Highly active and regioselective hydroaminomethylation of olefins catalyzed by Rh/sulfoxantphos with ZSM-5.

Rh-catalyzed hydroaminomethylation has been developed with acid sulfoxantphos and ZSM-5. Linear amines were obtained in good yields (71-95%) with high l/b ratios (up to 132.4) and excellent TON values (up to 23 760). The ZSM-5 and SO3H group of ligands improved the performances of hydroformylation and reductive amination.

Mn-Based Mullites for Environmental and Energy Applications.

Mn-based mullite oxides AMn2O5 (A = lanthanide, Y, Bi) is a novel type of ternary catalyst in terms of their electronic and geometric structures. The coexistence of pyramid Mn3+-O and octahedral Mn4+-O makes the d-orbital selectively active toward various catalytic reactions. The alternative edge- and corner-sharing stacking configuration constructs the confined active sites and abundant active oxygen species. As a result, they tend to show superior catalytic behaviors and thus gain great attention in environmental treatment and energy conversion and storage. In environmental applications, Mn-based mullites have been demonstrated to be highly active toward low-temperature oxidization of CO, NO, volatile organic compounds (VOCs), etc. Recent research further shows that mullites decompose O3 and ozonize VOCs from -20 °C to room temperature. Moreover, mullites enhance oxygen reduction reactions (ORR) and sulfur reduction reactions (SRR), critical kinetic steps in air-battery and Li-S batteries, respectively. Their distinctive structures also facilitate applications in gas-sensitive sensing, ionic conduction, high mobility dielectrics, oxygen storage, piezoelectricity, dehydration, H2O2 decomposition, and beyond. A comprehensive review from basic physicochemical properties to application certainly not only gains a full picture of mullite oxides but also provides new insights into designing heterogeneous catalysts.

Influencing factors and spatiotemporal heterogeneity of livestock greenhouse gas emission: Evidence from the Yellow River Basin of China.

Livestock is one of major sources of greenhouse gas (GHG) emissions in China. Clarifying spatiotemporal characteristics of GHG emissions from livestock and exploring influencing factors can provide reference for grasping regional changes of GHG emission and formulate strategies of carbon reduction for livestock industry. However, existing literatures considered both spatial and temporal impacts and dynamic evolution trend of these factors seldomly. This paper used the life cycle assessment (LCA) method to estimate GHG emissions of livestock in 114 cities of the YRB from 2000 to 2021. On this basis, spatiotemporal heterogeneity of influencing factors was analyzed by using geographically and temporally weighted regression (GTWR) model. Finally, future evolution trend of GHG emissions from livestock was predicted by combining traditional and spatial Markov chain. Four main results were listed as follows. Firstly, GHG emission in the life cycle of livestock industry increased from ××carbon dioxide equivalent (CO2e) in 2000 to 77.568 Mt CO2e in 2021. Secondly, structure of livestock industry, labor flow and mechanization were vital factors that led to increase of GHG emissions from livestock. Positive effects of labor flow and mechanization were increasing year by year, while negative effect of urbanization and positive effect of economic development were decreasing year by year. Markov chain analysis shown that probability of keeping high level of GHG emissions of livestock in the YRB unchanged were 96% (T = 1) and 90% (T = 5), and there also existed a Matthew effect. In addition, probability of level transfer of GHG emission in urban livestock was spatially dependent. Government should formulate strategies for livestock development and optimize low-carbon transformation of energy structure for livestock and poultry husbandry based on local conditions and key driving factors in the future. Meanwhile, boundaries of administrative divisions should be broken to promote reduction of GHG emissions in livestock comprehensively.

Aging induces region-specific dysregulation of hormone synthesis in the primate adrenal gland.

Adrenal glands, vital for steroid secretion and the regulation of metabolism, stress responses and immune activation, experience age-related decline, impacting systemic health. However, the regulatory mechanisms underlying adrenal aging remain largely uninvestigated. Here we established a single-nucleus transcriptomic atlas of both young and aged primate suprarenal glands, identifying lipid metabolism and steroidogenic pathways as core processes impacted by aging. We found dysregulation in centripetal adrenocortical differentiation in aged adrenal tissues and cells in the zona reticularis region, responsible for producing dehydroepiandrosterone sulfate (DHEA-S), were highly susceptible to aging, reflected by senescence, exhaustion and disturbed hormone production. Remarkably, LDLR was downregulated in all cell types of the outer cortex, and its targeted inactivation in human adrenal cells compromised cholesterol uptake and secretion of dehydroepiandrosterone sulfate, as observed in aged primate adrenal glands. Our study provides crucial insights into endocrine physiology, holding therapeutic promise for addressing aging-related adrenal insufficiency and delaying systemic aging.

Anti-synthetase syndrome is associated with a higher risk of hospitalization among patients with idiopathic inflammatory myopathy and COVID-19.

