Avoiding Sabatier's limitation through pulsed electrocatalysis for enhanced nitrogen oxidation performance

1.Introduction The activation and conversion of the Earth’s abundant inert nitrogen resources into high-value-added products epitomize one of nature’s most critical processes[1-3].Nitric acid(HNO_(3)),as a pivotal industrial raw material,showcases an extensive range of applications and possesses substantial economic value in the production of indispensable chemical compounds[4-6].

Synergistic enhancement on mechanical properties and corrosion resistance of biodegradable Mg-Zn-Y alloy via V-microalloying

For the sake of improving the mechanical properties and corrosion resistance of biodegradable Mg alloy synergistically,various content of element V(0,0.05,0.10,0.15,0.20 wt.%)are introduced into an Mg-Zn-Y alloy with long-period stacking ordered(LPSO)structure,and the effects of V on its microstructure,mechanical properties and corrosion resistance are investigated systematically.The results indicate that the grains are effectively refined by V addition,and the primaryα-Mg in Mg-Zn-Y-V0.1 alloy is most significantly refined,with grain size being decreased by 62%.The amount of 18R LPSO structure is increased owing to the V addition.The growth mode of the second phase(W-phase and 18R LPSO structure)is transformed to divorced growth pattern,which ascribes to the thermodynamic drive force of V to promote the nucleation of LPSO phase.Thus,18R LPSO structure presents a continuous distribution.Due to grains refinement and modification of second phase,the tensile strength and strain of alloys are both enhanced effectively.Especially,the ultimate tensile strength and the elongation of V0.1 alloy are 254 MPa and 15.26%,which are 41%and 61%higher than those of V-free alloy,respectively.Owing to the continuously distributed 18R LPSO structure with refined grains and stable product film,the weight loss and hydrogen evolution corrosion rates of V0.1 alloy are 7.1 and 6.2 mmy^(-1),respectively,which are 42.6%and 45.4%lower than those of V-free alloy.

Mechanical properties and charge signal characteristics in coal material failure under different loading paths

Rock burst is a catastrophic dynamic disaster caused by sudden failure and instability of coal, loading paths play an important role in the failure of coal, the coal failure process is associated with charge exception infonnation. Hence, violent coal failure mechanics and time-frequency domain distribution of charge signal such as rock burst under different loading paths should be studied in-depth. In this paper, grade and cyclic loading test were carried out for coal with impact tendency samples produced by blocks cored from 800 depth in Xiaoqing coal mine of the Tiefa coal group in northeast China. Theory discussion was carried out for the result of stress and strain, frequency-spectra analysis was conducted for the wavelet charge data, figures showing the evolution mechanism of mechanical properties and the relationship of timefrequency domain amplitude of charge signals in coal with different loading paths and stage were obtained. The failure process and characteristics of coal under different loading paths were summarized. It found that the loading path changed the manner of energy accelerate-release, there were more plastic strain generation in coal under cyclic loading than that under grade loading, the former was more likely to cause greater damage and failure, then the strength of coal under cyclic loading is generally lower than that under grade loading, an energy conversion mechanical model of stress, damage and deformation was developed and explained the effect of the loading path. Charge signal was primarily distributed in the strengthening and peak stages, where there was a high amplitude pulse at each stress drop. The charge pulse was a type of low frequency signal with a primary frequency distribution range of 1 -100Hz. Discussion on the charge generating mechanism from the perspective of friction slip, it demonstrated that the charge obtained during the coal failure process directly to stress loaded on and damage, the result verified it better. We propose that the research results in this study could be efficiently applied to daily mining activities, to provide an early warning and effectively avoid rock burst disaster.

