Oxidative Cleavage Research Articles

Molecular-strain induced phosphinidene reactivity of a phosphanorcaradiene

Phosphanorcaradienes are an appealing class of phosphorus compounds that can serve as synthons of transient phosphinidenes. However, the synthesis of such species is a formidable task owing to their intrinsic high reactivity. Herein we report straightforward synthesis, characterization and reactivity studies of a phosphanorcaradiene, in which one of the benzene rings in the flanking fluorenyl substituents is intramolecularly dearomatized through attachment to the phosphorus atom. It is facilely obtained by the reduction of phosphorus(III) dichloride precursor with potassium graphite. Despite being thermally robust, it acts as a synthetic equivalent of a transient phosphinidene. It reacts with trimethylphosphine and isonitrile to yield phosphanylidene-phosphorane and 1-phospha-3-azaallene, respectively. When it is treated with one and two molar equivalents of azide, iminophosphane and bis(imino)phosphane are isolated, respectively. Moreover, it is capable of activating ethylene and alkyne to afford [1 + 2] cycloaddition products, as well as oxidative cleavage of Si–H and N–H bonds to yield secondary phosphines. All the reactions proceed smoothly at room temperature without the presence of transition metals. The driving force for these reactions is most likely the high ring-constraint of the three-membered PC2 ring and recovery of the aromaticity of the benzene ring.

A process-based geochemical framework for carbonate sediments during marine diagenesis

A significant proportion of marine calcium carbonate sediments are comprised of metastable minerals that are susceptible to diagenetic alterations during burial. These reactions can reset the geochemical signature of sediments and pore fluids and influence elemental cycling in the ocean. However, the timing and mechanisms by which these reactions take place are poorly constrained. This study uses cores drilled on the slope of the Great Bahama Bank to provide quantitative constraints on important diagenetic reactions; namely respiration-driven dissolution, authigenic carbonate mineral formation, and conversion of aragonite to low Mg calcite (LMC). We perform detailed mineralogical characterization using newly acquired, high resolution X-ray diffraction (XRD) data and over 1000 reanalyzed XRD scans, characterize sediments texturally and elementally using electron microprobe data, calculate pore fluid saturation state with respect to aragonite using a Pitzer ion interaction approach, and use pore fluid chemistry and experimental distribution coefficients to predict authigenic carbonate compositions. These data suggest that aerobic organic matter oxidation, enabled by the advection of oxygenated seawater throughout the upper ∼ 30 m interval of sediment, causes undersaturation and thus dissolution of biogenic high Mg calcite (HMC) and aragonite. Deeper, anaerobic organic matter oxidation takes over and causes supersaturation, promoting authigenic precipitation in the form of HMC, which in turn decreases pore fluid Mg/Ca and promotes aragonite conversion to LMC. One novel aspect of this study is the identification of three types of calcites using the newly acquired XRD and electron microprobe data. Based on their unique crystallographic characteristics and chemical compositions, these types of calcites are interpreted to represent pelagic biogenic LMC, bank-derived biogenic HMC, and authigenic HMC precipitated from pore fluids. Notably, the composition of the authigenic calcite matches that predicted to precipitate from pore fluids using an empirical Mg partition coefficient in calcite. Calcites that form authigenically and from aragonite via replacement are suggested to recrystallize with burial as evidenced by the decrease in Mg content and micro-strain. This process-based geochemical framework assigns diagenetic processes to a specific depth window within the sediment column and paves the way for a mechanistic understanding of carbonate diagenesis, one that is rooted in thermodynamic and kinetic bases.

Primary Radical Effectiveness: Do the Different Chemical Reactivities of Hydroxyl and Chlorine Radicals Matter for Tropospheric Oxidation?

