A Two-Phase Hydrogenation Membrane for Contaminants Reduction at High Hydrogen Reagent Utilization Efficiency.

Heterogeneous hydrogenation is surging as a promising strategy for selective removal of water pollutants, yet numerous efforts rely on catalyst design to advance catalytic activity. Herein, we enhanced the mass transfer and the utilization of hydrogen reagent through construction of a two-phase flow-through membrane reaction device (Pd/SiC-MR). Pd/SiC-MR displays high efficiency and selectivity toward removal of multiple pollutants. For instance, rapid (∼0.35 s) and exclusive hydrogenation (>99%) of carbon-chlorine bond in organohalogens were realized at high water flux (220 L/m2/h). More importantly, the two-phase Pd/SiC-MR reaction system achieved 31.4% utilization of hydrogen reagent, 1-3 orders of magnitude higher than those by classical slurry or fixed-bed reactor. The high hydrogenation performance is attributed to the close proximity of the hydrogen source, reactive hydrogen atom, and pollutant under high molecular collision frequency in membrane pores. Our study opens an approach for improved hydrogen reagent utilization while reserving the high pollutant removal efficiency through altering operating conditions, beyond complex material design limitations in hydrogenation water purification.

Strong Metal-Support Interaction Triggered by Molten Salts.

Strong metal-support interaction (SMSI) plays a vital role in tuning the geometric and electronic structures of metal species. Generally, a high-temperature treatment (>500 °C) in reducing atmosphere is required for constructing SMSI, which may induce the sintering of metal species. Herein, we use molten salts as the reaction media to trigger the formation of high-intensity SMSI at reduced temperatures. The strong ionic polarization of the molten salt promotes the breakage of Ti-O bonds in the TiO2 support, and hence decreases the energy barrier for the formation of interfacial bonds. Consequently, a high-intensity SMSI state is achieved in TiO2 supported Ir nanoclusters, evidenced by a large number of Ir-Ti bonds at the interface, at a low temperature of 350 °C. Moreover, this method is applicable for triggering SMSI in various supported metal catalysts with different oxide supports including CeO2 and SnO2. This newly developed SMSI construction methodology opens a new avenue and holds significant potential for engineering advanced supported metal catalysts toward a broad range of applications.

ß-Methylation of Primary Alcohols with Methanol Catalyzed by a Metal-Ligand Bifunctional Iridium Catalyst.

The development of efficient methods for the direct introduction of a methyl group into molecules is becoming increasingly important. Herein, the ß-methylation of primary alcohols with methanol has been accomplished under environmentally benign conditions using [Cp*Ir(2,2'-bpyO)(H2O)] as a catalyst. It was found that functional groups in the ligand are crucially important for the activity of the iridium complex. Furthermore, the mechanistic research and application potential of our catalytic system are also presented.

Towards large-scale single-shot millimeter-wave imaging for low-cost security inspection.

Millimeter-Wave (MMW) imaging is a promising technique for contactless security inspection. However, the high cost of requisite large-scale antenna arrays hinders its widespread application in high-throughput scenarios. Here, we report a large-scale single-shot MMW imaging framework, achieving low-cost high-fidelity security inspection. We first analyzed the statistical ranking of each array element through 1934 full-sampled MMW echoes. The highest-ranked elements are preferentially selected based on the ranking, building the experimentally optimal sparse sampling strategy that reduces antenna array cost by one order of magnitude. Additionally, we derived an untrained interpretable learning scheme, realizing robust and accurate MMW image reconstruction from sparsely sampled echoes. Last, we developed a neural network for automatic object detection, and experimentally demonstrated successful detection of concealed centimeter-sized targets using 10% sparse array, whereas all the other contemporary approaches failed at such a low sampling ratio. With the strong detection ability and order-of-magnitude cost reduction, we anticipate that this technique provides a practical way for large-scale single-shot MMW imaging.

Nitroreductase DnrA, Utilizing Strategies Secreted in Bacillus sp. Za and SCK6, Enhances the Detoxification of Acifluorfen.

