Hydrocarbon Substrates Research Articles

Hydrocarbon-Oxidizing Bacteria of the Bottom Ecotopes of the Barents and Pechora Seas

Microorganisms capable of degrading hydrocarbons are regular components of natural microbial communities and play an important role in self-purification of marine environments from oil contamination. High-throughput sequencing of the 16S rRNA gene V4 variable region was used to analyze microbial communities of the Barents and Pechora seas and of the microcosms with a spectrum of hydrocarbon substrates: oil, n-nonane, n-undecane, and phenanthrene. The Barents Sea communities of hydrocarbon-oxidizing microorganisms were characterized by predominance of the genera Pseudoalteromonas, Pseudomonas, Porticoccus, and Oleispira, while those of the Pechora Sea contained members of the genera Rhodococcus, Dietzia, Sphingorhabdus, and Hyphomonas. Pure cultures of these microorganisms were shown to utilize the major oil hydrocarbons: n-alkanes, cycloalkanes, and aromatic compounds.

Novel, active, and uncultured hydrocarbon-degrading microbes in the ocean.

Given the vast quantity of oil and gas input to the marine environment annually, hydrocarbon degradation by marine microorganisms is an essential ecosystem service. Linkages between taxonomy and hydrocarbon degradation capabilities are largely based on cultivation studies, leaving a knowledge gap regarding the intrinsic ability of uncultured marine microbes to degrade hydrocarbons. To address this knowledge gap, metagenomic sequence data from the Deepwater Horizon (DWH) oil spill deep-sea plume was assembled to which metagenomic and metatranscriptomic reads were mapped. Assembly and binning produced new DWH metagenome-assembled genomes that were evaluated along with their close relatives, all of which are from the marine environment (38 total). These analyses revealed globally distributed hydrocarbon-degrading microbes with clade-specific substrate degradation potentials that have not been reported previously. For example, methane oxidation capabilities were identified in all Cycloclasticus. Furthermore, all Bermanella encoded and expressed genes for non-gaseous n-alkane degradation; however, DWH Bermanella encoded alkane hydroxylase, not alkane 1-monooxygenase. All but one previously unrecognized DWH plume member in the SAR324 and UBA11654 have the capacity for aromatic hydrocarbon degradation. In contrast, Colwellia were diverse in the hydrocarbon substrates they could degrade. All clades encoded nutrient acquisition strategies and response to cold temperatures, while sensory and acquisition capabilities were clade specific. These novel insights regarding hydrocarbon degradation by uncultured planktonic microbes provides missing data, allowing for better prediction of the fate of oil and gas when hydrocarbons are input to the ocean, leading to a greater understanding of the ecological consequences to the marine environment.IMPORTANCEMicrobial degradation of hydrocarbons is a critically important process promoting ecosystem health, yet much of what is known about this process is based on physiological experiments with a few hydrocarbon substrates and cultured microbes. Thus, the ability to degrade the diversity of hydrocarbons that comprise oil and gas by microbes in the environment, particularly in the ocean, is not well characterized. Therefore, this study aimed to utilize non-cultivation-based 'omics data to explore novel genomes of uncultured marine microbes involved in degradation of oil and gas. Analyses of newly assembled metagenomic data and previously existing genomes from other marine data sets, with metagenomic and metatranscriptomic read recruitment, revealed globally distributed hydrocarbon-degrading marine microbes with clade-specific substrate degradation potentials that have not been previously reported. This new understanding of oil and gas degradation by uncultured marine microbes suggested that the global ocean harbors a diversity of hydrocarbon-degrading bacteria, which can act as primary agents regulating ecosystem health.

Comparative Bioremediation of Tetradecane, Cyclohexanone and Cyclohexane by Filamentous Fungi from Polluted Habitats in Kazakhstan.

