Selective and slow: The effects on the photophysics of a single salicylideneaniline molecule, induced by confinement in an all‐organic, weakly interacting molecular capsule of a matching size, are studied by time‐resolved spectroscopy. The capsule acts efficiently to select only one deactivation pathway after photoexcitation and keeps the photochromism in the solid state with a 300‐fold retardation—relative to the solution state—in the decay time of the photochromic product (see picture).
Abstract. Comprehensive techniques to describe the organic
composition of atmospheric aerosol are needed to elucidate pollution
sources, gain insights into atmospheric chemistry, and evaluate changes in
air quality. Fourier transform infrared absorption (FT-IR) spectrometry can
be used to characterize atmospheric organic matter (OM) and its composition
via functional groups of aerosol filter samples in air monitoring networks
and research campaigns. We have built FT-IR spectrometry functional group
calibration models that improve upon previous work, as demonstrated by the
comparison of current model results with those of previous models and other
OM analysis methods. Laboratory standards that simulated the breadth of the
absorbing functional groups in atmospheric OM were made: particles of
relevant chemicals were first generated, collected, and analyzed. Challenges
of collecting atmospherically relevant particles and spectra were addressed
by including interferences of particle water and other inorganic aerosol
constituents and exploring the spectral effects of intermolecular
interactions. Calibration models of functional groups were then constructed
using partial least-squares (PLS) regression and the collected laboratory
standard data. These models were used to quantify concentrations of five
organic functional groups and OM in 8 years of ambient aerosol samples
from the southeastern aerosol research and characterization (SEARCH)
network. The results agreed with values estimated using other methods,
including thermal optical reflectance (TOR) organic carbon (OC;
R2=0.74) and OM calculated as a difference between total aerosol mass
and inorganic species concentrations (R2=0.82). Comparisons with
previous calibration models of the same type demonstrate that this new, more
complete suite of chemicals has improved our ability to estimate oxygenated
functional group and overall OM concentrations. Calculated characteristic
and elemental ratios including OM∕OC, O∕C, and H∕C agree with those from
previous work in the southeastern US, substantiating the aerosol composition
described by FT-IR calibration. The median OM∕OC ratio over all sites and
years was 2.1±0.2. Further results discussing temporal and spatial
trends of functional group composition within the SEARCH network will be
published in a forthcoming article.
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