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Bromophenols (BPs) have both natural and artificial sources in the environment and are frequently detected in plants. Herein, the ubiquitous 2,4,6-TriBP was hydroponically exposed to rice seedlings at two concentrations (0.2 and 2.0 mg/L) to characterize the dose-dependent abiotic stress responses of rice plants to BPs. The 2,4,6-TriBP induced oxidative damage to rice roots and subsequently inhibited plant transpiration and growth at the end of exposure in both concentrations. Moreover, the gene expression of

As a process intensification technology, semicontinuous distillation uses less equipment to achieve the separation of multiple components. However, there is still a lack of systematic guidance for the design of semicontinuous distillation. In this paper, we propose a new method to guide the design of semicontinuous distillation via multi-objective optimization (MOO) and control. Conventional continuous distillation, dividing wall column (DWC) distillation and semicontinuous distillation for separation of n-alkanes are optimized through multi-objective genetic algorithm (MOGA). Several different control schemes are proposed for semicontinuous distillation, and the temperature-concentration cascade control scheme CS5 is selected as the optimal control scheme. The economic benefits of semicontinuous distillation based on dynamic simulation are evaluated by the comparison with the conventional continuous distillation and DWC under a series of throughput. It is found that the total annual cost (TAC) of the semicontinuous distillation is smaller than that of conventional continuous distillation when the annual throughput is less than 7.73 × 104 kmol/yr. And the TAC of the semicontinuous distillation is less than that of DWC when the annual throughput is less than 5.29 × 104 kmol/yr. Therefore, we can conclude that the semicontinuous distillation has better economic benefits than the other two configurations within the smaller annual throughput.

Dynamic process intensification technology is an emerging technology of process intensification. It adopts a nonsteady-state operation mode, which can improve the time-averaged performance of the r...

By using the low loading of the conductor filler to achieve high conductivity is a challenge associated with electrically conductive adhesion. In this study, we show an assembling of nickel-coated polystyrene (Ni@PS) microspheres into 3-dimensional network within the epoxy resin with the assistance of an electric field. The morphology evolution of the microspheres was observed with optical microscopy and scanning electron microscopy (SEM). The response speed of Ni@PS microsphere to the electric field were investigated by measuring the viscosity and shear stress variation of the suspension at a low shear rate with an electrorheological instrument. The SEM results revealed that the Ni@PS microspheres aligned into a pearl-alike structure. The AC impedance spectroscopy confirmed that the conductivity of this pearl-alike alignment was significantly enhanced when compared to the pristine one. The maximum enhancement in conductivity is achieved at 15 wt. % of Ni@PS microspheres with the aligned composites about 3 orders of magnitude as much as unaligned one, typically from ~10−5 S/m to ~10−2 S/m.

High-performance adsorption toward Congo red and Cr(VI) depends on the design of hierarchical nanostructures. Herein, hierarchical porous Ni/Co-layered double hydroxide (NiCo-LDH) hollow dodecahedra were synthesised by etching zeolitic imidazolate framework-67 (ZIF-67) as a self-sacrificing template with Ni(NO3)2. The synthesised NiCo-LDH showed better adsorption property for adsorbing Congo red and Cr(VI) ions (Cr2O72−) than NiCo2O4-NiO, which was obtained by calcining NiCo-LDH at 350 °C. The adsorption processes of Congo red and Cr(VI) ions very well fitted the pseudo-second-order model. The Langmuir model was more suitable than the Freundlich model in describing the adsorption isotherm, and the theoretical maximum adsorption capacities of Congo red and Cr(VI) ions were 909.2 and 99.9 mg g−1 at 30 °C, respectively. Furthermore, the synthesised NiCo-LDH was recyclable and could selectively adsorb anionic dyes. This work can serve as a basis for designing and manufacturing excellent adsorbents for water treatment.

Reactive dividing wall column (RDWC) is the integration of reactive distillation and dividing wall column, which simultaneously has the advantages of both process intensification techniques. Howeve...

MoO3 is a promising n-type anode interfacial layer (AIL) with high work function for polymer solar cells (PSCs). However, due to the limited electron blocking ability of n-type metal oxide, the interfacial recombination occurs inevitably in the MoO3/organic interface. Herein, we for the first time strategically introduced minimal amount of p-type NiOx into n-type MoO3 to enhance the electron blocking ability of AIL. The MoO3 doped with NiOx layer (MoO3:NiOx) is highly transparent with a conduction band of 3.25 eV and a work function of 5.10 eV, which prolongs the electron lifetime of PBDB-T:IT-M based device from 0.63 to 5.05 μs. Benefiting from the prolonged lifetime and enhanced charge collection of MoO3:NiOx AIL, the average power conversion efficiency (PCE) of PBDB-T:IT-M based devices is significantly improved to 10.81%, much higher than that of control devices with PEDOT:PSS (9.79%), MoO3 (8.97%) and NiOx (9.51%) AILs. Our findings provide a new approach to tuning the energy level of cost-efficient and simply processed metal oxide interfacial materials for high performance and stable nonfullerene PSCs.

