Pd^(0)-O v-Ce^(3+) Interfacial Sites with Charge Redistribution for Enhanced Hydrogenation of Methyl Oleate to Methyl Stearate

Improving the efficiency of metal/reducible metal oxide interfacial sites for hydrogenation reactions of unsaturated groups(e.g.,C=C and C=O)is a promising yet challenging endeavor.In our study,we developed a Pd/CeO_(2) catalyst by enhancing the oxygen vacancy(O V)concentration in CeO_(2) through high-temperature treatment.This process led to the formation of an interface structure ideal for supporting the hydrogenation of methyl oleate to methyl stearate.Specifi cally,metal Pd^(0) atoms bonded to the O V in defective CeO_(2) formed Pd^(0)-O v-Ce^(3+)interfacial sites,enabling strong electron transfer from CeO_(2) to Pd.The interfacial sites exhibit a synergistic adsorption eff ect on the reaction substrate.Pd^(0) sites promote the adsorption and activation of C=C bonds,while O V preferably adsorbs C=O bonds,mitigating competition with C=C bonds for Pd^(0) adsorption sites.This synergy ensures rapid C=C bond activation and accelerates the attack of active H*species on the semi-hydrogenated intermediate.As a result,our Pd/CeO_(2)-500 catalyst,enriched with Pd^(0)-O v-Ce^(3+)interfacial sites,dem-onstrated excellent hydrogenation activity at just 30℃.The catalyst achieved a Cis-C18:1 conversion rate of 99.8% and a methyl stearate formation rate of 5.7 mol/(h·g metal).This work revealed the interfacial sites for enhanced hydrogenation reactions and provided ideas for designing highly active hydrogenation catalysts.

Conceptual carbon-reduction process design and quantitative sustainable assessment for concentrating high purity ethylene from wasted refinery gas

The direct emission of waste refinery gas after combustion will cause a severe greenhouse effect.Recovering high-value-added ethylene from wasted refinery gas has fundamental economic and environmental significance. Due to the complexity of the composition of refinery waste gas, designing and optimizing the whole recovery process is still a challenging task. Herein, a novel process(SCOAS) was proposed to obtain polymer-grade ethylene from wasted refinery gas through a direct separation process,and heat pump-assisted thermal integration optimization(HPSCOAS) was carried out. The unique feature of the novel approach is that a new stripper and ethylene reabsorber follow the dry gas absorber to ensure ethylene recovery and methane content. An industrial model, shallow cooling oil absorption(SCOA), and concentration combined cold separation system of ethylene unit using wasted refinery gas was established to analyze the technology and environment. Based on the detailed process modeling and simulation results, the quantitative sustainability assessment of economy and environment based on product life cycle process is carried out. The results show that compared with the traditional process when the same product is obtained, the total annual cost of the HPSCOAS process is the lowest, which is 15.4% lower than that of the SCOA process and 6.1% lower than that of the SCOAS process. In addition,compared with the SCOA process and the HPSCOAS process, the SCOAS process has more environmental advantages. The non-renewable energy consumed by SCOAS is reduced by about 24.8% and 6.1%, respectively. The CO_(2) equivalent is reduced by about 38.6% and 23.7%.

Engineering three-layer core–shell S-1/TS-1@dendritic-SiO_(2) supported Au catalysts towards improved performance for propene epoxidation with H_(2) and O_(2)

The advocacy of green chemical industry has led to the development of highly efficient catalysts for direct gas-phase propene epoxidation with green,sustainable and simple essence.The S-1/TS-1@dendritic-SiO_(2) material with three-layer core–shell structure was developed and used as the support for Au catalysts,which showed simultaneously fantastic PO formation rate,PO selectivity and stability(over 100 h)for propene epoxidation with H_(2) and O_(2).It is found that silicalite-1(S-1)core and the middle thin layer of TS-1 offer great mass transfer ability,which could be responsible for the excellent stability.The designed dendritic SiO_(2) shell covers part of the acid sites on the external surface of TS-1,inhibiting the side reactions and improving the PO selectivity.Furthermore,three kinds of SiO_(2) shell morphologies(i.e.,dendritic,net,mesoporous shell)were designed,and relationship between shell morphology and catalytic performance was elucidated.The results in this paper harbour tremendous guiding significance for the design of highly efficient epoxidation catalysts.