A novel method towards improving the hydrogen storage properties of hypoeutectic Mg-Ni alloy via ultrasonic treatment

Ultrasonic treatment has great contributions on modifying the morphology,dimension and distribution of constituent phases during solidification,which serve as dominate factors influencing the hydrogen storage performance of Mg-based alloys.In this research,ultrasonic treatment is utilized as a novel method to enhance the de-/hydriding properties of Mg-2Ni(at.%)alloy.Due to ultrasonic treatment,the microstructure of as-cast alloy is significantly refined and homogenized.Ascribing to the increased eutectic boundaries and shortened distance insideα-Mg for hydrogen atoms diffusion,the hydrogen uptake capacities and isothermal de-/hydriding rates improve effectively,especially at lower temperature.The peak desorption temperature reduces from 392.99°C to 345.56°C,and the dehydriding activation energy decreases from 101.93 k J mol^(-1)to 88.65 k J mol^(-1).Weakened hysteresis of plateau pressures and slightly optimized thermodynamics are determined from the pressure-composition isotherms.Owing to the refined primary Mg,a larger amount of hydrogen with the higher hydriding proportion is absorbed in the first stage when hydrides nucleate in eutectic region and grow on primary Mg periphery subsequently before MgH2colonies impinging,resulting in the enhancement of hydrogenation rates and capacities.

Cooperative Angles-Only Relative Navigation Algorithm for Multi-Spacecraft Formation in Close-Range

As to solve the collaborative relative navigation problem for near-circular orbiting small satellites in close-range under GNSS denied environment,a novel consensus constrained relative navigation algorithm based on the lever arm effect of the sensor offset from the spacecraft center of mass is proposed.Firstly,the orbital propagation model for the relative motion of multi-spacecraft is established based on Hill-Clohessy-Wiltshire dynamics and the line-of-sight measurement under sensor offset condition is modeled in Local Vertical Local Horizontal frame.Secondly,the consensus constraint model for the relative orbit state is constructed by introducing the geometry constraint between the spacecraft,based on which the consensus unscented Kalman filter is designed.Thirdly,the observability analysis is done and the necessary conditions of the sensor offset to make the state observable are obtained.Lastly,digital simulations are conducted to verify the proposed algorithm,where the comparison to the unconstrained case is also done.The results show that the estimated error of the relative position converges very quickly,the location error is smaller than 10m under the condition of 10−3 rad level camera and 5m offset.

Study on Wave Field Characteristics and Imaging of Collapse Column in Three-Dimensional Detection with Love Channel Wave Reflected outside the Working Face

The safety accidents caused by collapse column water diversion occur frequently, which has great hidden danger to the safety production of coal mine. Limited by the space of underground, the detection of collapse column on the outside of working face has been a difficult problem. Based on this, numerical simulation and imaging research were carried out in this paper. The results indicate that when a seismic source near the roadway is excited, a part of seismic wave propagates along the roadway direction, namely direct P-wave, direct S-wave and direct Love channel wave. When the body waves and Love channel wave propagating to the outside of working face meet the interface of collapse column, the reflected Love channel wave and reflected body waves are generated. Reflection body waves and direct waves are mixed in time domain, which is difficult to identify in seismic records, while reflected Love channel wave whose amplitude is relatively strong. The reflected Love channel wave which has a large interval from other wave trains in the time domain is easily recognizable in seismic record, which makes it suitable for advanced detection of collapse column. The signal-to-noise ratio of X component is higher than that of Y component and Z component. According to the seismic records, polarization filtering was carried out to enhance the effective wave, which removed the interference waves, and the signal was migrated to get the position parameters of collapse column interface, which was basically consistent with the model position.

基于下咽癌病灶的异质性手术治疗策略的选择与探讨

下咽癌是上消化呼吸道恶性程度最高的肿瘤之一。目前对于下咽癌的治疗,首选治疗方法是以手术治疗为主的综合治疗。基于肿瘤病灶的异质性,我们选择不同治疗策略。肿瘤原发灶的位置决定手术入路;病灶不同的临床特点,如小病灶大转移、浅表扩展癌、多点多灶癌等,其治疗策略具有差异性;手术切缘的范围一直是探讨和争论的热点。本文针对于以上问题,进行经验分享及相关文献总结。针对不同类型的下咽癌,为其制定最佳的个性化的治疗策略,以改善预后,提高生存率。

Neuroprotective effects of autophagy inhibition on hippocampal glutamate receptor subunits after hypoxia-ischemia-induced brain damage in newborn rats