Background: Data with fine granularity about COVID-19-related outcomes and risk factors were still limited in the idiopathic inflammatory myopathies (IIMs) population. This study aimed to investigate clinical factors associated with hospitalized and severe COVID-19 in patients with IIMs, particularly those gauged by myositis-specific antibodies. Methods: This retrospective cohort study was conducted in the Renji IIM cohort in Shanghai, China, under an upsurge of SARS-CoV-2 omicron variant infections from December 2022 to January 2023. Clinical data were collected and analyzed by multivariable logistic regression to determine risk factors. High-dimensional flow cytometry analysis was performed to outline the immunological features. Results: Among 463 infected patients in the eligible cohort (n=613), 65 (14.0%) were hospitalized, 19 (4.1%) suffered severe COVID-19, and 10 (2.2%) died. Older age (OR=1.59/decade, 95% CI 1.18 to 2.16, p=0.003), requiring family oxygen supplement (2.62, 1.11 to 6.19, 0.028), patients with anti-synthetase syndrome (ASyS) (2.88, 1.12 to 7.34, 0.027, vs. other dermatomyositis), higher IIM disease activity, and prednisone intake >10mg/day (5.59, 2.70 to 11.57, <0.001) were associated with a higher risk of hospitalization. Conversely, 3-dose inactivated vaccination reduced the risk of hospitalization (0.10, 0.02 to 0.40, 0.001, vs. incomplete vaccination). Janus kinase inhibitor (JAKi) pre-exposure significantly reduced the risk of severe COVID-19 in hospitalized patients (0.16, 0.04 to 0.74, 0.019, vs. csDMARDs). ASyS patients with severe COVID-19 had significantly reduced peripheral CD4+ T cells, lower CD4/CD8 ratio, and fewer naive B cells but more class-switched memory B cells compared with controls. Conclusion: ASyS and family oxygen supplement were first identified as risk factors for COVID-19-related hospitalization in patients with IIMs. JAKi pre-exposure might protect IIM patients against severe COVID-19 complications.

Orbital Occupancy Modulation to Optimize Intermediate Absorption for Efficient Electrocatalysts in Water Electrolysis and Zinc-Ethanol-Air Battery.

Spin engineering is a promising way to modulate the interaction between the metal d-orbital and the intermediates and thus enhance the catalytic kinetics. Herein, an innovative strategy is reported to modulate the spin state of Co by regulating its coordinating environment. o-c-CoSe2 -Ni is prepared as pre-catalyst, then in situ electrochemical impedance spectroscopy (EIS) and in situ Raman spectroscopy are employed to prove phase transition, and CoOOH/Co3 O4 is formed on the surface as active sites. In hybrid water electrolysis, the voltage has a negative shift, and in zinc-ethanol-air battery, the charging voltage is lowered and the cycling stability is greatly increased. Coordinated atom substitution and crystalline symmetry change are combined to regulate the absorption ability of reaction intermediates with balanced optimal adsorption. Coordinated atom substitution weakens the adsorption while the crystalline symmetry change strengthens the adsorption. Importantly, the tetrahedral sites are introduced by Ni doping which enables the co-existence of four-coordinated sites and six-coordination sites in o-c-CoSe2 -Ni. The dz2 + dx2 -y2 orbital occupancy decreases after the atomic substitution, while increases after replacing the CoSe6 -Oh field with CoSe6 -Oh /CoSe4 -Td . This work explores a new direction for the preparation of efficient catalysts for water electrolysis and innovative zinc-ethanol-air battery.

Single-cell transcriptomic Atlas of aging macaque ocular outflow tissues.

The progressive degradation in the trabecular meshwork (TM) is related to age-related ocular diseases like primary open-angle glaucoma. However, the molecular basis and biological significance of the aging process in TM have not been fully elucidated. Here, we established a dynamic single-cell transcriptomic landscape of aged macaque TM, wherein we classified the outflow tissue into 12 cell subtypes and identified mitochondrial dysfunction as a prominent feature of TM aging. Furthermore, we divided TM cells into 13 clusters and performed an in- depth analysis on cluster 0, which had the highest aging score and the most significant changes in cell proportions between the two groups. Ultimately, we found that the APOE gene was an important differentially expressed gene in cluster 0 during the aging process, highlighting the close relationship between cell migration and extracellular matrix regulation, and TM function. Our work further demonstrated that silencing the APOE gene could increase migration and reduce apoptosis by releasing the inhibition on the PI3K-AKT pathway and downregulating the expression of extracellular matrix components, thereby increasing the aqueous outflow rate and maintaining intraocular pressure within the normal range. Our work provides valuable insights for future clinical diagnosis and treatment of glaucoma.

Ion-retention properties of graphene oxide/zinc oxide nanocomposite membranes at various pH and temperature conditions.

Laminar graphene oxide (GO) is a promising candidate material for next-generation highly water-permeable membranes. Despite extensive research, there is little information known concerning GO's ion-sieving properties at high acidic/basic pH and temperatures. In this study, the ion-blockage properties of the pristine GO and GO/zinc oxide (ZnO) nanocomposite membranes were tested using a non-pressure-driven filtration setup over a wide range of pH and temperatures. The ZnO nanoparticles within the composite membranes were synthesized via the room-temperature oxidation of zinc acetate and zinc acrylate precursors and were uniformly distributed across the composite membrane. It is observed that partially replacing the zinc acetate precursor with zinc acrylate improves the blockage performance of the composite membranes under extreme basic conditions by 42%. Moreover, photocatalytically-reduced composite membranes blocked copper sulfate ions 28% more than as-prepared composite membranes. Further, it was discovered that the composition of the membrane plays a vital role in its ion blockage performance at higher temperatures.