Three-dimensional hierarchical Al2O3@ZnO core-shell composite was designed and fabricated by a multistep strategy, involving an initial hydrothermal reaction, a subsequent chemical bath deposition process and a final calcination treatment. Electron microscopy images revealed that the Al2O3@ZnO composite was uniform in size and possessed a structure constituted by an Al2O3 core and a shell of crumpled ZnO nanosheets on which numerous pores were found. The as-synthesized Al2O3@ZnO core-shell composite exhibited fast kinetics and outstanding adsorption capacity for Congo red (CR) due to its unique structure and highly porous texture, which was much superior to those of bare Al2O3 core and ZnO microspheres. The pseudo-second-order kinetic model could represent the adsorption kinetics for CR adsorption, whereas the Langmuir isotherm model was suitable for describing the adsorption isotherm. The as-synthesized hierarchical Al2O3@ZnO microfibres with maximal adsorption capacity of 714 mg g−1 are highly competitive in terms of CR adsorption.

For the most complex artificial chlorinated environmental contaminants, much less is known for medium-chain CPs than short-chain CPs. In this research, the spatial distributions of MCCPs and SCCPs in farmland soil and maize leaves near a CP production facility were found marginally influenced by seasonal winds. The levels of ∑MCCPs and ∑SCCPs were in the ranges of

The most environmentally abundant bromophenol congener, 2,4,6-tribromophenol (2,4,6-TBP, 6.06 μmol/L), was exposed to rice for 5 d both in vivo (intact seedling) and in vitro (suspension cell) to systematically characterize the fate of its sulfation and glycosylation conjugates in rice. The 2,4,6-TBP was rapidly transformed to produce 6 [rice cells (3 h)] and 8 [rice seedlings (24 h)] sulfated and glycosylated conjugates. The predominant sulfation conjugate (TP(408), 93.0–96.7%) and glycosylation conjugate (TP(490), 77.1–90.2%) were excreted into the hydroponic solution after their formation in rice roots. However, the sulfation and glycosylation conjugates presented different translocation and compartmentalization behaviors during the subsequent Phase III metabolism. Specifically, the sulfated conjugate could be vertically transported into the leaf sheath and leaf, while the glycosylation conjugates were sequestered in cell vacuoles and walls, which resulted in exclusive compartmentalization within the rice roots. These results showed the micromechanisms of the different compartmentalization behaviors of 2,4,6-TBP conjugates in Phase III metabolism. Glycosylation and sulfation of the phenolic hydroxyl groups orchestrated by plant excretion and Phase III metabolism may reduce the accumulation of 2,4,6-TBP and its conjugates in rice plants.

Short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) are mixtures of complex chemical compounds with intensive usage. They are frequently detected in various environmental samples. However, the interaction between CPs and plants, especially the biotransformation behaviors of CPs within plants, is poorly understood. In this study, 1,2,5,6,9,10-hexachlorodecane (CP-4, a typical standard of individual SCCP congeners) and 52%-MCCP (a commercial mixture standard of MCCPs with 52% chlorine content by mass) were selected as representative chemicals to explore the metabolic behaviors of SCCPs and MCCPs using suspension rice cell culture exposure systems. Both 79.53% and 40.70% of CP-4 and 52%-MCCP were metabolized by suspension rice cells, respectively. A complementary suspected screening strategy based on the pair mass distances (PMD) analysis algorithm was used to study the metabolism of CPs mediated by the plant cells. Forty and 25 metabolic products for CP-4 and 52%-MCCP, respectively, were identified, including (multi-) hydroxylation, dechlorination, -HCl- elimination metabolites, (hydroxylation-) sulfation, and glycosylation conjugates. Here, we propose a comprehensive metabolic molecular network and provide insight on degradation pathways of SCCPs and MCCPs in plants for the first time, aiding in further understanding of the transformation behaviors of CPs.

To develop multifunctional anticancer nanomedicines, photothermal nanogels with multistimulative properties are fabricated by hybridizing graphene oxide (GO) with poly(N-isopropylacrylamide, PNIPAM...

The fates, especially the phase I, phase II, and phase III metabolisms of typical halogenated organic pollutants in plants are attracting more and more research interests. A series of reactions and pathways are involved in metabolism of halogenated organic pollutants in plants, including dehalogenation, hydroxylation, methylation, combination with glucose (or glycoside), glutathione, and other groups, and final generation of the water-soluble, less toxic, and non-reactive substances. This article reviewed the metabolism of several typical organic halogenated pollutants and the role of related enzymes in plants. The prospect for the future was also proposed.

