Influence of metal-support interactions on reaction pathways over Ni/CeZrOx–Al2O3 catalysts for ethanol steam reforming

This work investigates selective Ni locations over Ni/CeZrO_x–Al₂O₃ catalysts at different Ni loading contents and their influences on reaction pathways in ethanol steam reforming (ESR). Depending on the Ni loading contents, the added Ni selectively interacts with CeZrO_x–Al₂O₃, resulting in the stepwise locations of Ni over CeZrO_x–Al₂O₃. This behavior induces a remarkable difference in hydrogen production and coke formation in ESR. The selective interaction between Ni and CeZrO_x for 10-wt.% Ni generates more oxygen vacancies in the CeZrO_x lattice. The Ni sites near the oxygen vacancies enhance reforming via steam activation, resulting in the highest hydrogen production rate of 1863.0 μmol/g_cat·min. In contrast, for 15 and 20-wt.% Ni, excessive Ni is additionally deposited on Al₂O₃ after the saturation of Ni–CeZrO_x interactions. These Ni sites on Al₂O₃ accelerate coking from the ethylene produced on the acidic sites, resulting in a high coke amount of 19.1 mg_c/g_cat·h (20Ni/CZ-Al).     

Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold

Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal-rich silicon phosphides RuSi₄P₄ and IrSi₃P₃ are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X-ray diffraction and ²⁹Si and ³¹P magic angle spinning NMR. In agreement with previous report RuSi₄P₄ crystallizes in NCS space group P1, while IrSi₃P₃ is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi₄P₄ and IrSi₃P₃ to be wide bandgap (E_g) semiconductors, E_g = 1.9 and 1.8 eV, respectively. RuSi₄P₄ and IrSi₃P₃ outperform the current state-of-the-art infrared SHG material, AgGaS₂, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi₄P₄ and IrSi₃P₃ are promising candidates for longer wavelength NLO materials.     

Systemic Inflammation and the Breakdown of Intestinal Homeostasis Are Key Events in Chronic Spinal Cord Injury Patients

Our aim was to investigate the subset distribution and function of circulating monocytes, proinflammatory cytokine levels, gut barrier damage, and bacterial translocation in chronic spinal cord injury (SCI) patients. Thus, 56 SCI patients and 28 healthy donors were studied. The levels of circulating CD14^+highCD16⁻, CD14^+highCD16⁺, and CD14^+lowCD16⁺ monocytes, membrane TLR2, TLR4, and TLR9, phagocytic activity, ROS generation, and intracytoplasmic TNF-α, IL-1, IL-6, and IL-10 after lipopolysaccharide (LPS) stimulation were analyzed by polychromatic flow cytometry. Serum TNF-α, IL-1, IL-6 and IL-10 levels were measured by Luminex and LPS-binding protein (LBP), intestinal fatty acid-binding protein (I-FABP) and zonulin by ELISA. SCI patients had normal monocyte counts and subset distribution. CD14^+highCD16⁻ and CD14^+highCD16⁺ monocytes exhibited decreased TLR4, normal TLR2 and increased TLR9 expression. CD14^+highCD16⁻ monocytes had increased LPS-induced TNF-α but normal IL-1, IL-6, and IL-10 production. Monocytes exhibited defective phagocytosis but normal ROS production. Patients had enhanced serum TNF-α and IL-6 levels, normal IL-1 and IL-10 levels, and increased circulating LBP, I-FABP, and zonulin levels. Chronic SCI patients displayed impaired circulating monocyte function. These patients exhibited a systemic proinflammatory state characterized by enhanced serum TNF-α and IL-6 levels. These patients also had increased bacterial translocation and gut barrier damage.     

Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Centimeter-scale low-damage micromachining on single-crystal 4H–SiC substrates using a femtosecond laser with square-shaped Flat-Top focus spots

Femtosecond (fs) lasers have been proved to be reliable tools for high-precision and high-quality micromachining of ceramic materials. Nevertheless, fs laser processing using a single-mode beam with a Gaussian intensity distribution is difficult to obtain large-area flat and uniform processed surfaces. In this study, we utilize a customized diffractive optical element (DOE) to redistribute the laser pulse energy from Gaussian to square-shaped Flat-Top profile to realize centimeter-scale low-damage micromachining on single-crystal 4H–SiC substrates. We systematically investigated the effects of processing parameters on the changes in surface morphology and composition, and an optimal processing strategy was provided. Mechanisms of the formation of surface nanoparticles and the removal of surface micro-burrs were discussed. We also examined the distribution of subsurface defects caused by fs laser processing by removing a thin surface layer with a certain depth through chemical mechanical polishing (CMP). Our results show that laser-induced periodic surface structures (LIPSSs) covered by fine SiO₂ nanoparticles form on the fs laser-processed areas. Under optimal parameters, the redeposition of SiO₂ nanoparticles can be minimized, and the surface roughness Sa of processed areas reaches 120 ± 8 nm after the removal of a 10 μm thick surface layer. After the laser processing, micro-burrs on original surfaces are effectively removed, and thus the average profile roughness Rz of 2 mm long surface profiles decreases from 920 ± 120 nm to 286 ± 90 nm. No visible micro-pits can be found after removing ~1 μm thick surface layer from the laser-processed substrates.     

成型温度对PBX装药内部质量及性能的影响

针对压制成型的PBX炸药装药，选择CT无损检测、巴西实验和扫描电镜检测等技术，对比研究了室温和加热两种温度下压制成型的炸药装药内部质量、静态力学性能和细观破坏形式。结果表明，加热压制有利于改善炸药装药的内部质量，可避免产生初始损伤，且提高了装药的力学性能。细观尺度上，室温压制成型的装药主要发生界面脱黏破坏，加热压制成型装药的主要破坏形式是穿晶断裂。     

The Age-Sensitive Efficacy of Calorie Restriction on Mitochondrial Biogenesis and mtDNA Damage in Rat Liver

Calorie restriction (CR) is the most efficacious treatment to delay the onset of age-related changes such as mitochondrial dysfunction. However, the sensitivity of mitochondrial markers to CR and the age-related boundaries of CR efficacy are not fully elucidated. We used liver samples from ad libitum-fed (AL) rats divided in: 18-month-old (AL-18), 28-month-old (AL-28), and 32-month-old (AL-32) groups, and from CR-treated (CR) 28-month-old (CR-28) and 32-month-old (CR-32) counterparts to assay the effect of CR on several mitochondrial markers. The age-related decreases in citrate synthase activity, in TFAM, MFN2, and DRP1 protein amounts and in the mtDNA content in the AL-28 group were prevented in CR-28 counterparts. Accordingly, CR reduced oxidative mtDNA damage assessed through the incidence of oxidized purines at specific mtDNA regions in CR-28 animals. These findings support the anti-aging effect of CR up to 28 months. Conversely, the protein amounts of LonP1, Cyt c, OGG1, and APE1 and the 4.8 Kb mtDNA deletion content were not affected in CR-28 rats. The absence of significant differences between the AL-32 values and the CR-32 counterparts suggests an age-related boundary of CR efficacy at this age. However, this only partially curtails the CR benefits in counteracting the generalized aging decline and the related mitochondrial involvement.     

