Carbon Substrate Research Articles

Ultrafine Co-MoC particles in porous carbon derived from polyoxometalate-based metal organic framework for efficient hydrogen evolution reaction

Accurately regulating ultrafine molybdenum carbide (MoC)-based catalysts is a significant challenge in the rational design of hydrogen evolution reaction (HER) electrocatalysts. Herein, under the guidance of the first principle calculations, we proposed an in-situ polyoxometalate-confined strategy for creating uniformly distributed ultrafine Co-MoC bimetallic nanoparticles in porous carbon nanostars, with the assistance of precisely designed metal–organic framework (MOF). The Co-MoC@C electrocatalyst has a high specific surface area of 969 m2·g−1 because of the conductive carbon substrate with abundant mesopores, which makes for exposing more active sites of Co-MoC nanocrystals (∼1.5 nm) and facilitating electron/ion transport. Thus, Co-MoC@C electrocatalyst shows the excellent electrochemical activity with overpotentials of 88.4 mV and 66.6 mV at a current density of 10 mA·cm−2 under acidic and alkaline conditions, respectively. The in-situ polyoxometalate-confined strategy will provide a new guideline for the design and preparation of efficient HER electrocatalysts.

Soil microbial functional diversity is primarily affected by soil nitrogen, salinity and alkalinity in wetland ecosystem

Wetland ecosystems, recognized as important carbon sinks, face challenges due to climate change. Although wetland soil microorganisms play a major role in the wetland carbon cycle, the mechanisms influencing their spatial distribution remain elusive. Here, we investigate the impact of soil properties on the spatial distribution of soil microorganisms across five saline-alkali wetlands (Xianghai [XH], Niuxintaobao [NX], Momoge [MMG], Zhalong [ZL], and Halahai [HLH]) within the Songnen Plain, China. We utilized the Biolog-ECO method to assess the carbon metabolic activity, microbial diversity, and carbon source utilization preference of soil microorganisms. Using the structural equation model, we analyzed factors influencing microbial carbon metabolic activity and microbial diversity. Results indicate that southern wetlands harbor soil microbial communities exhibiting higher carbon metabolic activity, Shannon index, and substrate richness, compared to their northern counterparts. Specifically, soil microorganisms in NX and XH wetlands demonstrate a preference for labile organic carbon, whereas those in HLH and ZL wetlands preferred to use recalcitrant carbon. Furthermore, soil microbial carbon metabolic activity is primarily regulated by soil total nitrogen content, whereas soil microbial diversity is primarily regulated by soil salinity and alkalinity. Our findings revealed the distribution characteristics and influencing factors of soil microorganisms in the Songnen Plain wetland, contributing to understanding the maintenance mechanism of wetland carbon sink function.

Urea promoted soil microbial community and reduced the residual ciprofloxacin in soil and its uptake by Chinese flowering cabbage.

Antibiotics in agricultural soil can be accumulated in crops and might pose a potential risk to human health. Nevertheless, there is a lack of knowledge about the impact of nitrogen fertilizers on the dissipation and uptake of antibiotics in soils. Therefore, our aim in this study is to investigate the effects of urea fertilizer on the residues of ciprofloxacin and its uptake by Chinese flowering cabbage (Brassica parachinensis L.) as affected by the associated changes on the soil microbial community. A pot experiment has been conducted using spiked soil with 20 mg ciprofloxacin /kg soil and fertilized with urea at dosages equal to 0, 0.2, 0.4, 0.8 t/ha. Application urea especially at 0.4 t/ha decreased the residue of ciprofloxacin in the soil and its uptake by the roots and its translocation to the shoots of Chinese flowering cabbage. The translocation factors (TFs) for ciprofloxacin were significantly decreased (P < 0.05) only at the treatment of 0.4 t/ha, while no significant difference of bio-concentration factors (BCFs). The average well color development (AWCD) values, Shannon diversity, and richness index were higher in the fertilized than the un-fertilized soils, and all such indicators were greater at the treatment of 0.4 t/ha than at 0.2 and 0.8 t/ha. The carbon substrate utilization of phenolic acids at the treatments of 0.4 t/ha were greater than with other levels of urea fertilizer. In conclusion, moderate urea addition significantly increased soil microbial activity and abundance, which in turn promoted the ciprofloxacin dissipation in soil and plant tissue. The present study provides an economical and operational strategy for the remediation of ciprofloxacin contaminated soils.

