Anaerobic Degradation of Alkanes by Marine Archaea.

Alkanes are saturated apolar hydrocarbons that range from their simplest form, methane, to high-molecular-weight compounds. Although alkanes were once considered biologically recalcitrant under anaerobic conditions, microbiological investigations have now identified several microbial taxa that can anaerobically degrade alkanes. Here we review recent discoveries in the anaerobic oxidation of alkanes with a specific focus on archaea that use specific methyl coenzyme M reductases to activate their substrates. Our understanding of the diversity of uncultured alkane-oxidizing archaea has expanded through the use of environmental metagenomics and enrichment cultures of syntrophic methane-, ethane-, propane-, and butane-oxidizing marine archaea with sulfate-reducing bacteria. A recently cultured group of archaea directly couples long-chain alkane degradation with methane formation, expanding the range of substrates used for methanogenesis. This article summarizes the rapidly growing knowledge of the diversity, physiology, and habitat distribution of alkane-degrading archaea.

A Family of Hexacopper Phenylsilsesquioxane/Acetate Complexes: Synthesis, Solvent-Controlled Cage Structures, and Catalytic Activity.

Convenient self-assembly synthesis of copper(II) complexes via double (phenylsilsesquioxane and acetate) ligation allows to isolate a family of impressive sandwich-like cage compounds. An intriguing feature of these complexes is the difference in the structure of a pair of silsesquioxane ligands despite identical (Cu6) nuclearity and number (four) of acetate fragments. Formation of particular combination of silsesquioxane ligands (cyclic/cyclic vs condensed/condensed vs cyclic/condensed) was found to be dependent on the synthesis/crystallization media. A combination of Si4-cyclic and Si6-condensed silsesquioxane ligands is a brand new feature of cage metallasilsesquioxanes. A representative Cu6-complex (4) (with cyclic silsesquioxanes) exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. Maximum yield of the products of cyclohexane oxidation attained 30 %. The compound 4 was also tested as catalyst in the Baeyer-Villiger oxidation of cyclohexanone by m-chloroperoxybenzoic acid: maximum yields of 88 % and 100 % of ϵ-caprolactone were achieved upon conventional heating at 50 °C for 4 h and MW irradiation at 70 or 80 °C during 30 min, respectively. It was also possible to obtain the lactone (up to 16 % yield) directly from the cyclohexane via a tandem oxidation/Baeyer-Villiger oxidation reaction using the same oxidant.

Exoproteome analysis of Pseudomonas aeruginosa response to high alkane stress.

Microbial biodegradation serves as an effective approach to treat oil pollution. However, the application of such methods for the degrading long-chain alkanes still encounters significant challenges. Comparative proteomics has extensively studied the intracellular proteins of bacteria that degrade short- and medium-chain alkanes, but the role and mechanism of extracellular proteins in many microorganism remain unclear. To enhance our understanding of the roles of extracellular proteins in the adaptation to long-chain alkanes, a label-free LC-MS/MS strategy was applied for the relative quantification of extracellular proteins of Pseudomonas aeruginosa SJTD-1-M (ProteomeXchange identifier PXD014638). 444 alkane-sentitive proteins were acquired and their cell localization analysis was performed using the Pseudomonas Genome Database. Among them, 111 proteins were found to be located in extracellular or Outer Membrane Vesicles (OMVs). The alkane-induced abundance of 11 extracellular or OMV target proteins was confirmed by parallel reaction monitoring (PRM). Furthermore, we observed that the expression levels of three proteins (Pra, PA2815, and FliC) were associated with the carbon chain length of the added alkane in the culture medium. The roles of these proteins in cell mobility, alkane emulsification, assimilation, and degradation were further discussed. OMVs were found to contain a number of enzymes involved in alkane metabolism, fatty acid beta-oxidation, and the TCA cycle, suggesting their potential as sites for facilitated alkane degradation. In this sense, this exoproteome analysis contributes to a better understanding of the role of extracellular proteins in the hydrocarbon treatment process.

Prospect of Controlled Autoxidation to Produce High-Value Products from the Low-Value Petroleum Fractions.