The atmospheric oxidation of organics occurs primarily via reaction cycles involving gas phase radical species, catalysed by nitric oxide (NO), which result in the production of secondary pollutants such as ozone. For these oxidation cycles to occur, they must be initialized by a primary radical, i.e., a radical formed from non-radical precursors. Once formed, these primary radicals can result in the oxidation of organic compounds to produce peroxy radicals that, providing sufficient NO is present, can re-generate "secondary" radicals which can go on to oxidize further organics. Thus, one primary radical can result in the catalytic oxidation of multiple organics. Although the photolysis of ozone in the presence of water vapor to form two hydroxyl (OH) radicals is accepted as the dominant tropospheric primary radical source, multiple other primary radical sources exist and can dominate in certain environments. The chemical reactivity of different radicals to organic and inorganic compounds can be very different, however, and how these differences in radical chemistry impact atmospheric organic oxidation under different atmospheric conditions has not been previously demonstrated. In this work, we use a series of model simulations to investigate the impact of the chemical reactivity of the primary radical on the effectiveness in initializing organic oxidation and thus the production of the secondary pollutant ozone. We compare the chemistries of the OH and atomic chlorine (Cl) radicals and their effectiveness at initializing organic oxidation under different nitrogen oxide and organic concentrations. The OH radical is the dominant tropospheric radical, with both primary and secondary sources. In contrast, Cl has primary sources that show significant spatial heterogeneity throughout the troposphere but is not typically regenerated in catalytic cycles. Both primary OH and Cl can initiate organic oxidation, but this work shows that the relative effectiveness with which they oxidize organics and produce ozone depends on their balance of propagation vs termination reactions which is in turn determined by the chemical environment in which they are produced. In particular, our work shows that in high NOx radical-limited environments, like those found in many urban areas, Cl will be more efficient at oxidizing organics than OH.

Cofactor-independent C-C bond cleavage reactions catalyzed by the AlpJ family of oxygenases in atypical angucycline biosynthesis.

Biosynthesis of atypical angucyclines involves unique oxidative B-ring cleavage and rearrangement reactions, which are catalyzed by AlpJ-family oxygenases, including AlpJ, JadG, and GilOII. Prior investigations established the essential requirement for FADH2/FMNH2 as cofactors when utilizing the quinone intermediate dehydrorabelomycin as a substrate. In this study, we unveil a previously unrecognized facet of these enzymes as cofactor-independent oxygenases when employing the hydroquinone intermediate CR1 as a substrate. The enzymes autonomously drive oxidative ring cleavage and rearrangement reactions of CR1, yielding products identical to those observed in cofactor-dependent reactions of AlpJ-family oxygenases. Furthermore, the AlpJ- and JadG-catalyzed reactions of CR1 could be quenched by superoxide dismutase, supporting a catalytic mechanism wherein the substrate CR1 reductively activates molecular oxygen, generating a substrate radical and the superoxide anion O2 •-. Our findings illuminate a substrate-controlled catalytic mechanism of AlpJ-family oxygenases, expanding the realm of cofactor-independent oxygenases. Notably, AlpJ-family oxygenases stand as a pioneering example of enzymes capable of catalyzing oxidative reactions in either an FADH2/FMNH2-dependent or cofactor-independent manner.

Dual single atomic Fe-Ni sites in N‑doped nanoporous carbon for high-efficiency potassium periodate activation toward pollutant abatement

Diatomic catalysts (DACs) with atomically isolated metal pairs hold the potential for activating potassium periodate (PI) in sustainable pollution control, yet their synthesis poses a significant challenge. In this study, Fe/Ni species anchored to a nitrogen-doped carbon as diatomic catalysts (FeNi-NC DACs) were precisely synthesized by direct carbonization of metal–organic frameworks (MOFs) assembled by Fe/Ni-doped ZnO nanoparticles and used for the effective decomposition of organic pollutants through PI activation. As anticipated, FeNi-NC exhibited superior catalytic properties due to the abundance of adjacent bimetallic active sites (Fe/Ni-Nx), rich doped nitrogen, high specific surface area, and electron transport conductivity, surpassing single-atom Fe-NC and Ni-NC, as well as nonmetallic NC catalysts. Free radical quenching, electron paramagnetic resonance, and electrochemical experiments have shown that the FeNi-NC/PI system can oxidize organic compounds through non-free radical oxidation pathways, including singlet oxygen (1O2) oxidation and mediated electron transfer processes. Electron transfer mediated by FeNi-NC/PI* complexes is the primary mechanism for organic oxidation. Additionally, the FeNi-NC catalyst demonstrated remarkable stability in both inorganic-containing and real water samples, as well as in continuous-flow microreactors. This study introduces a novel approach for designing highly efficient DACs and offers fundamental insights into the mechanism of PI-activated oxidation of organic pollutants.