Biosynthetic and catabolic pathways control amino acid δ2H values in aerobic heterotrophs.

The hydrogen isotope ratios (δ2HAA values) of amino acids in all organisms are substantially fractionated relative to growth water. In addition, they exhibit large variations within microbial biomass, animals, and human tissues, hinting at rich biochemical information encoded in such signals. In lipids, such δ2H variations are thought to primarily reflect NADPH metabolism. Analogous biochemical controls for amino acids remain largely unknown, but must be elucidated to inform the interpretation of these measurements. Here, we measured the δ2H values of amino acids from five aerobic, heterotrophic microbes grown on different carbon substrates, as well as five Escherichia coli mutant organisms with perturbed NADPH metabolisms. We observed similar δ2HAA patterns across all organisms and growth conditions, which-consistent with previous hypotheses-suggests a first-order control by biosynthetic pathways. Moreover, δ2HAA values varied systematically with the catabolic pathways activated for substrate degradation, with variations explainable by the isotopic compositions of important cellular metabolites, including pyruvate and NADPH, during growth on each substrate. As such, amino acid δ2H values may be useful for interrogating organismal physiology and metabolism in the environment, provided we can further elucidate the mechanisms underpinning these signals.

In-situ construction of porous carbon substrate from sodium carboxymethyl cellulose boosting ultra-long lifespan for Na3V2(PO4)3 cathode material

Na3V2(PO4)3 (trisodium divanadium (III) tris (orthophosphate [NVP]), the cathode material for sodium ion batteries, faces several challenges, such as lower intrinsic electronic and ionic conductivities, which hinder its commercial viability. In this work, NVP system is modified by introducing sodium carboxymethyl cellulose (Na CMC) to achieve triple modification effects: sodium-rich, cross-linked carbon coating network, and carbon layer surface modification. Meanwhile, CMC, as a porous carbon substrate with large pores, provides a fast migration channel for Na+. Similarly, carbon nanotubes (CNTs) grown from the active particles become the connecting carriers between the active particles, thus effectively improving the electron transport. Notably, the scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images after cycling verify the stabilized porous structure of the Na3V2(PO4)3/C@0.7wt.%CMC@CNTs (0.7wt.%CMC@CNTs) composite. Distinctively, the modified 0.7wt.%CMC@CNTs reveals a capacity of 111.4 mAh/g at 0.1 C. It submits a high value of 105.0 mAh/g at 1 C with a capacity retention rate of 84.10% after 1,000 cycles. Even at 15 C, it still releases 86.6 mAh/g with a low capacity decay rate of 0.0230% per cycle after 3,600 cycles. Notably, its capacity retention reaches an astonishing 96.09% after 13,000 cycles at an ultra-high rate of 80 C.

Yarrowia lipolytica CMGB32 Biosurfactants Produced Using n-Hexadecane: Developing Strategies for Environmental Remediation