The residues of acifluorfen present a serious threat to the agricultural environment and sensitive crops. DnrA, a nitroreductase, is an intracellular enzyme that restricts the application of wild-type Bacillus sp. Za in environmental remediation. In this study, two strategies were employed to successfully secrete DnrA in strains SCK6 and Za, and the secretion expression conditions were optimized to achieve rapid degradation of acifluorfen. Under the optimal conditions, the relative activities of the DnrA supernatant from strains SCK6-D and Za-W were 3.06-fold and 3.53-fold higher than that of strain Za, respectively. While all three strains exhibited similar tolerance to different concentrations of acifluorfen, strains SCK6-D and Za-W demonstrated significantly faster degradation efficiency compared to strain Za. Furthermore, the DnrA supernatant from strains SCK6-D and Za-W could effectively reduce the toxicity of acifluorfen on maize and cucumber seedlings. This study provides an effective technical approach for the rapid degradation of acifluorfen.

Separators Modified with Ultrathin Montmorillonite/Polymer Nanocoatings Achieve Dendrite-Free Lithium Deposition at High Current Densities.

Fatal dendritic growth in lithium metal batteries is closely related to the composition and thickness of the modified separator. Herein, an ultrathin nanocoating composed of monolayer montmorillonite (MMT), poly(vinyl alcohol) (PVA) on a polypropylene separator is prepared. The MMT was exfoliated into monolayers (only 0.96 nm) by intercalating PVA under ultrasound, followed by cross-linking with glutaraldehyde. The thickness of the nanocoating on the polypropylene separator, as determined using the pull-up method, is only 200-500 nm with excellent properties. As a result, the lithium-symmetric battery composed of it has a low overpotential (only 40 mV) and a long lifespan of more than 7900 h at high current density, because ion transport is unimpeded and Li+ flows uniformly through the ordered ion channels between the MMT layers. Additionally, the separator exhibited excellent cycling stability in Li-S batteries. This study offers a new idea for fabricating ultrathin clay/polymer modified separators for metal anode stable cycling at high current densities.

The metabolic pathways of carbon assimilation and polyhydroxyalkanoate production by Rhodospirillum rubrum in response to different atmospheric fermentation.

The purple nonsulfur bacteria, Rhodospirillum rubrum, is recognized as a potential strain for PHAs bioindustrial processes since they can assimilate a broad range of carbon sources, such as syngas, to allow reduction of the production costs. In this study, we comparatively analyzed the biomass and PHA formation behaviors of R. rubrum under 100% CO and 50% CO gas atmosphere and found that pure CO promoted the PHA synthesis (PHA content up to 23.3% of the CDW). Hydrogen addition facilitated the uptake and utilization rates of CO and elevated 3-HV monomers content (molar proportion of 3-HV up to 9.2% in the presence of 50% H2). To elucidate the genetic events culminating in the CO assimilation process, we performed whole transcriptome analysis of R. rubrum grown under 100% CO or 50% CO using RNA sequencing. Transcriptomic analysis indicated different CO2 assimilation strategy was triggered by the presence of H2, where the CBB played a minor role. An increase in BCAA biosynthesis related gene abundance was observed under 50% CO condition. Furthermore, we detected the α-ketoglutarate (αKG) synthase, converting fumarate to αKG linked to the αKG-derived amino acids synthesis, and series of threonine-dependent isoleucine synthesis enzymes were significantly induced. Collectively, our results suggested that those amino acid synthesis pathways represented a key way for carbon assimilation and redox potential maintenance by R. rubrum growth under syngas condition, which could partly replace the PHA production and affect its monomer composition in copolymers. Finally, a fed-batch fermentation of the R. rubrum in a 3-l bioreactor was carried out and proved H2 addition indeed increased the PHA accumulation rate, yielding 20% ww-1 PHA production within six days.

Metallic Ru─Ru Interaction in Ruthenium Oxide Enabling Durable Proton Exchange Membrane Water Electrolysis.

