Abstract Photothermal catalysis has emerged as a promising route for CO2 conversion; however, whether light serves as a heat source or actively modulates catalytic active sites remains an open question. This work reports a defect-enhanced metal–carbon interaction strategy for tuning the electronic structure of cobalt species supported on carbon nanotubes (CNTs), enabling a highly selective reverse water–gas shift (RWGS) reaction to CO through light-induced electronic and adsorption modulation. Among catalysts with different cobalt nanoparticle sizes, 3Co/CNTs shows the highest photothermal catalytic performance, delivering a CO production rate of 299.3 mmol gcat–1 h–1 (10.0 mol gCo–1 h–1) and a CO selectivity of 98%, substantially outperforming both lower and higher Co loadings and showing a clear advantage over thermal catalysis at identical temperatures. Wavelength-dependent activity and a reduced apparent activation energy under irradiation confirm a non-thermal light effect. Spectroscopic analyses, including XPS, EPR, and in situ DRIFTs, together with CO2-TPD and H2-TPD measurements, reveal that light irradiation induces charge redistribution at the defect-cobalt interface and dynamically modulates CO2 and H2 adsorption. Density functional theory calculations further demonstrate that light-induced upshifting of the Co d-band center enhances adsorbate-metal interactions, providing an electronic basis for the observed photothermal enhancement. These findings establish dynamic modulation of metal-support electronic coupling and adsorption energetics as a key mechanism for photothermal CO2 reduction, offering a general strategy for designing light-responsive catalytic interfaces.

Covalent organic frameworks (COFs) have demonstrated superior performance in wide-ranging applications, yet their practical deployment has been long hindered by their inconvenient synthesis protocols. Toxic solvents, tedious procedures and long reaction times are typically involved in their synthesis, and microcrystalline powders are commonly obtained, which are unfavorable in practical use. Unfortunately, newly developed methods aiming to resolve these challenges often lead to deteriorated COF crystallinity and porosity. Here we develop a solid-phase hot-pressing method to fabricate 15 types of highly crystalline COF platelet of various linkage types, including imine-, hydrazone-, β-ketoenamine- and imide-linked COFs. Moreover, COF platelets with complex chemical structures, including a COF with three-dimensional geometry and a COF with multiple monomer components, have been successfully obtained. In particular, all COF platelets can be obtained within a short processing time of 0.5–5 min, with high crystallinity and porosity. Finally, as a proof-of-concept application, a β-ketoenamine-linked COF platelet is directly assembled into an atmospheric water harvesting device, demonstrating excellent water collecting performance. A solid-phase hot-pressing method is introduced, which can rapidly produce highly crystalline covalent organic framework platelets in a convenient, solvent-free manner. Fifteen platelets of various linkage types are produced, with a proof-of-concept demonstration of the resulting high-performing platelet type in an atmospheric water harvesting device.

Achieving a synergistic, rapid, and concentrated energy release process of ammonium perchlorate (AP) is of vital significance for boosting the thrust of composite solid propellants. However, conventional catalytic promoters often exhibit suboptimal catalytic kinetics due to inefficient utilization of active sites. Herein, atomically dispersed Cu-coordinated covalent organic frameworks (COFs)-based catalytic promoters are reported, decorating with energetic anion groups. The highly accessible single Cu sites confined in the COFs significantly contribute to the raid and concentrated energy release of AP, yielding a sharply narrowed decomposition peak at 341.3 °C with a peak width of only 9 °C. This performance is markedly superior to the dispersed exothermic process of raw AP (410.3 °C with a peak width of 30 °C). Additionally, the energetic COF promoter considerably increased the output energy via collaboratively promoting the chemical energy release of AP and its own decomposition. Correlating in situ spectroscopies and theoretical calculations reveals that the incorporated anionic groups effectively modulate the local electronic structure of the Cu sites. This alteration promotes the key step of cleavage of Cl─O bonds in AP intermediates to produce reactive oxygen species and also boosts the oxidation of NH3 to high-valence nitrogen oxides, thereby accelerating the combustion reaction kinetic.

