Integration of microbial reductive dehalogenation with persulfate activation and oxidation(Bio-RD-PAO)for complete attenuation of organohalides

Due to the toxicity of bioaccumulative organohalides to human beings and ecosystems,a variety of biotic and abiotic remediation methods have been developed to remove organohalides from contaminated environments.Bioremediation employing organohalide-respiring bacteria(OHRB)-mediated microbial reductive dehalogenation(Bio-RD)represents a cost-effective and environmentally friendly approach to attenuate highly-halogenated organohalides,specifically organohalides in soil,sediment and other anoxic environments.Nonetheless,many factors severely restrict the implications of OHRB-based bioremediation,including incomplete dehalogenation,low abundance of OHRB and consequent low dechlorination activity.Recently,the development of in situ chemical oxidation(ISCO)based on sulfate radicals(SO_(4)^(·−))via the persulfate activation and oxidation(PAO)process has attracted tremendous research interest for the remediation of lowly-halogenated organohalides due to its following advantages,e.g.,complete attenuation,high reactivity and no selectivity to organohalides.Therefore,integration of OHRB-mediated Bio-RD and subsequent PAO(Bio-RD-PAO)may provide a promising solution to the remediation of organohalides.In this review,we first provide an overview of current progress in Bio-RD and PAO and compare their limitations and advantages.We then critically discuss the integration of Bio-RD and PAO(Bio-RD-PAO)for complete attenuation of organohalides and its prospects for future remediation applications.Overall,Bio-RD-PAO opens up opportunities for complete attenuation and consequent effective in situ remediation of persistent organohalide pollution.

Visible Light Catalyzed Reductive Cross-Coupling of α-CF_(3)-alkyl Bromide and Alkynyl Bromide

Traditional reduction coupling reactions of two bromides typically rely on transition metal catalysis.Here,we introduce the development of a visible-light catalytic direct reduction coupling reaction between α-CF_(3)-alkyl bromides and alkynyl bromides to access valuable organic frameworks.Our research confirms the excellent compatibility of this reaction with various functional groups,which could be used to modify the substrate with biologically active molecular fragments.Mechanistic investigations,including control experiments,fluorescence quenching studies,and light-switching experiments,have provided insights into the reaction mechanism.This study paves the way for the application of visible-light catalysis in diverse synthetic transformations,offering a sustainable and efficient approach to organic synthesis.

Modular Synthesis of Multi-substituted Cyclobutanones Enabled by Oxyallyl Cations

Stereoselective synthesis of multi-substituted cyclobutanes with different substituents is still a daunting challenge in organic synthesis.We report here a practical and facile approach to synthesizing all-trans 2,3,4-trisubstituted cyclobutanones from readily available dichlorocyclobutanones.The substitution reaction proceeds smoothly via oxyallyl cation intermediates under mild basic conditions.Further transformation to the synthesis of 1,2,3,4-tetrasubstituted cyclobutanes was also explored.

Photoinduced Dehalocyclization to Access Oxindoles Using Formate as a Reductant

Herein,we report an efficient and practical protocol for the photoinduced dehalocyclization of ortho-halophenylacrylamides with formate by the engagement of a CO_(2) radical anion to access substituted oxindoles.This method proceeds smoothly under mild conditions and exhibits a wide range of substrate as well as remarkable functional group compatibility.

Electrochemical Atom Transfer Radical Addition of Polychloroalkanes to Olefins Promoted by 4,4-Di-tert-butyl Bipyridine

A new electrochemical strategy for the atom transfer radical addition(ATRA)of polychloroalkanes across olefins has been realized by the synergism of paired electrolysis and halogen bonding activation.Notably,readily accessible 4,4-di-tert-butyl bipyridine(dtbpy),acting as a halogen bonding acceptor,shifted the reduction potential of C—Cl bonds positively by 110 mV.The decreased operating potential leads to a wide substrate scope and excellent functional group compatibility.A diverse array of terminal and internal alkenes such as(hetero)aryl olefins,unactive aliphatic olefins,and natural products and drugs-derived olefins were well compatible.

