All-Nitrogen Energetic Material Cubic Gauche Polynitrogen: Plasma Synthesis and Thermal Performance.

Numerous theoretical calculations have demonstrated that polynitrogen with an extending polymeric network is an ultrahigh-energy all-nitrogen material. Typical samples, such as cubic gauche polynitrogen (cg-N), have been synthesized, but the thermal performance of polynitrogen has not been unambiguously determined. Herein, macroscopic samples of polynitrogen were synthesized utilizing a coated substrate, and their thermal decomposition behavior was investigated. Polynitrogen with carbon nanotubes was produced using a plasma-enhanced chemical vapor deposition method and characterized using infrared, Raman, X-ray diffraction X-ray photoelectron spectroscopy and transmission electron microscope. The results showed that the structure of the deposited polynitrogen was consistent with that of cg-N and the amount of deposition product obtained with coated substrates increased significantly. Differential scanning calorimetry (DSC) at various heating rates and TG-DSC-FTIR-MS analyses were performed. The thermal decomposition temperature of cg-N was determined to be 429 °C. The apparent activation energy (Ea) of cg-N calculated by the Kissinger and Ozawa equations was 84.7 kJ/mol and 91.9 kJ/mol, respectively, with a pre-exponential constant (lnAk) of 12.8 min-1. In this study, cg-N was demonstrated to be an all-nitrogen material with good thermal stability and application potential to high-energy-density materials.

Photodynamic Inactivation Using Natural Bioactive Compound Prevents and Disrupts the Biofilm Produced by Staphylococcus saprophyticus.

Staphylococcus saprophyticus, the food-borne bacteria present in dairy products, ready-to-eat food and environmental sources, has been reported with antibiotic resistance, raising concerns about food microbial safety. The antimicrobial resistance of S. saprophyticus requires the development of new strategies. Light- and photosensitizer-based antimicrobial photodynamic inactivation (PDI) is a promising approach to control microbial contamination, whereas there is limited information regarding the effectiveness of PDI on S. saprophyticus biofilm control. In this study, PDI mediated by natural bioactive compound (curcumin) associated with LED was evaluated for its potential to prevent and disrupt S. saprophyticus biofilms. Biofilms were treated with curcumin (50, 100, 200 µM) and LED fluence (4.32 J/cm2, 8.64 J/cm2, 17.28 J/cm2). Control groups included samples treated only with curcumin or light, and samples received neither curcumin nor light. The action was examined on biofilm mass, viability, cellular metabolic activity and cytoplasmic membrane integrity. PDI using curcumin associated with LED exhibited significant antibiofilm activities, inducing biofilm prevention and removal, metabolic inactivation, intracellular membrane damage and cell death. Likewise, scanning electronic microscopy observations demonstrated obvious structural injury and morphological alteration of S. saprophyticus biofilm after PDI application. In conclusion, curcumin is an effective photosensitizer for the photodynamic control of S. saprophyticus biofilm.

Immobilization of laccase onto meso-MIL-53(Al) via physical adsorption for the catalytic conversion of triclosan.

Due to the abundant binding sites and high stability, a synthesized meso-MIL-53(Al) was selected as the backbone and used for immobilizing laccase (Lac-MIL-53(Al)) to catalytically degrade of TCS. XRD, BET and FTIR analyses proved that the carboxyl groups on PTA of meso-MIL-53(Al) could provide sufficient adsorption sites for physically immobilizing laccase through hydrogen bonds and electrostatic interactions. Although the catalytic efficiency of Vmax/Km slightly decreased from 785 to 607 min-1 due to the mass transfer limitation upon immobilized, Lac-MIL-53(Al) showed high activity recovery (93.8%) and stability. The conformational analysis indicated the laccase could partially enter into the MOF by conformational changes without impairing laccase, although the laccase molecular (6.5 nm × 5.5 nm × 4.5 nm) was larger than the mesopore sizes of the MOF (4 nm). The kinetics indicated that Lac-MIL-53(Al) could remove 99.24% of TCS within 120 min due to the synergy effect of the adsorption of meso-MIL-53(Al) and catalytic degradation of laccase. Meanwhile, Lac-MIL-53(Al) could remain approximately 60% of activity for up to 8 times reuse without desorption. The GC/MS and LC/MS/MS analyses further confirmed that TCS could be transformed to 2, 4-DCP by laccase via the breakage of the ether bond, or to passivated dimers, trimers and tetramers by the self-coupling and oxidization of the phenoxyl radicals, and finally removed by precipitation. In summary, enzyme-MOF composite might be a potential strategy to control the micropollutants in the wastewater.