Developing efficient and robust electrocatalysts toward the oxygen evolution reaction (OER) is critical for proton exchange membrane water electrolysis (PEMWE). RuO2 possesses intrinsically high OER activity, but the concurrent electrochemical dissolution leads to rapid deactivation. Here a unique RuO2 catalyst containing metallic Ru─Ru interactions (m-RuO2) is reported, which maintains stability in practical PEMWE for 100 h at 60 °C and 1 A cm-2. Experimental and theoretical investigations suggest that the presence of Ru─Ru interactions significantly increases the energy barrier for the formation of RuO2(OH)2, which is a key intermediate for Ru dissolution, and hence substantially mitigates the electrochemical corrosion of m-RuO2. Meanwhile, the Ru4d band center downshifts, accordingly, ensuring the high OER activity, and the participation of lattice oxygen in the OER is also suppressed at the Ru─Ru sites, further contributing to the enhanced durability. Interestingly, such enhanced stability is also dependent on the size of metallic Ru─Ru cluster, where the energy barrier is further increased for Ru3, but is decreased for Ru5. These results highlight the significance of local coordination structure modulation on the electrochemical stability of RuO2 and open a feasible avenue toward the development of robust OER electrocatalysts for high-performance PEMWE.

Unraveling the Unique Strong Metal-Support Interaction in Titanium Dioxide Supported Platinum Clusters for the Hydrogen Evolution Reaction.

Strong metal-support interaction (SMSI) is crucial to modulating the nature of metal species, yet the SMSI behaviors of sub-nanometer metal clusters remain unknown due to the difficulties in constructing SMSI at cluster scale. Herein, we achieve the successful construction of the SMSI between Pt clusters and amorphous TiO2 nanosheets by vacuum annealing, which requires a relatively low temperature that avoids the aggregation of small clusters. In situ scanning transmission electron microscopy observation is employed to explore the SMSI behaviors, and the results reveal the dynamic rearrangement of Pt atoms upon annealing for the first time. The originally disordered Pt atoms become ordered as the crystallizing of the amorphous TiO2 support, forming an epitaxial interface between Pt and TiO2. Such a SMSI state can remain stable in oxidation environment even at 400 °C. Further investigations prove that the electron transfer from TiO2 to Pt occupies the Pt 5d orbitals, which is responsible for the disappeared CO adsorption ability of Pt/TiO2 after forming SMSI. This work not only opens a new avenue for constructing SMSI at cluster scale but also provides in-depth understanding on the unique SMSI behavior, which would stimulate the development of supported metal clusters for catalysis applications.

The temporal protein signature analyses of developing human deciduous molar tooth germ.

The tooth serves as an exemplary model for developmental studies, encompassing epithelial-mesenchymal transition and cell differentiation. The essential factors and pathways identified in tooth development will help understand the natural development process and the malformations of mineralized tissues such as skeleton. The time-dependent proteomic changes were investigated through the proteomics of healthy human molars during embryonic stages, ranging from the cap-to-early bell stage. A comprehensive analysis revealed 713 differentially expressed proteins (DEPs) exhibiting five distinct temporal expression patterns. Through the application of weighted gene co-expression network analysis (WGCNA), 24 potential driver proteins of tooth development were screened, including CHID1, RAP1GDS1, HAPLN3, AKAP12, WLS, GSS, DDAH1, CLSTN1, AFM, RBP1, AGO1, SET, HMGB2, HMGB1, ANP32A, SPON1, FREM1, C8B, PRPS2, FCHO2, PPP1R12A, GPALPP1, U2AF2, and RCC2. Then, the proteomics and transcriptomics expression patterns of these proteins were further compared, complemented by single-cell RNA-sequencing (scRNA-seq). In summary, this study not only offers a wealth of information regarding the molecular intricacies of human embryonic epithelial and mesenchymal cell differentiation but also serves as an invaluable resource for future mechanistic inquiries into tooth development.

Roles of Oxygen-Containing Functional Groups in Carbon for Electrocatalytic Two-Electron Oxygen Reduction Reaction.