The yeast Yarrowia lipolytica degrades petroleum compounds, including alkanes, via the monoterminal oxidation pathway, the hydrophobic carbon substrate assimilation is mediated by biosurfactants, and extracellular amphiphilic molecules are produced by the yeast cell. This study focuses on the ability of the strain Y. lipolytica CMGB32 to degrade n-hexadecane by producing biosurfactants with high potential for bioremediation. The hydrocarbon-degrading potential of the yeast strain was observed via a 2,6-dichlorophenolindophenol (DCPIP) test in Bushnell–Hass medium with 1% n-hexadecane, and cell hydrophobicity was expressed as microbial adhesion to hydrocarbons (MATH). Biosurfactant production on yeast peptone (YP) with 1% n-hexadecane was estimated after 72 h using the emulsification index (E24%) against toluene. Crude biosurfactant (cell-free broth) stability tests were performed at different temperatures (4 °C, 70 °C) and NaCl concentrations (2–10%). The effects of a biosurfactant on synthetic wastewater remediation comprised the growth curves (OD measurements) of natural heavy metal degrader Rhodotorula mucilaginosa, determination of nutrients (spectrophotometrically), physico-chemical parameters, and removal capacity of lead and cadmium ions (via inductively coupled plasma mass spectrometry—ICP-MS). The antimicrobial and anti-adherence activities of 20 mg/mL and 40 mg/mL of the biosurfactant against pathogenic Candida krusei strains involved growth observations and the crystal violet microtiter method. The DCPIP decolorization occurred after six days, corresponding to the maximum growth phase of the Y. lipolytica culture. After 72 h, the cells presented high hydrophobicity (82.61% MATH) and stable biosurfactant production (E24% 47%). The crude biosurfactant (5%) increased the growth of R. mucilaginosa strains cultivated on synthetic wastewater cultures contaminated with Pb2+ and Cd2+, increased the conductivity and COD (86%) of the samples, and determined Pb2+ (66%) and Cd2+ (42%) ions reduction. The concentrated biosurfactant inhibited C. krusei growth (70%) and biofilm adherence. In conclusion, Y. lipolytica CMGB32 shows important potential for development of biosurfactant-based technologies for the remediation of heavy-metal- and emerging pathogen-contaminated wastewaters.

Assessment of Near-Surface Geophysical Methods Used to Discover Karst Bauxite Deposits in the Dinarides Using the Example of Posušje Area, Bosnia and Herzegovina

Geophysical exploration of bauxite deposits has been carried out in the area of Posušje in Bosnia and Herzegovina, which were formed on an Upper Cretaceous carbonate substrate, whereas the hanging wall rocks can be Paleogene limestones and sedimentary clastic rocks. Karst terrains are demanding for geophysical exploration due to the relatively complex geological relationships and exceptional near-surface inhomogeneities that generate large noises and challenging conditions for taking field measurements. The fundamental question is whether geophysical research can detect exceptionally irregular karst bauxite deposits with relatively small dimensions. The basic idea is to combine several geophysical methods and a joint interpretation of several data sets to increase the efficiency of geophysical surveying in detecting complex bauxite deposits in karst terrains. Therefore, fundamental near-surface research methods, electrical tomography and seismic refraction are used. In addition, magnetometry was used to examine whether bauxite deposits yield potential magnetic anomalies that could help in detecting them. Research undertaken in the area of Posušje was carried out in the first step on already discovered and known bauxite deposits to determine whether geophysical responses correlate with the occurrence of bauxite deposits and to evaluate the effectiveness of each of the applied surface geophysical methods. Measurements were taken at several locations, and results for two micro-locations, Krstače and Mratnjača, are shown. Geophysical measurements were firstly performed on discovered bauxite deposits in order to reliably determine the possibility of identifying deposits in geophysical inverse models. Bauxite deposits were clearly recognised as characteristic geophysical responses in inversion models using both methods, electrical tomography and seismic refraction. Although the response of bauxite deposits is expressed in both models, resistivity and velocity, it is much more evident in resistivity models. The characteristic resistivity response was confirmed by the discovery of a new deposit. Therefore, the conclusion is that electrical resistivity tomography should be considered a basic method for exploring karst bauxite deposits. Seismic refraction provides a better characterisation of deposits and reduces the interpretation ambiguity. This solution can generally be applied to the problem of researching bauxite deposits in the Dinarides and similar geological models in the Mediterranean. Magnetometric measurements have shown that no magnetic anomalies could be associated with bauxite deposits, and only magnetometry was not successful in discovering bauxite deposits.