Autophagy has been suggested to participate in the pathology of hypoxic-ischemic brain damage（HIBD）.However,its regulatory role in HIBD remains unclear and was thus examined here using a rat model.To induce HIBD,the left common carotid artery was ligated in neonatal rats,and the rats were subjected to hypoxia for 2 hours.Some of these rats were intraperitoneally pretreated with the autophagy inhibitor 3-methyladenine（10 m M in 10 μL） or the autophagy stimulator rapamycin（1 g/kg） 1 hour before artery ligation.Our findings demonstrated that hypoxia-ischemia-induced hippocampal injury in neonatal rats was accompanied by increased expression levels of the autophagy-related proteins light chain 3 and Beclin-1 as well as of the AMPA receptor subunit GluR 1,but by reduced expression of GluR 2.Pretreatment with the autophagy inhibitor 3-methyladenine blocked hypoxia-ischemia-induced hippocampal injury,whereas pretreatment with the autophagy stimulator rapamycin significantly augmented hippocampal injury.Additionally,3-methyladenine pretreatment blocked the hypoxia-ischemia-induced upregulation of Glu R1 and downregulation of GluR2 in the hippocampus.By contrast,rapamycin further elevated hippocampal Glu R1 levels and exacerbated decreased GluR2 expression levels in neonates with HIBD.Our results indicate that autophagy inhibition favors the prevention of HIBD in neonatal rats,at least in part,through normalizing Glu R1 and GluR2 expression.

TP53-induced glycolysis and apoptosis regulator alleviates hypoxia/ischemia-induced microglial pyroptosis and ischemic brain damage

Our previous studies have demonstrated that TP53-induced glycolysis and apoptosis regulator(TIGAR)can protect neurons after cerebral ischemia/reperfusion.However,the role of TIGAR in neonatal hypoxic-ischemic brain damage(HIBD)remains unknown.In the present study,7-day-old Sprague-Dawley rat models of HIBD were established by permanent occlusion of the left common carotid artery followed by 2-hour hypoxia.At 6 days before induction of HIBD,a lentiviral vector containing short hairpin RNA of either TIGAR or gasdermin D(LV-sh_TIGAR or LV-sh_GSDMD)was injected into the left lateral ventricle and striatum.Highly aggressively proliferating immortalized(HAPI)microglial cell models of in vitro HIBD were established by 2-hour oxygen/glucose deprivation followed by 24-hour reoxygenation.Three days before in vitro HIBD induction,HAPI microglial cells were transfected with LV-sh_TIGAR or LV-sh_GSDMD.Our results showed that TIGAR expression was increased in the neonatal rat cortex after HIBD and in HAPI microglial cells after oxygen/glucose deprivation/reoxygenation.Lentivirusmediated TIGAR knockdown in rats markedly worsened pyroptosis and brain damage after hypoxia/ischemia in vivo and in vitro.Application of exogenous nicotinamide adenine dinucleotide phosphate(NADPH)increased the NADPH level and the glutathione/oxidized glutathione ratio and decreased reactive oxygen species levels in HAPI microglial cells after oxygen/glucose deprivation/reoxygenation.Additionally,exogenous NADPH blocked the effects of TIGAR knockdown in neonatal HIBD in vivo and in vitro.These findings show that TIGAR can inhibit microglial pyroptosis and play a protective role in neonatal HIBD.The study was approved by the Animal Ethics Committee of Soochow University of China(approval No.2017LW003)in 2017.