Enhancing the dynamic electron transfer of Au species on wormhole-like TS-1 for boosting propene epoxidation performance with H_(2) and O_(2)

Engineering unique electronic structure of catalyst to boost catalytic performance is of prime scientific and industrial importance.Herein,the identification of intrinsic electronic sensitivity for direct propene epoxidation was first achieved over highly stable Au/wormhole-like TS-1 catalyst.Results show that the electron transfer of Au species can be regulated by manipulating the dynamic evolutions and contents of Au valence states,thus resulting in different catalytic performance in 100 h time-on-stream.By DFT calculations,kinetic analysis and multicharacterizations,it is found that the Au^(0) species with higher electronic population can easily transfer more electrons to activate surface O_(2) compared with Au^(1+) and Au^(3+) species.Moreover,there is a positive correlation between Au^(0) content and activity.Based on this correlation,a facile strategy is further proposed to boost Au^(0) percentage,resulting in the reported highest PO formation rate without adding promoters.This work harbors tremendous guiding significance to the design of highly efficient Au/Ti-containing catalyst for propene epoxidation with H_(2) and O_(2).

An Active Anti-Jamming Approach for Frequency Diverse Array Radar with Adaptive Weights

Due to the rapid development of electronic countermeasures(ECMs),the corresponding means of electronic counter countermeasures(ECCMs)are urgently needed.In this paper,an act-ive anti-jamming method based on frequency diverse array radar is proposed.By deriving the closed form of the phase center in a uniform line array FDA,we establish a model of the FDA signal based on adaptive weights and derive the effect of active anti-jamming in this regime.The pro-posed active anti-jamming method makes it difficult for jammers to detect or locate our radar.Fur-thermore,the effectiveness of the two frequency increment schemes in terms of anti-jamming is ana-lyzed by comparing the deviation of phase center.Finally,the simulation results verify the effective-ness and superiority of the proposed method.

Engineering the efficient three-dimension hollow cubic carbon from vacuum residuum with enhanced mass transfer ability towards H2O2 production

Constructing efficient carbon material with enhanced mass transfer ability from vacuum residuum(VR)is of prime industrial and scientific significance.Herein,we demonstrated a one-pot synthesis of metal-free and highly symmetric hollow carbon cubes(HCCs)using cost-efficient vacuum residuum(VR)as a C/N/S source.By multi-techniques such as TEM,SEM,Raman,XPS,and XRD,it is found that the CTAB surfactant plays an important role in emulsifying and forming oil-in-water suspension particles.Subsequently,high aromatics contents in VR favor the formation of HCCs shell by graphitization on the surface of Na Cl template.Notably,heavy metals(e.g.,V,Ni)are not enriched in carbon skeleton due to the unique graphitization mechanism.This metal-free HCCs catalyst showed good catalytic stability and high selectivity towards direct and local electrochemical production of hydrogen peroxide(H_(2)O_(2))through two-electron O_(2)reduction due to enhanced mass transfer ability.The results provide a novel avenue to synthesize metal-free cubic carbon material from low-cost and plentiful VR,which are essential to the design of more efficient catalysts for O_(2)reduction to H_(2)O_(2).

Transferrin receptor-targeted immunostimulant for photodynamic immunotherapy against metastatic tumors through β-catenin/CREB interruption

The immunosuppressive phenotype of tumor cells extensively attenuates the immune activation effects of traditional treatments.In this work,a transferrin receptor(TfR)targeted immunostimulant(PTI)is fabricated for photodynamic immunotherapy against metastatic tumors by interrupting β-catenin signal pathway.To synthesize PTI,the photosensitizer conjugated TfR targeting peptide moiety(Palmitic-K(PpIX)-HAIYPRH)is unitized to encapsulate the transcription interrupter of ICG-001.On the one hand,the recognition of PTI and TfR can promote drug delivery into tumor cells to destruct primary tumors through photodynamic therapy and initiate an immunogenic cell death with the release of tumorassociated antigens.On the other hand,PTI will interrupt the binding between b-catenin andcAMP response element-binding protein(CREB),regulating the gene transcription to downregulate programmed death ligand 1(PD-L1)while upregulating CeC motif chemokine ligand 4(CCL4).Furthermore,the elevated CCL4 can recruit the dendritic cells to present tumor-specific antigens and promote T cells activation and infiltration,and the downregulated PD-L1 can avoid the immune evasion of tumor cells and activate systemic anti-tumor immunity to eradicate lung metastasis.This work may inspire the development of antibody antibody-free strategy to activate systemic immune response in consideration of immunosuppressive conditions.

Morphology effect on catalytic performance of ebullated-bed residue hydrotreating over Ni-Mo/Al_(2)O_(3)catalyst:a kinetic modeling study

Upgrading of vacuum residue is of prime industrial significance due to the increasing demand for light oils.Elucidating the effect of catalyst morphology on vacuum residue hydrotreating performance by kinetic modeling is therefore of great importance.Herein,kinetic analysis of hydrodemetallization(HDM)and hydrodeconradsoncarbon-residue(HDCCR)performances on industrial Ni-Mo/Al_(2)O_(3)catalysts with spherical and cylindrical morphologies in ebullated-bed were evaluated for more than 1600 h.It was found that the percentage of light impurities easier to be removed on spherical catalysts were 78.20%and 39.43%in HDM and HDCCR reactions,respectively,higher than 65.20%and 17.50%on cylindrical catalysts.This suggests that catalyst morphology affects the impurity removal ability and the impurity properties,resulting in better hydrotreating performance of spherical catalysts.This work not only combines catalyst morphology with impurity removal capability through kinetic modeling,but also provides new insights into the design of efficient hydrotreating catalysts.

Bisulfite-free mapping of DNA cytosine modifications:challenges and perspectives

The mapping of DNA cytosine modifications is crucial for understanding the dynamic landscape of epigenetic regulation.While bisulfite sequencing has been the gold standard for decades,it suffers from limitations such as DNA degradation and low library quality due to harsh chemical treatment.In recent years,bisulfite-free methods have emerged as promising alternatives for detecting and quantifying DNA cytosine modifications.These methods employ enzymatic and chemical strategies to investigate cytosine modifications without the need for bisulfite treatment.This review provides an overview of the historical context of bisulfite-based methods and presents the current landscape of bisulfite-free methods.The advantages and limitations of each approach are discussed,along with insights into their applications.Furthermore,the review explores the existing challenges in the field and presents future perspectives and potential directions for advancing bisulfite-free mapping methods.The continued progress in bisulfite-free techniques holds great promise for unraveling the intricate nature of DNA cytosine modifications and their functional implications in diverse biological processes and diseases.

Fuzzy Logic-based Management of Hybrid Distribution Transformers Using LoRa Technology

Hybrid distribution transformers(HDTs)have better performance than traditional distribution transformers in improving power quality through reducing harmonics,unbalance,voltage fluctuations and low power factors in future smart power distribution systems.In order to increase the service life and reliability of hybrid distribution transformers,this paper proposes a remote management system using LoRa technology based on fuzzy logic.HDT based on a fuzzy logic judgment system(FLJS)replaces the Boolean logic with fuzzy logic and several power quality problems including power factors,load-side current harmonics and voltage unbalance are considered,as well as grid-side voltage deviation and unbalance.This management system can dynamically adjust the working states of HDT according to the output results of the FLJS to reduce the use time of power electronic devices.Due to the application of LoRa,this management system can remotely adjust the parameters of the FLJS in real time for different distribution network nodes to avoid frequent switching of HDT working states.In addition,it is able to remotely monitor the real-time working states and fault states of HDT to reduce recovery time and maintenance costs in case of HDT failure.Finally,simulation and experimental results are presented to verify the effectiveness of the proposed management system for HDT.

钛硅分子筛催化剂高效钛位点的理性构筑与调控及催化烯烃环氧化的性能

随着化工产品高端化战略的不断推进,以TS-1为代表的钛硅分子筛催化剂由于具备独特的选择性氧化能力而引起了广泛关注,目前已经成功应用于烯烃环氧化、环己酮氨氧化、苯酚羟基化等领域.TS-1型钛硅分子筛也因此被誉为分子筛催化领域的里程碑.理性设计与精准构筑TS-1中高性能钛位点是高效催化烯烃环氧化的关键.本文首先综述了构筑高性能TS-1钛位点的三大策略,包括在原子尺度上设计钛位点的配位结构、在界面上调节钛位点的微环境,以及在纳米颗粒中改善钛位点的可接触性.此外,详细阐述了上述不同策略对烯烃环氧化的影响机制及相应的构效关系,总结了不同策略下的构筑方法和表征手段,并分析了高性能钛硅分子筛当前面临的挑战与未来的发展方向.

Mapping the epigenetic modifications of DNA and RNA

Over 17 and 160 types of chemical modifications have been identified in DNA and RNA,respectively.The interest in understanding the various biological functions of DNA and RNA modifications has lead to the cutting-edged fields of epigenomics and epitranscriptomics.Developing chemical and biological tools to detect specific modifications in the genome or transcriptome has greatly facilitated their study.Here,we review the recent technological advances in this rapidly evolving field.We focus on high-throughput detection methods and biological findings for these modifications,and discuss questions to be addressed as well.We also summarize third-generation sequencing methods,which enable long-read and single-molecule sequencing of DNA and RNA modification.

Magnetic field-induced strategy for synergistic CI/Ti_(3)C_(2)T_(x)/PVDF multilayer structured composite films with excellent electromagnetic interference shielding performance

Lightweight,scalable,mechanically flexible conductive polymer composite was always desirable for electromagnetic interference(EMI)shielding applications.In this work,we showcased a novel approach to the superior EMI shielding composite materials by orchestrating the multilayered structure and synergistic system.The asymmetric structure with the carbonyl irons(CI)-rich Ti_(3)C_(2)T_(x)/poly(vinylidene fluoride)(PVDF)magneto-electric layer jointly behind the Ti_(3)C_(2)T_(x) nanosheets filled PVDF layer was designed and fabricated with the aid of a facile but efficient magnetic field-induced method and was then hotpressed into a multilayer structured film.Ti_(3)C_(2)T_(x) nanosheets were excluded by CI agglomeration layer in the asymmetric film to form the complete 3D electrical conductive skeletons.Based on this strategy,EMI shielding properties of the asymmetric multilayer structured composite was superior to the homogeneous blend and sandwiched or alternating layered composites.In addition,an increase in CI content in the composite referred to the thickening of CI-rich layers,making it gain the most powerful EMI SE values,i.e.42.8 d B for DCMP20–10 film(20 wt%CI,10 wt%Ti_(3)C_(2)T_(x))at a thickness of 0.4 mm.More importantly,the composite transformed from a reflection type to an absorption dominating EMI shielding material due to the multireflections and magneto-electric synergism in the CI-rich Ti_(3)C_(2)T_(x)/PVDF layers.Meanwhile,the EMI SE of the composites can be adjusted by increase of either theoverall thickness,or the layer numbers of m-DCMP sheets.The thickness specific EMI SE was calculated as 165.25 d B mm^(-1)for 4-sheet composite film,a record high value among the high efficiency polymer-based EMI shielding materials.This method offered an alternative protocol for preferential integration of excellent EMI shielding performance with high mechanical performance in CPC materials.