Studying the fates of oil components and their interactions with ecological systems is essential for developing comprehensive management strategies and enhancing restoration following oil spill incidents. The potential expansion of Kazakhstan's role in the global oil market necessitates the existence of land-specific studies that contribute to the field of bioremediation. In this study, a set of experiments was designed to assess the growth and biodegradation capacities of eight fungal strains sourced from Kazakhstan soil when exposed to the hydrocarbon substrates from which they were initially isolated. The strains were identified as Aspergillus sp. SBUG-M1743, Penicillium javanicum SBUG-M1744, SBUG-M1770, Trichoderma harzianum SBUG-M1750 and Fusarium oxysporum SBUG-1746, SBUG-M1748, SBUG-M1768 and SBUG-M1769 using the internal transcribed spacer (ITS) region. Furthermore, microscopic and macroscopic evaluations agreed with the sequence-based identification. Aspergillus sp. SBUG-M1743 and P. javanicum SBUG-M1744 displayed remarkable biodegradation capabilities in the presence of tetradecane with up to a 9-fold biomass increase in the static cultures. T. harzianum SBUG-M1750 exhibited poor growth, which was a consequence of its low efficiency of tetradecane degradation. Monocarboxylic acids were the main degradation products by SBUG-M1743, SBUG-M1744, SBUG-M1750, and SBUG-M1770 indicating the monoterminal degradation pathway through β-oxidation, while the additional detection of dicarboxylic acid in SBUG-M1768 and SBUG-M1769 cultures was indicative of the fungus' ability to undertake both monoterminal and diterminal degradation pathways. F. oxysporum SBUG-M1746 and SBUG-M1748 in the presence of cyclohexanone showed a doubling of the biomass with the ability to degrade the substrate almost completely in shake cultures. F. oxysporum SBUG-M1746 was also able to degrade cyclohexane completely and excreted all possible metabolites of the degradation pathway. Understanding the degradation potential of these fungal isolates to different hydrocarbon substrates will help in developing effective bioremediation strategies tailored to local conditions.

Molecular Basis for Chemoselectivity Control in Oxidations of Internal Aryl-Alkenes Catalyzed by Laboratory Evolved P450s.

P450 enzymes naturally perform selective hydroxylations and epoxidations of unfunctionalized hydrocarbon substrates, among other reactions. The adaptation of P450 enzymes to a particular oxidative reaction involving alkenes is of great interest for the design of new synthetically useful biocatalysts. However, the mechanism that these enzymes utilize to precisely modulate the chemoselectivity and distinguishing between competing alkene double bond epoxidations and allylic C-H hydroxylations is sometimes not clear, which hampers the rational design of specific biocatalysts. In a previous work, a P450 from Labrenzia aggregata (P450LA1) was engineered in the laboratory using directed evolution to catalyze the direct oxidation of trans-β-methylstyrene to phenylacetone. The final variant, KS, was able to overcome the intrinsic preference for alkene epoxidation to directly generate a ketone product via the formation of a highly reactive carbocation intermediate. Here, additional library screening along this evolutionary lineage permitted to serendipitously detect a mutation that overcomes epoxidation and carbonyl formation by exhibiting a large selectivity of 94 % towards allylic C-H hydroxylation. A multiscalar computational methodology was applied to reveal the molecular basis towards this hydroxylation preference. Enzyme modelling suggests that introduction of a bulky substitution dramatically changes the accessible conformations of the substrate in the active site, thus modifying the enzymatic selectivity towards terminal hydroxylation and avoiding the competing epoxidation pathway, which is sterically hindered.

Study on optimized culture of microbial strains and their ability in wax removal and viscosity reduction of paraffin-based crude oil

High-viscosity paraffin-based crude oil is prone to wax deposition at low temperatures, hindering development and transportation efficiency while posing safety risks. Microbial technology offers a safe, eco-friendly, and economically viable solution. In this study, strain B-1 is isolated and cultivated optimally using statistical multifactorial synergistic optimization. Species identification reveals strain B-1 to be a new Gram-positive aerobic bacterium. After optimization, strain B-1′s growth activity increases by 11.5 %. Lipopeptide surfactants produced by strain B-1 reduce wax content and viscosity of the crude oil by 37.29 % and 23 %, respectively. It also shows a significant impact on long carbon chain heavy component hydrocarbon substrates, degrading C17-C40 hydrocarbons by 37.93 % on average. Moreover, strain B-1 transforms aggregated wax crystals into dispersed microcrystals, improving flowability. These findings offer a promising solution for enhancing reservoir development efficiency and ensuring pipeline transportation safety.