Substantial amounts of low-value light petroleum fractions and low-value heavy petroleum fractions, such as light naphtha, HVGO, and vacuum residue, are generated during the upgrading and refining of conventional and unconventional petroleum resources. The oil industry emphasizes economic diversification, aiming to produce high-value products from these low petroleum fractions through cost-effective and sustainable methods. Controlled autoxidation (oxidation with air) has the potential to produce industrially important oxygenates, including alcohols, and ketones, from the low-value light petroleum fractions. The produced alcohols can also be converted to olefin through catalytic dehydration. Following controlled autoxidation, the low-value heavy petroleum fractions can be utilized to produce value-added products, including carbon fiber precursors. It would reduce the production cost of a highly demandable product, carbon fiber. This review highlights the prospect of developing an alternative, sustainable, and economic method to produce value-added products from the low-value petroleum fractions following a controlled autoxidation approach.

Genome-Centric Metatranscriptomics Reveals Multiple Co-occurring Routes for Hydrocarbon Degradation in Chronically Contaminated Marine Microbial Mats.

Long-term hydrocarbon pollution is a devious threat to aquatic and marine ecosystems. However, microbial responses to chronic pollution remain poorly understood. Combining genome-centric metagenomic and metatranscriptomic analyses of microbial mat samples that experienced chronic hydrocarbon pollution for more than 80 years, we analyzed the transcriptomic activity of alkane and aromatic hydrocarbon degradation pathways at the population level. Consistent with the fluctuating and stratified redox conditions of the habitat, both aerobic and anaerobic hydrocarbon degradation pathways were expressed by taxonomically and metabolically contrasted lineages including members of Bacteroidiales, Desulfobacteraceae, Pseudomonadales; Alcanivoraceae and Halieaceae populations with (photo)-heterotrophic, sulfur- and organohalide-based metabolisms, providing evidence for the co-occurrence and activity of aerobic and anaerobic hydrocarbon degradation pathways in shallow marine microbial mats. In addition, our results suggest that aerobic alkane degradation in long-term pollution involved bacterial families that are naturally widely distributed in marine habitats, but hydrocarbon concentration and composition were found to be a strong structuring factor of their intrafamily diversity and transcriptomic activities.

History of organic pollution in montane lake Issyk-Kul, Kyrgyzstan, Central Asia, inferred from a sediment core.

In arid regions, montane lakes are valuable water sources and play important ecological roles. However, recent human-induced inputs of organic pollutants are threatening lake ecology in such regions and becoming a matter of great concern. To investigate pollutant histories and sources, we measured polycyclic aromatic hydrocarbons (PAHs) and n-alkanes in a dated sediment core that spans the last ∼350 years, from montane Lake Issyk-Kul (Kyrgyzstan, Central Asia). Results showed that organic pollutants were delivered to Lake Issyk-Kul in four stages and that their concentrations increased from Stage I (∼1670-1800 CE) to Stage IV (∼2000-2010 CE). Furthermore, we tracked the sources of sedimented PAHs using their ratios combined with n-alkanes data. Ratios of PAHs Ant/(Ant + Phe), Flt/(Flt + Pyr) and Bap/BghiP indicated that inputs during Stage II (∼1800-1970 CE) and Stage III (∼1970-2000 CE) came mainly from high-temperature combustion of coal and vehicle emissions. PAHs in Stage I and Stage IV, however, were mainly derived from low-temperature combustion and petrogenic sources. Diagnostic PAH ratios, combined with the natural n-alkane ratio (NAR＜0) and unresolved complex mixtures (UCM), showed that the sources of PAHs in Stage I were mainly from erosion of bedrock and partly influenced by forest wildfires, different from the source during Stage IV, which was mainly from refined petroleum caused by accidental spills. Our assessment of the contamination history of the lake indicates that toxicity risk to the waterbody from sediment PAHs is low, but recent discharges arising from traffic deserve attention.

Beauveria bassiana transcriptomics reveal virulence-associated shifts during insect lipid assimilation.