Recent years have witnessed great research interests in developing high-performance electrocatalysts for the two-electron (2e-) oxygen reduction reaction (ORR) that enables the sustainable and flexible synthesis of H2O2. Carbon-based electrocatalysts exhibit attractive catalytic performance for the 2e- ORR, where oxygen-containing functional groups (OFGs) play a decisive role. However, current understanding is far from adequate, and the contribution of OFGs to the catalytic performance remains controversial. Therefore, a critical overview on OFGs in carbon-based electrocatalysts toward the 2e- ORR is highly desirable. Herein, we go over the methods for constructing OFGs in carbon including chemical oxidation, electrochemical oxidation, and precursor inheritance. Then we review the roles of OFGs in activating carbon toward the 2e- ORR, focusing on the intrinsic activity of different OFGs and the interplay between OFGs and metal species or defects. At last, we discuss the reasons for inconsistencies among different studies, and personal perspectives on the future development in this field are provided. The results provide insights into the origin of high catalytic activity and selectivity of carbon-based electrocatalysts toward the 2e- ORR and would provide theoretical foundations for the future development in this field.

Randomized controlled trial comparing the impacts of Saccharomyces boulardii and Lactobacillus rhamnosus OF44 on intestinal flora in cerebral palsy rats: insights into inflammation biomarkers and depression-like behaviors.

Background: Cerebral palsy (CP) is a unique neurological disorder which adversely affects motion. Cytokines and gut microbial composition contribute to CP and other diseases, such as reproductive tract inflammation and bone loss. Importantly, Saccharomyces boulardii (S. boulardii) reduces the degree of inflammation and improves overall health status. As our previous study showed that Lactobacillus rhamnosus (L. rhamnosus) OF44, a selected strain of gut bacteria originally used to treat reproductive tract inflammation and bone loss, has effects similar to that of S. boulardii, we decided to use L. rhamnosus OF44 on CP rats. Validation of the effects of L. rhamnosus OF44 on CP adds to its confirmed effects in treating osteoporosis and reproductive tract microbiota disorders, increasing its potential as a probiotic. The purpose of this was to ascertain whether L. rhamnosus OF44 can alleviate the symptoms of CP. Methods: CP rat models were created through left carotid artery ligation. Following this, 100-day old CP rats were exposed to L. rhamnosus OF44, S. boulardii, or normal saline gastric gavage daily for 28 days. Grouping of the rats is determined randomly. Before and after the gavage, behavioral experiments were conducted and the inflammation levels assessed via measurements of interleukin (IL)-1ß, IL-6, IL-8, and tumor necrosis factor alpha (TNF-α) inflammatory markers. The efficacy of the outcome is measured by performing statistical analysis like the t-test on the data to see its significance. Additionally, variations inside gut microbiome were evaluated via 16S ribosomal RNA sequencing. Results: Before intervention, CP rats failed to exhibit depression-like behavior (P=0.6). L. rhamnosus OF44 treatment significantly reduced the level of IL-6 (P=4.8e-05), S. boulardii treatment significantly reduced the level of TNF-α (P=0.04). In addition, both treatments altered the composition and complexity of the gut microbiome. Conclusions: Our results indicated that L. rhamnosus OF44 has potential in alleviating inflammation and altering the gut microbial composition in CP, and that it has the potential to clinically treat CP. There are some limitations of this study. For example, dietary differences and their effects on gastrointestinal dysfunction are not considered in this study, and only two behavioral experiments were used.

Colossal Magnetoresistance in Layered Diluted Magnetic Semiconductor Rb(Zn,Li,Mn)4As3 Single Crystals.

Diluted magnetic semiconductors (DMSs) with tunable ferromagnetism are among the most promising materials for fabricating spintronic devices. Some DMS systems have sizeable magnetoresistances that can further extend their applications. Here, we report a new DMS Rb(Zn1-x-yLiyMnx)4As3 with a quasi-two-dimensional structure showing sizeable anisotropies in its ferromagnetism and transverse magnetoresistance (MR). With proper charge and spin doping, single crystals of the DMS display Curie temperatures up to 24 K. Analysis of the critical behavior via Arrott plots confirms the long-range ferromagnetic ordering in the Rb(Zn1-x-yLiyMnx)4As3 single crystals. We observed remarkable intrinsic MR effects in the single crystals (i.e., a positive MR of 85% at 0.4 T and a colossal negative MR of -93% at 7 T).

Hydrogenation of Quinones to Hydroquinones under Atmospheric Pressure Catalyzed by a Metal-Ligand Bifunctional Iridium Catalyst.