Influence of heavy Canadian crude oil on pristine freshwater boreal lake ecosystems in an experimental oil spill.

The overall impact of a crude oil spill into a pristine freshwater environment in Canada is largely unknown. To evaluate the impact on the native microbial community, a large-scale in situ model experimental spill was conducted to assess the potential role of the natural community to attenuate hydrocarbons. A small volume of conventional heavy crude oil (CHV) was introduced within contained mesocosm enclosures deployed on the shoreline of a freshwater lake. The oil was left to interact with the shoreline for 72h and then free-floating oil was recovered using common oil spill response methods (i.e. freshwater flushing and capture on oleophilic absorptive media). Residual polycyclic aromatic hydrocarbon (PAH) concentrations returned to near preoiling concentrations within 2 months, while the microbial community composition across the water, soil, and sediment matrices of the enclosed oligotrophic freshwater ecosystems did not shift significantly over this period. Metagenomic analysis revealed key polycyclic aromatic and alkane degradation mechanisms also did not change in their relative abundance over the monitoring period. These trends suggest that for small spills (<2l of oil per 15 m2 of surface freshwater), physical oil recovery reduces polycyclic aromatic hydrocarbon concentrations to levels tolerated by the native microbial community. Additionally, the native microbial community present in the monitored pristine freshwater ecosystem possesses the appropriate hydrocarbon degradation mechanisms without prior challenge by hydrocarbon substrates. This study corroborated trends found previously (Kharey et al. 2024) toward freshwater hydrocarbon degradation in an environmentally relevant scale and conditions on the tolerance of residual hydrocarbons in situ.

The effect of ancillary ligands on hydrocarbon C-H bond functionalization by uranyl photocatalysts.

The aqueous uranyl dication has long been known to facilitate the UV light-induced decomposition of aqueous VOCs (volatile organic compounds), via the long-lived highly efficient, uranyl excited state. The lower-energy visible light excited uranyl ion is also able to cleave unactivated hydrocarbon C-H bonds, yet the development of this reactivity into controlled and catalytic C-H bond functionalization is still in its infancy, with almost all studies still focused on uranyl nitrate as the precatalyst. Here, hydrocarbon-soluble uranyl nitrate and chloride complexes supported by substituted phenanthroline (Ph2phen) ligands are compared to each other, and to the parent salts, as photocatalysts for the functionalization of cyclooctane by H atom abstraction. Analysis of the absorption and emission spectra, and emission lifetimes of Ph2phen-coordinated uranyl complexes demonstrate the utility of the ligand in light absorption in the photocatalysis, which is related to the energy and kinetic decay profile of the uranyl photoexcited state. Density functional theory computational analysis of the C-H activation steps in the reaction show how a set of dispersion forces between the hydrocarbon substrate and the Ph2phen ligand provide control over the H atom abstraction, and provide predictions of selectivity of H atom abstraction by the uranyl oxo of the ring C-H over the ethyl C-H in an ethylcyclohexane substrate.

Reinforced Membranes with PTFE Matrix and Sulfonated Hydrocarbon Electrolyte for PEM Fuel Cells

Proton exchange membrane fuel cells (PEMFCs) have emerged as a promising technology for clean energy conversion with various potential applications. Due to its cost-effectiveness, sulfonated hydrocarbon has been researched as an alternative to Nafion, a commercial proton exchange membrane. However, sulfonated hydrocarbon's mechanical and chemical stability remains a critical challenge that needs to be addressed, as the membrane must withstand harsh operating conditions, such as wet-dry mechanisms in high-temperature operations. To compete with perfluorosulfonic acid (PFSA), sulfonated hydrocarbon should be reinforced with a polytetrafluoroethylene (PTFE) substrate. However, there are significant issues with incompatibility between sulfonated hydrocarbon and PTFE substrate.To improve the impregnation, simple and reproducible chemical treatment has been developed to enhance the hydrophilicity of PTFE using a mixture of acids and oxidizing agents. Moreover, surfactant was added to increase compatibility and improve impregnation. After the reinforced membrane was fabricated, the membranes were characterized, including their water uptake and dimensional stability. The reinforced membrane also showed superior mechanical properties, including gas permeability, tensile strength, and dynamic mechanical analysis. To evaluate the degree of impregnation, the transparency of the reinforced membrane was checked for haziness and further analyzed with scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) mapping to quantify the impregnation degree. Finally, the performance and durability of the reinforced membrane were measured by single-cell and wet-dry cycling tests.