Insect cuticular lipids, especially epicuticular hydrocarbons (CHC), have a significant role in insect ecology and interactions with other organisms, including fungi. The CHC composition of a specific insect species may influence the outcome of the interaction with a specific fungal strain. Some insects, such as Piezodorus guildinii, have low susceptibility towards fungal infections seemingly due to their CHC composition. The entomopathogenic fungus Beauveria bassiana can assimilate CHC and incorporate them as building blocks via cytochrome P450 monooxygenases (CYPs). However, little is known about other enzymes that promote the degradation/assimilation of these cuticular components. In this study, we performed a transcriptomic analysis to evaluate the in vitro response of two virulence-contrasting B. bassiana strains when grown on three different P. guildinii CHC sources. We found a different expression profile of virulence-related genes, as well as different GO and KEGG parameters enriched at 4 days post-inoculation, which could help account for the intrinsic virulence and for an alkane-priming virulence enhancement effect. The hypovirulent strain predominantly showed higher expression of cuticle penetration genes, including chitinases, proteases, and CYPs, with GO term categories of "heme binding," "monooxygenase activity," and "peroxisome" pathways enriched. The hypervirulent strain showed higher expression of cell wall remodeling and cell cycle genes, and cuticle adhesion and a distinct set of CYPs, with GO categories of "DNA-binding transcription factor activity" and KEGG pathways corresponding to "meiosis-yeast" and "cell cycle" enriched. These results suggest a delay and alternate routes in pathogenicity-related metabolism in the hypovirulent strain in comparison with the hypervirulent strain. KEY POINTS: •Transcriptomics of two B. bassiana strains grown in P. guildinii cuticular components •Virulence-related genes correlated with virulence enhancement towards P. guildinii •Differentially expressed genes, GOs and KEGGs showed different metabolic timelines associated with virulence.

Alkane-translocated cells of Rhodococcus strains utilize dissolved oxygen in the alkane phase of an aqueous-alkane two-phase culture.

To clarify the growth mechanisms of Rhodococcus in the alkane phase, we measured oxygen utilization in the alkane phase. The results showed that dissolved oxygen decreased significantly when viable cells were present in the alkane phase. The findings suggested that Rhodococcus strains can grow in alkanes and utilize the resident dissolved oxygen.

Phytochemistry and Micromorphology of Epicuticular Waxes in Four Juniper Species With Fragmented Distribution in the Balkans.

The cuticle is important in the interaction between the plant and its environment, especially in the dry areas. Four species of junipers from the section Sabina wild growing in the Balkans were selected to study leaf wax composition using GC/MS and GC-FID and its surface morphology under SEM to understand the correlation between the distribution and/or habitat of these species and their cuticles. SEM micrographs showed continuous, smooth epicuticular layers with crusts in all species but with a species-specific distribution of different 3D crystalloid types and different cuticle thickness. n-C33 alkane was the most abundant compound, followed by n-C29, n-C31, and n-C35, depending on the species and the site. The average chain length (N) was the lowest in J. phoenicea, but with the greatest dispersion around it. At the same time, the two most continental species (J. foetidissima and J. excelsa) show the N with the lowest dispersion around it. The statistical analyses confirmed the significance of climate on the evolution of the specific epicuticular wax composition in studied junipers.

Distribution, sources and ecological risks of PAHs and n-alkanes in water and sediments of typically polluted estuaries: Insights from the Xiaoqing River.

Seasonal water and sediment samples were collected from the Xiaoqing River estuary and the neighboring sea to study the spatial and temporal distributions, sources and ecological risks of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes. The results showed significant spatial and temporal differences in the concentrations of PAHs and n-alkanes under the influence of precipitation, temperature, and human activities. The concentrations of PAHs in water were lower in the wet season than in the dry season, and those in sediments were higher in the wet season than in the dry season. The concentrations of n-alkanes were higher in the rainy season than in the dry season for both water and sediments. The spatial distributions of PAHs and n-alkanes were estuarine > offshore. The concentration ranges of ∑PAHs in water and sediments were 230.66-599.86 ng/L and 84.51-5548.62 ng/g, respectively, in the wet season and 192.46-8649.55 ng/L and 23.39-1208.92 ng/g, respectively, in the dry season. The proportion of three-ring PAHs in water (57.03% and 78.27% in the wet and dry seasons, respectively) was high, followed by two-ring PAHs (27.31% and 13.59% in the wet and dry seasons, respectively). The proportion of four-ring PAHs was higher in sediments (24.79% and 32.20% in the wet and dry seasons, respectively). The ecological risk of PAHs assessed using the toxicity equivalent quotient and risk quotient was at moderate to moderately high risk levels. The high concentration of n-alkane fraction C16 (611.65-75594.58 ng/L) in the water is indicative of petroleum or other fossil fuel inputs. The main peaks of n-alkanes in river sediments were C27, C29 and C31, indicating higher inputs of plant sources. The sediments in the estuary showed dominance of both short-chain C16 and long-chain C25-C31, indicating a combined input of higher plants and petroleum. The diagnostic ratios of PAHs and n-alkanes indicated that their sources were mainly oil/coal/biomass combustion and petroleum spills attributed to frequent vehicular, vessel and mariculture activities. Given the potential ecological risks of PAHs and n-alkanes in water and sediments, future studies should focus on their bioaccumulation and biotoxicity.