Directional Formation of Reactive Oxygen Species Via a Non-Redox Catalysis Strategy That Bypasses Electron Transfer Process.

A broad range of chemical transformations driven by catalytic processes necessitates the electron transfer between catalyst and substrate. The redox cycle limitation arising from the inequivalent electron donation and acceptance of the involved catalysts, however, generally leads to their deactivation, causing substantial economic losses and environmental risks. Here, a "non-redox catalysis" strategy is provided, wherein the catalytic units are constructed by atomic Fe and B as dual active sites to create tensile force and electric field, which allows directional self-decomposition of peroxymonosulfate (PMS) molecules through internal electron transfer to form singlet oxygen, bypassing the need of electron transfer between catalyst and PMS. The proposed catalytic approach with non-redox cycling of catalyst contributes to excellent stability of the active centers while the generated reactive oxygen species find high efficiency in long-term catalytic pollutant degradation and selective organic oxidation synthesis in aqueous phase. This work offers a new avenue for directional substrate conversion, which holds promise to advance the design of alternative catalytic pathways for sustainable energy conversion and valuable chemical production.

Discovery of (±)-Penindolenes Reveals an Unusual Indole Ring Cleavage Pathway Catalyzed by P450 Monooxygenase.

(±)-Penindolenes A-D (1-4), the first representatives of indole terpenoids featuring a γ-lactam skeleton, were isolated from the mangrove-derived endophytic fungus Penicillium brocae MA-231. Our bioactivity tests revealed their potent antimicrobial and acetylcholinesterase inhibitory activities. The biosynthetic reactions by the five enzymes PbaABCDE leading to γ-lactam ring formation were identified with heterologous expression and in vitro enzymatic assays. Remarkably, the cytochrome P450 monooxygenase PbaB and its homolog in Aspergillus oryzae catalyzed the 2,3-cleavage of the indole ring to generate two keto groups in 1. This is the first example of the oxidative cleavage of indole by a P450 monooxygenase. In addition, rare secondary amide bond formation by the glutamine synthetase-like enzyme PbaD was reported. These findings will contribute to the engineered biosynthesis of unnatural, bioactive indole terpenoids.

Discovery of (±)‐Penindolenes Reveals an Unusual Indole Ring Cleavage Pathway Catalyzed by P450 Monooxygenase

Abstract(±)‐Penindolenes A−D (1–4), the first representatives of indole terpenoids featuring a γ‐lactam skeleton, were isolated from the mangrove‐derived endophytic fungus Penicillium brocae MA‐231. Our bioactivity tests revealed their potent antimicrobial and acetylcholinesterase inhibitory activities. The biosynthetic reactions by the five enzymes PbaABCDE leading to γ‐lactam ring formation were identified with heterologous expression and in vitro enzymatic assays. Remarkably, the cytochrome P450 monooxygenase PbaB and its homolog in Aspergillus oryzae catalyzed the 2,3‐cleavage of the indole ring to generate two keto groups in 1. This is the first example of the oxidative cleavage of indole by a P450 monooxygenase. In addition, rare secondary amide bond formation by the glutamine synthetase‐like enzyme PbaD was reported. These findings will contribute to the engineered biosynthesis of unnatural, bioactive indole terpenoids.

Protein-Labeling Reagents Selectively Activated by Copper(I).