Activating the Ni‐Contenting Carbon Nanotube by Covalent Triazine Frameworks to Form Atomically Dispersed Ni Sites with Curvature Effect for Electrocatalytic CO2 Reduction

N‐coordinated Ni sites (NiNx) are effective catalysts for the electrochemical reduction of CO2 to CO. In most researches, modulating the coordination environment of Ni atoms is focused on to improve electrochemical CO2 reduction (ECR) performance. However, the influence of the carbon substrate's structure on the intrinsic activity of NiNx is seldom investigated. The highly curved surface of carbon nanotubes (CNT) may provide a unique curvature effect on NiNx. It is found that the Ni residues in CNT can be atomized to form NiNx sites on the surface of CNT (Ni‐N/CNT@covalent triazine framework [CTF]) through high‐temperature pyrolysis, using a soluble CTF nanosheet as N precursor. The π‐conjugated and ultrathin 2D structure of CTF enables closer interfacial contact between CTF and CNT, which avoids the formation of a thick carbon layer to maximize the curvature effect. Theoretical data reveal that the NiN3 configuration may act as a highly active ECR site, and the curvature effect from CNT can further tune the electronic structure of NiN3, thus improving the ECR kinetics. The Ni‐N/CNT@CTF‐based flow‐cell electrolyzer exhibits a jCO of 201 mA cm−2 at −0.9 V with a high FECO of 98%.

Microrespirometric Validation of a Two-stage Process for Polyhydroxyalkanoates Production from Peanut Oil and Propionate with Cupriavidus necator

Introduction Poly(3-hydroxyalkanoates) (PHA) is a biodegradable polyester synthesized by various bacteria, including Cupriavidus necator. The composition of PHA is influenced by the type of microorganism, cultivation conditions, and carbon substrate. The selection of a carbon source is critical for PHA production, significantly impacting process costs. Therefore, the common goal is scalability, with the design and optimization of PHA production relying on experimental determination of constitutive parameters. Methods In this work, a two-stage process for PHA production was conducted in shaking flasks functioning as mini reactors with the bacteria Cupriavidus necator. During the first stage, fructose was used as the sole carbon source. Once fructose was exhausted, a second stage commenced with a new carbon source, either peanut oil or propionate, to enhance PHA production. Ex-situ pulse respirometry approach was employed during the two-stage process to follow the kinetics of substrate consumption. Results The results indicated that the use of peanut oil would be advantageous over propionate, resulting in 12.2% more biomass and 13.9% more PHA. Conclusion Additionally, the growth rate was 88.9% higher with peanut oil. The characterization by pulse respirometry applied in microreactors, i.e., micro respirometry, allowed for the performance of up to 216 biological experiments to determine four important kinetic and stoichiometric parameters, namely maximum oxygen uptake (rO2max), substrate affinity constant (KS), growth yield (YX/S), and substrate oxidation yield (YO2/S). The values of these parameters indicated that peanut oil would be the best carbon source to promote PHA production during the second stage. The implementation of the microrespirometry technique during the screening of carbon sources for PHA production provided reliable information within a short period and with significantly less experimental effort.

Study of the effect of implantation temperature on the migration behaviour of Xe implanted into glassy carbon.

The effect of implantation temperature on the migration behaviour of xenon (Xe) implanted into glassy carbon and the effect of annealing on radiation damage retained by ion implantation were investigated. Glassy carbon substrates were implanted with 320keV Xe+ to a fluence of 2×1016cm-2. The implantation process was performed at room temperature (RT) and 100°C Some of the as-implanted samples were isochronally annealed in vacuum at temperatures ranging from 300°C to 700°C in steps of 100°C for 10h. The as-implanted and annealed samples were characterized using Rutherford backscattering spectrometry (RBS) and Raman spectroscopy. The RT implanted depth profiles indicated that the migration of Xe towards the surface of glassy carbon was accompanied by a loss of Xe ions. The samples implanted at 100°C indicated no diffusion or loss of Xe after annealing at 300°C. However, annealing at temperatures ranging from 400°C to 700°C resulted in a slight shift in the Xe profile tail-end towards the bulk of glassy carbon. The diffusion coefficients (D) in the temperature range of 300°C-700°C for the RT and 100°C implanted samples, activation energies (Ea), and pre-exponential factors (Do), were extracted. The values of D ranged from (9.72±0.48)×10-21 to (1.87±0.09)×10-20m2/s with an activation energy of (6.25±0.31)×10-5eV for RT implanted samples, and the samples implanted at 100°C, D ranged from (3.85±0.19)×10-21 to (6.96±0.34)×10-20m2/s with activation energy of (4.10±0.02)×10-5eV. The Raman analysis revealed that implantation at the RT amorphised the glassy carbon structure while the samples implanted at 100°C showed mild damage compared to RT implantation. Annealing of the RT-implanted sample resulted in some recovery of the damaged region as a function of increasing annealing temperature.