A Low-Noble-Metal Ru@CoMn2O4 Spinel Catalyst for the Efficient Oxidation of Propane.

Noble metals have become a research hotspot for the oxidation of light alkanes due to their low ignition temperature and easy activation of C-H; however, sintering and a high price limit their industrial applications. The preparation of effective and low-noble-metal catalysts still presents profound challenges. Herein, we describe how a Ru@CoMn2O4 spinel catalyst was synthesized via Ru in situ doping to promote the activity of propane oxidation. Ru@CoMn2O4 exhibited much higher catalytic activity than CoMn2O4, achieving 90% propane conversion at 217 °C. H2-TPR, O2-TPD, and XPS were used to evaluate the catalyst adsorption/lattice oxygen activity and the adsorption and catalytic oxidation capacity of propane. It could be concluded that Ru promoted synergistic interactions between cobalt and manganese, leading to electron transfer from the highly electronegative Ru to Co2+ and Mn3+. Compared with CoMn2O4, 0.1% Ru@CoMn2O4, with a higher quantity of lattice oxygen and oxygen mobility, possessed a stronger capability of reducibility, which was the main reason for the significant increase in the activity of Ru@CoMn2O4. In addition, intermediates of the reaction between adsorbed propane and lattice oxygen on the catalyst were monitored by in situ DRIFTS. This work highlights a new strategy for the design of a low-noble-metal catalyst for the efficient oxidation of propane.

Study on the changes and transformation characteristics of intermediate liquid products in hydrogen sulfide production from lignite degraded by sulfate-reducing bacteria.

The changes and transformation laws of intermediate liquid-phase products during the anaerobic degradation of lignite by sulfate-reducing bacteria in the formation of hydrogen sulfide play an important role in supplementing and improving the existing theories on the genesis of hydrogen sulfide gas in coal mines. In this paper, H2S gas and key intermediate liquid-phase products produced during the anaerobic degradation of lignite by sulfate-reducing bacteria were detected and analyzed by gas chromatography and gas chromatography-mass spectrometry. The results showed that the process of hydrogen sulfide production from lignite degradation by sulfate-reducing bacteria can be roughly divided into four stages: slow production phase, rapid growth phase, steady production phase, and slight decline phase. In this reaction system, the SO42- concentration showed a decreasing trend, the pH value showed an increasing trend, and the ORP value decreased and then slightly increased with time. Ten volatile component types were detected during the experiment: straight-chain alkanes, branched-chain alkanes, alcohols, aldehydes, ketones, olefins, amines, lipids, acids and phenols. The key components in the intermediate liquid phase products were straight chain alkanes, straight chain alkanes, acids, alcohols, phenols and amines. PAHs, alkanes, and phenols are closely related to H2S production, while amides stimulate nitrogen production. The process is divided into three stages: hydrolysis stage, H2S gas production stage, and decay stage. Liquid-phase intermediates play an important role in the formation process of coal mine BSR hydrogen sulfide and the mechanism of coal mine H2S genesis.

Abiotic/Biotic Stress and Substrate Dictated Metabolic Diversity of Azotobacter Chroococcum: Synthesis of Alginate, Antifungal n-Alkanes, Lactones, and Indoles.

The current paper deals with new metabolites of different groups produced by Azotobacter chroococcum XU1. The strain's metabolic diversity is strongly altered by different factors, and some secondary metabolites are being reported for the first time for this species. As an abiotic/biotic stress response, the strain produced a broad spectrum of indole ring-containing compounds, n-alkanes (eicosane, heneicosane, docosane, tetracosane, and hexacosane), alkanes (7-hexyl eicosane and 2-methyloctacosane), saturated fatty acids (hexanoic and octanoic acids), esters (hexadecanoic acid methyl and pentadecanoic acid-14-methyl-methyl esters), and amides (9-Octadecenamide, (Z)- and 13-Docosenamide, (Z)-). Furthermore, to mitigate the abiotic stress the strain actively produced exopolysaccharide (EPS) to biosorb the Na+ ions. Apart from these metabolites, A. chroococcum XU1 synthesized lactones, namely 1,5-d-gluconolactone and d, l-mevalonic acid lactone in response to carbon source modification. Supplementary Information: The online version contains supplementary material available at 10.1007/s12088-024-01212-x.

