Local Chain Feature Mandated Self-Assembly of Block Copolymers.

This work demonstrates an effective and robust approach to regulate phase behaviors of a block copolymer by programming local features into otherwise homogeneous linear chains. A library of sequence-defined, isomeric block copolymers with globally the same composition but locally different side chain patterns were elaborately designed and prepared through an iterative convergent growth method. The precise chemical structure and uniform chain length rule out all inherent molecular defects associated with statistical distribution. The local features are found to exert surprisingly pronounced impacts on the self-assembly process, which have yet to be well recognized. While other molecular parameters remain essentially the same, simply rearranging a few methylene units among the alkyl side chains leads to strikingly different phase behaviors, bringing about (i) a rich diversity of nanostructures across hexagonally packed cylinders, Frank-Kasper A15 phase, Frank-Kasper σ phase, dodecagonal quasicrystals, and disordered state; (ii) a significant change of lattice dimension; and (iii) a substantial shift of order-to-disorder transition temperature (up to 40 °C). Different from the commonly observed enthalpy-dominated cases, the frustration due to the divergence between the native molecular geometry originating from side chain distribution and the local packing environment mandated by lattice symmetry is believed to play a pivotal role. Engineering the local chain feature introduces another level of structural complexity, opening up a new and effective pathway for modulating phase transition without changing the chemistry or composition.

A novel fate and transport model for evaluating the presence and environmental risk of per-/poly-fluoroalkyl substances (PFASs) among multi-media in Lingang hybrid constructed wetland, Tianjin, China.

Accurately revealing and predicting the presence and risks of per-/poly-fluoroalkyl substances (PFASs) in constructed wetlands (CWs) is great significant for the construction and management of CWs, but very challenging. In this work, a novel fate and transport model was for the first time established to evaluate the spatially continuous distribution and environmental risks of PFASs among multi-media in Lingang hybrid CW fed by industry tailwater. 20 PFASs were detected from the Lingang CW, and the total concentration of the detected PFASs in water and sediments were in the range of 38.94-81.65 ng/L and 1.23-4.31 ng/g, respectively. PFOA, PFOS and PFBS were the main pollutants in water and sediments. A fate and transport model describing the distribution characteristics and fate of PFASs in Lingang hybrid CW was constructed, and its reliability was verified. The simulated results suggested that PFASs were mainly accumulated in sediments and long-chain PFASs were more easily adsorbed by sediments compared with short-chain PFASs. According to the principal component analysis-multiple linear regression (PCA-MLR), PFASs mainly came from the tailwater from the surrounding sewage treatment plants. Besides, the environmental risks were predicted by this novel model, suggesting that the risks still cannot be neglected due to the accumulation and continuous input of PFASs although the environmental risks of Lingang CW were low. This work provides a novel model for the understanding of presence and risks of PFASs among multi-media in CWs.

Perfluoroalkyl substances in the Lingang hybrid constructed wetland, Tianjin, China: occurrence, distribution characteristics, and ecological risks.

In this study, the occurrence, spatial distribution, sources, and ecological risks of perfluoroalkyl substances (PFASs) in the surface waters of the Lingang hybrid constructed wetland were systematically investigated. Twenty-three PFASs were analyzed from 7 representative sampling zones. The obtained results indicated that PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFBS, PFOS, and HFPO-DA were frequently detected; and PFBA, PFOA, and PFOS were the dominant PFASs with the relative abundances in ranges of 26.91 to 52.26%, 11.79 to 28.79%, and 0 to 31.98%, respectively. The total concentrations of 8 PFASs (Σ8PFASs) ranged from 25.9 to 56.6 ng/L, and the highest concentration was observed in subsurface flow wetland. Moreover, HFPO-DA with high toxicity was detected in wetlands for the first time. Based on the principal component analysis-multiple linear regression (PCA-MLR) analysis, three sources and their contributions were fluoropolymer processing aids (67.6%), fluororesin coatings and metal plating (17.9%), and food packaging materials and atmospheric precipitation (14.5%), respectively. According to the risk quotients (RQs), the ecological risk of 8 PFASs was low to the aquatic organisms.

Selective adsorption of PHC and regeneration of washing effluents by modified diatomite.

Selective removal of petroleum hydrocarbons (PHCs) from soil washing effluents is the key to the surfactant-enhanced soil washing technology. In this study, the diatomite was modified by nonionic surfactant TX-100 and applied in the selective adsorption of PHCs in the soil washing effluents. The modified diatomites were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, N2 adsorption/desorption and X-ray photoelectron spectroscopy respectively. The adsorption process followed the pseudo-second-order model and the adsorption isotherms indicated that the interaction between PHCs and modified diatomite was monolayer adsorption. The important operating factors such as TX-100 dosage, adsorbent dosage, time and temperature were optimized. With the participation of the low-cost adsorbent TX3-Db with high adsorption capacity, the recovery efficiency of the washing effluents was still up to 78.9% after three cycles. A selective adsorption mechanism, based on steric hindrance and electrostatic repulsion, was proposed to explain the removal of PHCs from washing effluents.

Regeneration of Washing Effluents for Remediation of Petroleum-Hydrocarbons-Contaminated Soil by Corncob-Based Biomass Materials.

Surfactant-enhanced soil washing is an effective remediation method for petroleum-hydrocarbons-contaminated soil. The residual petroleum hydrocarbons in the washing effluents reduce the elution ability of the washing effluents and cause secondary pollution to the environment. In this work, modified corncobs were prepared and used as selective adsorbents to remove the residual petroleum hydrocarbons in washing effluents. The structure of adsorbent was characterized and the adsorption conditions were optimized. With the adsorption by corncob-based adsorbents, washing effluents can be regenerated and recycled. After five cycles, the recovery efficiency of the washing effluents is still as high as 75.4%. The optimal adsorbent linear alkylbenzene sulfonates (LAS-Cb) also exhibited excellent recyclability, which can be recycled five times. The selective adsorption mechanism of the LAS-Cb for petroleum hydrocarbons in washing effluents, related to its huge hydrophobic core and surface electronegativity, is proposed.