Distribution characteristics and microbial synergistic degradation potential of polyethylene and polypropylene in freshwater estuarine sediments.

The microbial degradation of polyethylene (PE) and polypropylene (PP) resins in rivers and lakes has emerged as a crucial issue in the management of microplastics. This study revealed that as the flow rate decreased longitudinally, ammonia nitrogen (NH4+-N), heavy fraction of organic carbon (HFOC), and small-size microplastics (< 1 mm) gradually accumulated in the deep and downstream estuarine sediments. Based on their surface morphology and carbonyl index, these sediments were identified as the potential hot zone for PE/PP degradation. Within the identified hot zone, concentrations of PE/PP-degrading genes, enzymes, and bacteria were significantly elevated compared to other zones, exhibiting strong intercorrelations. Analysis of niche differences revealed that the accumulation of NH4+-N and HFOC in the hot zone facilitated the synergistic coexistence of key bacteria responsible for PE/PP degradation within biofilms. The findings of this study offer a novel insight and comprehensive understanding of the distribution characteristics and synergistic degradation potential of PE/PP in natural freshwater environments.

Interaction patterns and keystone taxa of bacterial and eukaryotic communities during sulfamethoxazole mineralization in lake sediment.

Sulfamethoxazole (SMX) is a common antibiotic pollutant in aquatic environments, which is highly persistent under various conditions and significantly contributes to the spread of antibiotic resistance. Biodegradation is the major pathway to eliminate antibiotics in the natural environment. The roles of bacteria and eukaryotes in the biodegradation of antibiotics have received considerable attention; however, their successions and co-occurrence patterns during the biodegradation of antibiotics remain unexplored. In this study, 13C-labled SMX was amended to sediment samples from Zhushan Bay (ZS), West Shore (WS), and Gonghu Bay (GH) in Taihu Lake to explore the interplay of bacterial and eukaryotic communities during a 30-day incubation period. The cumulative SMX mineralization on day 30 ranged from 5.2 % to 19.3 %, which was the highest in WS and the lowest in GH. The bacterial community showed larger within-group interactions than between-group interactions, and the positive interactions decreased during incubation. However, the eukaryotic community displayed larger between-group interactions than within-group interactions, and the positive interactions increased during incubation. The proportion of negative interactions between bacteria and eukaryotes increased during incubation. Fifty genera (including 46 bacterial and 4 eukaryotic genera) were identified as the keystone taxa due to their dominance in the co-occurrence network and tolerance to SMX. The cumulative relative abundance of these keystone taxa significantly increased during incubation and was consistent with the SMX mineralization rate. These taxa closely cooperated and played vital roles in co-occurrence networks and microbial community interactions, signifying their crucial role in SMX mineralization. These findings broadened our understanding of the complex interactions of microorganisms under SMX exposure and their potential functions during SMX mineralization, providing valuable insights for in situ bioremediation.

DNDMH-mediated direct nitration of aryl alkenes.

N-nitro type reagents have been demonstrated as mild nitration tools in recent years. This work presents an exploration of direct nitration of aryl alkenes mediated by DNDMH, a novel N-nitro type reagent developed in our previous study. It exhibits herein a new property of DNDMH as an effective direct nitration reagent for aryl alkenes, through probably the delivery of nitro radicals with the aid of TEMPO and Cu(OAc)2.

Transition of organic matter from allochthonous to autochthonous alters benthic nutrient dynamics via microbial food webs.