Cross-Coupling of Gaseous Alkanes with (Hetero)Aryl Bromides via Dual Nickel/Photoredox Catalysis.

Gaseous alkanes represent the most abundant carbon-based chemical feedstocks in our planet. However, the intrinsic inertness of their C-H bonds has rendered the use of these alkanes very difficult for purposes beyond aerobic combustion and energy intensive processes. Thus, clean and energy-efficient transformations for their use in synthetic organic chemistry are still rare. Here we report a catalytic methodology for the direct cross-coupling of gaseous alkanes with (hetero)aryl bromides through the combination of metallaphotoredox-mediated hydrogen atom transfer and nickel catalysis. This protocol provides an efficient platform for the addition of short alkyl groups into diverse (hetero) aromatic rings, providing a wide range of high-value alkyl(hetero)arenes, and bypassing the longstanding need of using preactivated alkylating agents in C(sp2)-C(sp3) cross-couplings. The method features high chemoselectivity, regioselectivity and a remarkable functional group tolerance, operates under mild conditions, and exhibits operational simplicity.

C1-4 Alkylation of Aryl Bromides with Light Alkanes enabled by Metallaphotocatalysis in Flow.

The homologous series of gaseous C1-4 alkanes represents one of the most abundant sources of short alkyl fragments. However, their application in synthetic organic chemistry is exceedingly rare due to the challenging C-H bond cleavage, which typically demands high temperatures and pressures, thereby limiting their utility in the construction of complex organic molecules. In particular, the formation of C(sp2)-C(sp3) bonds is crucial for constructing biologically active molecules, including pharmaceuticals and agrochemicals. In this study, we present the previously elusive coupling between gaseous alkanes and (hetero)aryl bromides, achieved through a combination of Hydrogen Atom Transfer (HAT) photocatalysis and nickel-catalyzed cross coupling at room temperature. Utilizing flow technology allowed us to conduct this novel coupling reaction with reduced reaction times and in a scalable fashion, rendering it practical for widespread adoption in both academia and industry. Density Functional Theory (DFT) calculations unveiled that the oxidative addition constitutes the rate-determining step, with the activation energy barrier increasing with smaller alkyl radicals. Furthermore, radical isomerization observed in propane and butane analogues could be attributed to the electronic properties of the bromoarene coupling partner, highlighting the crucial role of oxidative addition in the observed selectivity of this transformation.

Chloride and Hydride Transfer as Keys to Catalytic Upcycling of Polyethylene into Liquid Alkanes.

Transforming polyolefin waste into liquid alkanes through tandem cracking-alkylation reactions catalyzed by Lewis-acid chlorides offers an efficient route for single-step plastic upcycling. Lewis acids in dichloromethane establish a polar environment that stabilizes carbenium ion intermediates and catalyzes hydride transfer, enabling breaking of polyethylene C-C bonds and forming C-C bonds in alkylation. Here, we show that efficient and selective deconstruction of low-density polyethylene (LDPE) to liquid alkanes is achieved with anhydrous aluminum chloride (AlCl3) and gallium chloride (GaCl3). Already at 60 °C, complete LDPE conversion was achieved, while maintaining the selectivity for gasoline-range liquid alkanes over 70 %. AlCl3 showed an exceptional conversion rate of 5000 g L D P E m o l c a t - 1 h - 1 ${{{\rm g}}_{{\rm L}{\rm D}{\rm P}{\rm E}}{{\rm \ }{\rm m}{\rm o}{\rm l}}_{{\rm c}{\rm a}{\rm t}}^{-1}{{\rm \ }{\rm h}}^{-1}}$ , surpassing other Lewis acid catalysts by two orders of magnitude. Through kinetic and mechanistic studies, we show that the rates of LDPE conversion do not correlate directly with the intrinsic strength of the Lewis acids or steric constraints that may limit the polymer to access the Lewis acid sites. Instead, the rates for the tandem processes of cracking and alkylation are primarily governed by the rates of initiation of carbenium ions and the subsequent intermolecular hydride transfer. Both jointly control the relative rates of cracking and alkylation, thereby determining the overall conversion and selectivity.

"Magic Numbers" in Self-Faceting of Alcohol-Doped Emulsion Droplets.