Organic solar cells (OSCs) with a fused-ring dye, ITIC, and fullerene derivative PC71BM as the acceptor materials were fabricated. Compared to PC71BM-based cells, which reach a power conversion efficiency of 6.91%, the ITIC device shows a significantly higher power conversion efficiency (9.20%). The broader absorption range of ITIC helps to improve the short-circuit current density, which leads to better device efficiency. Electrical characterization, including electrical simulations and impedance analysis, was performed to investigate the physical processes in these OSCs. The results suggest that the charge-recombination loss in the non-fullerene device is even higher than that in PC71BM cells. Morphological analysis reveals that a poor phase-separation in the photoactive layer is responsible for the large recombination loss. Our results indicate that fused-ring acceptor materials are promising candidates for high-efficiency OSCs. Furthermore, if recombination loss could be suppressed effectively, the energy conversion efficiency of non-fullerene organic solar cells can be even higher.

The oriented 1D nanostructure arrays of PANI have great potential applications in various devices. In this paper, we report a simple and facile one-step template-free way to assemble highly oriented arrays of PANI nanofibers using chemical oxidative polymerization on the glass and polymer flexible substrates. The diameters of the individual nanofibers range from 10 nm to 33 nm, and the average length of the aligned nanofibers is up to 48–139 nm. The PANI nanofiber arrays can be uniformly distributed on the whole substrates via this method, which are confirmed by the results of SEM images and Raman mapping. The as-prepared PANI nanofiber arrays can be potentially used in flexible low-voltage electronics, anti coatings, self-cleaning surfaces and chemical sensors, and so on.

Sodium alginate was used to fabricate biopolymer microgels to encapsulate two proanthocyanidins (PAs) fractions (F1 and F2) isolated from Choerospondias axillaris (C. axillaris) fruit peels. The impact of the molecular mass of the PAs on their entrapment efficiency and release profile was then established. Additionally, the antioxidant and prebiotic activities of the two PA fractions were investigated. The F1 fraction mainly contained oligomers, while the F2 fraction contained higher molecular weight polymers. Both F1 and F2 fractions exhibited strong antioxidant and prebiotic activities at certain concentrations. The entrapment efficiency of F1 and F2 fractions in alginate beads were 43.4 ± 3.2% and 62.2 ± 4.1%, respectively. The entrapment of the F2 fraction was significantly higher than that of the F1 fraction (p

Ternary zero-valent iron/phos photungstic acid/g-C3N4 composite (Fe0@PTA/g-C3N4) was synthesized via photoreduction of iron (II) ions assisted by phosphotungstic acid (PTA) over g-C3N4 flakes. The as-prepared Fe0@PTA/g-C3N4 was investigated for removal of As(III) and As(V) species from water. The result showed that Fe0@PTA/g-C3N4 exhibited a better performance for As(V) removal than As(III) species from water, and the maximum adsorption capacity for As(V) was 70.3 mg/g, much higher than most of the reported adsorbents. As(V) removal by the Fe0@PTA/g-C3N4 adsorbent is mainly via a chemical process, synergistically occurring of reduction of As(V) and oxidation of Fe0. Moreover, the Fe0@PTA/g-C3N4 adsorbent showed effective As(V) removal from the simulated industrial wastewater and underground water. This study demonstrates that Fe0@PTA/g-C3N4 can be a potential adsorbent for As(V) removal due to its high performance, and simple one-pot synthesis process.

Organic bulk heterojunction solar cells with a high fullerene content (larger than 70%) have been studied in this work. The device performances of this kind of solar cell could be tuned by adjusting the blend ratio in the active layer. An appropriate amount of p-type semiconductor in the high fullerene content active blend layer is beneficial for light absorbance and exciton dissociation. The proper energy alignment between the highest occupied molecular orbital of a p-type material and an n-type fullerene derivative has a strong influence on the exciton dissociation efficiency. In addition, the mechanism of photogenerated charge recombination in the solar cells has been identified through intensity-dependent current density–voltage (J–V) measurements and results show that the mechanisms governing the recombination are crucial for solar cell performance.