Knocking down TRPM2 expression reduces cell injury and NLRP3 inflammasome activation in PC12 cells subjected to oxygen-glucose deprivation

Transient receptor potential melastatin 2(TRPM2) is an important ion channel that represents a potential target for treating injury caused by cerebral ischemia. However, it is unclear whether reducing TRPM2 expression can help repair cerebral injury, and if so what the mechanism underlying this process involves. This study investigated the protective effect of reducing TRPM2 expression on pheochromocytoma(PC12) cells injured by oxygen-glucose deprivation(OGD). PC12 cells were transfected with plasmid encoding TRPM2 shRNAS, then subjected to OGD by incubation in glucose-free medium under hypoxic conditions for 8 hours, after which the cells were allowed to reoxygenate for 24 hours. Apoptotic cells, mitochondrial membrane potentials, reactive oxygen species levels, and cellular calcium levels were detected using flow cytometry. The relative expression of C-X-C motif chemokine ligand 2(CXCL2), NACHT, LRR, and PYD domain–containing protein 3(NALP3), and caspase-1 were detected using fluorescence-based quantitative reverse transcription-polymerase chain reaction and western blotting. The rates of apoptosis, mitochondrial membrane potentials, reactive oxygen species levels, and cellular calcium levels in the TRPM2-shRNA + OGD group were lower than those observed in the OGD group. Taken together, these results suggest that TRPM2 knockdown reduces OGD-induced neuronal injury, potentially by inhibiting apoptosis and reducing oxidative stress levels, mitochondrial membrane potentials, intracellular calcium concentrations, and NLRP3 inflammasome activation.

The role of pineal microRNA-325 in regulating circadian rhythms after neonatal hypoxic-ischemic brain damage

Circadian rhythm disorder is a common,but often neglected,consequence of neonatal hypoxic-ischemic brain damage(HIBD).However,the underlying molecular mechanisms remain largely unknown.We previously showed that,in a rat model of HIBD,up-regulation of microRNA-325(miR-325)in the pineal gland is responsible for the suppression of Aanat,a key enzyme involved in melatonin synthesis and circadian rhythm regulation.To better understand the mechanism by which miR-325 affects circadian rhythms in neonates with HIBD,we compared clinical samples from neonates with HIBD and samples from healthy neonates recruited from the First Affiliated Hospital of Soochow University(Dushuhu Branch)in 2019.We found that circulating miR-325 levels correlated positively with the severity of sleep and circadian rhythm disorders in neonates with HIBD.Furthermore,a luciferase reporter gene assay revealed that LIM homeobox 3(LHX3)is a novel downstream target of miR-325.In addition,in miR-325 knock-down mice,the transcription factor LHX3 exhibited an miR-325-dependent circadian pattern of expression in the pineal gland.We established a neonatal mouse model of HIBD by performing doublelayer ligation of the left common carotid artery and exposing the pups to a low-oxygen environment for 2 hours.Lhx3 mRNA expression was significantly down-regulated in these mice and partially rescued in miR-325 knockout mice subjected to the same conditions.Finally,we showed that improvement in circadian rhythm-related behaviors in animals with HIBD was dependent on both miR-325 and LHX3.Taken together,our findings suggest that the miR-325-LHX3 axis is responsible for regulating circadian rhythms and provide novel insights into the identification of potential therapeutic targets for circadian rhythm disorders in patients with neonatal HIBD.The clinical trial was approved by Institutional Review Board of Children’s Hospital of Soochow University(approval No.2015028)on July 20,2015.Animal experiments were approved by Animal Care and Use Committee,School of Medicine,Soochow University,China(approval No.XD-2016-1)on January 15,2016.

Breaking the linear correlations for enhanced electrochemical nitrogen reduction by carbon-encapsulated mixed-valence Fe_(7)(PO_(4))_(6)

Electrochemical nitrogen reduction(NRR)is deemed as a consummate answer for the traditional Haber–Bosch technology.Breaking the linear correlations between adsorption and transition-state energies of intermediates is vital to improve the kinetics of ammonia synthesis and obtain a less energy-intensive process.Herein,carbon-encapsulated mixed-valence Fe_(7)(PO_(4))_(6) was prepared and applied as an electrocatalyst for high-efficiency NRR.A dramatic faradaic efficiency(FE)of 36.93%and an NH_(3) production rate of 13.1μg h^(-1) mg_(cat)^(-1) were obtained at-0.3 V versus RHE,superior to nearly all Fe-based catalysts.Experiments and DFT calculations revealed that the superior performance was ascribed to the synergistic effect of mixed-valence iron pair,which braked the linear correlations to improve the kinetics of ammonia from collaborative hydrogenation and*NH_(3) separation.This work proves the feasibility of mixedvalence catalysts for nitrogen reduction and thus opening a new avenue towards artificial nitrogenfixation catalysts.

