Zeolite-templated carbons as effective sorbents to remove methylsiloxanes and derivatives:A computational screening

Though widely used in our daily lives,volatile methylsiloxanes and derivatives are emerging contaminants and becoming a high-priority environment and public health concern.Developing effective sorbent materials can remove siloxanes in a cost-effective manner.Herein,by means of Grand Canonical Monte Carlo(GCMC)simulations,we evaluated the potentials of the recently proposed 68 stable zeolite-templated carbons(ZTCs)(PNAS 2018,115,E8116-E8124)for the removal of four linear methylsiloxanes and derivatives as well as two cyclic methylsiloxanes by the calculated average loading and average adsorption energy values.Four ZTCs,namely ISV,FAU1,FAU3,and H8326836,were identified with the top 50%adsorption performance toward all the six targeted contaminants,which outperform activated carbons.Further first principles computations revealed that steric hindrance,electrostatic interactions(further enhanced by charge transfer),and CH-p interactions account for the outstanding adsorption performance of these ZTCs.This work provides a quick procedure to computationally screen promising ZTCs for siloxane removal,and help guide future experimental and theoretical investigations.

Occurrence and fate of chlorinated methylsiloxanes in surrounding aqueous systems of Shengli oilfield, China

Mono-chlorinated products of cyclic volatile methylsiloxanes(cVMS),i.e.,Monochlormethylheptamethylcyclotetrasiloxane[D3D(CH_(2)Cl)],monochlormethylnonamethylcyclopentasiloxane[D4D(CH_(2)Cl)],and monochlormethylundemethylcyclohexasiloxane[D5D(CH_(2)Cl)],were detected in water[<LOQ(Limit of quantitation)-86.3 ng/L,df(detection frequency)=23%-38%,n=112]and sediment samples[<LOQ-504 ng/g dw(dry weight),df=33%-38%,n=112]from 16 lakes located in Shengli oilfield of China,and had apparent increasing trends(31%-34%per annum)in sediments during Year 2014-2020.Simulated experiments showed that chloro-cVMS in sediment-water system had approximately 1.7-2.0 times slower elimination rates than parent cVMS.More specifically,compared with those of parent cVMS,volatilization(86-2558 days)and hydrolysis(135-549 days)half-lives of chlorocVMS were respectively 1.3-2.0 and 1.8-2.1 times longer.In two species of freshwater mussels(n=1050)collected from six lakes,concentrations of chloro-cVMS ranged from 9.8-998 ng/g dw in Anodonta woodiana and 8.4-970 ng/g dw in Corbicula fluminea.Compared with parent cVMS,chloro-cVMS had 1.1-1.5 times larger biota-sediment accumulation factors(2.1-3.0)and 1.1-1.7 times longer half-lives(13-42 days).Their stronger persistence in sediment and bioaccumulation in freshwatermussels suggested that environmental emission,distribution and risks of chloro-cVMS deserve further attention.

Distribution of methylsiloxanes in benthic mollusks from the Chinese Bohai Sea

Methylsiloxanes are a class of silicone compounds that have been widely used in various industrial processes and personal care products for several decades. This study investigated the spatial distribution of three cyclic methylsiloxanes(D4–D6) and twelve linear methylsiloxanes(L5–L16) in mollusks collected from seven cities along the Bohai Sea. D4–D6(df = 71%–81%) and L8–L16(df = 32%–40%) were frequently detectable in the mollusk samples, while L5–L7 were not found in any mollusk samples. Cyclic methylsiloxanes(D4–D6) were found in mollusks with the mean concentrations of 15.7 ± 12.3 ng/g ww for D4,24.6 ± 15.8 ng/g ww for D5 and 34.0 ± 23.0 ng/g ww for D6. Among the seven sampling cities, the cyclic methylsiloxanes were predominant in mollusks, with the total cyclic methylsiloxanes(sum of D4–D6, ∑ CMS) accounting for 74.2%–80.7% of the total methylsiloxanes. ∑ CMS along the coastline demonstrated a clear gradient, with the highest concentrations in mollusks at the sampling sites located in the western part of the Bohai Sea and the lowest concentrations in mollusks from cities located in the eastern part of the Bohai Sea. The biota-sediment accumulation factors for cyclic methylsiloxanes(D4–D6) and linear methylsiloxanes(L8–L16) were estimated as 0.42 ± 0.06–0.53 ± 0.06 and0.13 ± 0.03–0.19 ± 0.05, respectively.

A Versatile Coating Approach to Fabricate Superwetting Membranes for Separation of Water-in-Oil Emulsions

Separation of oil/water mixtures, especially for the emulsified oil/water mixtures, is important because of the frequent occurrence of oil spill accidents. Utilizing superwetting porous membrane has become a promising approach to separate either surfactant-free or surfactant-stabilized emulsions. Herein we report a facile and versatile strategy for preparing hydrophobic/under-oil superhydrophobic membranes by coating the skeletons of the membranes with the poly[（3,3,3- trifluoropropyl）methylsiloxane] （PTFPMS） nanoparticles. The obtained membranes could be used to separate various water- in-oil emulsions with high flux and separation efficiency. In addition, owning to the outstanding resistance of PTFPMS to the most organic solvents or oils, the modified membranes exhibited the excellent reusability and the antifouling properties that were critical in the practical applications. Many commercially available membranes can be modified by such a simple method.

Synthesis and characterization of dendronized poly(methylsiloxane) with appendent Fréchet-type dendrons

A new kind of dendronized poly(methylsiloxane) (3a and 3b) with appendent Fréchet-type poly(aryl ether) dendrons has been synthesized and characterized by GPC, DSC, TGA, fluorescence and UV-Vis spectra.