HsGDY 3D Framework-Encapsulated Cu2O Quantum Dots for High-Efficiency Energy Storage.

Nanostructured electrode materials become a vital component for future electrode materials because of their short electron and ion transport distances for fast charge and discharge processes and sufficient space between particles for volume expansion. So, achieving a smaller size of the nanomaterial with stable structure and high electrode performance is always the pursuit. Herein, the hybrid electrode material system hydrogen-substituted graphdiyne (HsGDY)/Cu2O-quantum dots (QDs) composed of an active carbon substrate and vibrant metal oxide QD load was established by HsGDY and cuprous oxide. The HsGDY frame with conjugated structure not only delivers impressive capacity by a self-exchange mechanism but also characterizes a matrix to forge strong connections with numerous active Cu2O-QDs for the prevention of aggregation, leading to a homogeneous storage and transport of charge in a bulk material of crisscross structural pores. QD-based electrode materials would exhibit desired capacities by their large surface area, abundant active surface atoms, and the short diffusion pathway. The hybrid system of HsGDY/Cu2O-QDs delivers an ultrahigh capacity of 1230 mA h g-1 with loading density reaching up to 1 mg cm-2. In the meantime, the electrode exhibits a long cycle stability of over 8000 cycles. The synergistic effect endows the hybrid system electrode with an approximately theoretical energy density, suggesting the great potential of such carbon/QD hybrid material system applied for high-performance batteries.

Positive Electronic Nickel Active Site Enhances N─H/C─H Bonds Breaking for Electrooxidation of Amines to Nitriles Coupling with Hydrogen Production

AbstractElectrocatalytic conversion of amines to nitriles can be used as biomass upgrading to assist hydrogen production in water electrolysis. However, achieving efficient N─H/C─H bond breaking in amines oxidation remains a challenge. Herein, the nitrogen‐doped carbon supported NiO nanoparticles with positive electronic nickel active site are simply synthesized to achieve ∽99% selectivity and complete conversion in electrooxidizing amines to nitriles, and the onset potential of the whole reaction is as low as 1.32 V vs. RHE. Detailed in situ characterizations and theoretical calculations prove that the carbon substrate enhances the interaction between the N 2p orbital of amines and the Ni 3d orbital, which favors the construction of an indirect oxidation intermediate state R‐CH2NH2···NiO(OH)abs and promotes the subsequent stepwise dehydrogenation to nitriles. This whole reaction produces 16.4 times more hydrogen than pure water splitting, facilitating the development of the chemicals industry and energy utilization.

Growth and mortality of aerobic anoxygenic phototrophs in the North Pacific Subtropical Gyre.