α-Tertiary Primary Amine Synthesis via Photocatalytic C(sp3)-H Aminoalkylation.

Facile access to sterically hindered α-tertiary primary amines via photocatalytic radical coupling of native C(sp3)-H substrates with N-unsubstituted ketimines is reported. LiBr was used as a hydrogen atom transfer reagent to cleave C(sp3)-H bonds to get alkyl radicals. The in situ-generated HBr can then serve as a Bronsted acid to activate N-unsubstituted ketimines readily for single-electron reduction to deliver α-amino radicals. As a consequence, radical-radical coupling affords primary amines with a congested α-tertiary substituent. This reaction is highlighted by simple and mild conditions, 100% atom-economy, and broad hydrocarbon substrate scope for benzyl ethers, cyclic ethers, benzyl alcohols, alkylarenes, and carbocycles.

HMDB: A curated database of genes involved in hydrocarbon monooxygenation reaction with homologous genes as background

The investigation of hydrocarbon degradation potential of environmental microorganisms is an important research topic, whether for the global carbon cycle or oil pollution remediation. Under aerobic conditions, the microorganisms employ a range of monooxygenases to use hydrocarbons substrates as a source of carbon and energy. With the explosion of sequencing data, mining genes in genomes or metagenomes has become computationally expensive and time-consuming. We proposed the HMDB, which is a professional gene database of hydrocarbon monooxygenases. HMDB contains 38 genes, which encode 11 monooxygenases responsible for the hydroxylation of 8 hydrocarbons. To reduce false positives, the strategy of using homologous genes as background noise was applied for HMDB. We added 10,095 gene sequences of homologous enzymes which took non-hydrocarbons as substrates to HMDB. The classic BLAST method and best-hit strategy were recommended for HMDB usage, but not limited. The performance of HMDB was validated using 264,402 prokaryote genomes from RefSeq and 51 metagenomes from SRA. The results showed that HMDB database had high sensitivity and low false positive rate. We release the HMDB database here, hoping to speed up the process for investigation of hydrocarbon monooxygenases in massive metagenomic data. HMDB is freely available at http://www.orgene.net/HMDB/.

Moving from Fuel to Feedstock

Carbon-hydrogen bond activations and their subsequent functionalisation have long been an important target in chemistry because C–H bonds are ubiquitous throughout nature, making C–H derivatisation reactions highly desirable. The selective and efficient functionalisation of this bond into many more useful carbon-element bonds (for example, C–B, C–Si, C–O and C–S bonds) would have many uses in pharmaceutical and bulk chemical synthesis. Activation of the C–H bond is, however, challenging due to the high strength and low bond-polarity of this bond rendering its cleavage unfavourable. With the correct choice of reagents and systems, especially those utilising directing groups, kinetically and thermodynamically favourable catalytic processes have been developed. However, a key remaining challenge is the development of undirected, intermolecular reactions using catalysts that are both selective and active enough to make useful processes. In this review, the progress towards optimising Group 9 C–H activation catalysts is discussed, particularly focusing on undirected reactions that are kinetically more difficult, starting with a brief history of C–H activation, identifying the importance of auxiliary ligands including the nature of anionic ligand (for example, cyclopentadienyl, indenyl, fluorenyl and trispyrazolylborate) and neutral ligands (such as phosphines, carbonyl, alkenes and N-heterocyclic carbenes (NHCs)) that contribute towards the stability and reactivity of these metal complexes. The tethering of the anionic ligand to strong σ-donating ligands is also briefly discussed. The focus of this review is primarily on the Group 9 metals rhodium and iridium, however, C–H activation using Group 8 and 10 metals are compared where useful. The most recent advances in this field include the development of C–H borylation of many small hydrocarbon substrates such as arenes, heterocycles and n-alkanes as well as the more challenging substrate methane.

Hydrocarbon Oxidation by a Porphyrin-π-Cation Radical Complex.