The impoundment of rivers by dams has significantly modified sedimentation patterns and trophic structures. As a result, the algal-derived organic matter (OM), as opposed to terrestrial-derived OM, plays an increasingly important role along the river-reservoir gradient. This study utilized water-sediment microcosms to explore the impacts of allochthonous and autochthonous OM deposition on benthic nutrient dynamics mediated by microbial food webs. Our results revealed that OM addition led to increased fluxes of NH4+ and CO2, with the highest flux induced by cyanobacteria OM, followed by diatom and allochthonous OM. N2 release flux was promoted by allochthonous and diatom OM deposition but inhibited by cyanobacteria OM deposition. The amendment of autochthonous OM increased the activity of dehydrogenase and urease, while allochthonous OM with a higher C/N ratio enhanced the catalytic abilities of polyphenol oxidase and ß-glucosidase. Furthermore, OM deposition significantly reduced microbial community richness and diversity, except for eukaryotic richness, and induced pronounced changes in bacterial and eukaryotic community structures. Allochthonous OM deposition stimulated the utilization of bacteria and protozoan on native OM, resulting in a positive priming effect of 26.78 %. In contrast, diatom and cyanobacteria OM additions exerted negative priming effects of -44.53 % and -29.76 %, respectively. Bayesian stable isotope mixing models showed that diatom OM was primarily absorbed by protozoan and metazoan, while cyanobacteria OM was more easily decomposed by bacteria and transferred to higher trophic levels through microbial food webs. In addition, bacterial ammonification accounted for 74.5 % of NH4+ release in the allochthonous OM deposition treatment, whereas eukaryotic excretion contributed separately 83.3 % and 83.1 % to NH4+ release in the diatom and cyanobacteria OM addition treatments. These findings highlight the significance of accounting for the regulatory capacity of OM deposition when studying benthic metabolism within river-reservoir systems.

Influence of rapid vertical mixing on bacterial community assembly in stratified water columns.

Water column mixing homogenizes thermal and chemical gradients which are known to define distribution of microbial communities and influence the prevailing biogeochemical processes. Little is however known about the effects of rapid water column mixing on the vertical distribution of microbial communities in stratified reservoirs. To address this knowledge gap, physicochemical properties and microbial community composition from 16 S rRNA amplicon sequencing were analyzed before and after mixing of vertically stratified water-column bioreactors. Our results showed that α-diversity of bacterial communities decreased from bottom to surface during periods of thermal stratification. After an experimental mixing event, bacterial community diversity experienced a significant decrease throughout the water column and network connectivity was disrupted, followed by slow recovery. Significant differences in composition were seen for both total (DNA) and active (RNA) bacterial communities when comparing surface and bottom layer during periods of stratification, and when comparing samples collected before mixing and after re-stratification. The dominant predicted community assembly processes for stratified conditions were deterministic while such processes were less important during recovery from episodic mixing. Water quality characteristics of stratified water were significantly correlated with bacterial community diversity and structure. Furthermore, structural equation modeling analyses showed that changes in sulfur may have the greatest direct effect on bacterial community composition. Our results imply that rapid vertical mixing caused by episodic weather extremes and hydrological operations may have a long-term effect on microbial communities and biogeochemical processes.

Climate and local environment co-mediate the taxonomic and functional diversity of bacteria and archaea in the Qinghai-Tibet Plateau rivers.

Understanding the environmental response patterns of riverine microbiota is essential for predicting the potential impact of future environmental change on river ecosystems. Vulnerable plateau ecosystems are particularly sensitive to climate and local environmental changes, however, the environmental response patterns of the taxonomic and functional diversity of riverine microbiota remain unclear. Here, we conducted a systematic investigation of the taxonomic and functional diversity of bacteria and archaea from riparian soils, sediments, and water across the elevation of 1800- 4800 m in the Qinghai-Tibet Plateau rivers. We found that within the elevation range of 1800 to 3800 m, riparian soils and sediments exhibited similarities and stabilities in microbial taxonomic and functional diversity, and water microbiomes were more sensitive with great fluctuations in microbial diversity. Beyond the elevation of 3800 m, microbial diversity declined across all riverine matrixes. Local environmental conditions can influence the sensitivity of microbiomes to climate change. The combination of critical climate and local environmental factors, including total nitrogen, total organic carbon, as well as climate variables associated with temperature and precipitation, provided better explanations for microbial diversity than single-factor analyses. Under the extremely adverse scenario of high greenhouse gas emission concentrations (SSP585), we anticipate that by the end of this century, the bacterial, archaeal, and microbial functional diversity across the river network of the Yangtze and Yellow source basin would potentially change by -16.9- 5.2 %, -16.1- 5.7 %, and -9.3- 6.4 %, respectively. Overall, climate and local environments jointly shaped the microbial diversity in plateau river ecosystems, and water microbiomes would provide early signs of environmental changes. Our study provides effective theoretical foundations for the conservation of river biodiversity and functional stability under environmental changes.

