Formation Pathways Research Articles

Topology Testing and Demographic Modeling Illuminate a Novel Speciation Pathway in the Greater Caribbean Sea Following the Formation of the Isthmus of Panama.

Recent genomic analyses have highlighted the prevalence of speciation with gene flow in many taxa and have underscored the importance of accounting for these reticulate evolutionary processes when constructing species trees and generating parameter estimates. This is especially important for deepening our understanding of speciation in the sea where fast moving ocean currents, expanses of deep water, and periodic episodes of sea level rise and fall act as soft and temporary allopatric barriers that facilitate both divergence and secondary contact. Under these conditions, gene flow is not expected to cease completely while contemporary distributions are expected to differ from historical ones. Here we conduct range-wide sampling for Pederson's cleaner shrimp (Ancylomenes pedersoni), a species complex from the Greater Caribbean that contains three clearly delimited mitochondrial lineages with both allopatric and sympatric distributions. Using mtDNA barcodes and a genomic ddRADseq approach, we combine classic phylogenetic analyses with extensive topology testing and demographic modeling (10 site frequency replicates x 45 evolutionary models x 50 model simulations/replicate = 22,500 simulations) to test species boundaries and reconstruct the evolutionary history of what was expected to be a simple case study. Instead, our results indicate a history of allopatric divergence, secondary contact, introgression, and endemic hybrid speciation that we hypothesize was driven by the final closure of the Isthmus of Panama and the strengthening of the Gulf Stream Current ~3.5 million years ago. The history of this species complex recovered by model-based methods that allow reticulation differs from that recovered by standard phylogenetic analyses and is unexpected given contemporary distributions. The geologically and biologically meaningful insights gained by our model selection analyses illuminate what is likely a novel pathway of species formation not previously documented that resulted from one of the most biogeographically significant events in Earth's history.

HIGD1B, as a novel prognostic biomarker, is involved in regulating the tumor microenvironment and immune cell infiltration; its overexpression leads to poor prognosis in gastric cancer patients.

HIGD1B (HIG1 Hypoxia Inducible Domain Family Member 1B) is a protein-coding gene linked to the occurrence and progression of various illnesses. However, its precise function in gastric cancer (GC) remains unclear. The expression of HIGD1B is determined through the TCGA and GEO databases and verified using experiments. The association between HIGD1B and GC patients' prognosis was analyzed via the Kaplan-Meier (K-M) curve. Subsequently, the researchers utilized ROC curves to assess the diagnostic capacity of HIGD1B and employed COX analysis to investigate risk factors for GC. The differentially expressed genes (DEGs) were then subjected to functional enrichment analysis, and a nomogram was generated to forecast the survival outcome and probability of GC patients. Additionally, we evaluated the interaction between HIGD1B and the immune cell infiltration and predicted the susceptibility of GC patients to therapy. HIGD1B is markedly elevated in GC tissue and cell lines, and patients with high HIGD1B expression have a poorer outcome. In addition, HIGD1B is related to distinct grades, stages, and T stages. The survival ROC curves of HIGD1B and nomogram for five years were 0.741 and 0.735, suggesting appropriate levels of diagnostic efficacy. According to Cox regression analysis, HIGD1B represents a separate risk factor for the prognosis of gastric cancer (p<0.01). GSEA analysis demonstrated that the HIGD1B is closely related to cancer formation and advanced pathways. Moreover, patients with high HIGD1B expression exhibited a higher level of Tumor-infiltration immune cells (TIICs) and were more likely to experience immune escape and drug resistance after chemotherapy and immunotherapy. This study explored the potential mechanisms and diagnostic and prognostic utility of HIGD1B in GC, as well as identified HIGD1B as a valuable biomarker and possible therapeutic target for GC.