F-53B, the commercial product of chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs), has been used in Chinese chrome plating industry for 30 years, and was recently identified in the environment, which caused great concerns. So far, limited investigations have been performed on their environmental occurrence, fate and impact. In this study, we demonstrated the wide occurrence of Cl-PFESAs and their trophic transfer behavior in marine organisms from Chinese Bohai Sea. 6:2 Cl-PFESA (0.016-0.575 ng/g wet weight) was the dominant congener, and 8:2 Cl-PFESA (0.022-0.040 ng/g) was occasionally detected. Compared to other perfluoroalkyl and polyfluoroalkyl substances (PFASs) of concern, the levels of Cl-PFESAs were relatively lower in marine organisms. Based on the comparative analysis of Cl-PFESA contamination in mollusk samples collected in 2010-2014, both the concentrations and detection frequencies of Cl-PFESAs tended to increase in this region. And this kind of chemicals were more vulnerable to be accumulated in marine organisms at relatively higher trophic levels. Similar to perfluorooctanesulfonate (PFOS) and the long chain perfluorinated carboxylates (PFCAs), 6:2 Cl-PFESA could be magnified along the food chain. Accordingly, the potential threat might be posed to the wildlife and human beings due to unintended exposure to Cl-PFESAs.

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant (BFR), and it bioaccumulates throughout the food chains. Its fate in the first trophic level, plants, is of special interest. In this study, a four-day hydroponic exposure of TBBPA at a concentration of 1 μmol L(−1) to pumpkin seedlings was conducted. A nontarget screening method for hydrophilic bromine-containing metabolites was modified, based on both typical isotope patterns of bromine and mass defect, and used to process mass spectra data. A total of 20 glycosylation and malonyl glycosylation metabolites were found for TBBPA in the pumpkin plants. Representative glycosyl TBBPA reference standards were synthesized to evaluate the contribution of this glycosylation process. Approximately 86% of parent TBBPA was metabolized to form those 20 glycosyl TBBPAs, showing that glycosylation was the most dominant metabolism pathway for TBBPA in pumpkin at the tested exposure concentration.

Bromophenols occur naturally and are used globally as man-made additives in various industrial products. They are decomposition products of many emerging organic pollutants, such as tetrabromobisphenol A, polybrominated dibenzo- p-dioxin (PBDD), polybrominated diphenyl ethers (PBDE), and others. To characterize their biotransformation pathways, bromophenol congener 2,4,6-tribromophenol, being used most frequently in the synthesis of brominated flame retardants and having the greatest environmental abundance, was selected to hydroponically expose rice plants. After exposure for 5 days, 99.2% of 2,4,6-tribromophenol was metabolized by rice. Because of the lack of relative reference standards, an effective screening strategy was used to screen for potential metabolites that were further qualitatively identified by gas and liquid chromatography combined with high-resolution mass spectrometry. Forty transformation products were confirmed or tentatively identified at different confidence levels, including 9 phase I and 31 phase II metabolites. A large number of metabolites (39) were found in rice root, and 10 of them could be translocated and detected in rice stems or leaves. Many transformation pathways were proposed, including debromination, hydroxylation, methylation, coupling reactions, sulfation, and glycosylation. It was remarkable that a total of seven hydrophobic, persistent, and toxic OH-PBDEs and PBDD/Fs were found, indicating the biotic dimeric reactions of 2,4,6-tribromophenol that occurred in the rice plants. These results improve our understanding of the transformation and environmental fates of bromophenols, and they indicate new potential sources for OH-PBDEs and PBDD/Fs in the environment, especially in food chains.

Short chain chlorinated paraffins (SCCPs) are a group of complex emerging persistent organic pollutants. In this study, the uptake, translocation, and transformation of four constitutionally defined SCCP isomers were studied using whole pumpkin (Cucurbita maxima × C. moschata) and soybean (Glycine max L. Merrill) seedlings via hydroponic exposure. Results showed that the daughter SCCPs were C(10)Cl(5–8) and C(11–13)Cl(5–6). The metabolic transformation of all tested isomers included dechlorination and chlorine rearrangement. In addition, carbon chain decomposition products were found for isomers with trichlorinated carbon atoms (CCl(3)-groups) in both pumpkin and soybean seedlings. This study provides the first evidence of carbon chain decomposition of SCCPs in whole plants, and it suggests new metabolism pathways of SCCPs in the environment. The influence of carbon chain length and degree of chlorination of SCCPs on their fate and behavior within different plant species were also investigated. Bioaccumulation of SCCPs in pumpkin and soybean increased with increasing carbon chain length and degree of chlorination. In comparison, soybean translocated and degraded parent SCCPs faster and to a greater extent than pumpkin, but pumpkin accumulated parent SCCPs to a greater extent than soybean. After 10 days exposure, less than 4% of the initial mass of exposed chemicals remained in solution of exposure groups. The parent chemicals accumulated in roots ranging from 23.6% to 59.9% for pumpkin and 1.98% to 54.5% for soybean and in stems ranging from 0.7% to 3.81% for pumpkin and 0.50% to 2.54% for soybean. These results give new perspectives on the transport, transformation, and fate of SCCPs in the environment.