Enantioselective Total Synthesis of (-)-Cephalotanin B.

Cephalotaxus diterpenoids are attractive natural products with intriguing molecular frameworks and promising biological features. As a structurally unusual member, (-)-cephalotanin B possesses an extraordinarily congested heptacyclic skeleton, three lactone units, and nine consecutive stereocenters. Herein, we report an enantioselective total synthesis of (-)-cephalotanin B based on a divergent asymmetric Michael addition reaction, a novel Pauson-Khand/deacyloxylation process discovered in the development of a second-generation stereoselective Pauson-Khand reaction protocol, and an epoxide-opening/elimination/dual-lactonization cascade to construct the challenging propeller-shaped A-B-C ring system as key transformations.

Geological challenges and stabilization strategies for phyllite rock slopes: a case study of Guang-Gansu expressway in Western China.

The increased occurrence and severity of natural disasters, such as landslides, have impacted the stability of phyllite rock slopes in the complex geological regions of Western China. This situation presents significant challenges for infrastructure development in the area. This study investigates the upper span bridgehead slope of Guang-Gansu expressway K550 + 031 as a case study to analyze the sliding failure mechanism of thousand rock slopes in the seismic fault zone and the supporting structure failure through field investigation and exploration. The analysis shows that the slope's rock mass is extensively fractured, primarily influenced by the Qingchuan fault zone. This geological activity leads to slope instability, worsened by seasonal rainfall. The phyllite undergoes alternating dry and wet cycles, weakening its mechanical strength, forming cracks, and accelerating slope displacement, subsidence, and cracking. This results in front slope instability, followed by gradual backward and step-by-step traction sliding deformation on both sides. The geological structure and seasonal rainfall damage the original bolt-grid beam-supporting structure. To address this issue, an anti-slide pile combined with a grid beam treatment method is proposed, and its effectiveness is verified through deep displacement monitoring. This study emphasizes the significance of integrating geological structure and seasonal rainfall impacts into infrastructure design within complex geological areas, ensuring slope and supporting structure stability.

Unraveling antibiotic resistomes associated with bacterial and viral communities in intertidal mudflat aquaculture area.

The extensive use of antibiotics in intertidal mudflat aquaculture area has substantially increased the dissemination risk of antibiotic resistance genes (ARGs). As hosts of ARGs, bacteria and virus exert vital effects on ARG dissemination. However, the insights for the interrelationships among ARGs, bacteria, and virus have not been thoroughly explored in intertidal mudflat. Therefore, this study attempts to unravel the occurrence, dissemination, evolution, and driving mechanisms of ARGs associated with bacterial and viral communities using metagenomic sequencing in a typical intertidal mudflat. Abundant and diverse ARGs (22 types and 437 subtypes) were identified and those of ARGs were higher in spring than in autumn. It is worthy noted that virus occupied a more essential position than bacteria for ARGs dissemination through network analysis. Meanwhile, nitrogen exerted indirect effect on ARG profiles by shaping viral and bacterial diversity. According to the results of neutral and null models, deterministic processes dominated the ARG community assembly by controlling sediment nitrogen and antibiotics. Homogeneous and variable selection dominated phylogenetic turnover of ARG community, contributing 46.15% and 45.90% of the total processes, respectively. This study can hence theoretically support for the ARG pollution control and management in intertidal mudflat aquaculture area.

How nutrient loading leads to alternative stable states in microbially mediated N-cycle pathways: A new insight into bioavailable nitrogen removal in urban rivers.