Rapid formation of binary asteroid systems post rotational failure: A recipe for making atypically shaped satellites

Binary asteroid formation is a highly complex process, which has been highlighted with recent observations of satellites with unexpected shapes, such as the oblate Dimorphos by the NASA DART mission and the contact binary Selam by NASA’s Lucy mission. There is no clear consensus on which dynamical mechanisms determine the final shape of these objects. In turn, we explore a formation pathway where spin-up and rotational failure of a rubble pile asteroid lead to mass-shedding and a wide circumasteroidal debris disk in which the satellite forms. Using a combination of smooth-particle hydrodynamical and N-body simulations, we study the dynamical evolution in detail. We find that a debris disk containing matter corresponding to a few percent of the primary asteroid mass extending beyond the fluid Roche limit can consistently form both oblate and bilobate satellites via a series of tidal encounters with the primary body and mergers with other gravitational aggregates. Principally, satellites end up prolate (elongated) and on synchronous orbits, accreting mainly in a radial direction while tides from the primary asteroid keep the shape intact. However, close encounters and mergers can break the orbital state, leading to orbital migration and deformation. Satellite–satellite impacts occurring in this regime have lower impact velocities than merger-driven moon formation in e.g. planetary rings, leading to soft impacts between differently sized, non-spherical bodies. The resulting post-merger shape of the satellite is highly dependent on the impact geometry. Only moons having experienced a prior mild or catastrophic tidal disruption during a close encounter with the primary asteroid can become oblate spheroids, which is consistent with the predominantly prolate observed population of binary asteroid satellites.

Regulation of metal utilization ratio and active sites of nickel phyllosilicates for enhanced CO2 methanation

This paper proposes a ball milling trio strategy that integrates mechanical exfoliation, liquid-phase exfoliation, and hydrogen peroxide modification to synthesize ultrathin defect-rich Ni-phyllosilicate for CO2 methanation. The obtained catalyst exhibits a unique layered structure with a thickness of only 0.86–1.37 nm and numerous holes, which results in weakened metal-support interaction, enhanced metal utilization ratio, and an appropriate coordination environment for Ni species. Consequently, it displays competitive catalytic activity with a turnover efficiency of CO2 (TOFCO2) of 8.0 × 10–2 s−1 and a low active energy (Ea) of 41.49 KJ·mol−1 for CO2 methanation; importantly, it maintains high stability without Ni sintering and coking in a 100 h-long term test. In-situ diffuse reflectance infrared Fourier transform spectroscopy (in-situ DRIFTS) results confirms the coexistence of *HCOO and *CO intermediates, and density functional theory (DFT) calculations indicate the formate pathway is thermodynamically more feasible, with the rate-determining step of *CO+*OH+*H→*CHO+*OH (ΔE=0.73 eV). Moreover, this method demonstrates high universality in preparing various metal (Fe, Co, Ni, Cu) phyllosilicates and possesses the in-situ regeneration capacity for the deactivated Ni/SiO2 catalyst.

Transcending antibiotic resistance: The potential of mass Galla chinensis et camelliae Fermentata to Dismantle Helicobacter pylori biofilms and enhance anti-biotic activity