Ultrathin two-dimensional metal–organic framework nanosheets for efficient electrochemical CO_(2) reduction

Electrochemical CO_(2) reduction into CO or high-value products is regarded as a feasible pathway for energy conversion,which has attracted universal attention in recent years [1-3].However,the reduction of CO_(2) molecule is a thermodynamically uphill process,which involves multiple elemental steps and the competition of hydrogen evolution reaction(HER) in aqueous solution.

Fucoidan antagonizes diet-induced obesity and inflammation in mice

Obesity is an escalating global pandemic posing a serious threat to human health.The intervention therapy using weight-reducing drugs,accompanied by lifestyle modification,is a strategy for the treatment of obesity.In the present study,we explored the role of fucoidan,a seaweed compound,on high-fat diet(HFD)-induced obesity in mice.We found that fucoidan treatment significantly reduced the body fat and caused redistribution of visceral and subcutaneous fat in HFD-fed mice.Meanwhile,fucoidan treatment inhibited adipocyte hypertrophy and inflammation in adipose tissue.Collectively,these results suggest that fucoidan may be a promising treatment for obesity and obesity-induced complications.

Expression of Clock genes in the pineal glands of newborn rats with hypoxic-ischemic encephalopathy

Clock genes are involved in circadian rhythm regulation, and surviving newborns with hypoxic-ischemic encephalopathy may present with sleep-wake cycle reversal. This study aimed to determine the expression of the clock genes Clock and Bmall, in the pineal gland of rats with hypoxic-ischemic brain damage. Results showed that levels of Clock mRNA v^re not significantly changed within 48 hours after cerebral hypoxia and ischemia. Expression levels of CLOCK and BMAL1 protein were significantly higher after 48 hours. The levels of Bmall mRNA reached a peak at 36 hours, but were significantly reduced at 48 hours. Experimental findings indicate that Clock and Bmall genes were indeed expressed in the pineal glands of neonatal rats. At the initial stage （within 36 hours） of hypoxic-ischemic brain damage, only slight changes in the expression levels of these two genes were detected, followed by significant changes at 36-48 hours. These changes may be associated with circadian rhythm disorder induced by hypoxic-ischemic brain damage.

Carrier Envelope Phase Description for an Isolated Attosecond Pulse by Momentum Vortices

As a crucial parameter for a few-cycle laser pulse, the carrier envelope phase(CEP) substantially determines the laser waveform. We propose a method to directly describe the CEP of an isolated attosecond pulse(IAP) by the vortex-shaped momentum pattern, which is generated from the tunneling ionization of a hydrogen atom by a pair of time-delayed, oppositely and circularly polarized IAP-IR pulses. Superior to the angular streaking method that characterizes the CEP in terms of only one streak, our method describes the CEP of an IAP by the features of multiple streaks in the vortex pattern. The proposed method may open the possibility of capturing sub-cycle extreme ultraviolet dynamics.

pH-activatable oxidative stress amplifying dissolving microneedles for combined chemo-photodynamic therapy of melanoma