Positive effects of bio-nano Pd (0) toward direct electron transfer in Pseudomona putida and phenol biodegradation.

This study constructed a biological-inorganic hybrid system including Pseudomonas putida (P. putida) and bioreduced Pd (0) nanoparticles (NPs), and inspected the influence of bio-nano Pd (0) on the direct electron transfer and phenol biodegradation. Scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM-EDX) showed that bio-nano Pd (0) (~10 nm) were evenly dispersed on the surface and in the periplasm of P. putida. With the incorporation of bio-nano Pd (0), the redox currents of bacteria in the cyclic voltammetry (CV) became higher and the oxidation current increased as the addition of lactate, while the highest increase rates of two electron transfer system (ETS) rates were 63.97% and 33.79%, respectively. These results indicated that bio-nano Pd (0) could directly promote the electron transfer of P. putida. In phenol biodegradation process, P. putida-Pd (0)- 2 showed the highest k (0.2992 h-1), µm (0.035 h-1) and Ki (714.29 mg/L) and the lowest apparent Ks (76.39 mg/L). The results of kinetic analysis indicated that bio-nano Pd (0) markedly enhanced the biocatalytic efficiency, substrate affinity and the growth of cells compared to native P. putida. The positive effects of bio-nano Pd (0) to the electron transfer of P. putida would promote the biodegradation of phenol.

The metallic state in neutral radical conductors: dimensionality, pressure and multiple orbital effects.

Pressure-induced changes in the solid-state structures and transport properties of three oxobenzene-bridged bisdithiazolyl radicals 2 (R = H, F, Ph) over the range 0-15 GPa are described. All three materials experience compression of their π-stacked architecture, be it (i) 1D ABABAB π-stack (R = Ph), (ii) quasi-1D slipped π-stack (R = H), or (iii) 2D brick-wall π-stack (R = F). While R = H undergoes two structural phase transitions, neither of R = F, Ph display any phase change. All three radicals order as spin-canted antiferromagnets, but spin-canted ordering is lost at pressures <1.5 GPa. At room temperature, their electrical conductivity increases rapidly with pressure, and the thermal activation energy for conduction Eact is eliminated at pressures ranging from ∼3 GPa for R = F to ∼12 GPa for R = Ph, heralding formation of a highly correlated (or bad) metallic state. For R = F, H the pressure-induced Mott insulator to metal conversion has been tracked by measurements of optical conductivity at ambient temperature and electrical resistivity at low temperature. For R = F compression to 6.2 GPa leads to a quasiquadratic temperature dependence of the resistivity over the range 5-300 K, consistent with formation of a 2D Fermi liquid state. DFT band structure calculations suggest that the ease of metallization of these radicals can be ascribed to their multiorbital character. Mixing and overlap of SOMO- and LUMO-based bands affords an increased kinetic energy stabilization of the metallic state relative to a single SOMO-based band system.

Evidence for the feasibility of transmembrane proton gradient regulating oxytetracycline extracellular biodegradation mediated by biosynthesized palladium nanoparticles.

Extracellular biodegradation is a promising technology for removing antibiotics and repressing the spread of resistance genes, but the strategy is limited by the low extracellular electron transfer (EET) efficiency of microorganisms. In this work, biogenic Pd0 nanoparticles (bio-Pd0) were introduced in cells in situ to enhance oxytetracycline (OTC) extracellular degradation and the effects of transmembrane proton gradient (TPG) on EET and energy metabolism mediated by bio-Pd0 were investigated. The results indicated that the intracellular OTC concentration gradually decreased with increase in pH due to the simultaneous decreases of OTC adsorption and TPG-dependent OTC uptake. On the contrary, the efficiency of OTC biodegradation mediated by bio-Pd0@B. megaterium showed a pH-dependent increase. The negligible intracellular OTC degradation, the high dependence of OTC biodegradation on respiration chain and the results on enzyme activity and respiratory chain inhibition experiments showed that NADH-dependent (rather than FADH2-dependent) EET process mediated by substrate-level phosphorylation modulated OTC biodegradation due to high energy storage and proton translocation capacity. Moreover, the results showed that altering TPG is an efficient approach to improve EET efficiency, which can be attributed to the increased NADH generation by the TCA cycle, enhanced transmembrane electron output efficiency (as evidenced by increased intracellular electron transfer system (IETS) activity, the negative shift of onset potential, and enhanced one-electron transfer through bound flavin) and stimulation of substrate-level phosphorylation energy metabolism catalyzed by succinic thiokinase (STH) under low TPG conditions. The results of structural equation model that OTC biodegradation was directly and positively modulated by the net outward proton flux as well as STH activity, and indirectly regulated by TPG through NADH level and IETS activity confirmed the previous findings. This study provides a new perspective for engineering microbial EET and application of bioelectrochemistry processes in bioremediation.