Ethnopharmacological relevanceHelicobacter pylori (H. pylori) infections are on the rise, presenting a significant global health challenge. Mass Galla chinesis et camelliae Fermentata (Chinese gall leaven, CGL), a traditional Chinese medicinal product made from the fermentation of Rhus chinensis Mill., is frequently employed to address digestive system ailments. Contemporary pharmacological research reveals that CGL exhibits anti-inflammatory, anti-diarrheal, and enzyme-inhibitory activities and holds potential as a treatment for H. pylori infections. However, the precise mechanisms underlying CGL's efficacy against H. pylori remain to be fully elucidated. AimThe objective of the study is to evaluate CGL's ability to disrupt the H. pylori biofilm and to explore its synergistic potential with antibiotics in targeting the biofilm-efflux pump system, a mechanism implicated in bacterial resistance. MethordsThe study determined the Minimum Inhibitory Concentration (MIC) of CGL and metronidazole against H. pylori and evaluated their effects on H. pylori biofilms using an in vitro model. Structural changes induced by drug interventions were compared to those in untreated and antibiotic-treated models through scanning electron microscopy and laser confocal microscopy. The accumulation of H33342 dye in planktonic and biofilm H. pylori before and after drug treatment was assessed to evaluate cell viability and biofilm disruption. The study also involved adding experimental drugs to a biofilm H. pylori medium containing D-glucose, measuring glucose concentrations post-intervention using the glucose oxidase method, and calculating changes in glucose uptake. Finally, the relative expression levels of several genes in planktonic and biofilm H. pylori treated with CGL alone or in combination with antibiotics were measured to understand the impact on the biofilm-efflux pump system. ResultsBoth CGL alone and in combination with metronidazole demonstrated effective disruption of H. pylori biofilms. The combination therapy was particularly effective in reducing the biofilm transfer-enhancing effect of metronidazole and decreasing SpoT expression in the 'SpoT-(p)ppGpp' pathway, especially in biofilms. It showed a greater inhibition of the 'σ54-gluP-sugar uptake' pathway, with significant reductions in rpoN and gluP expression under biofilm conditions compared to CGL or metronidazole alone. The treatment also suppressed H. pylori proliferation and may have altered glucose uptake mechanisms. Moreover, it significantly inhibited the 'hp0939/hp0497/hp0471-RND efflux pump' pathway, with a notable reduction in gene expression compared to the 1/2 MIC metronidazole treatment. ConclusionThis study demonstrates that CGL effectively hinders the development of drug resistance in H. pylori by targeting biofilm formation and critical molecular pathways associated with antibiotic resistance. The synergistic effect of combining CGL with metronidazole notably enhances biofilm disruption and inhibits the bacterium's metabolic and reparative mechanisms. Further in vivo studies are needed to confirm these results and to investigate additional mechanisms of CGL's action.

Unraveling the core microorganisms and metabolic pathways related to off-flavor compounds formation during Jiang-flavor Baijiu fermentation

Off-flavor is one of the most frequent and serious causes for the aroma deterioration in Jiang-flavor Baijiu. However, the key compounds and their formation mechanism responsible for off-flavor are still unclear. This study identified 271 volatile compounds from 1 normal and 5 types of off-flavor fermented grains (putrid, rancidity, mud, musty, and burnt) by headspace solid-phase microextraction combined with gas chromatography–mass spectrometry. Using VIP and OAV analysis, 47 key flavor compounds including indole, phenol, isoamyl alcohol, diacetyl, acetic acid, isobutyric acid, and isovaleric acid were found to distinguish normal and off-flavor fermented grains. Furthermore, 40 microbial genera (mainly Monascus, Enterococcus, Dyadobacter, Ottowia, Pseudoxanthomonas, Stenotrophomonas, Pseudomonas, and Xanthomonas) were significantly (p < 0.05, Pearson correlation) related to these 47 compounds. Finally, metabolic pathways for off-flavor compounds formation were constructed. This study provides comprehensive information on the off-flavor compounds and their potential formation mechanism during Jiang-flavor Baijiu fermentation.

Probing nitro(so) and chloro byproducts and their precursors in natural organic matter during UV/NH2Cl treatment by FT-ICR MS with machine learning insights

The UV/monochloramine (UV/NH2Cl) process, while efficiently eliminating micropollutants, produces toxic byproducts. This study utilized Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to investigate molecular-level changes in natural organic matter (NOM) and to disclose formation pathways of nitro(so) and chloro byproducts in the UV/NH2Cl process. The UV/NH2Cl process significantly increased the saturation and oxidation levels and altered the elemental composition of NOM. Using 15N labeling and a screening workflow, nitro(so) byproducts with nitrogen originating from inorganic sources (i.e., reactive nitrogen species (RNS) and/or NH2Cl) were found to exhibit total intensities comparable to those from NOM. RNS, rather than NH2Cl, played a significant role in incorporating nitrogen into NOM. Through linkage analysis, nitro(so) addition emerged as an important reaction type among the 25 reaction types applied. By using phenol as a representative model compound, the nitro byproducts were confirmed to be mainly generated through the oxidation of nitroso byproducts instead of nitration. Machine learning and SHAP analysis further identified the major molecular indices distinguishing nitro(so) and chloro precursors from non-precursors. This study enhances our fundamental understanding of the mechanisms driving the generation of nitro(so) and chloro byproducts from their precursors in complex NOM during the UV/NH2Cl process.