Photodynamic therapy(PDT)-mediated oxidation treatment is extremely attractive for skin melanoma ablation,but the strong hydrophobicity and poor tumor selectivity of photosensitizers,as well as the oxygen-consuming properties of PDT,leading to unsatisfactory therapeutic outcomes.Herein,a tumor acidic microenvironment activatable dissolving microneedle(DHA@HPFe-MN)was developed to realize controlled drug release and excellent chemo-photodynamic therapy of melanoma via oxidative stress amplification.The versatile DHA@HPFe-MN was fabricated by crosslinking a self-synthesized protoporphyrin(PpIX)-ADH-hyaluronic acid(HA)conjugate HA-ADH-PpIX with“iron reservoir”PA-Fe 3+complex in the needle tip via acylhydrazone bond formation,and dihydroartemisinin(DHA)was concurrently loaded in the hydrogel network.HA-ADH-PpIX with improved water solubility averted undesired aggregation of PpIX to ensure enhanced PDT effect.DHA@HPFe-MN with sharp needle tip,efficient drug loading and excellent mechanical strength could efficiently inserted into skin and reach the melanoma sites,where the acidic pH triggered the degradation of microneedles,enabling Fe-activated and DHA-mediated oxidation treatment,as evidenced by abundant reactive oxygen species(ROS)generation.Moreover,under light irradiation,a combined chemo-photodynamic therapeutic effect was achieved with amplified ROS generation.Importantly,the Fe-catalyzed ROS production of DHA was oxygen-independent,which work in synergy with the oxygen-dependent PDT to effectively destroy tumor cells.This versatile microneedles with excellent biosafety and biodegradability can be customized as a promising localized drug delivery system for combined chemo-photodynamic therapy of melanoma.

Insights into electrolyte effects on photoactivities of dye-sensitized photoelectrochemical cells for water splitting

Dye-sensitized photoelectrochemical cell（DS-PEC） is an especially attractive method to generate hydrogen via visible light driven water splitting. Electrolyte, an essential component of DS-PEC, plays a great role in determining the photoactivities of devices for water splitting. When using phosphate buffer（pH = 6.4）as electrolyte, the DS-PEC displayed much higher photoactivity than using 0.1 M Na;SO;（pH = 6.4） as electrolyte. The insight is phosphate anion gathers together to form a negative electrostatic field on TiO;surface, which increases the resistance in the TiO;/catalyst and electrolyte interface and validly reduces the charge recombination from TiO;to the oxidized catalyst.

Influences of the adsorption state of catalyst on the performance of DS-PEC for visible light driven water splitting

Adsorption state of catalyst on photoanode is an important factor on influencing the performance of dye-sensitized photoelectrochemical cells (DS-PECs) for water splitting. Photoanode TiO2(1 + 2) was assembled with Ru(bpy)(3) phosphoric acid derivative (complex 1) as photosensitizer and complex 2 as water oxidation catalyst to compare with photoanode TiO2(1 + 3). The photocurrent density of photoanode TiO2(1 + 3) with catalyst 3 synthesized with only one end fixing on the surface of TiO2 is about four-fold of the photoanode assembled with catalyst 2 fixing with two claws on the surface of TiO2. The phenomenon should be caused by the littery arrangement and shorter distance of catalyst 2 from the active center of catalyst to TiO2 on the surface of semiconductor which led to lowly efficient electron transfer. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved

High-temperature deformation resistance and creep resistance of a TiAl-based alloy fabricated by cold crucible directional solidification technology

In order to improve the high-temperature deformation resistance and creep resistance of TiAl-based alloys,cold crucible directional solidification(CCDS)technology was employed.Aβ-type TiAl-based alloy with the nominal composition of Ti44Al6Nb1Cr2V was prepared using the optimized CCDS parameters of 45 kW input power and 0.5 mm·min^-1 solidification rate.Thermo-compression testing was utilized to evaluate the hightemperature deformation resistance and creep resistance of the CCDS Ti44Al6Nb1Cr2V alloy.Results show that the CCDS Ti44Al6Nb1Cr2V alloy billets contain aligned columnar grains and a high percentage of small-angle lamellae.Thermo-compression testing results in the radial direction of the CCDS alloy show a much higher peak stress than other reported results in similar conditions.The much higher hardening exponent and deformation activation energy are obtained,corresponding to the excellent high-temperature deformation resistance and creep resistance,which are because of the hard-oriented grains,weaker stress-strain coordination capability of lamella structure and relatively more hysteretic dynamic recrystallization.Thermo-compression testing results in the longitudinal direction of the CCDS Ti44Al6Nb1Cr2V alloy show the much higher peak stress than that in the radial direction,indicating the better high-temperature deformation resistance and creep resistance attributed to the hard-oriented lamellae in this condition.