Excessive nutrients have disrupted pathways of microbial-mediated nitrogen (N) cycle in urban rivers and caused bioavailable N to accumulate in sediments, while remedial actions sometimes fail to recover degraded river ecosystems even when environmental quality has been improved. It is not sufficient to revert the ecosystem to its original healthy state by restoring the pre-degradation environmental conditions, as explained by alternative stable states theory. Understanding the recovery of disrupted N-cycle pathways from the perspective of alternative stable states theory can benefit effective river remediation. Previous studies have found alternative microbiota states in rivers; however, the existence and implications of alternative stable states in microbial-mediated N-cycle pathway remain unclear. Here, high-throughput sequencing and N-related enzyme activities measurement were combined in the field investigation to provide empirical evidence for the bi-stability in microbially mediated N-cycle pathways. According to the behavior of bistable ecosystems, the existence of alternative stable states in microbial-mediated N-cycle pathway have been shown, and nutrient loading, mainly total nitrogen and total phosphorus, were identified as key driver of regime shifts. In addition, potential analysis revealed that reducing nutrient loading shifted the N-cycle pathway to a desirable state characterized by high ammonification and nitrification, probably avoiding the accumulation of ammonia and organic N. It should be noted that the improvement of microbiota status can facilitate the recovery of the desirable pathway state according to the relationship between microbiota states and N-cycle pathway states. Keystone species, including Rhizobiales and Sphingomonadales, were discerned by network analysis, and the increase in their relative abundance may facilitate the improvement of microbiota status. The obtained results suggested that the nutrient reduction should be combined with microbiota management to benefit the bioavailable N removal in urban rivers, therefore providing a new insight into alleviating adverse effects of the nutrient loading on urban rivers.

Responses of bacterial community and N-cycling functions stability to different wetting-drying alternation frequencies in a riparian zone.

Wetting-drying alternation (WD) of the soil is one of the key characteristics of riparian zones shaped by dam construction, profoundly impacting the soil microenvironment that determines the bacterial community. Knowledge concerning the stability of bacterial community and N-cycling functions in response to different frequencies of WD remains unclear. In this study, samples were taken from a riparian zone in the Three Gorges Reservoir (TGR) and an incubation experiment was conducted including four treatments: constant flooding (W), varied wetting-drying alternation frequencies (WD1 and WD2), and constant drying (D) (simulating water level of 145 m, 155 m, 165 m, and 175 m in the riparian zone respectively). The results revealed that there was no significant difference in the diversity among the four treatments. Following the WD1 and WD2 treatments, the relative abundances of Proteobacteria increased, while those of Chloroflexi and Acidobacteriota decreased compared to the W treatment. However, the stability of bacterial community was not affected by WD. Relative to the W treatment, the stability of N-cycling functions estimated by resistance, which refers to the ability of functional genes to adapt to changes in the environment, decreased following the WD1 treatment, but showed no significant change following the WD2 treatment. Random forest analysis showed that the resistances of the nirS and hzo genes were core contributors to the stability of N-cycling functions. This study provides a new perspective for investigating the impacts of wetting-drying alternation on soil microbes.

Diversity, abundance and distribution characteristics of potential polyethylene and polypropylene microplastic degradation bacterial communities in the urban river.

Carbon chain microplastics, polyethylene (PE), and polypropylene (PP) are the main types of refractory organics. Compared to heterochain microplastics, PE/PP degrading bacterial community and their distribution characteristics in natural rivers are unclear. In this study, the field in situ experiment and indoor enrichment experiment with PE/PP resin as only carbon sources were conducted for a total period of 1150 days. The microbial degradation of pure PE/PP resin was determined by SEM, FTIR, CLSM, GC-MS, and GPC. The Chao 1 index and Invsimpson index of the bacterial community significantly reduced after a series of incubation, demonstrating that the bacterial community was selectively enriched. Empirical core PE/PP degrading bacteria (C-bacteria) and resuscitated PE/PP degrading bacteria (R-bacteria) were screened based on the variation of the abundance of OTUs, and co-occurrence analysis displayed that C-bacteria presented higher betweenness centrality than R-bacteria. The higher abundance and diversity of R-bacteria in biofilms suggest the presence of many rare or low abundance bacteria in natural rivers that may be potential PE/PP degrading bacteria or PE/PP degrading bacteria to be activated, while the lower abundance and diversity of C-bacteria support the slow degradation rate of PE and PP in waters. Compared to the isolated and indicatory PE/PP degrading bacterial genera, the C-bacteria OTUs or genera enriched in this study displayed higher richness and abundance. Enriched PE/PP degrading bacteria occurred in all sampled sites of the Qinhuai River with higher abundance and standard betweenness centrality in sediments (averaging 0.01354 and 0.44421, respectively) than those in overlying water (averaging 0.00536 and 0.17571, respectively), while the highest abundance of degrading bacteria presented in the eutrophic sediments. Inorganic nitrogen was determined to be significantly correlated with the distribution of PE/PP degrading bacteria in sediments via redundancy analysis. This study provides a new perspective on the natural degradation potential of carbon chain microplastics by microbial communities in rivers.