CpxR negatively regulates IncFII-replicon plasmid pEC011 conjugation by directly binding to multi-promoter regions.

CpxAR is a global regulatory protein and has important roles in plasmid mating. However, except for traJ, the regulatory effect of CpxAR on other tra genes is unclear. The aim of this study was to explore the effects of CpxAR on conjugative transfer of the epidemic plasmid pEC011 (IncFII replicon) in Escherichia coli. The plasmid mating frequencies were significantly higher for the single deletion mutant strain FΔcpxR than for the parental strain F25922. Additionally, expression levels of traM, traJ and traY in FΔcpxR were significantly higher than those in F25922. Further investigations revealed that His6-CpxR protein could directly bind to the traM, traJ and traY promoter regions with the binding sites of 5'-TTTACATT-3' (PM), 5'-ATAAGAAT-3' (PJ), and 5'-AATTTTAT-3' (PY), respectively. Taken together, our results demonstrate that CpxAR can downregulate the expression of traM, traJ and traY by directly binding to the CpxR box-like sites of promoters, thus significantly reducing the mating rates of IncFII replicon plasmid pEC011.

Superconductivity above 200 K discovered in superhydrides of calcium.

Searching for superconductivity with Tc near room temperature is of great interest both for fundamental science & many potential applications. Here we report the experimental discovery of superconductivity with maximum critical temperature (Tc) above 210 K in calcium superhydrides, the new alkali earth hydrides experimentally showing superconductivity above 200 K in addition to sulfur hydride & rare-earth hydride system. The materials are synthesized at the synergetic conditions of 160~190 GPa and ~2000 K using diamond anvil cell combined with in-situ laser heating technique. The superconductivity was studied through in-situ high pressure electric conductance measurements in an applied magnetic field for the sample quenched from high temperature while maintained at high pressures. The upper critical field Hc(0) was estimated to be ~268 T while the GL coherent length is ~11 Å. The in-situ synchrotron X-ray diffraction measurements suggest that the synthesized calcium hydrides are primarily composed of CaH6 while there may also exist other calcium hydrides with different hydrogen contents.

Intra/extracellular electron transfer for aerobic denitrification mediated by in-situ biosynthesis palladium nanoparticles.

The slow electron transfer rate is the bottleneck to the biological wastewater treatment process, and the nanoparticles (NPs) has been verified as a feasible strategy to improve the biological degradation efficiency by accelerating the electron transfer. Here, we employed the Gram-positive Bacillus megaterium Y-4, capable of synthetizing Pd(0), to investigate the intra/extracellular electron transfer (IET/EET) mechanisms mediated by NPs in aerobic denitrification for the first time. Kinetic and thermodynamic results showed that the bio-Pd(0) could significantly promote the removal of both nitrate and nitrite by improving affinity and decreasing activation energy. The enzymic activity and the respiration chain inhibition experiment indicated that the bio-Pd(0) could facilitate the nitrate biotic reduction by improving the Fe-S center activity and serving as parallel H carriers to replace coenzyme Q to selectively increase the electron flux toward nitrate in IET, while promoting the nitrite reduction by abiotic catalysis. Most importantly, the detection of DPV peak at -226~-287 mV proved that the one-electron EET via multiheme cytochrome-bound flavins also occurred in Gram-positive bacteria and enhanced in Pd-loaded cells. In addition, the remarkable increase of the formal charge in EPS indicated that the bio-Pd(0) could act as an electron shuttle to increase the redox site in EPS, eventually accelerating the electron hopping in long-distance electron transfer. Overall, this study expanded our understanding of the roles of bio-Pd(0) on the aerobic denitrification process and provided an insight into the IET/EET of Gram-positive strains.

Genomic characteristics of mcr-1 and blaCTX-M-type in a single multidrug-resistant Escherichia coli ST93 from chicken in China.