Hazardous chemicals, such as explosives and chemical warfare agents, are commonly used during terrorist attacks, which have been threatening the global public safety. Real-time detection of specific hazardous chemicals is thus an important way to prevent terrorist activities but remains a significant technical challenge. In recent years, metal-organic frameworks (MOFs) have been widely studied as promising candidates to achieve highly sensitive and selective detection. In this review, we summarized the most recent research progress on MOF-based sensors for the precise and rapid detection of hazardous chemicals. We provided a general introduction into the various mechanisms for hazardous chemicals detection and the most recent research progress on the detection of various types of hazardous chemicals using MOFs. Finally, current challenges and possible future directions toward practical application were proposed. This review highlights the great premise of MOFs in the field of hazardous chemical detection.

Line strengths and line shape parameters of Ar- and N2 -perturbed CO2 R -branch transitions (82 <= J '' <= 90) in the v3 fundamental band were measured in a shock tube from 730 K to 2500 K and pressure below 1.13 atm using laser absorption spectroscopy (LAS). The retrieved absorption curves were fitted with the Voigt and the quadratic speed -dependent Voigt (qSDV) profiles to obtain the line strengths, broadening, and shift coefficients. Line strengths were compared to values in HITEMP, HITRAN2020, and Ames2021 databases, and the HITEMP shows the best agreement with the measured results. Ar- and N2 -broadening and shift coefficients were regressed into the power law and the double power law form to study the temperature dependence of the targeted lines. The speed -dependence parameter aw was temperature -dependent. The J -dependence of the derived broadening and shift coefficients was discussed. The results of this work will aid the development of the absorption model in the far -wing region and the design of CO2 LAS sensors for high -temperature measurement.

Reclaimed concrete may successfully accomplish concrete recycling, cut down on resource waste, and advance environmental and green development. This work studies the impermeability performance of totally recycled coarse aggregate concrete by designing the mix ratio using the coarse aggregate found in construction waste as the research point. The findings indicate that the seepage performance of recycled concrete will be influenced by the fly ash concentration, water ash ratio, and water reduction agent. The impermeability performance of reclaimed concrete decreases when the water cement ratio rises, but only to a limited extent. The best impermeability results from reclaimed concrete when the water reduction agent content is 0.5%; the best impermeability results from fly ash when it is 10%; and the greatest impermeability results from reclaimed concrete when it is not added.

Chemical warfare agents, such as sulfur mustard (HD), pose an ongoing global threat. To get closer to the actual scene, immediate detoxification of a flowing gaseous HD simulant is indispensable, yet which faces challenges for the current catalysts. Here, we systematically investigate the detoxification of a gaseous HD simulant (2-chloroethyl ethyl sulfide, CEES) by a continuous flow device in gas-solid conditions under visible light irradiation. Notably, a new catalyst (Ag-12-BDP-I) was successfully synthesized by ingeniously integrating a boron-dipyrromethene (BDP)-based linker modified with the heavy iodine and silver clusters as the secondary building unit. The adequate porosity, sufficient adsorbate-adsorbent interactions, and favorable hydrophobic microenvironments enable the immediate photocatalytic decontamination of CEES at a flow rate of 20 mL/min, even in the water vapor atmosphere. By combining catalytic characterization and density functional theory calculations, we elucidated the relationship between the material's structure and performance. This study offers valuable insights into the development of metal-organic frameworks for the decontamination of toxic gaseous substances.

Lead-zinc tailings (LZT) are hazardous solid wastes that threaten the environment safety and human health. As a bulk solid waste, coal gangue (CG) also caused pollution. This paper studied the feasibility of using a combi-nation of LZT and CG to produce ceramsite and realizing the solidification of heavy metals. The physical properties of ceramsite were evaluated, and the phase composition and microstructure were analyzed by XRD and SEM-EDS, respectively. The results showed that when the LZT content was <30 wt%, LZT and CG could be used for the preparation of ceramsite, and the prepared ceramsite met the requirements of environmental safety. Proportion of raw materials and sintering temperature affected physical properties of ceramsite. With the in-crease of LZT content, the apparent density, and the compressive strength of ceramsite first decreased and then increased. The increase of sintering temperature from 1150 C to 1250 degrees C reduced the apparent density and the compressive strength of ceramsite. Moreover, the presence of Pb and Zn decreased the apparent density, the compressive strength, and the water absorption of the ceramsite. The valence of Pb and Zn remained as Pb2+ and Zn2+ after the ceramsite sintering. The solidification of ceramsite could be related to chemical effect through the generation of crystals (e.g., Pb3(AsO4)2 and ZnFe2O4) and physical effect though encapsulation. This work provides a potential way to the reduction, recycling, and harmless utilization of LZT and CG.