Microbial community structure and denitrification responses to cascade low-head dams and their contribution to eutrophication in urban rivers.

Low-head dams are one of the most common hydraulic facilities, yet they often fragment rivers, leading to profound changes in aquatic biodiversity and river eutrophication levels. Systematic assessments of river ecosystem structure and functions, and their contribution to eutrophication, are however lacking, especially for urban rivers where low-head dams prevail. In this study, we address this gap with a field survey on microbial community structure and ecosystem function, in combination with hydrological, environmental and ecological factors. Our findings revealed that microbial communities showed significant differences among the cascade impoundments, which may be due to the environment heterogeneity resulting from the cascade low-head dams. The alternating lentic-lotic flow environment created by the low-head dams caused nutrient accumulation in the cascade impoundments, enhancing environmental sorting and interspecific competition relationships, and thus possibly contributing to the reduction in sediment denitrification function. Decreased denitrification led to excessive accumulation of nutrients, which may have aggravated river eutrophication. In addition, structural equation model analysis showed that flow velocity may be the key controlling factor for river eutrophication. Therefore, in the construction of river flood control and water storage systems, the location, type and water storage capacity of low-head dams should be fully considered to optimize the hydrodynamic conditions of rivers. To summarize, our findings revealed the cumulative effects of cascade low-head dams in an urban river, and provided new insights into the trade-off between construction and decommissioning of low-head dams in urban river systems.

A novel BC/g-C3N4 porous hydrogel carrier used in intimately coupled photocatalysis and biodegradation system for efficient removal of tetracycline hydrochloride in water.

Intimately coupled photocatalysis and biodegradation (ICPB) is a promising technology to remove refractory contaminants from water. The key to successful ICPB is a carrier capable of accumulating biofilm and adhering photocatalyst firmly. Herein, BC/g-C3N4 was prepared into a three dimensional porous hydrogel and used as a carrier in ICPB system for the first time. Degradation experiments revealed that the removal rate of tetracycline hydrochloride (TCH) in water by the ICPB system was 96.0% after 10 h, which was significantly higher than that by the photocatalysis (PC, 76.3%), biodegradation (B, 32.5%), adsorption (AD, 17.2%), and photolysis (P, 5.0%) systems. Photo-electrochemical tests confirmed that ICPB system had superior electron transfer ability between photocatalysts and microorganisms. The removal efficiency of COD proved that microorganisms played an important role in the mineralization process of TCH by the ICPB system. After the ICPB degradation experiment, microorganisms maintained high activity and Pseudomonas, Burkholderiaceae and Flavobacterium which had TCH degradation or electron transport ability, were enriched. In conclusion, the novel ICPB carrier overcame shortcomings of the traditional ICPB carrier and the novel ICPB system had superior degradation performance for TCH. This study provided a possible method to promote the practical application of ICPB technology.

Diversity and potential functional characteristics of phage communities colonizing microplastic biofilms.