Copper is an essential trace element that participates in many biological processes through its unique redox cycling between cuprous (Cu+) and cupric (Cu2+) oxidation states. To elucidate the biological functions of copper, chemical biology tools that enable selective visualization and detection of copper ions and proteins in copper-rich environments are required. Herein, we describe the design of Cu+-responsive reagents based on a conditional protein labeling strategy. Upon binding Cu+, the probes generated quinone methide via oxidative bond cleavage, which allowed covalent labeling of surrounding proteins with high Cu+ selectivity. Using gel- and imaging-based analyses, the best-performing probe successfully detected changes in the concentration of labile Cu+ in living cells. Moreover, conditional proteomics analysis suggested intramitochondrial Cu+ accumulation in cells undergoing cuproptosis. Our results highlight the power of Cu+-responsive protein labeling in providing insights into the molecular mechanisms of Cu+ metabolism and homeostasis.

The radical impact of oxygen on prokaryotic evolution-enzyme inhibition first, uninhibited essential biosyntheses second, aerobic respiration third.

Molecular oxygen is a stable diradical. All O2-dependent enzymes employ a radical mechanism. Generated by cyanobacteria, O2 started accumulating on Earth 2.4 billion years ago. Its evolutionary impact is traditionally sought in respiration and energy yield. We mapped 365 O2-dependent enzymatic reactions of prokaryotes to phylogenies for the corresponding 792 protein families. The main physiological adaptations imparted by O2-dependent enzymes were not energy conservation, but novel organic substrate oxidations and O2-dependent, hence O2-tolerant, alternative pathways for O2-inhibited reactions. Oxygen-dependent enzymes evolved in ancestrally anaerobic pathways for essential cofactor biosynthesis including NAD+, pyridoxal, thiamine, ubiquinone, cobalamin, heme, and chlorophyll. These innovations allowed prokaryotes to synthesize essential cofactors in O2-containing environments, a prerequisite for the later emergence of aerobic respiratory chains.

Computational investigation of cis-1,4-polyisoprene binding to the latex-clearing protein LcpK30.

Latex clearing proteins (Lcps) catalyze the oxidative cleavage of the C = C bonds in cis-1,4-polyisoprene (natural rubber), producing oligomeric compounds that can be repurposed to other materials. The active catalytic site of Lcps is buried inside the protein structure, thus raising the question of how the large hydrophobic rubber chains can access the catalytic center. To improve our understanding of hydrophobic polymeric substrate binding to Lcps and subsequent catalysis, we investigated the interaction of a substrate model containing ten carbon-carbon double bonds with the structurally characterized LcpK30, using multiple computational tools. Prediction of the putative tunnels and cavities in the LcpK30 structure, using CAVER-Pymol plugin 3.0.3, fpocket and Molecular Dynamic (MD) simulations provided valuable insights on how substrate enters from the surface to the buried active site. Two dominant tunnels were discovered that provided feasible routes for substrate binding, and the presence of two hydrophobic pockets was predicted near the heme cofactor. The larger of these pockets is likely to accommodate the substrate and to determine the size distribution of the oligomers. Protein-ligand docking was carried out using GOLD software to predict the conformations and interactions of the substrate within the protein active site. Deeper insight into the protein-substrate interactions, including close-contacts, binding energies and potential cleavage sites in the cis-1,4-polyisoprene, were obtained from MD simulations. Our findings provide further justification that the protein-substrate complexation in LcpK30 is mainly driven by the hydrophobic interactions accompanied by mutual conformational changes of both molecules. Two potential binding modes were identified, with the substrate in either extended or folded conformations. Whilst binding in the extended conformation was most favorable, the folded conformation suggested a preference for cleavage of a central double bond, leading to a preference for oligomers with 5 to 6 C = C bonds. The results provide insight into further enzyme engineering studies to improve catalytic activity and diversify the substrate and product scope of Lcps.

Impact of the Copper Second Coordination Sphere on Catalytic Performance and Substrate Specificity of a Bacterial Lytic Polysaccharide Monooxygenase.