Aryl sulfides are in great demands in drugs and materials sciences. To avoid using nucleophilic and noxious thiols, many efforts have been focused on exploring novel sulfide resources. Herein, a reductive Pd-catalyzed, Ni-mediated method to synthesize aryl sulfides via a sulfide transfer reaction is developed. The utility and scope of this reaction is exemplified by various aryl electrophiles and aryl sulfides. Mechanistic studies reveal two competing catalytic cycles of sulfide transfer and aryl transfer in this reaction, where the former one is favored over the later one because of the large energy barrier difference during the transmetalation. Moreover, two important chemicals are late-stage functionalized by this method, exhibiting the potential applications in drugs and materials science.

A series of mesoporous nickel cobalt oxides with different Ni/Co was synthesized by a mild hydrothermal method. The physical and chemical properties of these oxides were characterized using XRD, N2-Physisorption, SEM/TEM, XPS, H2-TPR and O2-TPD. The catalytic performances for liquid-phase oxidation of benzyl alcohol by air were also investigated. It was found that the Ni/Co ratio had remarkable influences on the crystal phase, morphology, surface element composition, redox properties as well as their capability toward O2 activation. Compared with the monoxide, the mixed oxide showed enhanced conversion, particularly the Ni1Co3 with Ni/Co of 1/3 has the highest activity of all. In addition, the Ni1Co3 exhibited good recyclability upon recalcination prior to next run. The excellent performance of Ni1Co3 was closely related to the abundant oxygen vacancy or defect sites, which possibly resulted from the formation of distorted nickel cobalt spinel structure. They were responsible for the enhanced activation of O2 molecules and consequently higher conversion in benzyl alcohol oxidation.

Abstract Background The bifunctional enzyme β-carotene hydroxylase (CrtZ) catalyzes the hydroxylation of carotenoid β-ionone rings at the 3, 3’ position regardless of the presence of keto group at 4, 4’ position, which is an important step in the synthesis of astaxanthin. The level and substrate preference of CrtZ may have great effect on the amount of astaxanthin and the accumulation of intermediates. Results In this study, the substrate preference of PCcrtZ from Paracoccus sp. PC1 and PAcrtZ from Pantoea Agglomerans were certified and were combined utilization for increase astaxanthin production. Firstly, PCcrtZ from Paracoccus sp. PC1 and PAcrtZ from P. Agglomerans were expressed in platform strains CAR032 (β-carotene producing strain) and Can004 (canthaxanthin producing strain) separately to identify their substrate preference for carotenoids with keto groups at 4,4’ position or not. The results showed that PCcrtZ led to a lower zeaxanthin yield in CAR032 compared to that of PAcrtZ. On the contrary, higher astaxanthin production was obtained in Can004 by PCcrtZ than that of PAcrtZ. This demonstrated that PCCrtZ has higher canthaxanthin to astaxanthin conversion ability than PACrtZ, while PACrtZ prefer using β-carotene as substrate. Finally, Ast010, which has two copies of PAcrtZ and one copy of PCcrtZ produced 1.82 g/L of astaxanthin after 70 h of fed-batch fermentation. Conclusions Combined utilization of crtZ genes, which have β-carotene and canthaxanthin substrate preference respectively, can greatly enhance the production of astaxanthin and increase the ratio of astaxanthin among total carotenoids.