This study was undertaken to discern the transmission characteristics of mcr-1 and blaCTX-M-type in one multidrug-resistant Escherichia coli LWY24 from chicken in China. The genetic profiles of LWY24 isolate were determined by conjugation, S1-pulsed-field gel electrophoresis, southern blot hybridization, and whole genome sequencing analysis. Meanwhile, co-transfer of plasmids in LWY24 isolate was screened by dual conjugation assays. The LWY24 isolate was identified as ST93, and harbored 3 conjugative plasmids, pLWY24J-3 (blaCTX-M-55-bearing IncFⅡ), pLWY24J-mcr-1 (mcr-1-carrying IncI2), and pLWY24J-4 (non-resistance-conferring IncI1), and one nonconjugative plasmid pLWY24 (blaCTX-M-14-containing IncHI2/IncHI2A). Numerous resistance genes, insertion sequences (especially IS26), and transposons were found in the 4 plasmids, suggesting that horizontal transmission have occurred by plasmid mating, homologous recombination, and transpositions. Under the selection pressure of cefotaxime and colistin or cefotaxime alone, the mcr-1-bearing plasmid and the blaCTX-M-55-harboring plasmid could be co-transferred at a similar frequency, with 8.00 × 10-4 or 9.00 × 10-4 transconjugants per donor cell, respectively. The specific shufflon region in mcr-1-encoding plasmid could generate up to 6 diverse PilV structures, which may further accelerate the horizontal transfer of plasmid. In conclusion, the transmission characteristics of mcr-1 and blaCTX-M-type in LWY24 isolate could due to clonal spread of ST93, selective pressure of cefotaxime, IS26-mediate homologous recombination and transposition, and the specific shufflon region.

Construction of a nanofiber network within 3D printed scaffolds for vascularized bone regeneration.

Three-dimensional (3D) printed scaffolds provide a promising prospective for application in bone tissue engineering. 3D printed scaffolds with micro- and nano-fibrous structures that facilitate cell adhesion and migration, and combined vascularization and osteoinduction bioactivity will be ideal implants for bone defect repair. Here, we fabricated a 3D printed biodegradable poly (glycerol-co-sebacic acid-co-l-lactic acid-co-polyethylene glycol) (PGSLP)-based scaffold that was internally filled with gelatin nanofibers and allowed the local release of deferoxamine (DFO), which is essential for angiogenesis and osteogenesis in bone regeneration. The nanofibrous structured gelatin/PGSLP (NGP) scaffold was fabricated using a thermally induced phase separation (TIPS) technique, and the macroporous structured gelatin/PGSLP (MGP) scaffold was prepared by directly freeze-drying. The in vitro experiments demonstrated that both DFO-loaded NGP and DFO-loaded MGP scaffolds can promote the migration and tubular formation of human umbilical vein endothelial cells (HUVECs), and enhance the mineralized nodule formation and osteogenic-related gene expression during osteogenic differentiation of bone marrow-derived mesenchymal stem cells (BMSCs). In a rat critical-sized calvarial defect model, the results suggested that the scaffolds with DFO loading significantly promote the vascular formation and accelerate bone regeneration, while the enhancement of vascularization and osteogenesis in vivo in DFO-loaded NGP scaffold was better than that in DFO-loaded MGP scaffold. Therefore, the constructed PGLSP-based scaffolds with micro- and nano-fibrous structures would be promising candidates to match the structural and functional requirements for vascularized bone regeneration.

Effect of curcumin on the quality properties of millet fresh noodle and its inhibitory mechanism against the isolated spoilage bacteria.

Fresh noodle product has attracted increasing attention due to its nutritive value and convenience. However, the relative short shelf life of fresh noodle is still a concern that needs to resolve. The objective of this study was to evaluate the preservative effect of curcumin (CUR) on millet fresh noodle during storage and its inhibitory mechanism against two isolated spoilage bacteria (Bacillus cereus and Escherichia coli). The effects of CUR were evaluated with regard to the quality and sensory evaluation of millet fresh noodle, the changes of bacterial growth curve, cell intracellular substances, cell viability, and bacterial morphology. The results showed that CUR could decrease the total colony number and prolong the shelf life of millet fresh noodle stored at 25°C from 20 to 30 hr. Quality and sensory evaluations showed that addition of CUR caused no negative effect on noodle quality and was determined to be sensory acceptable. The minimum inhibitory concentration of CUR against B. cereus and E. coli was 0.125 and 0.5 mg/ml, respectively. The growth curve revealed that CUR presented good antibacterial effect against both bacteria. The leakage of intracellular substances, cell viability, and bacterial morphology change after CUR treatment confirmed the destructive effects of CUR on plasma membrane integrity. These results indicated that CUR had the potential to be applied as a natural preservative for controlling the growth of spoilage microorganisms and extending the shelf life of millet fresh noodle.

