RESUMO
Size-resolved gas-particle partitioning of semi-volatile organic compounds (SVOCs) can affect their environmental behaviors and health effects, which has not been widely studied in comparing with the gas-total suspended particle partitioning. Herein, the size-resolved gas-particle partitioning quotient (KPi) of polycyclic aromatic hydrocarbons (PAHs) in a large temperature range (-20.6 â â¼ 29.4 â) was firstly comprehensively studied. The log KPi values of PAHs related to fine particles were significantly higher than those related to coarse particles. When the logarithm of subcooled liquid-vapor pressure (log PL0) ∈ [-7, -1), the regression slopes of log KPi vs log PL0 related to the particle size > 1.0 µm were shallower than those with the particle size range of 0.10-1.0 µm, which indicated the influence of particle size on KPi. Among the three previous prediction equations of gas-particle partitioning quotient, the empirical equation based on the ambient temperature matched better with the measured log KPi. Therefore, a new prediction equation including ambient temperature and particle size as the two major parameters was established. For most particle size ranges, the new equation showed better prediction performance than the three previous equations. In summary, this study provided new insights for the size-resolved gas-particle partitioning mechanism and quotient.
RESUMO
Polycyclic aromatic hydrocarbons (PAHs) have the capability for solar radiation absorption related to climate forcing. Herein, pollution characteristics and absorption spectra of size-resolved PAHs in atmospheric particles in a cold megacity were comprehensively investigated. The mean concentrations of Σ18PAHs in all the 11 particle size ranges were 3.95 ± 4.77 × 104 pg/m3 and 2.17 ± 1.54 × 103 pg/m3 in heating period (HP) and non-heating period (NHP), respectively. Except for most PAHs with 2 and 3 benzene rings in NHP, most other PAHs showed a unimodal distribution pattern with the peak at 0.56-1.0 µm in both periods, which was caused by PAH emission sources. The PAH-related climate forcing was mainly caused by the solar radiation absorptions at â¼325 (â¼330) nm and â¼365 nm. In general, the absorption intensities were higher in HP than NHP. The absorption intensity in the particle size range of 0.56-1.0 µm was the highest, and benzo[e]pyrene was the dominant contributor. In colder periods in HP, higher PAH concentrations caused more intensive PAH-related climate forcing. This study provided new insights for pollution characteristics and absorption spectra of size-resolved PAHs in atmospheric particles, which will be useful for better understanding PAH-related climate forcing.
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Environmental persistent free radicals (EPFRs) have attracted more attentions recently due to their potential adverse effects to human. EPFRs in full-size range particles were comprehensively investigated in this study. The average EPFRs concentration during heating season was 3.01 × 1014 spins/m3, which was much higher than that in non-heating season (4.30 × 1013 spins/m3). The highest concentration of EPFRs presented in 0.56-1.0 µm particles during heating season, while it shifted to 5.6-10 µm particles during non-heating season. Besides, the contributions of EPFRs on PM>10 to the total concentration of EPFRs cannot be neglected, especially in the non-heating season. The International Commission on Radiological Protection model and the specific factors of the Chinese population were applied to evaluate the inhalation exposure risk of EPFRs. The results indicated that the exposure levels of EPFRs to the upper respiratory tract were much higher. The daily exposure dose of EPFRs suggested the inhalation exposure risk of 3-4 years old was higher than other age groups. In summary, these finding provided new insights for the full range particle size distribution and the inhalation exposure risk of EPFRs, which improved our understanding on the environmental fate and the health risk of EPFRs in atmosphere.
Assuntos
Poluentes Atmosféricos , Exposição por Inalação , Humanos , Pré-Escolar , Material Particulado/análise , Poluentes Atmosféricos/análise , Atmosfera , Radicais LivresRESUMO
Two novel thermally activated delayed fluorescence (TADF) emitters, 3-phenylquinolino[3,2,1- de]acridine-5,9-dione (3-PhQAD) and 7-phenylquinolino[3,2,1- de]acridine-5,9-dione (7-PhQAD), were designed and synthesized based on a rigid quinolino[3,2,1- de]acridine-5,9-dione (QAD) framework. With the effective superimposed resonance effect from electron-deficient carbonyls and electron-rich nitrogen atom, both emitters realize significant TADF characteristics with small Δ ESTs of 0.18 and 0.19 eV, respectively. And, molecular relaxations were dramatically suppressed for both emitters because of their conjugated structure. In the devices, 3-PhQAD realizes superior performance with a maximum external quantum efficiency (EQE) of 19.1% and a narrow full width at half-maximum (FWHM) of 44 nm, whereas a maximum EQE of 18.7% and an extremely narrow FWHM of 34 nm are realized for 7-PhQAD. These superior results reveal that apart from nitrogen and boron-aromatic systems, QAD framework can also act as a TADF matrix with effective resonance effect, and QAD derivatives are ideal candidates to develop TADF emitters with narrow FWHMs for practical applications.
RESUMO
Exciplexes are ideal candidates as effective thermally activated delayed fluorescence (TADF) emitters. However, efficient orange and red TADF exciplexes have been reported seldomly, because their significant non-radiative (NR) decay of excited states lead to unavoidable energy loss. Herein, we propose a novel strategy to construct efficient red TADF exciplexes by introducing phosphor as one component. Due to the strong spin-orbit coupling of heavy metal (e.g., Ir, Pt, et al.) ion cores, the NR decays will be evidently decreased for both singlet and triplet excitons, reducing the undesired exciton waste. Moreover, compared with the conventional exciplexes, phosphorescence plays an important role for such novel exciplexes, further improving the exciton utilization. Based on this strategy, we fabricated a red exciplex containing 1,3,5-triazine-2,4,6-triyl)tris(benzene-3,1-diyl)tris(diphenylphosphine oxide) (PO-T2T) and tris(2-phenylpyridine) iridium(III) (Ir(ppy)3) as components and realize a red emission with a peak at 604 nm, a CIE coordinate of (0.55, 0.44), and a high maximum external quantum efficiency of 5% in organic light-emitting device. This efficiency is 2.6 times higher than that of the device based on the conventional red exciplex emitter, proving the superiority of our novel strategy to construct TADF exciplexes with phosphors.