Artificial intelligence sensations have aroused scientific interest from electronic conductors to bio-inspired ionic conductors. The conductivity of electrons decreases with increasing temperature, while the ionic conductivity agrees with an Arrhenius equation or a modified Vogel-Tammann-Fulcher (VTF) equation. Herein, thermo-responsive poly(N-isopropyl amide) (PNIPAm) and single-ion-conducting poly(2-acrylamido-2-methyl-1-propanesulfonic lithium salt) (PAMPSLi) were copolymerized via a facile radical polymerization to demonstrate a very intriguing anti-Arrhenius ionic conductivity behaviour during thermally induced volume-phase transition. These smart hydrogels presented very promising scaffolds for architecting flexible, wearable or advanced functional ionic devices.

Device performance enhancement in quantum dot light-emitting diodes (QLEDs) is realized by adding a small amount of insulating polymer polymethyl methacrylate (PMMA) into the emitting quantum dot layer. Pool-Frenkel effect is observed through temperature-dependent current density-voltage experiments, indicating the important role of trap states, and the addition of the insulating PMMA helps to reduce the Poole-Frenkel barrier hence the trap depth. Reduced density and depth of trap states with PMMA are indeed observed through further capacitance measurements. This work contributes to a better understanding on the effects of traps in QLEDs.

5-Hydroxymethylcytosine (5hmC) is a deoxyribonucleic acid (DNA) epigenetic modification that has an important function in embryonic development and human diseases. However, the numerous methods that have been developed to detect and quantify 5hmC, require large amounts of DNA sample to be modified via chemical reactions, which considerably limits their application with cell-free DNA (cfDNA). Meanwhile, other antibody-based methods of detecting 5hmC do not offer information about the DNA sequence. Here, in this article DNA hybridization-based single-molecule immunofluorescent imaging is presented, an ultrasensitive method of detecting 5hmC modification in DNA. Via using the probe DNA to capture the DNA fragment of interest and the 5hmC antibody to detect the 5hmC modification in DNA, the fluorescent response signal of the 5hmC modification from the secondary antibody at the single-molecule level is successfully detected. Using the method, one could determine the quantity of 5hmC in the gene of interest within 6 h. In addition, it requires only 3 pg of the DNA sample and minimal experience and training for operation and analysis.

The influence of multi-walled carbon nanotube (i.e. MWCNT) architectures for facilitating charge transport in CdS semiconductor films was investigated. The power conversion efficiency (PCE) of the CdS nanoparticle-deposited multi-walled carbon nanotube nanohybrids (i.e. CdS@MWCNT) could be enhanced when the MWCNT was employed as the conducting scaffold in the CdS nanoparticle based photoelectrochemical cell. The CdS nanoparticles were deposited onto the MWCNT surface to improve photoinduced charge separation and transport of carriers (electrons and holes). The PCE of the CdS@MWCNT nanohybrids solar cell was found to be as high as 4.54%, contrasting sharply with the value (1.67%) for pure CdS nanoparticles. The outcome of the present work might provide a new avenue for designing optoelectronic and light-energy conversion devices.

Although the special architecture of two-dimensional (2D) nanomaterials endows them with unique properties, their poor colloidal stability remains a main bottleneck to fully exploit their applications in the biomedical field. Herein, this study aims to develop a simple and effective approach to in situ incorporate 2D graphene oxide (GO) nanoplatelets into a thermosensitive matrix to acquire hybrid nanogels with good stability and photothermal effect. In order to improve its stability, GO firstly underwent silanization to its surface with double bonds, followed by intercalation with N-isopropylacrylamide (NIPAM) in the presence of a disulfide-containing crosslinker via an emulsion method. Radical polymerization was then initiated to accelerate direct GO exfoliation in PNIPAM nanogels by forming covalent bonds between them. The well-dispersed GO nanopletlets in the nanogels not only displayed an enhanced photothermal effect, but also improved the encapsulation efficiency of an anticancer drug. The hybrid nanogels accelerate drug release under conditions mimicking the acidic/reducible solid tumor and intracellular microenvironments, most importantly, it can be further enhanced via remote photothermal treatment. The multifunctional nanogels potentiate their synergistic anticancer bioactivity as an ideal nanoplatform for cancer treatment.

In this paper, the effect of iodine on the photocurrent of conjugated polymer/inorganic semiconductor nanocomposites is investigated. Via a redox process, iodine nanoparticles are coated on the surface of highly active nanofiber of conjugated polyaniline (PANI), forming an electron donor (i.e., I 2 @PANI). After subsequent incorporation of CdS nanoparticles (serving as electron acceptors), the photocurrent of the I 2 @PANI–CdS system is greatly enhanced as compared to that of the PANI–CdS hybrid. This obvious enhancement is due to the fact that the existence of I 2 causes significant improvement in the charge transfer, which has favorable penetration ability into the porous semiconductor film, fast charge transfer and relatively slow recombination with injected photoelectrons. As a result, the total concentration of charge carriers in the CdS nanoparticles may increase as compared to that in bulk CdS. As a result, the photocurrent of CdS in I 2 @PANI–CdS nanocomposites is remarkably enhanced.