Chemical warfare agents (CWAs) are among the most lethal chemicals known to humans. Thus, developing multifunctional catalysts for highly efficient detoxification of various CWAs is of great importance. In this work, we developed a robust copper tetrazolate metal-organic framework (MOF) catalyst containing a dicopper unit similar to the coordination geometry of the active sites of natural phosphatase and tyrosinase enzymes. This catalyst aided in phosphate ester bond hydrolysis and hydrogen peroxide decomposition, ultimately achieving high detoxification efficiency against both a nerve agent simulant (diethoxy-phosphoryl cyanide (DECP)) with a half-life of 3.5 min and a sulfur mustard simulant (2-chloroethyl ethyl sulfide (CEES)) with a half-life of 4.5 min, making it competitive with other reported materials. The dicopper sites in ZZU-282 provide versatile binding modes with the substrates, thereby promoting the activation of substrates and enhancing the catalytic efficiency. A combination of postmodified metal exchange control experiments, density functional theory calculations, and catalytic evaluations confirmed that dual Cu sites are the active centers promoting the catalytic reaction. This study offers a new design perspective to achieve advanced catalysts for CWA detoxification.

Autonomous vehicles (AVs) are expected to eliminate many driver errors to save thousands of lives. As vulnerable road users, pedestrians and bicyclists are more likely to be injured or killed in accidents involving cars. Therefore, understanding the perceptions of vulnerable road users is crucial for developing and deploying AVs and solving public concerns because the acceptance of AVs relies on both AV users and other road users, such as vulnerable road users. This paper analyzed two surveys collected in 2017 and 2019 by BikePGH in Pittsburgh to understand vulnerable road users' perceptions of AVs in different years. The analysis showed that vulnerable road users' interactive experiences with AVs increased from 2017 to 2019 in Pittsburgh, and the interactive experiences with AVs positively affected vulnerable road users' perceived safety and receptivity toward AVs in 2017 and 2019. Specifically, vulnerable road users' perceived safety of AVs significantly increased from 2017 to 2019, while their receptivity toward AVs did not change significantly during that period. Additionally, autonomous driving accidents negatively affected vulnerable road users' perceptions of AVs. Therefore, we recommend that policymakers provide opportunities for the public to interact with AVs and guarantee vulnerable road users' safety and benefits in AV testing.

Formaldehyde wastewater, which is mainly from plastics, paper, resin and other industries, not only causes serious environmental problems, but also gives harmful effects to human health. With the increasing environmental concerns, the abatement of formaldehyde wastewater has become an urgent problem. Compared with the conventional technologies, such as the biological treatment, catalytic wet air oxidation (CWAO) has been shown to be an effective and environmentally-friendly way to remove the formaldehyde in water. CWAO technology uses air or oxygen as the oxidant, where the organic can be directly oxidized into CO2 and H2O or partially converted to the less toxic compounds by suitable catalysts at elevated temperature and pressure. The key issue of CWAO is to develop a promising catalyst that can work efficiently at low temperature. MnO2 is widely applied in the complete oxidation reactions due to its variable valence and abundant crystal structures, but is rarely used in the treatment of formaldehyde wastewater. In this article, Pt/R-MnO2 (Pt supported on rod-like-MnO2) with very low precious metal content (Pt, 0.1wt%) was prepared by impregnation method. For comparison, Pt/TiO2 and Pt/CeO2 catalysts were also prepared. The three catalysts with different supports were investigated in the CWAO of formaldehyde wastewater. Pt/TiO2 showed the lowest activity and the TOC conversion is less than 35% even at the temperature of 100 degrees C. Pt/CeO2 exhibited better catalyst performance. As the reaction temperature increased from 30 to 100 degrees C, the TOC conversion rose from 19.1% to 83.0%. Pt/R-MnO2 displayed the most excellent catalytic performance compared with Pt/TiO2 and Pt/CeO2. At the reaction temperatures of 50 and 80 degrees C, the TOC conversions of Pt/R-MnO2 are 82.2% and 89.0%, respectively. MnO2 possesses abundant morphologies, which may affect its catalytic performance. The effect of MnO2 morphologies on the catalytic performance of Pt/MnO2 in formaldehyde wastewater was investigated and the cocoon-like- and sheet-likeMnO(2) were also prepared. It was found that Pt/C-MnO2 catalyst (Pt supported on cocoon-like-MnO2) exhibited the best catalytic performance among the prepared Pt/MnO2 catalysts. At the temperature of 50 degrees C, Pt/C-MnO2 can achieve TOC conversion of 88.1%. TOC conversion can be retained at a level higher than 80% even after four consecutive runs. Pt/SMnO2 (Pt supported on sheet-like-MnO2) and Pt/R-MnO2 (Pt supported on rod-like-MnO2) showed lower activity and quicker deactivation with the reaction proceeding. After four consecutive runs, TOC conversion is decreased from 82.4% and 82.2% to 35.6% and 16.3% for Pt/S-MnO, and Pt/R-MnO2, respectively. The Pt/C-MnO2 showed the most excellent activity and stability for CWAO of aqueous formaldehyde at low temperature. Various characterizations were used to analyze the catalysts of Pt/C-MnO2, Pt/R-MnO2 and Pt/S-MnO2. The measurement of dispersion indicated that Pt/C-MnO2 catalyst has better dispersion, which is up to 36.0%, higher than 21.2% for Pt/S-MnO2 and 17.3% for Pt/R-MnO2. The results of XPS and O-2-TPD showed that Pt/C-MnO2 contains more reactive oxygen species. H-2-TPR revealed that Pt/C-MnO2 can be reduced at lower temperature and thus possesses better oxidizing ability. ICP analysis implied that Pt/C-MnO2 has a better ability to inhibit the leaching of Pt. The Pt content of Pt/S-MnO2 and Pt/R-MnO2 is severely lost after four reactions, which caused a sharp decrease in the activity of the two catalysts. Better dispersion, more reactive oxygen species, higher oxidizing ability and better anti-leaching capability contribute to the excellent performance of Pt/C-MnO2 in CWAO of aqueous formaldehyde reaction.