Heme and chlorin π-cation radical oxidants are widely implicated in biological and synthetic oxidation catalysis. Little insight into the role of π-cation radicals in proton coupled electron transfer (PCET) oxidation is available. We prepared a NiII-porphyrin-π-cation complex ([NiII(P•+)]) and found it to be capable of the oxidation of a variety of simple hydrocarbon substrates. Interestingly, some of the products were hydroxylated, with ([NiII(P•+)]) working in concert with atmospheric O2 to yield hydroxylated hydrocarbons. Kinetic data suggested that the porphyrin-π-cation radical species oxidised substrates via a concerted PCET mechanism, where the nickel porphyrin-π-cation radical accepted the electron, and the proton was transferred to a free anion. Our findings highlight the potential role of π-cation radicals as hydrocarbon activators, demonstrating that porphyrin ligand non-innocence could be a readily manipulated resource for oxidation catalyst development.

Hydrocarbon Oxidation by a Porphyrin‐π‐Cation Radical Complex

AbstractHeme and chlorin π‐cation radical oxidants are widely implicated in biological and synthetic oxidation catalysis. Little insight into the role of π‐cation radicals in proton coupled electron transfer (PCET) oxidation is available. We prepared a NiII‐porphyrin‐π‐cation complex ([NiII(P⋅+)]) and found it to be capable of the oxidation of a variety of simple hydrocarbon substrates. Interestingly, some of the products were hydroxylated, with ([NiII(P⋅+)]) working in concert with atmospheric O2 to yield hydroxylated hydrocarbons. Kinetic data suggested that the porphyrin‐π‐cation radical species oxidised substrates through a concerted PCET mechanism, where the porphyrin‐π‐cation radical accepted the electron, and the proton was transferred to a free anion. Our findings highlight the potential role of π‐cation radicals as hydrocarbon activators, demonstrating that porphyrin ligand non‐innocence could be a readily manipulated resource for oxidation catalyst development.

Photoexcited Nitroarenes as Anaerobic Oxygen Atom Transfer ­Reagents

AbstractApplications of photoexcited nitroarenes have been underdeveloped in organic synthesis. Since early reports on the direct excitation of nitroaromatics with harsh UV light, these synthetically useful reagents have not been tamed for use in modern synthetic chemistry. We have developed practical synthetic protocols for the anaerobic oxidation of hydrocarbon substrates using commercially available nitroarenes as photochemically activated oxidants under visible light. Using this approach, a wide variety of olefins are anaerobically cleaved to their corresponding carbonyls, and aliphatic C–H bonds are hydroxylated to give alcohols. The anaerobic reaction conditions enable oxidatively sensitive functional groups to be tolerated and the employment of visible light makes this method highly sustainable. Mechanistic studies support that the photoexcited nitroarene biradical intermediate is responsible for the oxygen atom transfer events.1 Introduction2 Alkene Cleavage Promoted by Photoexcited Nitroarenes3 Photoinduced Nitroarene-Mediated C–H Hydroxylation4 Conclusions

Quantification of biodegradation rate of hydrocarbons in a contaminated aquifer by CO2 δ13C monitoring at ground surface