The morphology of the photoactive layer critically affects the performance of the bulk heterojunction polymer solar cells (PSCs). To control the morphology, we introduced a hydrophobic fluoropolymer polyvinylidene fluoride (PVDF) as nonvolatile additive into the P3HT:PCBM active layer. The effect of PVDF on the surface and the bulk morphology were investigated by atomic force microscope and transmission electron microscopy, respectively. Through the repulsive interactions between the hydrophilic PCBM and the hydrophobic PVDF, much more uniform phase separation with good P3HT crystallinity is formed within the active layer, resulting enhanced light harvesting and improved photovoltaic performance in conventional devices. The PCE of the conventional device can improve from 2.40% to 3.07% with PVDF additive. The PVDF distribution within the active layer was investigated by secondary ion mass spectroscopy, confirming a bottom distribution of PVDF. Therefore, inverted device structure was designed, and the PCE can improve from 2.81% to 3.45% with PVDF additive. Our findings suggest that PVDF is a promising nonvolatile processing additive for high performance polymer solar cells.

It was found for the first time that Cs2CO3 serves as highly efficient catalyst for the direct hydroxylation reactions of phosphonates under mild conditions. This reaction provides an efficient approach to quaternary α-hydroxy phosphonates, which possess intriguing biological activities and are widely used in many areas.

A novel palladium/copper-catalyzed aerobic synthesis of bisaryl ketones from 1,2-diarylalkenes via C-C double bonds cleavage has been described. This reaction constitutes a new transformation from 1,2-diarylalkenes into bisaryl ketones, providing a unifying, simple and environmentally friendly complement to the available methods.

A novel flame-retardant aluminum β-carboxylethylmethylphosphinate [Al(CEP)] was synthesizedby a simple process. The effect of Al(CEP) on the curing of epoxy resin (EP) was investigated with differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy. The flame retardancy and thermal properties of Al(CEP)/EP were analyzed by a limiting oxygen index (LOI), vertical burning test (UL-94), scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX), gravimetric analyses, and DSC. Results disclosed that curing of EP is delayed by incorporating Al(CEP). The flexural strength of EP is reduced but the flexural modulus is increased by adding Al(CEP). Adding Al(CEP) depresses the decomposition of EP while leads to a increase in the glass transition temperature (Tg), in char formation and in flame retardancy of EP. EP containing 25 phr Al(CEP) provides LOI of 28.3% and passes UL-94 V-0 rating. SEM results show that the sample passing V-0 rating can form the condensed char whereas porous char is observed from the sample failing in V-0 rating after combustion. EDX analysis shows that the condensed char presents higher weight ratio of carbon to phosphorus than the porous char, indicating appropriate amount of Al(CEP) is necessary for formation of the stable char. POLYM. ENG. SCI., 55:657–663, 2015. © 2014 Society of Plastics Engineers

Although hexachlorobutadiene (HCBD) was recently proposed as a candidate persistent organic pollutant (POP) under the Stockholm Convention, information about its environmental levels and distributions is still very limited. In this work, HCBD was determined in the sewage sludge from 37 wastewater treatment plants (WWTPs) in 23 cities and 17 soils near a chemical plant in China. Three chlorobenzenes (CBs) (1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, and hexachlorobenzene) were simultaneously studied to help better understand the environmental behavior of HCBD. Concentrations of HCBD in sludge samples ranged from

Exploring anatase TiO2 with a superior photocatalytic activity is worthwhile as well as challenging. 3D hierarchical anatase TiO2 with a high percentage of exposed {001} facets has been successfully synthesized through a simple one-pot solvothermal strategy in the presence of ammonium fluoride and ethylene glycol solution. It was found that both NH4F and ethylene glycol played an essential role in directing a 3D hierarchical structure with exposed {001} facets. Characterization by SEM, TEM, XRD, and TG endorsed a plausible proposed formation mechanism of “nucleation–aggregation–recrystallization”. The product was proven to exhibit superior photocatalytic activity under the synergistic effect of improved light-harvesting ability and higher reactivity of exposed {001} facets.