采用浸渍法制备了一系列MTiO3(M=Mg、Ca、Sr、Ba)钙钛矿型氧化物负载的Ni催化剂(Ni的负载量为5％,质量分数),通过XRD、氮吸附、H2-TPR、CO2-TPD、XPS和TG等技术对催化剂进行了表征,对其甲烷二氧化碳重整反应的催化性能进行了研究.结果表明,M为不同碱土金属时,催化剂上金属载体相互作用、活性组分的表面原子浓度以及催化剂晶格氧的流动性都发生了变化.Ni/CaTiO3催化剂上金属载体相互作用较强,还原出的活性组分Ni的含量较多,晶格氧流动性较高,因而具有较好的催化性能.SrTiO3载体颗粒粒径较大,Ni/SrTiO3催化剂上Ni的分散度不高,金属载体的相互作用较弱,表面Ni原子相对含量较低,晶格氧的流动性较差,其甲烷二氧化碳重整反应活性也最低.

Abnormalities in tricarboxylic acid (TCA) cycle function were related to a variety of pathological processes.Fumarate hydratase (FH) is a required enzyme in the TCA cycle.To explore the general influence of FH knockout, we isolated FH +/-rat and normal rat lung fibroblasts and cultured these cells in vitro.The isolated fibroblasts with the current method were rather homogeneous and were confirmed spindle in morphology, positive for vimentin and negative for α-SMA (α-smooth muscle actin).Sequencing of the PCR (polymerase chain reaction) products flanking the FH gene mutation verified the FH +/-status, and the FH gene and protein expression were confirmed to be reduced in the FH +/-cells.No sign of ageing for the FH +/-cells after 61 passages was observed, but the controls died out at this stage.Flow cytometry revealed increased S-phase and decreased G1/G0 proportions with significantly less early apoptosis in FH +/-cells compared to that in control cells.At the same time, increased glucose consumption, intracellular fumarate production and extracellular lactate secretion were verified in the FH +/-cells.Correspondingly, FH +/-cells showed a lower basal oxygen consumption rate (OCR) but a higher level of reactive oxygen species (ROS) production.Single cell cloning and cell line establishment were successfully performed with the FH +/-cells at the 84 th passage.All the above results indicate an important role for FH +/-in the longevity or immortality of the FH +/-cells, in which increased p53 and TERT (telomerase reverse transcriptase) protein expression, decreased p21 and p16 protein expression and negative SA-β-Gal (senescence-associated beta-galactosidase) were verified along with metabolic reprogramming.

