We present a computational model for electrochemical
surface-enhanced
Raman scattering (EC-SERS). The surface excess of charge induced by
the electrode potential (V
el) was introduced
by applying an external electric field to a set of clusters [Ag
n
]
q
with (n, q) of (19, ±1) or (20, 0) on which
a molecule adsorbs. Using DFT/TD-DFT calculations, these metal–molecule
complexes were classified by the adsorbate partial charge, and the
main V
el-dependent properties were simultaneously
studied with the aid of vibronic resonance Raman computations, namely,
changes on the vibrational wavenumbers, relative intensities, and
enhancement factors (EFs) for all SERS mechanisms: chemical or nonresonant,
and resonance Raman with bright states of the adsorbate, charge-transfer
(CT) states, and plasmon-like excitations on the metal cluster. We
selected two molecules to test our model, pyridine, for which V
el has a remarkable effect, and 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene, which is almost insensitive
to the applied bias. The results nicely reproduced most of the experimental
observations, while the limitations of our approach were critically
evaluated. We detected that accounting explicitly for the surface
charges is key for EC-SERS models and that the highest calculated
EFs, up to 107 to 108, are obtained by interstate
coupling of bright local excitations of the metal cluster and CT states.
These results highlight the importance of nonadiabatic effects in
SERS and the capabilities of EC-SERS as a technique with potential
to study excited-state coupling by tuning the CT and plasmon-like
states by manipulating V
el.
The case of a 7 2-year-old female with a syndrome of malabsorption associated with prurigo nodularis is reported. The patient had been suffering from these disorders for 16 years. The pathological alteration of her malabsorption syndrome was an idiopathic sprue. 5 months after treatment with gluten-free diet supplemented with vitamins and iron, the disappearance of the clinical and analytical alterations was complete.
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