There is currently limited knowledge on PBDE metabolism in plants although they could play an important role in the environmental transformation of these persistent organic pollutants. In this study, pumpkin (Cucurbita maxima × C. moschata) was chosen as the model to understand the fate of BDE-28 in plants. MeO-tri-BDEs, OH-tri-BDEs, and OH-tri-BDEs were found as metabolites in plant samples of both in vivo hydroponic and in vitro tissue culture exposure. Three MeO-tri-BDEs were further identified as para-substituted metabolites. MeO-BDEs and OH-BDEs, respectively, accounted for about 1.6% and 1.5% (recovery corrected) of initial amount of BDE-28 according to the semiquantitative results. Other PBDEs, especially less brominated PBDEs as impurities in the standard of BDE-28, were also detected. The impurities and evaporation of the standard must be considered when trace metabolites are studied in exposure experiments.

A novel flame retardant zinc methylethylphosphinate (Zn(MEP)) was used to fill epoxy resins (EPs). The structure of Zn(MEP) was conformed with Fourier transform infrared, hydrogen nuclear magnetic resonance and phosphorus nuclear magnetic resonance, and X-ray fluorescent and X-ray diffraction. The flammability, decomposition behavior, and glass transition temperature (Tg) of cured EP/Zn(MEP) were investigated. Zn(MEP) is stable below 406°C. EP containing 20 phr of Zn(MEP) achieves 27.5% of limiting oxygen index and UL-94 V0 rating. Scanning electron microscopy-energy-dispersive X-ray and Fourier transform infrared spectroscopy investigations show that a condensed char layer with carbon-rich and phosphorus-rich components was formed during heating Zn(MEP)/EP, the atomic ratio of P to Zn on the surface of the char is reduced compared with the initial sample. The P-rich components and lower atomic ratio of P/Zn on the char surface implies that the Zn(MEP) acts in both condensed phase and gas phase. TGA investigation shows that there are interactions between Zn(MEP) and EP when they are copyrolyzed. The interactions lead to a modification in degradation process and promote the char forming. Compared with aluminum diethylphosphinate Zn(MEP) filled EP shows lower limiting oxygen index but higher Tg. In addition, the interactions between polymer and additive are different when aluminum diethylphosphinate instead of Zn(MEP) is added into EP. Copyright © 2013 John Wiley & Sons, Ltd.

6:2 FTI [F(CF2)6CH2CH2I] is a principal industrial raw material used to manufacture 6:2 FTOH [F(CF2)6CH2CH2OH] and 6:2 FTOH-based products and could enter aerobic environments from possible industrial emissions where it is manufactured. This is the first study to assess 6:2 FTI aerobic soil biotransformation, quantify transformation products, and elucidate its biotransformation pathways. 6:2 FTI biotransformation led to 6:2 FTOH as a key intermediate, which was subsequently biotransformed to other significant transformation products, including PFPeA [F(CF2)4COOH, 20 mol % at day 91], 5:3 acid [F(CF2)5CH2CH2COOH, 16 mol %], PFHxA [F(CF2)5COOH, 3.8 mol %], and 4:3 acid [F(CF2)4CH2CH2COOH, 3.0 mol %]. 6:2 FTI biotransformation also led to a significant level of PFHpA [F(CF2)6COOH, 16 mol % at day 91], perhaps via another putative intermediate, 6:2 FTUI [F(CF2)6CH ═ CHI], whose molecular identity and further biotransformation were not verified because of the lack of an authentic standard. Total recovery of the aforementioned per- and polyfluorocarboxylates accounted for 59 mol % of initially applied 6:2 FTI by day 91, in comparison to 56 mol % when soil was dosed with 6:2 FTOH, which did not lead to PFHpA. Thus, were 6:2 FTI to be released from its manufacture and undergo soil microbial biotransformation, it could form PFPeA, PFHpA, PFHxA, 5:3 acid, and 4:3 acid in the environment.

Polybrominated diphenyl ethers (PBDEs) are widely distributed persistent organic pollutants. In vitro and in vivo research using various animal models have shown that PBDEs might be transformed to hydroxylated PBDEs, but there are few studies on in vivo metabolism of PBDEs by intact whole plants. In this research, pumpkin plants (Cucurbita maxima × C. moschata) were hydroponically exposed to 2,2',4,4'-tetrabromodiphenyl ether (BDE-47). A debromination product (BDE-28) and four hydroxylated metabolites (5-OH-BDE-47, 6-OH-BDE-47, 4'-OH-BDE-49, and 4-OH-BDE-42) were detected in different parts of the whole plant. In addition, 4-methoxylated-2,2',3,4'-tetraBDE (4-MeO-BDE-42) was observed as a methoxylation product. Root exudates in solution were found to play an important role in metabolizing BDE-47 to a specific OH-PBDE: 4'-OH-BDE-49. BDE-28 was found to translocate more easily and accumulate in shoots than BDE-47 due to the lower hydrophobicity and molecular weight. The concentration ratio between metabolites and parent compound BDE-47 was lower for OH-PBDEs than that for both BDE-28 and 4-MeO-BDE-42. The metabolism pathway of BDE-47 in young whole plants was proposed in this study.

