Combination of oxidative and reductive effects of phenolic compounds on the degradation of aniline disinfection by-products by free radicals.

In this study, we selected 13 phenolic compounds containing -COOH, -CHO, -OH, and -COCH3 functional groups as model compounds for dissolved organic matter (DOM), and explored the redox reactions during the co-degradation of phenolic compounds with aniline disinfection by-products (DBPs) at the molecular level. When phenolic compounds and aniline DBPs were degraded, phenoxy radicals and aniline radicals were the most important intermediates. Phenoxy radicals can degrade aniline DBPs via hydrogen atom abstraction (HAA) reactions, and the reaction rates were related to the reduction potentials of the compounds. Compounds containing electron-withdrawing groups were more likely to oxidize aniline DBPs. Aniline DBPs were more easily degraded by phenoxy radicals when they contained electron-donating groups, and the increase in the number of chlorine atoms inhibited the reaction rates of aniline DBPs degradation by phenoxy radicals. Although phenolic compounds can reduce aniline DBPs, there was no significant correlation between the reaction rates and the reduction potentials of the compounds. Considering the redox effects of phenolic compounds on aniline DBPs, co-degradation simulations showed that phenolics inhibited the degradation efficiency of aniline DBPs. This work provided new insights into the transformation mechanisms and degradation efficiencies of DOM and aniline DBPs when they were co-degraded.

Theoretical evidence for a pH-dependent effect of carbonate on the degradation of sulfonamide antibiotics.

Carbonate (CO32-/HCO3-) have a significant impact on advanced oxidation processes (AOPs) by consuming reactive free radicals such as HO• to generate CO3•-. However, research on the mechanisms and kinetics of CO3•- remains limited. This study investigates the degradation mechanism and kinetics of sulfonamide antibiotics (SAs) by CO3•- through theoretical calculations. The calculation results revealed that the effect of CO3•- on SAs degradation is pH-dependent due to the dissociable sulfonamide group (-SO2NH-) of SAs in the common water treatment pH range (3-8). The main reaction type of CO3•- with both neutral and anionic molecules of SAs is single electron transfer reaction. Frontier molecular orbital theory (FMO) illustrated that deprotonation of the sulfonamide group of SAs decreases the charge density on the heterocyclic ring, facilitating the electrophilic addition of CO3•-. The second-order rate constants of the neutral and anionic molecules of SAs with CO3•- were calculated as 7.57 × 101∼1.84 × 108 and 1.81 × 107∼7.94 × 109 M-1 s-1, respectively, resulting in an increase in the apparent reaction rate constants with pH. Stepwise multiple linear regression was employed to predict reactivity with anionic sulfonamide antibiotics (SAs-). Two models with outstanding prediction and stability were developed with coefficients of determination R2 of 0.660 and 0.681, respectively. The degradation kinetics simulation indicated that in the UV/H2O2 process in the presence of carbonate, the degradation rate of SAs increased with pH. Furthermore, the contribution of CO3•- to SMX degradation increased while that of HO• decreased. This study highlights the contribution of carbonates to the micropollutant degradation in the UV/H2O2 process as the model, providing theoretical insights into the development of carbonate-based AOPs.

Homogeneous and heterogeneous atmospheric ozonolysis of chlorobenzene:Mechanism, kinetics and ecotoxicity assessment.

The reactions between chlorobenzene(CB) and ozone have been studied comprehensively in this paper. Chlorobenzene is a commonly found chlorinated aromatic volatile organic compound(VOC), and its emission into the atmosphere can cause harm to the ecosystem and human health. The frequent occurrence of mineral particles from sandstorms exerts a significant influence on the atmospheric chemistry of the troposphere. Mineral particles are abundant in SiO2 and Al2O3 content. Therefore, we investigated the homogeneous and heterogeneous reaction processes of CB and ozone in the atmosphere by using density functional theory (DFT) method at the M06-2X/6-311++g(3df,2p)//M06-2X/6-31+g(d,p) level. The atmospheric fate, reaction rate and toxicity evaluation of CB ozonation were studied in the gas-phase section. Toxicity evaluation results showed that ozonation of CB could effectively reduce its toxicity. For the heterogeneous process, we simulated three types of SiO2 clusters and nine types of (Al2O3)n clusters, and studied the configurations of CB adsorbed on the cluster surfaces. We found that adsorption of CB on the SiO2 clusters was achieved through hydrogen bonding, while adsorption of CB on the Al2O3 clusters was achieved through both hydrogen bonding and metal bonding. The energy for CB adsorption on the (Al2O3)n cluster surface was higher than that for the SixOy(OH)z cluster surface, and both types of clusters exhibited efficient adsorption of CB. As the SixOy(OH)z clusters grew larger, the rates for the reactions between O3 and CB increased. CB travelled long distances along the Al2O3 clusters, leading to an extended influence range.

Improving Luttinger-liquid plasmons in carbon nanotubes by chemical doping.

We realized the real-space imaging of Luttinger-liquid plasmons in semiconducting single-walled carbon nanotubes (s-SWCNTs) and studied the effects of chemical-doping-induced charge carrier density modulation on plasmons. Using scattering-type scanning near-field optical microscopy (s-SNOM), we compared the Luttinger-liquid plasmonic behavior in pre- and post-HNO3-doped SWCNTs. Raman measurements revealed that the physical mechanism is P-type doping. Through HNO3 doping, we effectively increased the charge carrier density in s-SWCNTs and achieved quantum plasmons simultaneously with strong confinement (λ0/λp ≈ 70) and high quality factor (Q ≈ 20). The combination of high quality factor and strong subwavelength confinement in Luttinger-liquid plasmons is critical to the future application of plasmonic devices.

Heating-Enhanced Dielectrophoresis for Aligned Single-Walled Carbon Nanotube Film of Ultrahigh Density.

In this paper, we demonstrate that the alignment density of individualized single-walled carbon nanotubes (SWCNTs) can be greatly improved by heating-enhanced dielectrophoresis (HE-DEP) process. The observations by scanning electron microscope (SEM) suggest ultrahigh alignment density and good alignment quality of SWCNTs. The intuitive alignment density of individualized SWCNTs is much higher than the currently reported best results. The reason of this HE-DEP process is explained by simulation work and ascribed to the heating-enhanced convection process, and the "convection force" induced by the heating effect is assessed in a novel way.

Guided Photoluminescence from Integrated Carbon-Nanotube-Based Optical Waveguides.

Thin films and ridge waveguides based on large-diameter semiconducting single-wall carbon nanotubes (s-SWCNTs) dispersed in a polyfluorene derivative are fabricated and optically characterized. Ridge waveguides are designed with appropriate dimensions for single-mode propagation at 1550 nm. Using multimode ridge waveguides, guided s-SWCNT photoluminescence is demonstrated for the first time in the near-infrared telecommunications window.

Photonics based on carbon nanotubes.

Among direct-bandgap semiconducting nanomaterials, single-walled carbon nanotubes (SWCNT) exhibit strong quasi-one-dimensional excitonic optical properties, which confer them a great potential for their integration in future photonics devices as an alternative solution to conventional inorganic semiconductors. In this paper, we will highlight SWCNT optical properties for passive as well as active applications in future optical networking. For passive applications, we directly compare the efficiency and power consumption of saturable absorbers (SAs) based on SWCNT with SA based on conventional multiple quantum wells. For active applications, exceptional photoluminescence properties of SWCNT, such as excellent light-emission stabilities with temperature and excitation power, hold these nanometer-scale materials as prime candidates for future active photonics devices with superior performances.