Aerobic anoxygenic phototrophic (AAP) bacteria harvest light energy using bacteriochlorophyll-containing reaction centers to supplement their mostly heterotrophic metabolism. While their abundance and growth have been intensively studied in coastal environments, much less is known about their activity in oligotrophic open ocean regions. Therefore, we combined in situ sampling in the North Pacific Subtropical Gyre, north of O'ahu island, Hawaii, with two manipulation experiments. Infra-red epifluorescence microscopy documented that AAP bacteria represented approximately 2% of total bacteria in the euphotic zone with the maximum abundance in the upper 50 m. They conducted active photosynthetic electron transport with maximum rates up to 50 electrons per reaction center per second. The in situ decline of bacteriochlorophyll concentration over the daylight period, an estimate of loss rates due to predation, indicated that the AAP bacteria in the upper 50 m of the water column turned over at rates of 0.75-0.90 d-1. This corresponded well with the specific growth rate determined in dilution experiments where AAP bacteria grew at a rate 1.05 ± 0.09 d-1. An amendment of inorganic nitrogen to obtain N:P = 32 resulted in a more than 10 times increase in AAP abundance over 6 days. The presented data document that AAP bacteria are an active part of the bacterioplankton community in the oligotrophic North Pacific Subtropical Gyre and that their growth was mostly controlled by nitrogen availability and grazing pressure.IMPORTANCEMarine bacteria represent a complex assembly of species with different physiology, metabolism, and substrate preferences. We focus on a specific functional group of marine bacteria called aerobic anoxygenic phototrophs. These photoheterotrophic organisms require organic carbon substrates for growth, but they can also supplement their metabolic needs with light energy captured by bacteriochlorophyll. These bacteria have been intensively studied in coastal regions, but rather less is known about their distribution, growth, and mortality in the oligotrophic open ocean. Therefore, we conducted a suite of measurements in the North Pacific Subtropical Gyre to determine the distribution of these organisms in the water column and their growth and mortality rates. A nutrient amendment experiment showed that aerobic anoxygenic phototrophs were limited by inorganic nitrogen. Despite this, they grew more rapidly than average heterotrophic bacteria, but their growth was balanced by intense grazing pressure.

A fundamental study on cyclic voltammetry at porous carbon thin-film electrodes

Porous carbons represent an important group of electrode materials for electrochemical applications due to their high specific surface area, good conductivity, and intrinsic porosity. However, the often-neglected influence of the electrode porosity on the electrochemical results may lead to wrong interpretation of data. The aim of this work is therefore to provide comprehensive understanding of the effects of electrode porosity on cyclic voltammetry (CV) – a technique which is frequently used for initial characterization of novel electrode materials. Our approach consists of simulating experimental results, observed for the redox-reactions of [Fe(CN)6]3-/4− at porous CNT thin-film electrodes, with a mathematical model. The results demonstrate that the main difference between planar and porous electrode is the additional charge transferred in the porous electrode domain, which has the decisive contribution to the overall faradaic current at high scan rates. To further verify the applied model, the porosity of the porous CNT film is varied on purpose by changing the Nafion-Carbon-ratio (NCR). We are able to determine the electrochemically available pore volume (ECPV) of the electrode, which is strongly affected by the NCR, and correlate changes in the ECPV with changes in the scan-rate dependent CV. Moreover, we implement an approach for determination of reaction rate constants at porous electrodes, which was verified by simulated CV data. Evaluation of the experimental results shows that the reaction rate constant of the porous CNT material actually has the same order of magnitude as the planar glassy carbon substrate.

Biosurfactant production by a crude oil‐utilizing bacterium towards petroleum hydrocarbon biodegradation applications

AbstractBiosurfactants produced by microorganisms are green amphiphilic biomolecules. They have numerous advantages compared to chemical surfactants including a lower toxicity, better environmental compatibility and effective and stable properties under extreme conditions such as a wide range of temperature, pH and salinity. A highly bio‐surfactant‐producing strain of Bacillus, VTVK15 was selected among the Bacillus isolates from marine environment and oil contaminated sites in Ba Ria‐Vung Tau. Sequence analysis of 16S rDNA showed that the VTVK15 strain was 99% similar with 16s rDNA sequence of Bacillus megaterium. The suitable conditions for the bio‐surfactant production by the strain VTVK15 were 37 °C, pH 7; 2% w/v and 0.4% w/v for temperature, initial solution pH, concentration of carbon substrate (crude oil), and concentration of nitrogen substrate ((NH4)2SO4), respectively. The emulsification index (E24) increased from 51.8% to 67.7% with suitable conditions. The petroleum hydrocarbon degradation (TPH) efficiency by the strain Bacillus megaterium VTVK15 in crude oil estimated using TPH analysis was 72% after 14 days. These results revealed that the strain VTVK15 exhibited a tremendous potential for bioremediation of petroleum hydrocarbon contaminants.

Introduction of a Conductive Layer into Flood-Resistant Gas Diffusion Electrodes with Polymer Substrate for an Efficient Electrochemical CO2 Reduction with Copper Oxide.