Children with eosinophilic esophagitis non-responsive to combination therapy have distinct esophageal transcriptomic and microbiome profile.

A combination of proton-pump inhibitors (PPI) and topical steroids (TS) is used to treat children with eosinophilic esophagitis (EoE). However, a subset of children do not respond to this combination therapy. We aimed to identify the esophageal transcriptional, cell composition, and microbial differences between the non-responders (EoE-PPI-TSnr; n = 7) and responders (EoE-PPI-TSr; n = 7) to the combination therapy for EoE and controls (n = 9) using metatranscriptomics. Differential gene expression analysis was used to identify transcriptional differences, validated using the EoE diagnostic panel (EDP). Deconvolution analysis was performed to identify differences in their cell type composition. Microbiome analysis was conducted from esophageal biopsies RNAseq data, and microbial abundance was correlated with esophageal gene expression. In all, 3164 upregulated and 3154 downregulated genes distinguished EoE-PPI-TSnr from EoE-PPI-TSr. Eosinophilic inflammatory response, cytokine signaling, and collagen formation pathways were significantly upregulated in EoE-PPI-TSnr. There was a 56% overlap in dysregulated genes between EoE-PPI-TSnr and EDP, with a perfect agreement in the directionality of modulation. Eosinophils, dendritic cells (DCs), immature DCs, megakaryocytic-erythroid progenitors, and T helper type 1 cells were significantly higher in EoE-PPI-TSnr. There was no significant difference in microbiome diversity. The relative abundance of Fusobacterium sp. and Acinetobacter sp. notably differed in EoE-PPI-TSnr and correlated with the key pathways. Our results provide critical insights into the molecular, cellular, and microbial factors associated with the lack of response to PPI and TS combination therapy in children with EoE. This study advances our understanding of the pathobiology of EoE while guiding personalized treatment strategies.

Effect of water on formic acid and formaldehyde decomposition on the TiO2 (110) surface

The catalytic and photocatalytic performance of TiO2 in air pollutant degradation is significantly influenced by the adsorption of water. Here, we explore the molecular mechanism of formic acid and formaldehyde decomposition and their interaction with water on the TiO2 (110) surface, employing density functional theory (DFT) calculations and reactive molecular dynamics (RMD) simulations. RMD simulations indicate that due to the competitive adsorption of water at the surface Ti site, formic acid predominantly exists in a monodentate dissociative adsorption form on the TiO2 (110) surface. Moreover, on the TiO2 (110) surface, water molecules inhibit the adsorption and dissociation of formic acid, but they facilitate that of formaldehyde, forming methanediol (*CH2OHO) and dioxymethylene (*CH2O2). DFT calculations suggest that the formation pathway of *CH2OHO or *CH2O2 is energetically favorable, but the formation of formate is difficult. This contrasts with the adsorption of formaldehyde on the anatase surface, where formate species are formed.

H-151, a Selective STING Inhibitor, Has Potential as a Treatment for Neovascular Age-Related Macular Degeneration.

The cyclic guanosine monophosphate-adenosine monophosphate synthase (cGAS) stimulator of interferon gene (STING) pathway is a crucial cascade in the inflammatory response initiated by the recognition of cytosolic double-stranded DNA (dsDNA). The aim of this study was to evaluate the effect of STING inhibitor in murine choroidal neovascularization (CNV). To investigate whether the cGAS-STING pathway is activated during CNV, CNV was induced using laser photocoagulation in male C57BL/6J mice. The expression of change of cGAS and STING during CNV development was confirmed by Western-blotting. H-151, a potent STING palmitoylation antagonist, was used as a STING inhibitor. H-151 was administered intravitreally immediately after laser induction. To confirm the role of the cGAS-STING pathway in CNV formation, we evaluated CNV size and performed fundus fluorescein angiography. The expression levels of cGAS and STING were significantly upregulated in the RPE-choroid complex after CNV induction, and dsDNA merged with cGAS was observed in CNV lesions. Intravitreal administration of H-151 suppressed CNV development and fluorescent leakage from neovessels. In CNV lesions, the high expression of STING and cGAS was observed in infiltrating F4/80+ macrophages. H-151 administration attenuated downstream signals of the cGAS-STING pathway, including the phosphorylation of nuclear factor-κB, and downregulated the expression of interleukin 1β. These findings support that the inhibition of cGAS-STING pathway treats abnormal ocular angiogenesis.