Electrophotocatalytic Reductive 1,2-Diarylation of Alkenes with Aryl Halides and Cyanoaromatics

Comprehensive Summary The radical-mediated reductive functionalization of aryl halides has been extensively studied.However,the related radical-mediated intermolecular reductive 1,2-diarylation of alkenes,using aryl halides as aryl radical sources,remains unexplored.Herein,a new electrophotocatalytic intermolecular reductive 1,2-diarylation of alkenes is reported using aryl halides and cyanoaromatics to produce polyarylated alkanes.Using synergistic cathodic reduction and visible-light photoredox catalysis,various electron-rich and electron-deficient aryl halides are combined with various alkenes and cyanoaromatics to characterize the broad substrate scope,excellent functional group compatibility,and excellent selectivity of this reaction.Mechanistic investigations reveal that this reaction may proceed via a radical process initiated by the reductive generation of aryl radicals from aryl halides and terminated by radical-radical coupling with cyanoaromatic radical anions.

Distribution of polychlorinated biphenyls in effluent from a large municipal wastewater treatment plant: Potential for bioremediation?

This study involved an evaluation of the potential for bioremediation of polychlorinated biphenyls(PCBs) in the effluent from a large municipal wastewater treatment plant. It was focused on the presence of PCBs in two types of effluents: the continuous effluent present during dry weather conditions and the intermittently present effluent that was present during wet weather due to incoming stormwater. The annual discharge of PCBs for both types of effluent was calculated based on a five-year dataset(2011–2015). In addition, the toxicity and bioremediation potential of the PCBs in the effluent were also assessed. It was found that the continuous effluent was responsible for the majority of the discharged PCB into the receiving river(1821 g for five years), while the intermittent effluent contributed 260 g over the five years.The average number of chlorine per biphenyl for the detected PCB congeners showed a 19%difference between the two types of effluent, which indicated a potential for organohalide respiration of PCBs during the continuous treatment. This was further supported by a high level of tri-, tetra-and penta-chlorinated congeners accounting for 75% of the anaerobically respired PCBs. Potential for aerobic degradation and thus biomineralization of PCBs was identified for both effluents. Furthermore, toxicity of 12 dioxin-like PCBs showed that normal operation of the wastewater reduced the toxicity throughout the wastewater treatment plant.

Design, Synthesis and Application of a Robust d_(3)-Methyithiolating Reagent

A deuterated methylthiolating reagent with a broad spectrum,designated as DMTp,has been ingeniously formulated.This new reagent can be produced with high efficiency through the simple combination of commercially available methyl 3-thiopropanoate and CD_(3)l.This novel SCD_(3) reagent exhibits excellent reactivity with electrophiles such as alkyl iodides,benzyl chlorides,aryl halides(l,Br)and aryl triflates,resulting in high levels of deuterium content(99%D).Representative deuterated methylthiolated biomolecules,such as Sulfoxaflor,havebeen synthesizedforuse in pharmaceutical discoveryand development.

A General Protocol toward Oxindoles Bearing C_(3)-Allylic Quaternary Stereocenter via Domino Reaction:A Concise Synthesis of Heterocycle-Fused Indoline Alkaloids

An efficiently catalytic method toward the synthesis of indolin-2-ones featuring an allylic derived C_(3)-quaternary stereocenter via an intramolecular Heck cyclization/Suzuki coupling of N-substituted-N-(2-bromophenyl)acrylamides and organoboron reagents was successfully developed by using a 1,3-bis(2,6-diisopropylphenyl)acenaphthoimidazol-2-ylidene(AnIPr)-ligated oxazoline palladacycle.It enabled a very broad substrate scope tolerating different functional groups,electronic properties and steric bulkiness.Notably,it revealed a great potential to build diverse heterocycle-fused indoline alkaloids via the same intermediate 3-allyl-1,3-dimethylindolin-2-one.