are observed in the UVPD
spectra, although their relative intensities differ. The TDDFT absorption
spectra are symmetry-allowed transitions including A<sub>u</sub> ā
A<sub>g</sub>, E<sub>u</sub> ā A<sub>g</sub>, and E<sub>u</sub> ā E<sub>g</sub> irreducible representations. Comparing the
collision cross-sections with the X-ray structures for the related
clusters [Ag<sub>8</sub>Cu<sub>6</sub>(Cī¼C<i>t</i>Bu)<sub>12</sub>Cl]<sup>+</sup>, [Ag<sub>14</sub>(Cī¼C<i>t</i>Bu)<sub>12</sub>Br]<sup>+</sup>, and [Ag<sub>8</sub>Cu<sub>6</sub>(Cī¼C<i>t</i>Bu)<sub>12</sub>Br]<sup>+</sup> suggests that they maintain their condensed-phase structures in
the gas phase. The VUV spectra of [Ag<sub>8</sub>Cu<sub>6</sub>(Cī¼C<i>t</i>Bu)<sub>12</sub>Cl]<sup>+</sup> and [Ag<sub>14</sub>(Cī¼C<i>t</i>Bu)<sub>12</sub>Br]<sup>+</sup> exhibit similar fragmentation
channels and ionization onsets (8.86 Ā± 0.03 and 8.86 Ā± 0.05,
respectively) compared with [Ag<sub>14</sub>(Cī¼C<i>t</i>Bu)<sub>12</sub>Cl]<sup>+</sup>