Iodine Clusters in the Atmosphere I: Computational Benchmark and Dimer Formation of Oxyacids and Oxides.

The contribution of iodine-containing compounds to atmospheric new particle formation is still not fully understood, but iodic acid and iodous acid are thought to be significant contributors. While several quantum chemical studies have been carried out on clusters containing iodine, there is no comprehensive benchmark study quantifying the accuracy of the applied methods. Here, we present the first study in a series that investigate the role of iodine species in atmospheric cluster formation. In this work, we have studied the iodic acid, iodous acid, iodine tetroxide, and iodine pentoxide monomers and their dimers formed with common atmospheric precursors. We have tested the accuracy of commonly applied methods for calculating the geometry of the monomers, thermal corrections of monomers and dimers, the contribution of spin-orbit coupling to monomers and dimers, and finally, the accuracy of the electronic energy correction calculated at different levels of theory. We find that optimizing the structures either at the ωB97X-D3BJ/aug-cc-pVTZ-PP or the M06-2X/aug-cc-pVTZ-PP level achieves the best thermal contribution to the binding free energy. The electronic energy correction can then be calculated at the ZORA-DLPNO-CCSD(T0) level with the SARC-ZORA-TZVPP basis for iodine and ma-ZORA-def2-TZVPP for non-iodine atoms. We applied this methodology to calculate the binding free energies of iodine-containing dimer clusters, where we confirm the qualitative trends observed in previous studies. However, we identify that previous studies overestimate the stability of the clusters by several kcal/mol due to the neglect of relativistic effects. This means that their contributions to the currently studied nucleation pathways of new particle formation are likely overestimated.

The Influence of Gravity on the Frequency of Processes in Various Geospheres of the Earth. Biogenic and Abiogenic Pathways of Formation of HC Accumulations

Based on the results obtained in the study of the interaction of geological and biosphere processes, we found out that there is a close relationship between them. It was also found that the gravity of the bodies of the solar system on the Earth plays a significant role in the above relationship. The effect of gravity was demonstrated on the movement of lithosphere plates, on the processes in the atmosphere and hydrosphere, on related climatic cycles, and the biosphere processes, including "living" organisms' evolution and their mass extinctions. The periodicity of these processes due to gravity is shown. It is expressed in the alternation of short-term orogenic periods of the beginning of the processes with long-term geosynclinal periods of their development and completion. Both periods constitute the repetitive orogenic cycles. The relationship of the cycles with the evolution of photosynthesis, as well as with related Organic Matter (OM) accumulation in sediments after mass extinction of organisms, including OM transformation leading to the formation of Hydrocarbon (HC) accumulations, is shown. Biogenic processes accounting for the accumulation and transformation of organic matter in sediments constitute the biogenic pathway of the formation of hydrocarbon accumulations. It is shown that the influence of gravity extends to the processes in the inner geospheres, including the movement of magma in the asthenosphere under the lithosphere shell, to the movement of hydrogen gas coming from the Earth's core, combining with volatile compounds of elements present in magma, as well as to the rifting process. It is shown that rifting processes lead to the formation of gaseous HC accumulations and constitute a pathway called abiogenic. The obtained results shed light on the peculiarities of the formation of HC accumulations by biogenic and abiogenic pathways, allowing prediction of their chemical characteristics. This is essential when searching for oil and gas and planning exploration works.