A general method for the hydrogenation of quinones to hydroquinones under atmospheric pressure has been developed. In the presence of [Cp*Ir(2,2'-bpyO)(H2O)] (0.5-1 mol %), a range of products were obtained in high yields. Furthemore, the expansion of this catalytic system to the hydrogenation of 1,4-benzoquinone diimines was also presented. Functional groups in the bpy ligand were found to be crucial for the catalytic activity of iridium complexes.

Orthopedic manifestations in children with Prader-Willi syndrome.

BACKGROUND: Prader-Willi syndrome (PWS) is a rare genetic disease often associated with bone problems, mainly scoliosis and hip dysplasia (HD). This study aimed to analyze the clinical characteristics of orthopedic deformities in patients with PWS. METHODS: A retrospective study was conducted on 175 patients up to March 2023. The Cobb angle(CA) of the spine, the alpha angle of the hip joint, and the acetabular index (AI) were measured. This study aimed to evaluate the relationship between demographic parameters and bone deformities. RESULTS: Scoliosis was found in 66 patients (43.7%), including 52 (78.8%) with mild scoliosis, 10 (15.2%) with moderate scoliosis, and 4 (6.1%) with severe scoliosis. Only seven patients received orthopedic treatment (10.6%). The median age of scoliosis was 4.5 years old, and the prevalence of scoliosis increased rapidly at the age of 5 years and adolescence. The mean CA in this study increased gradually with age. HD was found in 47 patients (38.2%), and 6 patients received orthopedic treatment (12.7%). The median age at HD was 1.8 years old. The mean AI of the study population decreased with age. The prevalence of HD treated with recombinant human growth hormone (rhGH) was low. No significant differences were observed in sex, genotype, body mass index (BMI), obesity rate, or onset of scoliosis and HD. CONCLUSION: The prevalence of scoliosis and HD was higher in patients with PWS. The onset age and developmental trends of the different skeletal malformations were different. Early diagnosis and treatment are important for the prognosis and treatment of orthopedic diseases in patients with PWS.

Facile Route to Synthesize a Highly Sinterable Li1.3Al0.3Ti1.7(PO4)3 Solid Electrolyte.

NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP) is a widely used solid electrolyte in solid-state lithium batteries, owing to its excellent chemical stability against moisture and high total ionic conductivity. However, traditionally, densification of LATP has been achieved through a high-temperature sintering process (approximately 1000 °C) owing to its poor sinterability. Herein, we report a facile synthesis route to obtain highly sinterable LATP solid electrolyte using tetrabutyl titanate (C16H36O4Ti) as the titanium source and incorporating the traditional solid-state reaction method. The synthetic LATP powder mixed with a low ratio of LiTiPO5 exhibited a hybrid crystalline-amorphous phase structure, which facilitated grain fusion, promoted structural homogeneity, and facilitated structural densification under low-temperature sintering. The sintered LATP pellet, which exhibited an interconnected structure and indistinct grain boundaries, achieved a relative density of >90% and an ionic conductivity of 0.667 mS/cm at a sintering temperature of only 750 °C. Additionally, we systematically studied and demonstrated the synthesis reaction mechanism, sintering behavior, and ionic diffusion kinetics of LATP electrolytes. Our study paves the way for synthesizing highly sinterable LATP solid electrolytes using a simple, additive-free, and cost-effective method.

Fermentation characteristics and microbial community composition of wet brewer's grains and corn stover mixed silage prepared with cellulase and lactic acid bacteria supplementation.

OBJECTIVE: The objective of this study was to investigate how cellulase or/and lactic acid bacteria (LAB) affected the fermentation characteristic and microbial community in wet brewer's grains (WBG) and corn stover (CS) mixed silage. METHODS: The WBG was mixed thoroughly with the CS at 7:3 (w/w). Four treatment groups were studied: i) CON, no additives; ii) CEL, added cellulase (120 U/g fresh matter [FM]), iii) LAB, added LAB (2×106 cfu/g FM), and iv) CLA, added cellulase (120 U/g FM) and LAB (2×106 cfu/g FM). RESULTS: All additive-treated groups showed higher fermentation quality over the 30 d ensiling period. As these groups exhibited higher (p<0.05) LAB counts and lactic acid (LA) content, along with lower pH value and ammonia-nitrogen (NH3-N) content than the control. Specifically, cellulase-treated groups (CEL and CLA) showed lower (p<0.05) neutral detergent fiber and acid detergent fiber contents than other groups. All additives increased the abundance of beneficial bacteria (Firmicutes, Lactiplantibacillus, and Limosilactobacillus) while they decreased abundance of Proteobacteria and microbial diversity as well. CONCLUSION: The combined application of cellulase and LAB could effectively improve the fermentation quality and microbial community of the WBG and CS mixed silage.