Lytic polysaccharide monooxygenases (LPMOs) catalyze the oxidative cleavage of glycosidic bonds in recalcitrant polysaccharides, such as cellulose and chitin, using a single copper cofactor bound in a conserved histidine brace with a more variable second coordination sphere. Cellulose-active LPMOs in the fungal AA9 family and in a subset of bacterial AA10 enzymes contain a His-Gln-Tyr second sphere motif, whereas other cellulose-active AA10s have an Arg-Glu-Phe motif. To shine a light on the impact of this variation, we generated single, double, and triple mutations changing the His216-Gln219-Tyr221 motif in cellulose- and chitin-oxidizing MaAA10B toward Arg-Glu-Phe. These mutations generally reduced enzyme performance due to rapid inactivation under turnover conditions, showing that catalytic fine-tuning of the histidine brace is complex and that the roles of these second sphere residues are strongly interconnected. Studies of copper reactivity showed remarkable effects, such as an increase in oxidase activity following the Q219E mutation and a strong dependence of this effect on the presence of Tyr at position 221. In reductant-driven reactions, differences in oxidase activity, which lead to different levels of in situ generated H2O2, correlated with differences in polysaccharide-degrading ability. The single Q219E mutant displayed a marked increase in activity on chitin in both reductant-driven reactions and reactions fueled by exogenously added H2O2. Thus, it seems that the evolution of substrate specificity in LPMOs involves both the extended substrate-binding surface and the second coordination sphere.

Exogenous CaCl2 reduces the oxidative cleavage of carotenoids in shredded carrots by targeting CAMTA4-mediated transcriptional repression of carotenoid degradation pathway

Carotenoid oxidative cleavage is a significant factor contributing to the color changes of shredded carrots and treatment with calcium chloride (CaCl2, 1% w/v) has been observed to alleviate the whitening symptom and color loss. However, the specific mechanism by which CaCl2 treatment suppresses carotenoid degradation remains unclear. In this study, the effect of CaCl2 and EGTA (calcium ion chelating agent) treatment on carotenoid biosynthesis and degradation in shredded carrots and the mechanism involved was investigated. CaCl2 treatment promoted the expression and activity of carotenoid biosynthetic enzyme (phytoene synthase, PSY), but inhibited the increases of the degradative enzyme activity of carotenoid cleavage dioxygenase (CCD) and down-regulated the corresponding transcripts, thus delayed the degradation of total carotenoid and maintaining higher levels of major carotenoid compounds including β-carotene, α-carotene, lycopene, and lutein in shredded carrots during storage. However, EGTA treatment promoted the gene expression and enzyme activity of CCD and increased the degradation of carotenoid compounds in shredded carrots during storage. Furthermore, the CaCl2 treatment induced DcCAMTA4, identified as a calcium decoder in shredded carrots, which, in turn, suppressed the expressions of DcCCD1 and DcCCD4 by interacting with their promoters. The transient overexpression of DcCAMTA4 in tobacco leaves led to reduced expression of NtCCD1 and NtCCD4, maintaining a higher content of carotenoids. Thus, CaCl2 alleviated the oxidative cleavage of carotenoids in shredded carrots through the DcCAMTA4-mediated carotenoid degradation pathway.

Carboxylation of Alkenes with CO2 via Photocatalytic Cleavage of C=C Double Bonds

AbstractThe cleavage of double bonds in alkenes constitutes an integral process in converting feedstock materials into high-value synthetic intermediates. Well-known examples such as the oxidative cleavage of olefins and olefin metathesis only facilitate the synthesis of oxygen-containing compounds and the recombination of olefins. Therefore, it is appealing to extend C=C double bond cleavage to yield more abundant transformations. Herein, we report a novel photocatalytic approach for the deconstructive carboxylation of alkenes with CO2 for the synthesis of carboxylic acids in the absence of transition metals. Compared with reported carboxylations with CO2 during which carbon numbers are typically increased, we achieve the exchange of carbon dioxide with one of the carbons of the alkene double bond, thus providing carboxylic acids with unchanged carbon numbers when terminal alkenes are used.

Fostering a Holistic Understanding of the Full Volatility Spectrum of Organic Compounds from Benzene Series Precursors through Mechanistic Modeling.