Conversion of atmospheric carbon dioxide (CO2) into valuable feedstocks is a crucial technology, and electrochemical reduction of CO2 is a promising approach that can provide a useful source of ethylene (C2H4). Gas diffusion electrodes (GDEs) placed at the interface of the CO2 gas and electrolyte can achieve high current density through a sufficient supply of dissolved CO2 to the reaction site, making them indispensable in industrial applications. However, conventional GDEs with carbon substrate have suffered from electrolyte flooding and consequent loss of efficiency, posing an obstacle for practical application. While flood-resistant GDEs with hydrophobic polymer substrate have been proposed recently, only conductive materials can be employed as electrocatalysts because of their insulative properties, despite the high activities of oxide materials such as copper oxide. Here, we introduce an aluminum conductive layer in GDE with polymer substrate to enable the use of electrically resistive catalysts. Cuprous oxide (Cu2O) with silver particles was tested as a model material and has shown prolonged stability (>17 h) with high C2H4 Faraday efficiency (>50%) while suppressing flooding. A thorough characterization revealed that the conductive layer makes Cu2O an efficient electrocatalyst, even on the polymer substrate, by providing sufficient electrons through its conduction path. This research significantly expands the scope of electrode design by enabling the incorporation of a wide range of nonelectrically conductive materials on GDEs with polymer substrate.

A novel gluconeogenic route enables efficient use of erythritol in zoonotic Brucella.

Brucellosis is a worldwide extended zoonosis caused by pathogens of the genus Brucella. While most B. abortus, B. melitensis, and B. suis biovars grow slowly in complex media, they multiply intensely in livestock genitals and placenta indicating high metabolic capacities. Mutant analyses in vitro and in infection models emphasize that erythritol (abundant in placenta and genitals) is a preferred substrate of brucellae, and suggest hexoses, pentoses, and gluconeogenic substrates use in host cells. While Brucella sugar and erythritol catabolic pathways are known, growth on 3-4 carbon substrates persists in Fbp- and GlpX-deleted mutants, the canonical gluconeogenic fructose 1,6-bisphosphate (F1,6bP) bisphosphatases. Exploiting the prototrophic and fast-growing properties of B. suis biovar 5, we show that gluconeogenesis requires fructose-bisphosphate aldolase (Fba); the existence of a novel broad substrate bisphosphatase (Bbp) active on sedoheptulose 1,7-bisphosphate (S1,7bP), F1,6bP, and other phosphorylated substrates; that Brucella Fbp unexpectedly acts on S1,7bP and F1,6bP; and that, while active in B. abortus and B. melitensis, GlpX is disabled in B. suis biovar 5. Thus, two Fba-dependent reactions (dihydroxyacetone-phosphate + glyceraldehyde 3-phosphate ⇌ F1,6bP; and dihydroxyacetone-phosphate + erythrose 4-phosphate ⇌ S1,7bP) can, respectively, yield fructose 6-phosphate and sedoheptulose 7-phosphate for classical gluconeogenesis and the Pentose Phosphate Shunt (PPS), the latter reaction opening a new gluconeogenic route. Since erythritol generates the PPS-intermediate erythrose 4-phosphate, and the Fba/Fbp-Bbp route predicts sedoheptulose 7-phosphate generation from erythrose 4-phosphate, we re-examined the erythritol connections with PPS. Growth on erythritol required transaldolase or the Fba/Fbp-Bbp pathway, strongly suggesting that Fba/Fbp-Bbp works as a PPS entry for both erythritol and gluconeogenic substrates in Brucella. We propose that, by increasing erythritol channeling into PPS through these peculiar routes, brucellae proliferate in livestock genitals and placenta in the high numbers that cause abortion and infertility, and make brucellosis highly contagious. These findings could be the basis for developing attenuated brucellosis vaccines safer in pregnant animals.