Ground surface analysis of CO2 emissions with δ13C determination is experimentally demonstrated to be a potential methodology to monitor, on line, the dynamics of petroleum-hydrocarbon biodegradation in soil aquifers, thanks to the improvement of the Isotopic Ratio Infra Red Spectroscopy technique. Biodegradation rate of remaining hydrocarbon substrates in groundwater can be quantified using basic application of the Rayleigh equations, by δ13CCO2 analysis released at ground surface above the pollution plume instead of usual approaches based on groundwater hydrocarbons δ13C analysis, when physical and chemical properties for the contaminated site meet appropriate conditions.The validation approach for that gasoline contaminated specific site is discussed and verified by comparison of first order attenuation rate constant determined from δ13CCO2 analysis emitted at ground surface and from δ13CTOLUENE analysis in ground water. A kinetic fractionation factor α of 0.9979 (or ε value of −2.1 ± 0.5‰) is estimated for the biodegradation of the most reactive hydrocarbon substrates (TEX). The treatment of this Rayleigh equations by linear regression of δ13CCO2 values along the predominant direction of groundwater flow leads to the following results and conclusions for that site: (i) first order biodegradation rate constants (and annual variation) are maximum after the activation of a Permeable Reactive Barrier (PRB) in May 2014: 0.92(+0.29–0.17) year−1, and during July and October: 0.46(+0.14–0.09) year−1 and minimum in mid-winter in February 2015: 0.17(+0.05–0.03) year−1, given by the estimation range for ε. These results are in the lower range with reported in literature for similar contaminated sites (1.6–18 year−1) considering natural attenuation under sulfate reducing conditions and (ii) the seasonal variation of the first order biodegradation rate constant is mainly correlated with the seasonal variation of the CO2 flux, where maximum values are in summers and minimum values in winters. Both seasonal variations are mainly due to the annual cycle of the natural biodegradation activity at the scale of the pollution plume, rather than the activation of the PRB.This work demonstrates that δ13CCO2 analysis released at ground surface from biodegradation of groundwater hydrocarbons could provide, under characterized and appropriate conditions, a non-intrusive (without soil samplings), fast, and low-cost online method to monitor and therefore to optimize soil remediation processes in real time. (Monitored Natural Attenuation or Enhanced Bioremediation).

Antibacterial and antibiofilm potential of Lacticaseibacillus rhamnosus YT and its cell-surface extract

BackgroundFoodborne pathogens and spoilage bacteria survived in the biofilm pose a serious threat to food safety and human health. It is urgent to find safe and effective methods to control the planktonic bacteria as well as the biofilm formation. Substances with antibacterial and antibiofilm activity found in lactic acid bacteria were mainly metabolites secreted in the cell-free supernatant. Previously, Lacticaseibacillus rhamnosus YT was isolated because its cell pellets displayed distinguished antibacterial activity under neutral conditions. This study aimed to investigate the antibacterial and antibiofilm properties of the L. rhamnosus YT cells and its crude cell-surface extract.ResultsThe antibacterial activity of the L. rhamnosus YT cells constantly increased with cells growth and reached the peak value after the cells grew into stationary phase. After cocultivation with the L. rhamnosus YT cells, the biofilm formation of B. subtilis and S. enterica was reduced. The antibacterial activity of the L. rhamnosus YT cells was varied along with various culture conditions (carbon sources, nitrogen sources, medium pH and cultural temperatures) and the antibacterial intensity (antibacterial activity per cell) was disproportional to the biomass. Furthermore, the cell-surface extract was isolated and displayed broad antimicrobial spectrum with a bacteriostatic mode of action. The antibiofilm activity of the extract was concentration-dependent. In addition, the extract was stable to physicochemical treatments (heat, pH and protease). The extract performed favorable emulsifying property which could reduce the water surface tension from 72.708 mN/m to 51.011 mN/m and the critical micelle concentration (CMC) value was 6.88 mg/mL. Besides, the extract was also able to emulsify hydrocarbon substrates with the emulsification, index (E24) ranged from 38.55% (for n-hexane) to 53.78% (for xylene). The E24 for xylene/extract emulsion was merely decreased by 5.77% after standing for 120 h. The main components of the extract were polysaccharide (684.63 μg/mL) and protein (120.79 μg/mL).ConclusionThe properties of the extract indicated that it might be a kind of biosurfactant. These data suggested that L. rhamnosus YT and the cell-surface extract could be used as an alternative antimicrobial and antibiofilm agent against foodborne pathogens and spoilage bacteria in food industry.

Assessing Earthworm Influence on Remediating Potentials of Soil Micro-Organisms, and Bioavailable Hydrocarbon Pollutant in the Niger Delta, Nigeria