The multiple ecological influences and potential microbial degradation of microplastics are generally attributed to the microbial communities colonized on microplastics. Phages play an important role in the composition and function of their bacterial hosts, yet the occurrence and the potential functional characteristics of phages in the biofilms of microplastics have not been known. This study, for the first time, explored the diversity, composition, and potential function characteristics of phage communities living in the biofilms of PP, PE, and PET microplastics and stones, cultured in the same site, via the metagenome method. The results showed that a total of 240 non-redundant virus OTUs (vOTUs), distributed in at least four orders and seven families, were detected from biofilm metagenomes of microplastics. Compared to stones, some phages were selectively enriched by microplastic biofilms, with 13 vOTUs uniquely colonized on three microplastics, and these vOTUs mainly belong to the family Autographiviridae and Podoviridae. Except for the evenness of PP, the richness index, Chao 1 index, and abundance of phage communities of three microplastics were much higher than that of stone. At least 8 bacterial phyla and 72 genera were possibly infected by phages. Compared to the stones, both composition and abundance of the phages and hosts presented significant and strong correlations for three microplastics. Some of the bacterial hosts on microplastics were likely involved in the microplastic degradation, fermenters, nitrogen transformation processes, and so on. A total of 124 encoding auxiliary metabolic genes (AMGs) were detected from viral contigs. The abundance of AMGs in microplastics was much higher than that of stones, which may provide more direct or indirect support for the bacterial degradation of microplastics. This study provides a new perspective on the occurrence and potential functions of phages on microplastic biofilms, thus expanding our understanding of microbial communities on microplastic biofilms.

Trophic interactions regulate microbial responses to environmental conditions and partially counteract nitrogen transformation potential in urban river bends.

River bends are distinguished by high biodiversity and elevated rates of biogeochemical activities due to complex hydromorphological processes that form diverse geomorphic units, making it challenging to elucidate the impact of trophic interactions on community assembly and biogeochemical processes. Here, we clarify the effect of trophic interactions in determining the assembly of multi-trophic microbial communities and the impact on nitrogen transformation potential by distinguishing the direct and cascading effects of environmental conditions based on 32 samples collected from a typical urban river bends. It was found that both bacterial and micro-eukaryotic communities were determined by homogeneous selection (indicated by ß-nearest taxon index, accounted for 85% and 48.3%, respectively), whereas the dominant environmental factors were different, being sediment particle size (P < 0.05) and nitrogen (P < 0.05), respectively. Both the microbial co-occurrence network and the significant association (P < 0.05) between ß-nearest taxon index and trophic transfer efficiency changes showed that the trophic interactions strongly shaped microbial communities in the urban river bends. The path modeling suggested that environmental conditions resulted in an increase in abundance of multi-trophic microbial communities via direct effects (mean standardized effects = 0.21), but reductions in abundance of bacteria via cascading effects, i.e., trophic interaction (mean standardized effects = -0.1). When considering direct and cascading effects together, environmental conditions in urban river bends were found to enhance the abundance of microbial communities, with decreasing magnitude at the higher trophic level. Analogously, the path modeling also indicated the nitrogen transformation potential enhanced by environmental conditions via direct effects, but partly counteracted by trophic interactions via cascading effects. The obtained results could provide a theoretical basis for the regulation and restoration of urban rivers.

Hydrodynamics-driven community coalescence determines ecological assembly processes and shifts bacterial network stability in river bends.

Community coalescence, i.e., the mixing and merging of microbial communities and their surrounding environments, is prevalent in various ecosystems and potentially acts on ecological processes. River bends are distinguished by significant cross-stream velocities and spiral flow. The flow in river bends causes the mixing of microbial communities, thus making the resultant community (after mixing) different from its precursors (before mixing) through ecological processes. However, so far, no studies have explored the effect of community coalescence on ecological processes and network stability under the hydrodynamic processes of river bends. Here, we explored bacterial community assembly and community coalescence in river bends by coupling hydrodynamic profiling, aqueous biogeochemistry, DNA sequencing, and ecological theory. The results showed that the water flow dominated the community coalescence by regulating the movement of suspended sediments. The main ecological process determining the bacterial community compositions in water was the dispersal process, whereas in sediments it was the selection process. Furthermore, the negative cohesion results showed that community coalescence determined the stability of bacterial networks through competition and predation. This study depicted the bacterial community coalescence in river bends and highlighted their associations with network stability, which might provide new insights into bacterial community assembly and coalescence under complex hydrodynamics in the aquatic environment.