致密砂岩油藏基质渗透率低,存在天然和人工裂缝,CO2驱窜逸现象严重.通过测定成胶前的黏度和成胶后的强度评价了改性淀粉凝胶的注入性能和封堵能力,利用自制致密砂岩裂缝岩心,通过3种不同裂缝开度下的封堵、驱替实验评价了CO2气窜后改性淀粉凝胶对不同开度的裂缝封堵性能及提高采收率程度,并进一步探讨高强度淀粉凝胶改善致密砂岩裂缝性油藏CO2驱油效果的适用界限.研究结果表明,改性淀粉凝胶成胶前黏度低,有利于体系的顺利注入,成胶后强度高,可用于裂缝的强封堵,且在0.42 mm裂缝开度条件下可实现99％以上的封堵率,突破压力高达24.9 MPa,有效启动了低渗基质中的剩余油,提高原油采收率程度达到28％,具有良好的封堵适应性;在0.65 mm裂缝开度条件下,封堵效果有所下降,封堵率为92％,突破压力降至15.9 MPa,提高采收程度18％;在裂缝开度0.08 mm条件下,注入性明显变差,从而影响其封堵性能,封堵率为90％,突破压力为3.6 MPa,提高采收率9.8％.该淀粉凝胶对开度0.42 mm左右裂缝的致密砂岩裂缝性岩心的适应性最好.

为了探究CO2在低渗透油藏中与原油的混相条件及在近混相条件下的驱油效果,采用室内物理模拟方法,通过均质、非均质长方体岩心实验,在评价影响CO2驱油效果的渗透率、岩心长度、渗透率级差和压力因素的基础上,借助采收率与各影响因素参数指标,分析非混相、近混相和混相不同阶段的曲线特征,建立了近混相驱区域的确定方法.采用该岩心实验方法,在模拟油藏条件下,CO2与原油的最小混相压力为18.5 MPa左右,比传统细管实验确定的17.8 MPa高出0.7 MPa,同时根据驱油曲线特征,划分了CO2非混相、近混相和混相区域,并根据驱油效率确定出近混相驱的压力区域为16.5～18.5 MPa.建立的最小混相压力岩心测定方法和近混相驱区域划定的方法,为进一步深化CO2近混相驱油机理的认识及YC油田CO2矿场驱油方案的设计提供了参考.

Department of Oncology, The First Affili Zhengzhou, Henan Province, China. E-mai aliyun.com Department of Pathology, The Norwegian R Institute of Clinical Medicine, University of Department of Pathology, The Third Affil Zhengzhou, Henan Province, China Department of Chinese andWestern Integra of Zhengzhou University, Zhengzhou, China The Institute of Clinical Medicine, The University, Zhengzhou, Henan Province, Ch The Nephrology Center, The First Affilia Zhengzhou, Henan Province, China Department of Urology, The Norwegian Ra Oslo, 0379, Norway † These authors have contributed equally Cite this: RSC Adv., 2018, 8, 16636

Although abnormal metabolism in metabolic syndrome and tumours has been well described, the relationship between oxoglutarate dehydrogenase (OGDH) and obesity-related diseases is still largely unknown. This study aimed to investigate whether it was possible to use transcription activator-like effector nuclease (TALEN) technology to establish OGDH(-/-) rats and then study the effect of a high-fat diet (HFD) on these rats. However, after OGDH(+/-) rats were generated, we were unable to identify any OGDH(-/-) rats by performing mating experiments with the OGDH(+/-) rats for almost one year. During the past three years, only OGDH(+/-) rats were stably established, and correspondingly reduced OGDH expression in the tissues of the OGDH(+/-) rats was verified. No significant abnormal behaviour was observed in the OGDH(+/-) rats compared to the wild-type (WT) control rats. However, the OGDH(+/-) rats were revealed to have higher body weight, and the difference was even significantly greater under the HFD condition. Furthermore, blood biochemical and tissue histological examinations uncovered no abnormalities with normal diets, but a HFD resulted in liver dysfunction with pathological alterations in the OGDH(+/-) rats. Our results strongly indicate that OGDH homologous knockout is lethal in rats but heterologous OGDH knockout results in vulnerable liver lesions with a HFD. Therefore, the current study may provide a useful OGDH(+/-) rat model for further investigations of metabolic syndrome and obesity-related hepatic carcinogenesis.