Coprecipitation of amorphous silica and gold nanoparticles contributes to gold hyperenrichment

Hyperenrichment of Au in orogenic ores occurs overwhelmingly within quartz veins, but the formation pathway of quartz veins in orogenic systems remains enigmatic. We conducted hydrothermal experiments simulating coprecipitation of Au and amorphous silica and subsequent recrystallization to test whether this is a viable mechanism to generate Au nuggets within quartz veins. Within minutes, coprecipitation of amorphous silica and Au nanoparticles occurred, representing an effective Au deposition mechanism. Within one week, amorphous silica had recrystallized to quartz, causing the coarsening of Au particles and their relocation to quartz grain boundaries and fractures. The experimental textures are similar to those observed in high-grade zones of orogenic gold deposits. In addition to trapping Au, amorphous silica may increase competency contrasts that facilitate short-term fracture reactivation during earthquake aftershock periods or swarms, allowing further Au input from fresh fluids. These findings demonstrate that amorphous silica precipitation may be an important transient stage in orogenic gold deposit formation, with significant implications for metal accumulation in quartz veins.

Iron mineral type controls organic matter stability and priming in paddy soil under anaerobic conditions

Associations of iron (hydr)oxides (FeOx) with organic carbon are vital in regulating the stability of soil organic carbon (SOC). Like SOC, FeOx is chemically dynamic in soils, particularly under anaerobic conditions. However, previous research has not clarified how the stability of FeOx (goethite versus ferrihydrite) and the formation pathway of FeOx-OC associations (adsorption versus coprecipitation) affect the stability of FeOx-bound OC and, subsequently, the priming effect (PE) under anaerobic conditions. With an aim to bridge this gap, we incubated paddy soils for 80 d under anaerobic conditions after adding free 13C-glucose, ferrihydrite- or goethite-bound 13C-glucose formed by either adsorption or coprecipitation. Compared with the free glucose addition, the FeOx-bound glucose addition increased 13CO2 production by 8%–21% but reduced 13C–CH4 production by 7%–10%. Ferrihydrite-bound glucose was mineralised more than goethite-bound glucose; this is consistent with its lower crystallinity facilitating reduction and, thus, higher OC bioavailability. Glucose induced a negative priming effect (PE) for CO2 but a positive PE for CH4, whereas FeOx-bound glucose showed the opposite trend. This may be because FeOx-bound glucose provides an energy source and electron acceptor for Fe-reducing bacteria; this promotes the dissimilating reduction of iron and combines with an aggravated microbial P limitation resulting from the FeOx input. The crystallinity of FeOx affected the amount of primed CH4 rather than its formation pathway. In conclusion, the crystallinity of FeOx controls the stability of FeOx-OC associations and the PE of SOC decomposition under anaerobic conditions.

Characteristics and Source Analysis of Volatile Organic Compounds in Typical Ozone Pollution Processes During Summer in Jinan, China

Based on a typical ozone （O3） pollution process in Jinan City from June 16 to 26, 2021, the variation characteristics of O3 and its precursor volatile organic compounds （VOCs） during different pollution periods （clean period （CP）, pollution rise period （PRP）, heavy pollution period （HPP）, and pollution decline period （PDP）） in the urban area were analyzed. Both positive matrix factorization （PMF） and an observation-based model （OBM） were used to identify the main sources of VOCs, O3 production mechanisms, and sensitive species. The results showed that the average value of ρ（O3-8h） during the HPP period in the urban area was （246.67±11.24） μg·m-3, and ρ（O3-1h） had a peak value of 300 μg·m-3. The volume fractions of VOCs and NO2 concentration were affected by the decrease in planetary boundary layer and wind speed, which were 76.99%-145.36% and 127.78%-141.18% higher than those in the other three periods, respectively, and were the main reasons for the aggravation of O3 pollution. Alkanes, oxygenated volatile organic compounds （OVOCs）, and halogenated hydrocarbons accounted for 43.81%, 20.98%, and 17.43% of VOCs in urban areas, respectively. All of them showed significant growth during the HPP period, with acetone, propane, and ethane being the top three species by volume in each stage and isopentane showing the highest growth during the HPP period. Alkene, alkanes, and aromatic hydrocarbons accounted for 40.19%, 28.06%, and 21.92% of the ozone generation potential （OFP）. 1-butene, toluene, isopentane, and isoprene were the species with higher OFP. Isoprene had the highest OFP during the PRP phase, and 1-butene had the highest OFP during the HPP phase. The volume fraction of isopentane significantly increased OFP. The correlation coefficient between VOCs and CO preliminarily indicated that motor vehicle exhaust and oil and gas volatilization were the main sources of VOCs during the HPP period. Further use of PMF revealed that solvent use sources, combustion sources, motor vehicle exhaust+oil and gas volatilization sources, industrial emission sources, and plant sources were important sources of VOCs in urban areas. The contribution of motor vehicle exhaust+oil and gas volatilization sources in the HPP period to VOCs was 3.09-14.72 times higher than that in other periods. The contribution of solvent use sources to VOCs was approximately 2.50 times higher than that in the CP and PRP periods. The main sources of VOCs volume fraction increase were motor vehicle exhaust, oil and gas volatilization sources, and solvent use sources. Potential sources and concentration weight analysis found that VOCs were also affected by the transmission of VOCs to Binzhou and Dongying in the northeast direction. The OBM results indicated that the main pathway of O3 formation in urban areas was the reaction of peroxide hydroxyl radicals （HO2·） and methyl peroxide radicals （CH3O2·） with NO, and the net ozone generation rate during the HPP phase [P（O3）net] was 24×10-9 h-1. Based on the sensitivity experiment results, the alkene components of 1-butene, propylene, cis-2-butene, and ethylene were the dominant species for O3 production.