The Effects of Paroxetine on Benthic Microbial Food Web and Nitrogen Transformation in River Sediments.

Paroxetine is a common pharmaceutical to treat depression and has been found to pose threats to aquatic organisms. However, little is known about the effects of paroxetine on the nutrient cycle in aquatic environments. Therefore, DNA metabarcoding is used in this study to analyze the effects of paroxetine on multi-trophic microorganisms and nitrogen transformation in river sediments. Although paroxetine has no significant effect on the diversity of microbenthos, changes in benthic nitrogen-converting bacteria are consistent with the change in the various forms of nitrogen in the sediment, indicating that paroxetine affects the nitrogen conversion process by affecting nitrogen-converting bacteria. In addition, it is found that paroxetine has the ability to influence nitrogen transformation in an indirect way by affecting the trophic transfer efficiency of higher trophic levels (meiofauna and protozoa, protozoa and protozoa), subsequently affecting the growth of nitrogen-converting bacteria through a top-down mechanism (i.e., predation).The results show that paroxetine affects nitrogen transformation directly by affecting nitrogen-converting bacteria and indirectly through top-down effects, emphasizing that the assessment of paroxetine's ecological risks should consider species within different trophic levels.

Total Synthesis of (-)-Ceforalide B and (-)-Cephanolides B-D.

(-)-Ceforalide B (1) and (-)-cephanolides B-D (2-4) are benzenoid cephanolide diterpenoids possessing the same pentacyclic skeleton, which contains three C13-C15 substituent patterns and different benzylic oxidation states. An olefination/6π-electrocyclization/oxidative aromatization cascade has been verified as divergent access to three C13-C15 patterns. The benzylic aerobic oxidations enabled by the Co(OAc)2·4H2O/bromide salt/O2/PPh3/N-hydroxyphthalimide system have been developed to deliver expected site-selectivity and different oxidation states. Through the divergent strategy, total synthesis of (-)-ceforalide B and (-)-cephanolides B-D is accomplished.

Effect of water chemistry on nitrogen transformation, dissolved organic matter composition and microbial community structure in hyporheic zone sediment columns.

Controlled surface water systems, including those with dams lead to dynamic stage changes that alter the fluctuation directions of flow exchange in the hyporheic zones (HZ). However, the nitrogen transformation, dissolved organic matter (DOM) composition, and microbial community responding to variable scenarios of water source and hyporheic exchange are poorly studied. The present work investigated nitrogen transformation in HZ sediments, focusing on how microbial community structure and biological functions related to nitrogen transformation and sediment-attached DOM compositions. Upwelling of synthesized groundwater, downwelling of synthesized river water and exchangeable elution of both feed water created distinct microbial zonation and N-transformation processes. Mixing of river water and groundwater enhanced microbial diversity, microbial co-occurrence network complexity and N-transformation functions. In terms of the sediment-attached DOM properties after hyporheic exchanges, humic fractions occupied the predominant chromophoric DOM. Correlation analysis implied that there were more DOM properties, e.g., tryptophan-like proteins, humic-like fractions, and the source of humic fractions, involved in affecting the microbial community under downwelling flow. Co-occurrence network analysis verified that fluorescent components, protein-like and lignin-like fractions in sediment-detached DOM were clustered with microbial communities in one module in downwelling column, implying closer interactions among microbial communities and DOM fractions. The strains of Nitrospinae, Dinghuibacter, and Lentimicrobium etc. were key species collaborating to metabolize both nitrogen and DOM in HZ sediments. The work provides insights into how the nitrogen transformation, DOM compositional changes, as well as the linkages between community structure and DOM factions, response to the changes in water chemistry, leading to valuable insights into hyporheic zone functions.