A comprehensive understanding of the full volatility spectrum of organic oxidation products from the benzene series precursors is important to quantify the air quality and climate effects of secondary organic aerosol (SOA) and new particle formation (NPF). However, current models fail to capture the full volatility spectrum due to the absence of important reaction pathways. Here, we develop a novel unified model framework, the integrated two-dimensional volatility basis set (I2D-VBS), to simulate the full volatility spectrum of products from benzene series precursors by simultaneously representing first-generational oxidation, multigenerational aging, autoxidation, dimerization, nitrate formation, etc. The model successfully reproduces the volatility and O/C distributions of oxygenated organic molecules (OOMs) as well as the concentrations and the O/C of SOA over wide-ranging experimental conditions. In typical urban environments, autoxidation and multigenerational oxidation are the two main pathways for the formation of OOMs and SOA with similar contributions, but autoxidation contributes more to low-volatility products. NOx can reduce about two-thirds of OOMs and SOA, and most of the extremely low-volatility products compared to clean conditions, by suppressing dimerization and autoxidation. The I2D-VBS facilitates a holistic understanding of full volatility product formation, which helps fill the large gap in the predictions of organic NPF, particle growth, and SOA formation.

Oxygenolytic cleavage of 1,2-diols with dioxygen by a mononuclear nonheme iron complex: Mimicking the reaction of myo-inositol oxygenase

A mononuclear iron(II) complex, [(TpPh2)FeII(OTf)(CH3CN)] (1) (TpPh2 = hydrotris(3,5-diphenylpyrazol-1-yl)borate, OTf = triflate) has been isolated and its efficiency toward the aliphatic CC bond cleavage reaction of 1,2-diols with dioxygen has been investigated. Separate reactions between 1 and different 1,2-diolates form the corresponding iron(II)-diolate complexes in solution. While the iron(II) complex of the tetradentate TPA (tris(2-pyridylmethyl)amine) ligand is not efficient in affecting the CC cleavage of 1,2-diol with dioxygen, complex 1 displays catalytic activity to afford carboxylic acid and aldehyde. Isotope labeling studies with 18O2 reveal that one oxygen atom from dioxygen is incorporated into the carboxylic acid product. The oxygenative CC cleavage reactions occur on the 1,2-diols containing at least one α-H atom. The kinetic isotope effect value of 5.7 supports the abstraction of an α-H by an iron(III)-superoxo species to propagate the CC cleavage reactions. The oxidative cleavage of 1,2-diolates by the iron(II) complex mimics the reaction catalyzed by the nonheme diiron enzyme, myo-inositol oxygenase.

Reaction mechanism and kinetics for Pt/C and Au/C catalyzed aqueous phase glycerol oxidation to various carboxylic acids

Fundamental understanding of heterogeneously catalytic aerobic oxidation of polyol is highly desirable for sustainable and efficient chemical synthesis. Herein, based on the purpose of exploring the selectivity of various carboxylic acids on Pt-Au catalysts with different ratios, we conducted a comprehensive investigation into the reaction pathways of glycerol oxidation over pristine Pt/C and Au/C catalysts via experiments, kinetics analysis and DFT calculations. Structural characterizations revealed that Pt/C exhibits a higher metallic state and more d electrons, thus tending to strongly adsorb OH– and promote oxygen activation. Conversely, the weak oxygen activation of Au/C could be attributed to fewer cationic high valence state and d electrons. Furthermore, the Langmuir-Hinshelwood kinetic model and DFT calculations indicate both catalysts exhibit obvious differences in product distribution. Specifically, Pt demonstrated higher selectivity towards lactic acid by facilitating dehydration of C-OH in glyceraldehyde and promoting timely desorption of lactic acid species. In contrast, Au displayed more glycolic acid products caused by strengthening oxidative cleavage of C-C bond in glyceric acid. Expanding to bimetallic catalysts, it was observed that catalysts with higher Au content exhibit enhanced selectivity towards the oxidation of glyceric acid to glycolic acid, while those with a higher Pt ratio demonstrate increased selectivity for the oxidation of glycerol to lactic acid. These findings provide valuable insights for guiding the design and optimization of this catalytic process to achieve targeted product generation.