Long-term straw return promotes accumulation of stable soil dissolved organic matter by driving molecular-level activity and diversity

Agricultural management practices play pivotal roles in affecting soil organic matter formation pathways, particularly through changes in soil dissolved organic matter (DOM). The potential effects of long-term straw return on the molecular-level activity and transformations of DOM were investigated in this study. Over 9 years, the soil DOM from straw return had high stability, unsaturation degree, oxidability, and strong aromaticity. The relative abundance of biologically refractory DOM components (i.e., lignin-, condensed aromatic-, and tannin-like formulas) increased by 4 %-33 %, whereas the relative abundance of biodegradable DOM components (i.e., lipids and protein/amino sugar-like formulas) decreased by 15 %-23 % under straw return. Furthermore, the positive effects of straw return on the intergroup transformations of biologically refractory compounds favored the persistence of recalcitrant organic matter in the soil. Importantly, intragroup transformations of recalcitrant-active molecules and biologically refractory compounds were critical pathways for stable DOM accumulation under straw return, and these were mainly driven by thermodynamically limited processes. Thus, our results indicated that long-term straw return promoted the persistence of stabilized soil DOM by driving molecular-level activity and diversity.

Hydrogen sulfide and metal-enriched atmosphere for a Jupiter-mass exoplanet.

As the closest transiting hot Jupiter to Earth, HD 189733b has been the benchmark planet for atmospheric characterization1-3. It has also been the anchor point for much of our theoretical understanding of exoplanet atmospheres from composition4, chemistry5,6, aerosols7 to atmospheric dynamics8, escape9 and modelling techniques10,11. Previous studies of HD 189733b have detected carbon and oxygen-bearing molecules H2O and CO (refs. 12,13) in the atmosphere. The presence of CO2 and CH4 has been claimed14,15 but later disputed12,16,17. The inferred metallicity based on these measurements, a key parameter in tracing planet formation locations18, varies from depletion19,20 to enhancement21,22, hindered by limited wavelength coverage and precision of the observations. Here we report detections of H2O (13.4σ), CO2 (11.2σ), CO (5σ) and H2S (4.5σ) in the transmission spectrum (2.4-5.0 μm) of HD 189733b. With an equilibrium temperature of about 1,200 K, H2O, CO and H2S are the main reservoirs for oxygen, carbon and sulfur. Based on the measured abundances of these three main volatile elements, we infer an atmospheric metallicity of three to five times stellar. The upper limit on the methane abundance at 5σ is 0.1 ppm, which indicates a low carbon-to-oxygen ratio (<0.2), suggesting formation through the accretion of water-rich icy planetesimals. The low oxygen-to-sulfur and carbon-to-sulfur ratios also support the planetesimal accretion formation pathway23.

