There has been a surge of interest in interfacial ozone chemistry for its application in indoor air quality and public health. Squalene, one of the most abundant ozone reactive constituents in an indoor environment, has received increasing attention lately, and a number of studies have been devoted to its heterogeneous interaction with ozone in actual and simulated settings. At present, there is still a large discrepancy in the measurement of the reactive uptake coefficient of ozone onto a squalene surface, and knowledge about this system remains incomplete. In this work, we investigated the ozone initiated heterogeneous oxidation of squalene using attenuated total reflection infrared spectroscopy (ATR-IR). We measured pseudo-first-order rate constants and uptake coefficients based on time dependent absorbance changes in C═C (1668 cm(-1)) and C═O (1730 cm(-1)) vibration bands. The uptake coefficients are (1.7 ± 0.2) × 10(-4) from the C═C band and (5.1 ± 0.7) × 10(-4) from the C═O band. The latter is likely an upper limit of reaction probability for ozone uptake onto squalene. Studies of temperature (5-32 °C) and relative humidity (0 and 80% RH) dependence revealed that indoor temperatures and RHs did not affect reaction kinetics. The insignificant RH effect is probably due to the weak interaction between water and squalene molecules. We quantitatively characterized the hydrophilicity and redox activity of squalene before and after exposure to ozone for the first time, and observed considerable enhancements in both hydrophilicity and redox activity during reaction. This may imply that ozone initiated heterogeneous oxidation could pose a higher public health risk in an indoor environment, and it may help explain some of the adverse health effects associated with elevated indoor pollutants.

Plasmonic gold nanorods (Au NRs)-copper sulfide heterostructures have recently attracted much attention owing to the synergistically enhanced photothermal properties. However, the facile synthesis and interface tailoring of Au NRs-copper sulfide heterostructures remain a formidable challenge. In this study, the rational design and synthesis of Au NRs-Cu S heterostructures via a one-pot hydrothermal process is reported. Specifically, core-shell and dumbbell-like Au NRs-Cu S heterostructures are obtained with well-controlled interfaces by employing the Au NRs with different aspect ratios. Both core-shell and dumbbell-like Au NRs-Cu S have proven effective as photothermal therapy agents, which offer both high photothermal stability and significant photothermal conversion efficiency up to 62%. The finite-difference time domain simulation results confirm the coupling effect that leads to the enhanced local field as well as the optical absorption at the heterostructure interface. Importantly, these Au NRs-Cu S heterostructures can be compatibly used as an 808 nm laser-driven photothermal therapy agents for the efficient photothermal therapy of cancer cells in vitro. This study will provide new insight into the design of other noble metal-semiconductor heterostructures for a broad range of applications utilizing surface plasmon resonance enhancement phenomena.

The ozone initiated heterogeneous oxidation of erucic acid (EA) thin film was investigated using a flow system combined with attenuated total reflection infrared spectroscopy (ATR-IR) over wide ranges of ozone concentrations (0.25-60 ppm), thin film thickness (0.1-1.0 μm), temperatures (263-298 K), and relative humidities (0-80% RH) for the first time. Pseudo-first-order rate constants, kapp, and overall reactive uptake coefficients, γ, were obtained through changes in the absorbance of C[double bond, length as m-dash]O stretching bands at 1695 cm(-1), which is assigned to the carbonyl group in carboxylic acid. Results showed that the reaction followed the Langmuir-Hinshelwood mechanism and kapp was largely dominated by surface reaction over bulk phase reaction. In addition, both the kapp and the γ values showed very strong temperature dependences (∼two orders of magnitude) over the temperature range; in contrast, they only slightly increased with increasing RH values from 0-80%. According to the kapp values as a function of temperature, the activation energy for the heterogeneous reaction was estimated to be 80.6 kJ mol(-1). Our results have suggested that heterogeneous reactions between ozone and unsaturated solid surfaces likely have a substantially greater temperature dependence than liquid ones. Moreover, the hygroscopic properties of EA thin films before and after exposure to ozone were also studied by measurement of water uptake. Based on the hygroscopicity data, the insignificant RH effect on reaction kinetics was probably due to the relatively weak water uptake by the unreacted and reacted EA thin films.