SnO2/CoTeO3 heterojunction for smartly conducting hydrogen evolution linking to organics electrocatalytic oxidation

As a sustainable energy form, hydrogen can be most practically obtained from electrocatalytic water splitting. The familiar organics can be oxidized to more useful intermediates in chemical industries. Herein, a SnO2/(CoTeO3)2 heterojunction is designed as an electrocatalyst for hydrogen evolution reaction (HER) and organic electrocatalytic oxidation. The heterojunction has good electrocatalytic performances with overpotentials of 281 mV at 10 mA cm−2 in 1 M KOH+0.1 M glycerol, 358 mV at 10 mA cm−2 in 1 M KOH +0.33 M urea, 203 mV in 1 M KOH+0.1 M glucose, and 111 mV for HER in 1 M KOH. The glucose is electrocatalytically oxidized to gluconic acid and formic acid. Density functional theory computation shows the formation of the SnO2/(CoTeO3)2 heterojunction makes the total densities of states of SnO2 move to the Fermi level, which is beneficial for adsorption in the electrocatalysis. This work propagandizes a new avenue for heterojunction electrocatalyst is applied for organics oxidation linking to hydrogen production.

Mechanistic insights of efficient aromatic organic compounds oxidation using biochar derived from coking wastewater sludge

Coking wastewater sludge possessed potential environmental hazards and pyrolysis was a desirable approach which could converted it into one functional carbonous material. The sludge-based biochar (SC-N3) originated from the feedstock of sludge from the regenerated water treatment had various iron-containing species and exhibited the effective catalytic ability. Compared with the degradation of the four pollutants (i.e., phenol, pyridine, quinoline and indole) alone, the mixed of the four pollutants in simulated coking wastewater exhibited a prominent different degradation trend, where the removal rates of indole and quinoline were enhanced from 45% and 30% to 98.9% and 82.3%, respectively. The quinone intermediates from phenol degradation, played a critical role in enhancing the removal rates of indole and quinoline as the electron transfer medium. Both the free radical pathway dominated by •OH and non-radical pathway with 1O2 play the main role in indole degradation, while •OH was the main factor in the catalytic degradation of phenol, quinoline and pyridine. By analysis the intermediates elucidated by Fourier transform ion cyclotron resonance mass spectrometry and three-dimensional excitation-emission matrix fluorescence spectra, the degradation molecular characteristics and pathways of the four pollutants in simulated coking wastewater were deciphered. The findings indicated that the catalyst SC-N3 prepared from the coking wastewater sludge presented unique catalytic properties and possessed a promising application in the degradation of refractory wastewater.

Transcriptome analysis revealed endophytic Beauveria bassiana triggered methyl jasmonate pathway associated with resistance against stem weevil (Apion corchori)

The fungal entomopathogen Beauveria bassiana could be established as an endophyte within jute (Corchorus capsularis) plant through seed inoculation. The highest colonization was observed in ITCC 6063 followed by ITCC 5562 and ITCC 5408 which are statistically at par (p < 0.05). The lowest apion infestation was observed in ITCC 5408, ITCC 6063, ITCC 4512 and ITCC 4563 which are statistically at par (p < 0.05). Highest apion infestation was observed in case of two non-endophytic isolates ITCC 4644 and ITCC 4925. Transcriptome study showed that a significant number of stem-weevil (Apion corchori) resistant genes involved in biosynthesis of plant volatiles viz., oxidative cleavage of fatty acids, LEGO-like building blocks, salicylic acid activation pathway, methyl jasmonic acid synthesis pathway were activated in ten B. bassiana isolate treated plants. RNA Sequencing was used to identify 1017 DEGs between ‘endophyte colonised plant’ and ‘untreated plant’. 1117 genes were up-regulated and 279 genes were down regulated in treated plant.