Multi-functional hydrogen- and oxygen-capturing FeCo-N-C catalyst with improved hydrogenation of nitroarenes and ORR activity

Hydrogen energy storage and transportation are critical issues that must be addressed to ensure the development of alternatives to fossil fuel energy in the future. Herein, the poly(Schiff base) strategy is used to explore the carbon substrate, which is enclosed with binary metal Fe and Co as precursors. After the calcination and acid treatment steps, one of the FeCo alloy, termed FeCoNC-1000A900, was assembled with porous carbon skeleton as a shell and enclosed with FeCo alloy as a core. The FeCoNC-1000A900 exhibits outstanding H2 capture properties from NaBH4/EtOH mixtures circumstance owing to its large average particle size of 45 nm and high specific surface area of 462.07 m2/g. Notably, the FeCoNC-1000A900 acquires bi-functional catalysis efficacy, one is for chemoselectivity in the hydrogenation of nitroarene substrates and shows a high turnover frequency in 690 h−1 within the overall conversion yield. The other one is the O2 capture performance toward the oxygen reduction reaction with the excellent onset potential of 0.89 V, the half-wave potential of 0.77 V, and limiting current density of − 5.56 mA cm−2, which are comparable to those of the commercial Pt/C catalyst. In addition, the Tafel slope of 79.6 mV dec−1 is lower than those for other catalysts. Consequently, the development of the novel FeCoNC-1000A900 catalyst has two functional applications.

Selective genes expression and metabolites transformation drive a robust nitrite accumulation during nitrate reduction under alternating feast-famine condition

Nitrite production via denitrification has been regarded as a key approach for survival of anaerobic ammonium oxidation (anammox) bacteria. Despite the important carbon substrate, little is known about the role of differential genes expression and extracellular metabolite regulation among diverse microbial communities. In this study, a novel alternating feast-famine strategy was proposed and demonstrated to efficiently accumulate nitrite in a low-nitrogen loading rate (NLR) (0.2∼0.8 kg N/m3/d) denitrification system. Highly selective expression of denitrifying genes was revealed as key regulators. Interestingly, in absence of carbon source (ACS) condition, the expression of narG and narI/V genes responsible for reduction of nitrate to nitrite jumped to 2.5 and 5.1 times higher than that in presence of carbon source (PCS) condition with carbon to nitrate ratio of 3.0. This fortunately facilitated a rapid nitrite accumulation once acetate was added, despite a significantly down-regulated narG and narI/narV and up-regulated nirS/nirK. This strategy selected Thauera as the most dominant denitrifier (50.2 %) with the highest contribution to narG and narI/narV genes, responsible for the high nitrite accumulation. Additionally, extracellular xylose, pyruvate, and glucose jointly promoted carbon-central metabolic pathway of key denitrifiers in ACS stage, playing an important role in the process of self-growth and selective enrichment of functional bacteria. The relatively rapid establishment and robust performance obtained in this study shows an engineering-feasible and economically-favorable solution for the regulation of partial denitrification in practical application.

Responses of vascular plant fine roots and associated microbial communities to whole-ecosystem warming and elevated CO2 in northern peatlands.

Warming and elevated CO2 (eCO2) are expected to facilitate vascular plant encroachment in peatlands. The rhizosphere, where microbial activity is fueled by root turnover and exudates, plays a crucial role in biogeochemical cycling, and will likely at least partially dictate the response of the belowground carbon cycle to climate changes. We leveraged the Spruce and Peatland Responses Under Changing Environments (SPRUCE) experiment, to explore the effects of a whole-ecosystem warming gradient (+0°C to 9°C) and eCO2 on vascular plant fine roots and their associated microbes. We combined trait-based approaches with the profiling of fungal and prokaryote communities in plant roots and rhizospheres, through amplicon sequencing. Warming promoted self-reliance for resource uptake in trees and shrubs, while saprophytic fungi and putative chemoorganoheterotrophic bacteria utilizing plant-derived carbon substrates were favored in the root zone. Conversely, eCO2 promoted associations between trees and ectomycorrhizal fungi. Trees mostly associated with short-distance exploration-type fungi that preferentially use labile soil N. Additionally, eCO2 decreased the relative abundance of saprotrophs in tree roots. Our results indicate that plant fine-root trait variation is a crucial mechanism through which vascular plants in peatlands respond to climate change via their influence on microbial communities that regulate biogeochemical cycles.