The production of new blood vessels (angiogenesis) is an important stage in the growth and spread of cancerous tumors. Anti-angiogenesis is one strategy for controlling tumor progression. This study evaluated the antioxidant and anti-angiogenic activities of a proanthocyanidins (PAs) extract from Choerospondias axillaris peels. HPLC-MS analysis revealed that numerous oligomeric forms of the PAs were detected in the PAs extract, including dimers, trimers, tetramers, and flavan-3-ol monomers. The PAs extract possessed appreciable free radical scavenging activity (IC50/DPPH = 164 ± 7 μg/mL, IC50/ABTS = 154 ± 6 μg/mL), potent reducing power (0.930 ± 0.030 g AAE/g), and strong cellular antioxidant activity (EC50 = 10.2 ± 1.4 and 38.9 ± 2.1 μg/mL without or with PBS-wash, respectively). It could also retard various stages of angiogenesis, such as the migration of endothelial cells and the creation of tubes, without causing toxicity to the cells. With regard to intracellular signal transduction, the PAs extract attenuated the phosphorylation of Akt, ERK, and p38MAPK dose-dependently in endothelial cells from human umbilical veins. In transgenic zebrafish embryo, new blood vessel formation was suppressed by PAs extract in a concentration-dependent manner at 72 h post fertilization. Thus, these results suggest that PAs from C. axillaris peels could be a good source of natural inhibitors to target angiogenesis.

SUMMARY A novel aluminum phosphinate—aluminum methylcyclohexylphosphinate (Al(MHP))—was synthesized by reacting n-butyl methylphosphonite with cyclohexene, followed by reacting with anhydrous AlCl3. The products were characterized with gas chromatography, Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, phosphorus nuclear magnetic resonance, X-ray fluorescent spectroscopy, and thermogravimetric (TG) analyses. After blending with epoxy resin (EP), flame retardancy was estimated with the use of limited oxygen index (LOI) and UL-94 test, and thermal stability was investigated using TG analysis. The morphologies and composition of the char obtained after being heated at 300 °C for 20 min followed by 500 °C for 3 min in the muffle furnace were characterized by scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX) analysis. Results showed that Al(MHP) is an efficient flame retardant for EP, and Al(MHP)/EP can pass UL-94V-0 rating with an LOI of 28.8% by adding 15 wt.% of Al(MHP). TG results showed that the presence of Al(MHP) in EP increases the char yield and depresses the thermal decomposition. SEM-EDX analysis showed that the char obtained at 300 °C is coherent and consists of P-rich components; at higher temperature (500 °C), the char becomes tiny and loose and phosphorus element is released into gas. Compared with neat EP, composites have lower water absorption. Copyright © 2012 John Wiley & Sons, Ltd.

Epoxy resin (EP) is one of the main polymers in electrical and electronic applications. In this work, flame-retardant epoxy resin composites based on aluminum diethylphosphinate (Al(DEP)) and aluminum methylethylphosphinate (Al(MEP) were prepared using aromatic amine 4, 4-diaminodiphenylmethane as curing agent. The flammability, thermal degradation, flexural properties, and morphologies of composites were investigated with respect to the filler loading and filler type. Results showed that both Al(MEP) and Al(DEP) were efficient flame retardants for EP and a low dosage (15 wt%) is enough to achieve the important criterion UL 94 V-0. Limiting oxygen index (LOI) of composites is increased with filler loading (phosphorus content) and reached of 32.2% for 15 wt% of Al(MEP) and 29.8 for 15 wt% of Al(DEP). The char formation and flexural modulus of composites are also improved by adding the two fillers. However, the flexural strength of all the composites decreased with increasing filler loading. In comparison with Al(DEP)/EP, Al(MEP)/EP provides a higher flammability, better thermal stability and char formation but inferior flexural properties. Scanning electron microscopy revealed that the dispersion of Al(DEP) filler in the EP matrix is more uniform and exhibits better compatibility with EP matrix, which in turn generates better flexural strength and higher modulus when compared with Al(MEP)-filled EP composites. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers

6-Aryl substituted phenanthridines were synthesized via a visible-light-catalyzed cyclization of 2-isocyanobiphenyls with arylsulfonyl chlorides under oxidant-free and transition-metal-free conditions. This transformation represents an efficient and attractive synthetic utilization of arylsulfonyl chlorides.

A convenient and general method for acylation of free (N H) indoles via palladium-catalyzed decarboxylative cross-coupling reaction was developed. This process provided a useful method for the preparation of diverse 3-acylindoles in high yields utilizing a reaction with readily accessible reactants under mild conditions.