Theoretical study of the effects of surface Cu coordination environment on CO2 hydrogenation to CH3OH

The coordination environment of Cu (the coordination number and arrangement of surface atoms) plays an important role in CO2 hydrogenation to CH3OH. Compared with the extensive studies of the effects of coordination number, the comprehensive effects of coordination number and arrangement of surface atoms were seldom explored in literature. To unravel the effects of surface Cu coordination environment on CO2 hydrogenation to CH3OH, the adsorption and reaction behaviors of H2 and CO2 on Cu(111), (100), (110) and (211) with different coordination numbers and arrangement of surface Cu were systematically calculated by density functional theory (DFT) and kinetic Monte Carlo (kMC) simulation. It was found that the adsorption energies of intermediates in CO2 hydrogenation on Cu surfaces increase with the decrease of coordination number. When the Cu coordination numbers are similar, the charge density on the open surface derived from the different atom arrangement becomes larger and leads to stronger interaction with intermediates than that on the compact one. DFT calculation and kMC simulation indicate that methanol formation pathway follows CO2*→HCOO*→HCOOH*→H2COOH*→H2CO*→CH3O*→CH3OH* on four Cu facets; CO formation is via CO2 direct dissociation on Cu(111), (100) and (110) but COOH* dissociation on (211). The low-coordinated surface Cu with more openness on Cu(211) is the highly active site for CO2 hydrogenation to CH3OH with high turnover of frequency (3.71 × 10−4 s−1) and high selectivity (87.17 %) at 600 K, PCO2 = 7.5 atm and PH2 = 22.5 atm, which is much higher than those on Cu(111), (100) and (110). This work unravels the effects of coordination environment on CO2 hydrogenation at the molecular level and provides an important insight into the design and development of catalysts with high performance in CO2 hydrogenation to CH3OH.

Distinct electrochemical and metabolic responses of anode respiring bacteria to sulfamethoxazole in microbial fuel cells coupled with constructed wetlands

The influence of sulfamethoxazole (SMX) on the electrochemical activity, bacterial community, and metabolic state of anode respiring microbes was investigated in constructed-wetland-coupled microbial fuel cells (CW-MFCs). Results suggested that SMX shortened the acclimatisation period and enhanced the maximal power density of the CW-MFC at 0.1 mg/L. Cyclic voltammetry (CV) results indicated that SMX may trigger an electrocatalytic process related to an extra redox-active compound. Exposure to SMX significantly altered the bacterial communities, leading to decreased abundances of Desulfurivibrio and Pseudomonas, while increasing the contents of Rhodobacter and Anaerovorax. Furthermore, metabolites related to amino acids and nucleotide metabolism were suppressed at 10 mg/L SMX, while the related metabolites increased at 0.1 mg/L SMX. The upregulated pathway of biofilm formation indicated that the bacteria tended to form biofilms under the influence of SMX. This study provides valuable insights into the complex interactions between SMX and electrochemically active bacteria.

Effect of copper cluster on reaction pathways of carbon dioxide hydrogenation on magnesium hydride surface

Understanding the reaction mechanism of CO2 hydrogenation to produce value-added chemicals is essential for the rational design of catalysts to improve reaction activity and product selectivity. In this work, the first-principles calculations based on density functional theory were employed to study the effect of copper cluster on product selectivity in CO2 hydrogenation utilizing magnesium hydride as hydrogen source. The results show that on pristine MgH2 (0 0 1), CO2 molecule adsorbs on the surface with an O atom close to Mg atom, and the hydrogenation reaction follows formate pathway to yield CH3OH with an energy barrier only 1.09 eV for the rate-limiting step; however, the production of the most accessible C2-based product (CH2OH)2 needs to overcome an energy barrier up to 1.94 eV. On MgH2 (0 0 1) with Cu7 cluster, the C atom of CO2 molecule can strongly adsorb on a Cu atom of Cu7 cluster, and the hydrogenation more likely proceeds through reverse water-gas shift pathway, in which it is easy to generate C2 product C2H4 by the coupling of intermediate H2C*, with an energy barrier only 1.53 eV for the rate-limiting step. The findings utilizing transition metal cluster to change the reaction pathway and product selectivity of CO2 hydrogenation on magnesium hydride can provide novel perspectives for the design of catalysts.