Adaptation to Endoplasmic Reticulum Stress Enhances Resistance of Oral Cancer Cells to Cisplatin by Up-Regulating Polymerase η and Increasing DNA Repair Efficiency

Endoplasmic reticulum (ER) stress response is an adaptive program to cope with cellular stress that disturbs the function and homeostasis of ER, which commonly occurs during cancer progression to late stage. Late-stage cancers, mostly requiring chemotherapy, often develop treatment resistance. Chemoresistance has been linked to ER stress response; however, most of the evidence has come from studies that correlate the expression of stress markers with poor prognosis or demonstrate proapoptosis by the knockdown of stress-responsive genes. Since ER stress in cancers usually persists and is essentially not induced by genetic manipulations, we used low doses of ER stress inducers at levels that allowed cell adaptation to occur in order to investigate the effect of stress response on chemoresistance. We found that prolonged tolerable ER stress promotes mesenchymal–epithelial transition, slows cell-cycle progression, and delays the S-phase exit. Consequently, cisplatin-induced apoptosis was significantly decreased in stress-adapted cells, implying their acquisition of cisplatin resistance. Molecularly, we found that proliferating cell nuclear antigen (PCNA) ubiquitination and the expression of polymerase η, the main polymerase responsible for translesion synthesis across cisplatin-DNA damage, were up-regulated in ER stress-adaptive cells, and their enhanced cisplatin resistance was abrogated by the knockout of polymerase η. We also found that a fraction of p53 in stress-adapted cells was translocated to the nucleus, and that these cells exhibited a significant decline in the level of cisplatin-DNA damage. Consistently, we showed that the nuclear p53 coincided with strong positivity of glucose-related protein 78 (GRP78) on immunostaining of clinical biopsies, and the cisplatin-based chemotherapy was less effective for patients with high levels of ER stress. Taken together, this study uncovers that adaptation to ER stress enhances DNA repair and damage tolerance, with which stressed cells gain resistance to chemotherapeutics.     

Predicting Prostephanus truncatus (Horn) (Coleoptera: Bostrichidae) populations and associated grain damage in smallholder farmers’ maize stores: A machine learning approach

Prostephanus truncatus is a notorious pest of stored-maize grain and its spread throughout sub-Saharan Africa has led to increased levels of grain storage losses. The current study developed models to predict the level of P. truncatus infestation and associated damage of maize grain in smallholder farmer stores. Data were gathered from grain storage trials conducted in Hwedza and Mbire districts of Zimbabwe and correlated with weather data for each site. Insect counts of P. truncatus and other common stored grain insect pests had a strong correlation with time of year with highest recorded numbers from January to May. Correlation analysis showed insect-generated grain dust from boring and feeding activity to be the best indicator of P. truncatus presence in stores (r = 0.70), while a moderate correlation (r = 0.48) was found between P. truncatus numbers and storage insect parasitic wasps, and grain damage levels significantly correlated with the presence of Tribolium castaneum (r = 0.60). Models were developed for predicting P. truncatus infestation and grain damage using parameter selection algorithms and decision-tree machine learning algorithms with 10-fold cross-validation. The P. truncatus population size prediction model performance was weak (r = 0.43) due to the complicated sampling and detection of the pest and eight-week long period between sampling events. The grain damage prediction model had a stronger correlation coefficient (r = 0.93) and is a good estimator for in situ stored grain insect damage. The models were developed for use under southern African climatic conditions and can be improved with more input data to create more precise models for building decision-support tools for smallholder maize-based production systems.     

Irradiation-induced large bubble formation and grain growth in super nano-grained ceramic

In this work, 0.5TRPO•0.5Gd₂Zr₂O₇ ceramic with an average grain size of only ∼15 nm was prepared by a high pressure (5 GPa/520 °C) sintering method. Phase evolutions and microstructure changes of the as-fabricated super nano and micron-grained ceramics under a high-dose displacement damage induced by 300 keV Kr²⁺ ions were investigated. The results show that the super nano-grained ceramic has low degree of amorphization, obvious grain growth (2–3 times in grain size) and big Kr bubbles (10–68 nm) formation after irradiation. The micron-grained ceramic was severely amorphized after irradiation and many microcracks were formed parallel to its surface. The formation mechanism of Kr bubbles in the super nano-grained ceramic is on account of grain boundary diffusion and migration induced by the accumulation of the injecting Kr ions and irradiation defects. Nevertheless, microcracks formed in the micron-grained sample are caused by the accumulation of Kr atoms.