In the Niger Delta region of Nigeria, oil explorations and exploitations abound, causing environmental pollution with serious consequences on soil ecosystem and its biodiversity. In spite of the relationship between microbes and fauna in soil ecosystem, such that both organisms can metabolize certain range of petroleum hydrocarbon substrates with the fauna influencing the remediation potentials of bacteria, yet soil fauna is still not fully considered in bioremediation. The influence of earthworm; Lumbricus terrestris on the remediating potentials of soil bacteria in petroleum hydrocarbon contaminated soils was investigated. Eighteen pots were filled with 700 g of soil each, with nine treated with mixture of 3 levels crude oil and remediated with earthworm, while the other nine had no earthworm. The total petroleum hydrocarbon (TPH), soil physical, nutrient compositions, and TPH degrading bacteria biodiversity were determined before contamination or commencement of study and thirty days after. The results showed a decrease in TPH concentration of 55.58%, 62.57% and 67.07% in 1 ml, 2 ml and 3 ml crude oil contaminated soil, respectively. Species richness and abundance of bacteria organisms increased with high relative abundance in soils remediated with earthworms, hydrocarbon utilizing bacteria increased from less than 0.1 cfu/g to 0.4 cfu/g, and total heterotrophic bacteria 1.6 cfu/g at the end of the study. Earthworms increased rate of remediation potentials of bacteria, such that within 30 days post remediation treatment, 34.14% of reduced concentration was achieved over soil samples without earthworms at 3 ml, and 25.14% at 2 ml concentration. Reduction in pH levels in remediated soils was between 6.39 to 6.17 and 6.74 to 6.72 in unremediated soils, while moisture content was 6.73% to 6.77% unremediated and 5.85% to 6.62% in earthworm remediated soils. Total organic carbon, nitrates in soils inoculated with earthworms were lower in concentration than those without earthworms. Reverse was the case with potassium, phosphate and phosphorous concentrations which were above those without earthworms. Results indicate statistically, significant difference between reduction in TPH in earthworm remediated soils and unremediated soils, pointing out that earthworm is a good candidate for facilitation of bacteria remediation-petroleum hydrocarbon contamination.

Monitoring the degradation of total petroleum hydrocarbon in hydrocarbon impacted site using a consortium of hydrocarbon utilizing bacteria

Bacteria (Hydrocarbon utilizing Bacteria) are ever present in natural history, and they make use of these blends as the origin of carbon and energy, however bacteria with such potential are frequently utilized for bioremediation of fossil fuel polluted earth, and have develop corrective measures against petroleum contaminants, by improving the bonding capacity of their cells changing their exterior mechanism and secreting surface active biomolecule materials to augment contact to objective hydrocarbon substrates. The essence of the study is to examine the degradation of total petroleum hydrocarbon in fossil oil polluted soil matrix using consortium of bacteria in three concentrations. (10%, 1.0% 0.1%. for 16 weeks). Consortium of bacteria used is Bacillus thuringiensis, Bacillus velezensis and Stenotrophomonas species. However result from the Gas chromatography flame induction detector (GC-FID) analysis showed the extent of degradation 10% (948.46±0.07 mg/kg and 2.97±0.01 mg/kg), 1.0% (110.07±0.10 mg/kg and 21.95±0.08 mg/kg) and 0.1% (99.99±0.01 mg/kg and 13.88±0.04), at the initial and final stage of exposure respectively. The study specifies that, augmenting biodegradation prospective via the application of bacterial consortia with several catabolic genes, is practical and possible approach for facilitating the elimination competence of petroleum hydrocarbons from contaminated environments.

Visible-light-driven g-C3N4-doped Co catalyzed oxidation of benzylic hydroxylation of alkyl aromatic hydrocarbons

The functionalization of C(sp3)-H bonds of alkyl aromatic hydrocarbons is an important unit reaction in the petrochemical industry. In this work, a g-C3N4-doped Co photocatalyst was found, which can activate molecular oxygen to oxidize alkyl aromatic hydrocarbons benzylic C(sp3)-H bond hydroxylation at room temperature to prepare alcohol compounds. In the batch reaction system, the product can be obtained without additional free radical initiator and solvent, which is suitable for a variety of alkyl aromatic hydrocarbon substrates. In two different continuous flow strategies, no oxygen environment was required. 2-phenyl-2-propanol (BP) was prepared from cumene (CM) as a substrate, with the selectivity of BP can be increased from 89.3 % to 96.8 % and 97.7 %, respectively, and the reaction time can be shortened from 9 h to 100 min and 165 min. This work demonstrates the advantages of highly active carbon nitride-based photocatalysts in the field of green and sustainable chemistry.

Catalytic Nitrene Transfer by an FeIV -Imido Complex Generated by a Comproportionation Process.

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor.