Anti-tumor activity of a novel LAIR1 antagonist in combination with anti-PD-1 to treat collagen-rich solid tumors.

We recently reported that resistance to PD-1-blockade in a refractory lung cancer-derived model involved increased collagen deposition and the collagen-binding inhibitory receptor leukocyte-associated immunoglobulin-like receptor 1 (LAIR1), and thus we hypothesized that LAIR1 and collagen cooperated to suppress therapeutic response. Here, we report LAIR1 is associated with tumor stroma and is highly expressed by intratumoral myeloid cells in both human tumors and mouse models of cancer. Stroma-associated myeloid cells exhibit a suppressive phenotype and correlate with LAIR1 expression in human cancer. NGM438, a novel humanized LAIR1 antagonist monoclonal antibody, elicits myeloid inflammation and allogeneic T cell responses by binding to LAIR1 and blocking collagen engagement. Further, a mouse-reactive NGM438 surrogate antibody sensitized refractory KP mouse lung tumors to anti-PD-1 therapy and resulted in increased intratumoral CD8+ T cell content and inflammatory gene expression. These data place LAIR1 at the intersection of stroma and suppressive myeloid cells and support the notion that blockade of the LAIR1/collagen axis can potentially address resistance to checkpoint inhibitor therapy in the clinic.

Low-temperature NH3 abatement via selective oxidation over a supported copper catalyst with high Cu+ abundance.

Selective catalytic NH3-to-N2 oxidation (NH3-SCO) is highly promising for abating NH3 emissions slipped from stationary flue gas after-treatment devices. Its practical application, however, is limited by the non-availability of low-cost catalysts with high activity and N2 selectivity. Here, using defect-rich nitrogen-doped carbon nanotubes (NCNT-AW) as the support, we developed a highly active and durable copper-based NH3-SCO catalyst with a high abundance of cuprous (Cu+) sites. The obtained Cu/NCNT-AW catalyst demonstrated outstanding activity with a T50 (i.e. the temperature to reach 50% NH3 conversion) of 174°C in the NH3-SCO reaction, which outperformed not only the Cu catalyst supported on N-free O-functionalized CNTs (OCNTs) or NCNT with less surface defects, but also those most active Cu catalysts in open literature. Reaction kinetics measurements and temperature-programmed surface reactions using NH3 as a probe molecule revealed that the NH3-SCO reaction on Cu/NCNT-AW follows an internal selective catalytic reaction (i-SCR) route involving nitric oxide (NO) as a key intermediate. According to mechanistic investigations by X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray absorption spectroscopy, the superior NH3-SCO performance of Cu/NCNT-AW originated from a synergy of surface defects and N-dopants. Specifically, surface defects promoted the anchoring of CuO nanoparticles on N-containing sites and, thereby, enabled efficient electron transfer from N to CuO, increasing significantly the fraction of SCR-active Cu+ sites in the catalyst. This study puts forward a new idea for manipulating and utilizing the interplay of defects and N-dopants on carbon surfaces to fabricate Cu+-rich Cu catalysts for efficient abatement of slip NH3 emissions via selective oxidation.

Enhancement Effect Induced by the Second Metal to Promote Ozone Catalytic Oxidation of VOCs.

It is a promising research direction to develop catalysts with high stability and ozone utilization for low-temperature ozone catalytic oxidation of VOCs. While bimetallic catalysts exhibit excellent catalytic activity compared with conventional single noble metal catalysts, limited success has been achieved in the influence of the bimetallic effect on the stability and ozone utilization of metal catalysts. Herein, it is necessary to systematically study the enhancement effect in the ozone catalytic reaction induced by the second metal. With a simple continuous impregnation method, a platinum-cerium bimetallic catalyst is prepared. Also highlighted are studies from several aspects of the contribution of the second metal (Ce) to the stability and ozone utilization of the catalysts, including the "electronic effect" and "geometric effect". The synergistic removal rate of toluene and ozone is nearly 100% at 30 °C, and it still shows positive stability after high humidity and a long reaction time. More importantly, the instructive significance, which is the in-depth knowledge of enhanced catalytic mechanism of bimetallic catalysts resulting from a second metal, is provided by this work.

AflaILVB/G/I and AflaILVD are involved in mycelial production, aflatoxin biosynthesis, and fungal virulence in Aspergillus flavus.

Aflatoxins (AFs) are produced by fungi such as Aspergillus flavus and A. parasiticus and are one of the most toxic mycotoxins found in agricultural products and food. Aflatoxin contamination, which requires the control of A. flavus, remains problematic because of the lack of effective strategies and the exploration of new compounds that can inhibit A. flavus growth and mycotoxin production is urgently required to alleviate potential deleterious effects. Acetohydroxy acid synthase (AHAS) and dihydroxy acid dehydratase are important enzymes in the biosynthetic pathways of branched-chain amino acids (BCAAs), including isoleucine, leucine, and valine. Enzymes involved in BCAA biosynthesis are present in bacteria, plants, and fungi, but not in mammals, and are therefore, attractive targets for antimicrobial and herbicide development. In this study, we characterized AflaILVB/G/I and AflaILVD, which encode the catalytic and regulatory subunits of AHAS and dihydroxy acid dehydratase, from the pathogenic fungus Aspergillus flavus. The AflaILVB/G/I and AflaILVD deletion mutant grew slower and produced smaller colonies than the wild-type strain when grown on glucose minimal medium, potato dextrose agar, and yeast extract medium for three days at 28°C, and disruption of AflaILVB/G/I caused a significant reduction in conidia production when grown on all kinds of media. Cellular stress assays determined that all strains were sensitive to H2O2. Importantly, the pathogenicity and aflatoxin production were affected when AflaILVB/G/I and AflaILVD were knocked out, particularly AflaILVB/G/I. A series of genes that encoded enzymes involved in aflatoxin synthesis were downregulated, meaning that the knockout of AflaILVB/G/I influenced aflatoxin synthesis in A. flavus strain WT. Collectively, our results demonstrate the potential value of antifungals targeting AflaILVB/G/I in A. flavus.

Spatial Distribution of Brønsted Acid Sites Determines the Mobility of Reactive Cu Ions in the Cu-SSZ-13 Catalyst during the Selective Catalytic Reduction of NOx with NH3.

The formation of dimer-Cu species, which serve as the active sites of the low-temperature selective catalytic reduction of NOx with NH3 (NH3-SCR), relies on the mobility of CuI species in the channels of the Cu-SSZ-13 catalysts. Herein, the key role of framework Brønsted acid sites in the mobility of reactive Cu ions was elucidated via a combination of density functional theory calculations, in situ impedance spectroscopy, and in situ diffuse reflectance ultraviolet-visible spectroscopy. When the number of framework Al sites decreases, the Brønsted acid sites decrease, leading to a systematic increase in the diffusion barrier for [Cu(NH3)2]+ and less formation of highly reactive dimer-Cu species, which inhibits the low-temperature NH3-SCR reactivity and vice versa. When the spatial distribution of Al sites is uneven, the [Cu(NH3)2]+ complexes tend to migrate from an Al-poor cage to an Al-rich cage (e.g., cage with paired Al sites), which effectively accelerates the formation of dimer-Cu species and hence promotes the SCR reaction. These findings unveil the mechanism by which framework Brønsted acid sites influence the intercage diffusion and reactivity of [Cu(NH3)2]+ complexes in Cu-SSZ-13 catalysts and provide new insights for the development of zeolite-based catalysts with excellent SCR activity by regulating the microscopic spatial distribution of framework Brønsted acid sites.

Efficient Atomically Dispersed Co/N-C Catalysts for Formic Acid Dehydrogenation and Transfer Hydrodeoxygenation of Vanillin.

Atomically dispersed catalysts have gained considerable attention due to their unique properties and high efficiency in various catalytic reactions. Herein, a series of Co/N-doped carbon (N-C) catalysts was prepared using a metal-lignin coordination strategy and employed in formic acid dehydrogenation (FAD) and hydrodeoxygenation (HDO) of vanillin. The atomically dispersed Co/N-C catalysts showed outstanding activity, acid resistance, and long-term stability in FAD. The improved activity and stability may be attributed to the high dispersion of Co species, increased surface area, and strong Co-N interactions. XPS and XAS characterization revealed the formation of Co-N3 centers, which are assumed to be the active sites. In addition, DFT calculations demonstrated that the adsorption of formic acid on single-atom Co was stronger than that on Co13 clusters, which may explain the high catalytic activity. The Co/N-C catalyst also showed promising performance in the transfer HDO of vanillin with formic acid, without any external additional molecular H2.

Process-specified emission factors and characteristics of VOCs from the auto-repair painting industry.

Daily use of passenger vehicles leads to considerable emission of volatile organic compounds (VOCs), which are key precursors to the ground-level ozone pollution. While evaporative and tailpipe emission of VOCs from the passenger vehicles can be eliminated largely, or even completely, by electrification, VOCs emission from the use of coatings in auto-repair is unavoidable and has long been ignored. Here, we present for the first time, to the best of our knowledge, a comprehensive investigation on the emission factors and process-specified characteristics of VOCs from auto-repair painting, based on field measurements over 15 representative auto-repair workshops in the Pearl-River-Delta area, China. Replacement of solvent-borne coatings with water-borne counterparts, which was only achieved partially in the Basecoat step but not in the Putty, Primer and Clearcoat steps, could reduce the per automobile VOCs emission from 756.5 to 489.6 g and the per automobile ozone formation potential (OFP) from 2776.5 to 1666.4 g. Implementation of exhaust after-treatment led to a further reduction of the per automobile VOCs emission to 340.9 g, which is still ca. 42% higher than that from the state-of-art painting processes for the manufacture of passenger vehicles. According to the analysis of VOCs compositions, the Putty process was dominated by the emission of styrene, while Primer, Basecoat (solvent-borne) and Clearcoat steps were all characterized by the emission of n-butyl acetate and xylenes. By contrast, water-borne Basecoat step showed a prominent emission of n-amyl alcohol. Notably, for the full painting process to repair an automobile, n-butyl acetate emerged as the most abundant species in the VOCs emission, whereas xylenes contributed most significantly to the OFP. Scenario analysis suggested that reducing VOCs contents in the coatings, as well as improving the after-treatment efficiency, were highly potential solutions for effective reduction of VOCs emission from auto-repair. Our study contributes to an update of industrial inventories of VOCs emission, and may provide valuable insights for reducing VOCs emission and OFPs from the auto-repair industry.

ILT2 and ILT4 Drive Myeloid Suppression via Both Overlapping and Distinct Mechanisms.

Solid tumors are dense three-dimensional (3D) multicellular structures that enable efficient receptor-ligand trans interactions via close cell-cell contact. Immunoglobulin-like transcript (ILT)2 and ILT4 are related immune-suppressive receptors that play a role in the inhibition of myeloid cells within the tumor microenvironment. The relative contribution of ILT2 and ILT4 to immune inhibition in the context of solid tumor tissue has not been fully explored. We present evidence that both ILT2 and ILT4 contribute to myeloid inhibition. We found that although ILT2 inhibits myeloid cell activation in the context of trans-engagement by MHC-I, ILT4 efficiently inhibits myeloid cells in the presence of either cis- or trans-engagement. In a 3D spheroid tumor model, dual ILT2/ILT4 blockade was required for the optimal activation of myeloid cells, including the secretion of CXCL9 and CCL5, upregulation of CD86 on dendritic cells, and downregulation of CD163 on macrophages. Humanized mouse tumor models showed increased immune activation and cytolytic T-cell activity with combined ILT2 and ILT4 blockade, including evidence of the generation of immune niches, which have been shown to correlate with clinical response to immune-checkpoint blockade. In a human tumor explant histoculture system, dual ILT2/ILT4 blockade increased CXCL9 secretion, downregulated CD163 expression, and increased the expression of M1 macrophage, IFNγ, and cytolytic T-cell gene signatures. Thus, we have revealed distinct contributions of ILT2 and ILT4 to myeloid cell biology and provide proof-of-concept data supporting the combined blockade of ILT2 and ILT4 to therapeutically induce optimal myeloid cell reprogramming in the tumor microenvironment.

Mucosal vaccines for viral diseases: Status and prospects.

Virus-associated infectious diseases are highly detrimental to human health and animal husbandry. Among all countermeasures against infectious diseases, prophylactic vaccines, which developed through traditional or novel approaches, offer potential benefits. More recently, mucosal vaccines attract attention for their extraordinary characteristics compared to conventional parenteral vaccines, particularly for mucosal-related pathogens. Representatively, coronavirus disease 2019 (COVID-19), a respiratory disease caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), further accelerated the research and development efforts for mucosal vaccines by thoroughly investigating existing strategies or involving novel techniques. While several vaccine candidates achieved positive progresses, thus far, part of the current COVID-19 mucosal vaccines have shown poor performance, which underline the need for next-generation mucosal vaccines and corresponding platforms. In this review, we summarized the typical mucosal vaccines approved for humans or animals and sought to elucidate the underlying mechanisms of these successful cases. In addition, mucosal vaccines against COVID-19 that are in human clinical trials were reviewed in detail since this public health event mobilized all advanced technologies for possible solutions. Finally, the gaps in developing mucosal vaccines, potential solutions and prospects were discussed. Overall, rational application of mucosal vaccines would facilitate the establishing of mucosal immunity and block the transmission of viral diseases.

Investigation on chain segment motions of various starch molecules under different glycerol-water system.

The molecular motion of starch at different glycerol concentrations (0, 20, 50, and 80 %) was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. Fourier-transform infrared (FTIR) spectroscopy and 1H nuclear magnetic resonance (1H NMR) spectroscopy confirmed that hydroxyl groups at the C2 and C3 positions of glucose units in corn starch (CS), waxy corn starch (WCS), and high amylose corn starch (HCS) were labeled with 4-amino-TEMPO. The crystallinities of CS, WCS, and HCS after spin-labeling decreased from 30.68 % to 3.21 %, 39.36 % to 1.65 %, and 28.54 % to 8.08 %, respectively. The pseudoplastic fluid properties of the spin-labeled starch remained shear-thin at different glycerol concentrations. EPR revealed the fast- and slow-motion components of the spin-labeled starch molecules dispersed in water. At a glycerol concentration of 20 %, the slow-motion component disappeared, indicating a faster rotational motion of the starch chain segments. As the glycerol concentration increased to 50 and 80 %, the rotational motion slowed because of high viscosity. In particular, the mobility of the spin-labeled WCS chains increased owing to easier access of glycerol and water to the branched structure. This study directly observed the dynamics of the molecular behavior of starch in glycerol-water systems.

Transcriptomic and Proteomic Insights into the Effect of Sterigmatocystin on Aspergillus flavus.

Aspergillus flavus is an important fungus that produces aflatoxins, among which aflatoxin B1 (AFB1) is the most toxic and contaminates food and poses a high risk to human health. AFB1 interacts with another mycotoxin sterigmatocystin (STC), which is also a precursor of AFB1. Herein, we determined the effect of STC on AFB1 by evaluating A. flavus transcriptomic and proteomic profiles in the presence or absence of STC by RNA-seq and isobaric tagging, respectively. Overall, 3377 differentially expressed genes were identified by RNA-seq. These genes were mainly associated with the cellular component organisation and biosynthesis, the synthesis of valine, leucine, and isoleucine, and the synthesis of aflatoxin. Clustered genes responsible for AFB1 biosynthesis exhibited varying degrees of downregulation, and norB expression was completely suppressed in the experimental group. During proteomic analysis, 331 genes were differentially expressed in response to STC. These differentially expressed proteins were associated with cell parts and catalytic and antioxidant activities. Differentially expressed proteins predominantly participated in metabolic pathways associated with aflatoxin biosynthesis, glycolysis/gluconeogenesis, glutathione metabolism, and carbon metabolism. Notably, the upregulated and downregulated enzymes in carbohydrate and glutathione metabolisms may serve as potential gateways for inhibiting aflatoxin biosynthesis. Moreover, twelve proteins including seven downregulated ones involved in aflatoxin biosynthesis were identified; among them, AflG was the most downregulated, suggesting that it may be the key enzyme responsible for inhibiting aflatoxin synthesis. These findings provide novel insights into A. flavus control and the mechanisms regulating mycotoxin production.

Advances of nanoparticle-mediated diagnostic and theranostic strategies for atherosclerosis.

Atherosclerotic plaque remains the primary cause of morbidity and mortality worldwide. Accurate assessment of the degree of atherosclerotic plaque is critical for predicting the risk of atherosclerotic plaque and monitoring the results after intervention. Compared with traditional technology, the imaging technologies of nanoparticles have distinct advantages and great development prospects in the identification and characterization of vulnerable atherosclerotic plaque. Here, we systematically summarize the latest advances of targeted nanoparticle approaches in the diagnosis of atherosclerotic plaque, including multimodal imaging, fluorescence imaging, photoacoustic imaging, exosome diagnosis, and highlighted the theranostic progress as a new therapeutic strategy. Finally, we discuss the major challenges that need to be addressed for future development and clinical transformation.

Long Non-Coding RNA AL928768.3 Promotes Rheumatoid Arthritis Fibroblast-Like Synoviocytes Proliferation, Invasion and Inflammation, While Inhibits Apoptosis Via Activating Lymphotoxin Beta Mediated NF-κB Signaling Pathway.

Our previous study using RNA sequencing and reverse transcription quantitative polymerase chain reaction (RT-qPCR) validation identified a long non-coding RNA (lnc), lnc-AL928768.3, correlating with risk and disease activity of rheumatoid arthritis (RA), then the present study was conducted to further investigate the interaction of lnc-AL928768.3 with lymphotoxin beta (LTB) and their impact on proliferation, migration, invasion, and inflammation in RA-fibroblast-like synoviocytes (RA-FLS). Human RA-FLS was obtained and transfected with lnc-AL928768.3 overexpression, negative control overexpression, lnc-AL928768.3 short hairpin RNA (shRNA) and negative control shRNA plasmids. Then cell functions and inflammatory cytokine expressions were detected. Afterward, rescue experiments were conducted via transfecting lnc-AL928768.3 shRNA with or without LTB overexpression plasmids in RA-FLS. Lnc-AL928768.3 enhanced proliferation and invasion, inhibited apoptosis, while had little impact on migration in RA-FLS. In addition, lnc-AL928768.3 positively modulated interleukin-1ß (IL-1ß), IL-6 and IL-8 expressions in RA-FLS supernatant; moreover, it also positively regulated LTB mRNA expression, LTB protein expression, p-NF-κB protein expression, and p-IKB-α protein expression in RA-FLS. Furthermore, following experiment showed that lnc-AL928768.3 positively regulated LTB expression while LTB did not impact on lnc-AL928768.3 expression in RA-FLS. Furthermore, in rescue experiments, LTB overexpression curtailed the effect of lnc-AL928768.3 knock-down on regulating proliferation, invasion, apoptosis and inflammatory cytokine expressions in RA-FLS. Lnc-AL928768.3 promotes proliferation, invasion, and inflammation while inhibits apoptosis of RA-FLS via activating LTB mediated NF-κB signaling.

Copper Site Motion Promotes Catalytic NOx Reduction under Zeolite Confinement.

Ammonia-mediated selective catalytic reduction (NH3-SCR) is currently the key approach to abate nitrogen oxides (NOx) emitted from heavy-duty lean-burn vehicles. The state-of-art NH3-SCR catalysts, namely, copper ion-exchanged chabazite (Cu-CHA) zeolites, perform rather poorly at low temperatures (below 200 °C) and are thus incapable of eliminating effectively NOx emissions under cold-start conditions. Here, we demonstrate a significant promotion of low-temperature NOx reduction by reinforcing the dynamic motion of zeolite-confined Cu sites during NH3-SCR. Combining complex impedance-based in situ spectroscopy (IS) and extended density-functional tight-binding molecular dynamics simulation, we revealed an environment- and temperature-dependent nature of the dynamic Cu motion within the zeolite lattice. Further coupling in situ IS with infrared spectroscopy allows us to unravel the critical role of monovalent Cu in the overall Cu mobility at a molecular level. Based on these mechanistic understandings, we elicit a boost of NOx reduction below 200 °C by reinforcing the dynamic Cu motion in various Cu-zeolites (Cu-CHA, Cu-ZSM-5, Cu-Beta, etc.) via facile postsynthesis treatments, either in a reductive mixture at low temperatures (below 250 °C) or in a nonoxidative atmosphere at high temperatures (above 450 °C).

Effects of melittin on production performance, antioxidant function, immune function, heat shock protein, intestinal morphology, and cecal microbiota in heat-stressed quails.

The purpose of this study was to investigate the effects of melittin on production performance, antioxidant function, immune function, heat shock protein, intestinal morphology, and cecal microbiota of heat-stressed quails. A total of 120 (30-day-old) male quails were randomly divided into 3 groups. Each group consisted of 4 replicates with 10 birds per replicate. The ambient temperature of the control group (group W) was 24°C ± 2°C. The heat stress group (group WH) and the heat stress + melittin group (group WHA2) were subjected to heat stress for 4 h from 12:00 to 16:00 every day, and the temperature was 36°C ± 2°C for 10 d. The results showed that compared with the group W, heat stress significantly decreased growth performance, serum and liver antioxidative function, immune function, intestinal villus height (VH) and villus height-to-crypt depth ratio (VH/CD), and cecal microbiota Chao and ACE index (P < 0.05). The crypt depth (CD) in the small intestine, and HSP70 and HSP90 mRNA levels in the heart, liver, spleen, and kidney were significantly increased (P < 0.05). Dietary melittin significantly increased growth performance, serum and liver antioxidative function, immune function, intestinal VH and VH/CD, and cecal microbiota Shannon index in heat-stressed quails (P < 0.05). Melittin significantly decreased small intestinal CD, and HSP70 and HSP90 mRNA levels in the viscera (P < 0.05). Furthermore, dietary melittin could have balanced the disorder of cecal microbiota caused by heat stress and increased the abundance and diversity of beneficial microbiota (e.g., Firmicutes were significantly increased). PICRUSt2 functional prediction revealed that most of the KEGG pathways with differential abundance caused by high temperature were related to metabolism, and melittin could have restored them close to normal levels. Spearman correlation analysis showed that the beneficial intestinal bacteria Anaerotruncus, Bacteroidales_S24-7_group_norank, Lachnospiraceae_unclassified, Shuttleworthia, and Ruminococcaceae_UCG-014 increased by melittin were positively correlated with average daily feed intake, the average daily gain, serum and liver superoxide dismutase, IgG, IgA, bursa of Fabricius index, and ileum VH and VH/CD. In sum, our results demonstrate for the first time that dietary melittin could improve the adverse effects of heat stress on antioxidant function, immune function, heat shock protein, intestinal morphology, and cecal microbiota in quails, consequently improving their production performance under heat stress.

Revealing the Formation and Reactivity of Cage-Confined Cu Pairs in Catalytic NOx Reduction over Cu-SSZ-13 Zeolites by In Situ UV-Vis Spectroscopy and Time-Dependent DFT Calculation.

The low-temperature mechanism of chabazite-type small-pore Cu-SSZ-13 zeolite, a state-of-the-art catalyst for ammonia-assisted selective reduction (NH3-SCR) of toxic NOx pollutants from heavy-duty vehicles, remains a debate and needs to be clarified for further improvement of NH3-SCR performance. In this study, we established experimental protocols to follow the dynamic redox cycling (i.e., CuII ↔ CuI) of Cu sites in Cu-SSZ-13 during low-temperature NH3-SCR catalysis by in situ ultraviolet-visible spectroscopy and in situ infrared spectroscopy. Further integrating the in situ spectroscopic observations with time-dependent density functional theory calculations allows us to identify two cage-confined transient states, namely, the O2-bridged Cu dimers (i.e., µ-η2:η2-peroxodiamino dicopper) and the proximately paired, chemically nonbonded CuI(NH3)2 sites, and to confirm the CuI(NH3)2 pair as a precursor to the O2-bridged Cu dimer. Comparative transient experiments reveal a particularly high reactivity of the CuI(NH3)2 pairs for NO-to-N2 reduction at low temperatures. Our study demonstrates direct experimental evidence for the transient formation and high reactivity of proximately paired CuI sites under zeolite confinement and provides new insights into the monomeric-to-dimeric Cu transformation for completing the Cu redox cycle in low-temperature NH3-SCR catalysis over Cu-SSZ-13.

Unlocking High-Efficiency Methane Oxidation with Bimetallic Pd-Ce Catalysts under Zeolite Confinement.

Catalytic complete oxidation is an efficient approach to reducing methane emissions, a significant contributor to global warming. This approach requires active catalysts that are highly resistant to sintering and water vapor. In this work, we demonstrate that Pd nanoparticles confined within silicalite-1 zeolites (Pd@S-1), fabricated using a facile in situ encapsulation strategy, are highly active and stable in catalyzing methane oxidation and are superior to those supported on the S-1 surface due to a confinement effect. The activity of the confined Pd catalysts was further improved by co-confining a suitable amount of Ce within the S-1 zeolite (PdCe0.4@S-1), which is attributed to confinement-reinforced Pd-Ce interactions that promote the formation of oxygen vacancies and highly reactive oxygen species. Furthermore, the introduction of Ce improves the hydrophobicity of the S-1 zeolite and, by forming Pd-Ce mixed oxides, inhibits the transformation of the active PdO phase to inactive Pd(OH)2 species. Overall, the bimetallic PdCe0.4@S-1 catalyst delivers exceptional outstanding activity and durability in complete methane oxidation, even in the presence of water vapor. This study may provide new prospects for the rational design of high-performance and durable Pd catalysts for complete methane oxidation.

Facile and Scalable Mechanochemical Synthesis of Defective MoS2 with Ru Single Atoms Toward High-Current-Density Hydrogen Evolution.

Designing a facile strategy to prepare catalysts with highly active sites are challenging for large-scale implementation of electrochemical hydrogen production. Herein, a straightforward and eco-friendly method by high-energy mechanochemical ball milling for mass production of atomic Ru dispersive in defective MoS2 catalysts (Ru1 @D-MoS2 ) is developed. It is found that single atomic Ru doping induces the generation of S vacancies, which can break the electronic neutrality around Ru atoms, leading to an asymmetrical distribution of electrons. It is also demonstrated that the Ru1 @D-MoS2 exhibits superb alkaline hydrogen evolution enhancement, possibly attributing to this electronic asymmetry. The overpotential required to deliver a current density of 10 mA cm-2 is as low as 107 mV, which is much lower than that of commercial MoS2 (C-MoS2 , 364 mV). Further density functional theory (DFT) calculations also support that the vacancy-coupled single Ru enables much higher electronic distribution asymmetry degree, which could regulate the adsorption energy of intermediates, favoring the water dissociation and the adsorption/desorption of H*. Besides, the long-term stability test under 500 mA cm-2 further confirms the robust performance of Ru1 @D-MoS2 . Our strategy provides a promising and practical way towards large-scale preparation of advanced HER catalysts for commercial applications.

Sustainable total factor productivity of transport: considering safety issues and environmental impacts.

Economy, environment, and safety are three important components of sustainable transport. This paper proposes a productivity measurement standard that comprehensively considers economic growth, environmental impact, and safety issues, namely sustainable total factor productivity (STFP). We measure the growth rate of STFP in transport sector of OECD countries in terms of Malmquist-Luenberger productivity index by applying data envelopment analysis (DEA). It is found that the growth rate of total factor productivity in transport sector can be overestimated if safety is ignored. In addition, we discuss the influence of socio-economic factors on the measurement results, finding that there exists a threshold on the impact of environmental regulation intensity on the growth of STFP in transport. That is, STFP increases with environmental regulation intensity if it is smaller than 0.247, while STFP decreases if it is larger than 0.247.

Cold-Start NOx Mitigation by Passive Adsorption Using Pd-Exchanged Zeolites: From Material Design to Mechanism Understanding and System Integration.

It remains a major challenge to abate efficiently the harmful nitrogen oxides (NOx) in low-temperature diesel exhausts emitted during the cold-start period of engine operation. Passive NOx adsorbers (PNA), which could temporarily capture NOx at low temperatures (below 200 °C) and release the stored NOx at higher temperatures (normally 250-450 °C) to downstream selective catalytic reduction unit for complete abatement, hold promise to mitigate cold-start NOx emissions. In this review, recent advances in material design, mechanism understanding, and system integration are summarized for PNA based on palladium-exchanged zeolites. First, we discuss the choices of parent zeolite, Pd precursor, and synthetic method for the synthesis of Pd-zeolites with atomic Pd dispersions, and review the effect of hydrothermal aging on the properties and PNA performance of Pd-zeolites. Then, we show how different experimental and theoretical methodologies can be integrated to gain mechanistic insights into the nature of Pd active sites, the NOx storage/release chemistry, as well as the interactions between Pd and typical components/poisons in engine exhausts. This review also gathers several novel designs of PNA integration into modern exhaust after-treatment systems for practical application. At the end, we discuss the major challenges, as well as important implications, for the further development and real application of Pd-zeolite-based PNA in cold-start NOx mitigation.