Mineral Phase Reconfiguration Enables the High Enzyme-like Activity of Vermiculite for Antibacterial Application.

Phyllosilicates-based nanomaterials, particularly iron-rich vermiculite (VMT), have wide applications in biomedicine. However, the lack of effective methods to activate the functional layer covered by the external inert layer limits their future applications. Herein, we report a mineral phase reconfiguration strategy to prepare novel nanozymes by a molten salt method. The peroxidase-like activity of the VMT reconfiguration nanozyme is 10 times that of VMT, due to the electronic structure change of iron in VMT. Density-functional theory calculations confirmed that the upward shifted d-band center of the VMT reconfiguration nanozyme promoted the adsorption of H2O2 on the active iron sites and significantly elongated the O-O bond lengths. The reconfiguration nanozyme exhibited nearly 100% antibacterial activity toward Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), much higher than that of VMT (E. coli 10%, S. aureus 21%). This work provides new insights for the rational design of efficient bioactive phyllosilicates-based nanozyme.

Nanotechnological approaches for the treatment of placental dysfunction: recent trends and future perspectives.

The transitory placenta develops during pregnancy and mediates the blood flow between the mother and the developing baby. Placental dysfunction, including but not limited to placenta accreta spectrum, fetal growth restriction, preeclampsia and gestational trophoblastic disease, arises from abnormal placental development and can result in significant adverse maternal and fetal health outcomes. Unfortunately, there is a lack of treatment alternatives for these disorders. Nanocarriers offer versatility, including extended circulation, organ-specific targeting and intracellular transport, finely tuning therapeutic placental interactions. This thorough review explores nanotechnological strategies for addressing placental disorders, encompassing dysfunction insights, potential drug-delivery targets and recent strides in placenta-targeted nanoparticle (NP) therapies, instilling hope for effective placental malfunction treatment.

The placenta, essential for mother­baby blood exchange, may experience catastrophic abnormalities during pregnancy. Treating these issues is challenging since you must focus on the placenta while protecting the infant. Nanotechnology might be helpful in this scenario. Nanocarriers are small carriers that can transport medications to the placenta and other particular locations in the body. They can aid in the treatment of various placental issues. In our present review, we discuss nanotechnology's solutions to these issues. We discuss what goes wrong, potential therapeutic applications for nanocarriers and recent developments in their use. This might be a novel approach to treating placenta issues and maintaining the health of mothers and infants.

Low-Temperature In Situ Lithiation Construction of a Lithiophilic Particle-Selective Interlayer for Solid-State Lithium Metal Batteries.

Unexpected interface resistance and lithium dendrite puncture hinder the application of garnet-type solid-state electrolytes in high-energy-density systems. Different from the previous high-temperature (>180 °C) molten lithium that promotes the alloying reaction between the coating layer and Li to enhance the interface contact, herein, we introduce liquid-metal-like SbCl3 to construct a three-dimensional Li+ directional-selection interlayer by in situ low-temperature lithiation (80 °C). An interlayer with a more negative interface energy composed of SbLi3 and LiCl exhibits a superior affinity with Li and LGLZO, which reduces the interface resistance and suppresses the growth of Li dendrites by an insulated electron. The introduction of the SbCl3 modification layer into Li/Li symmetric cells enables charge/discharge at a current density of 6.0 mA cm-2 and operation for more than 1000 h under 2.0 mA cm-2 at room temperature. The full cells with the LiFePO4 cathode exhibit a high residual capacity of 144.8 mAh g-1 at 0.5 C after 1000 cycles and excellent cycling stability with a retention ratio of 94.7% at 1 C after 600 cycles. The low-temperature lithiation method based on an energy-saving perspective should be applied to other types of solid-state electrolyte modification strategies.