Oil-in-water emulsion droplets spontaneously adopt, below some temperature Td , counterintuitive faceted and complex non-spherical shapes while remaining liquid. This transition is driven by a crystalline monolayer formed at the droplets' surface. Here, we show that ppm-level doping of the droplet's bulk by long-chain alcohols allows tuning Td by >50 °C, implying formation of drastically different interfacial structures. Furthermore, "magic" alcohol chain lengths maximize Td . This we show to arise from self-assembly of mixed alcohol:alkane interfacial structures of stacked alkane layers, co-crystallized with hydrogen-bonded alcohol dimers. These structures are accounted for theoretically and resolved by direct cryogenic transmission electron microscopy (cryoTEM), confirming the proposed structures. The discovered tunability of key properties of commonly-used emulsions by minute concentrations of specific bulk additives should benefit these emulsions' technological applicability.

Tree tobacco (Nicotiana glauca) cuticular wax composition is essential for leaf retention during drought, facilitating a speedy recovery following rewatering.

Despite decades of extensive study, the role of cuticular lipids in sustaining plant fitness is far from being understood. We utilized genome-edited tree tobacco (Nicotiana glauca) to investigate the significance of different classes of epicuticular wax in abiotic stress such as cuticular water loss, drought, and light response. We generated mutants displaying a range of wax compositions. Four wax mutants and one cutin mutant were extensively investigated for alterations in their response to abiotic factors. Although the mutations led to elevated cuticular water loss, the wax mutants did not display elevated transpiration or reduced growth under nonstressed conditions. However, under drought, plants lacking alkanes were unable to reduce their transpiration, leading to leaf death, impaired recovery, and stem cracking. By contrast, plants deficient in fatty alcohols exhibited elevated drought tolerance, which was part of a larger trend of plant phenotypes not clustering by a glossy/glaucous appearance in the parameters examined in this study. We conclude that although alkanes have little effect on whole N. glauca transpiration and biomass gain under normal, nonstressed conditions, they are essential during drought responses, since they enable plants to seal their cuticle upon stomatal closure, thereby reducing leaf death and facilitating a speedy recovery.

Tuning the Mechanism of H/D Exchange for Isobutane on H-BEA by Loading Zn Species in Zeolite.

Kinetics of H/D hydrogen exchange between deuterated isobutane-d10 and Brønsted acid sites (BAS) of three zeolite samples (H-BEA, ZnO/H-BEA, Zn2+ /H-BEA) were monitored with 1 H MAS NMR in situ at 343-468 K. The regioselective H/D exchange in the methyl groups detected on H-BEA can be rationalized in terms of the mechanism of indirect exchange, which involves protonation of the intermediate olefin and further hydride abstraction from the other alkane molecule by the formed carbenium ion. Loading of Zn species in the zeolite results in a decrease of the rate and an increase of the activation energy of the exchange. The loaded Zn species provide the tuning effect on the reaction occurrence, changing the mechanism from the indirect one to the mechanism of the direct exchange.

Theoretical Study of the Hydroxyl-Radical-Initiated Degradation Mechanism, Kinetics, and Subsequent Evolution of Methyl and Ethyl Iodides in the Atmosphere.

The degradation and transformation of iodinated alkanes are crucial in the iodine chemical cycle in the marine boundary layer. In this study, MP2 and CCSD(T) methods were adopted to study the atmospheric transformation mechanism and degradation kinetic properties of CH3 I and CH3 CH2 I mediated by ⋅OH radical. The results show that there are three reaction mechanisms including H-abstraction, I-substitution and I-abstraction. The H-abstraction channel producing ⋅CH2 I and CH3 C ⋅ HI radicals are the main degradation pathways of CH3 I and CH3 CH2 I, respectively. By means of the variational transition state theory and small curvature tunnel correction method, the rate constants and branching ratios of each reaction are calculated in the temperature range of 200-600 K. The results show that the tunneling effect contributes more to the reaction at low temperatures. Theoretical reaction rate constants of CH3 I and CH3 CH2 I with ⋅OH are calculated to be 1.42×10-13 and 4.44×10-13  cm3 molecule-1 s-1 at T=298 K, respectively, which are in good agreement with the experimental values. The atmospheric lifetimes of CH3 I and CH3 CH2 I are evaluated to be 81.51 and 26.07 day, respectively. The subsequent evolution mechanism of ⋅CH2 I and CH3 C ⋅ HI in the presence of O2 , NO and HO2 indicates that HCHO, CH3 CHO, and I-atom are the main transformation end-products. This study provides a theoretical basis for insight into the diurnal conversion and environmental implications of iodinated alkanes.