Carbon selection for nitrogen degradation pathway by Stenotrophomonas maltophilia: Based on the balances of nitrogen, carbon and electron.

A novel strain DQ01 capable of simultaneous removal of nitrate and ammonium under the aerobic condition was isolated from the landfill leachate and identified as Stenotrophomonas maltophilia. The result showed that S. maltophilia had carbon selection for the nitrogen removal pathway, and preferred to utilize carboxylate rather than carbohydrate, as carboxylate could directly participate in TCA cycle without Embden Meyerhof Parmas (EMP). Nitrogen and carbon balances confirmed that the ammonium assimilation was the main or even sole removal pathway for S. maltophilia, and carboxylate was more conducive to heterotrophic nitrification-aerobic denitrification (HN-AD) process due to the serious self-alkalization and higher reduction potential of carboxylate, which followed: NH4+ → NO2- → NO3- → NO2- → NO due to the lack of nor and nos. Meanwhile, the higher C/N and nitrate could generate a more powerful ion transport driving force to accelerate the electron transfer in the denitrifying respiratory chain.

Simultaneous nitrification and denitrification without nitrite accumulation by a novel isolated Ochrobactrum anthropic LJ81.

Nitrogen contaminants are widespread presence in municipal wastewater, heterotrophic nitrification and aerobic denitrification (HN-AD) bacteria have advantages of dealing with multiple nitrogen. Strain LJ81 was isolated from domestic sludge, identified as Ochrobactrum anthropic, which was oxygen-dependent and could survive in a wide range of pH values. Results showed that strain LJ81 could achieve simultaneous nitrification and denitrification (SND) under aerobic condition, whilst more than 80% of initial nitrogen was converted into gaseous nitrogen. The removal rates of ammonia increased from 3.75 to 3.85 and 5.70 mg-N L-1 h-1 by adding nitrite and nitrate, respectively, while the nitrate denitrification was the rate-limiting step of SND process. Moreover, adding chlorate could inhibit not only the cell growth slightly but also denitrification of nitrate. All results indicated that O. anthropic strain LJ81 exhibited excellent performance on nitrogen removal without nitrite accumulation under aerobic condition.

Biomineralization of 2'2'4'4'-Tetrabromodiphenyl ether in a Pseudomonas putida and Fe/Pd nanoparticles integrated system.

Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants and challenges for water treatment due to their persistence and toxicity. In this study, the reduction of 2'2'4'4'-tetrabromodiphenyl ether (BDE-47) was investigated in a nano-bio-integrated system. Results showed that the introducing of P. putida could markedly accelerate the demineralization of BDE-47 in nZVI/Pd-P.p system; the continuous generation of acidic metaboliates by P. putida could decrease pH, which could alleviate the surface passivation to some extent, resulting in the releasing of Fe2+ and high generation of H2O2, the shift in reactive oxygen species from Fe(IV) to •OH. The BDE-47 was firstly debrominated to the DE by the highly reductive [Pd·2H] generated by nZVI/Pd, then oxidized to bromophenol and phenol, catechol as well as hydroquinone via the P. putida strain and the Fenton-like system. The toxicity assays confirmed the combined system could avert generation of nocuous intermediates, and could be an alternative strategy for complete remediation of recalcitrant POPs.

Pressure-induced spin transition and site-selective metallization in CoCl2.

The interplay between spin states and metallization in compressed CoCl2 is investigated by combining diffraction, resistivity and spectroscopy techniques under high-pressure conditions and ab-initio calculations. A pressure-induced metallization along with a Co2+ high-spin (S = 3/2) to low-spin (S = 1/2) crossover transition is observed at high pressure near 70 GPa. This metallization process, which is associated with the p-d charge-transfer band gap closure, maintains the localization of 3d electrons around Co2+, demonstrating that metallization and localized Co2+ -3d low-spin magnetism can coexist prior to the full 3d-electron delocalization (Mott-Hubbard d-d breakdown) at pressures greater than 180 GPa.