Hf and Co Dual Single Atoms Co-Doped Carbon Catalyst Enhance the Oxygen Reduction Performance.

Single-atom metal-doped M-N-C (M═Fe, Co, Mn, or Ni) catalysts exhibit excellent catalytic activity toward oxygen reduction reactions (ORR). However, their performance still has a large gap considering the demand for their practical applications. This study reports a high-performance dual single-atom doped carbon catalyst (HfCo-N-C), which is prepared by pyrolyzing Co and Hf co-doped ZIF-8 . Co and Hf are atomically dispersed in the carbon framework and coordinated with N to form Co-N4 and Hf-N4 active moieties. The synergetic effect between Co-N4 and Hf-N4 significantly enhance the catalytic activity and durability of the catalyst. In an acidic medium, the ORR half-wave potential (E1/2 ) of the catalyst is up to 0.82 V , which is much higher than that of the Co-N-C catalyst without Hf co-doping (0.80 V). The kinetic current density of the catalyst is up to 2.49 A cm-2 at 0.85 V , which is 1.74 times that of the Co-N-C catalyst without Hf co-doping. Moreover, the catalyst exhibits excellent cathodic performance in single proton exchange membrane fuel cells and Zn-air batteries. Furthermore, Hf co-doping can effectively suppress the formation of H2 O2 , resulting in significantly improved stability and durability.

CRL2APPBP2-mediated TSPYL2 degradation counteracts human mesenchymal stem cell senescence.

Cullin-RING E3 ubiquitin ligases (CRLs), the largest family of multi-subunit E3 ubiquitin ligases in eukaryotic cells, represent core cellular machinery for executing protein degradation and maintaining proteostasis. Here, we asked what roles Cullin proteins play in human mesenchymal stem cell (hMSC) homeostasis and senescence. To this end, we conducted a comparative aging phenotype analysis by individually knocking down Cullin members in three senescence models: replicative senescent hMSCs, Hutchinson-Gilford Progeria Syndrome hMSCs, and Werner syndrome hMSCs. Among all family members, we found that CUL2 deficiency rendered hMSCs the most susceptible to senescence. To investigate CUL2-specific underlying mechanisms, we then applied CRISPR/Cas9-mediated gene editing technology to generate CUL2-deficient human embryonic stem cells (hESCs). When we differentiated these into hMSCs, we found that CUL2 deletion markedly accelerates hMSC senescence. Importantly, we identified that CUL2 targets and promotes ubiquitin proteasome-mediated degradation of TSPYL2 (a known negative regulator of proliferation) through the substrate receptor protein APPBP2, which in turn down-regulates one of the canonical aging marker-P21waf1/cip1, and thereby delays senescence. Our work provides important insights into how CRL2APPBP2-mediated TSPYL2 degradation counteracts hMSC senescence, providing a molecular basis for directing intervention strategies against aging and aging-related diseases.

A single-nucleus transcriptomic atlas of primate liver aging uncovers the pro-senescence role of SREBP2 in hepatocytes.

Aging increases the risk of liver diseases and systemic susceptibility to aging-related diseases. However, cell type-specific changes and the underlying mechanism of liver aging in higher vertebrates remain incompletely characterized. Here, we constructed the first single-nucleus transcriptomic landscape of primate liver aging, in which we resolved cell type-specific gene expression fluctuation in hepatocytes across three liver zonations and detected aberrant cell-cell interactions between hepatocytes and niche cells. Upon in-depth dissection of this rich dataset, we identified impaired lipid metabolism and upregulation of chronic inflammation-related genes prominently associated with declined liver functions during aging. In particular, hyperactivated sterol regulatory element-binding protein (SREBP) signaling was a hallmark of the aged liver, and consequently, forced activation of SREBP2 in human primary hepatocytes recapitulated in vivo aging phenotypes, manifesting as impaired detoxification and accelerated cellular senescence. This study expands our knowledge of primate liver aging and informs the development of diagnostics and therapeutic interventions for liver aging and associated diseases.

Fe Cluster Modified Co9 S8 Heterojunction: Highly Efficient Photoelectrocatalyst for Overall Water Splitting and Flexible Zinc-Air Batteries.

Designing bifunctional low-cost photo-assisted electrocatalysts for converting solar and electric energy into hydrogen energy remains a huge challenge. Herein, a heterojunction (Fe cluster modified Co9 S8 loaded on carbon nanotubes, Co9 S8 -Fe@CNT) for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is demonstrated. Benefiting from the good electronic conductivity and spatial confinement of the carbon skeleton, as well as the electronic structure regulation of the Fe cluster, Co9 S8 -Fe@CNT exhibits excellent catalytic performance with a low overpotential of 150 mV for OER and 135 mV for HER at 10 mA cm-2 . Upon light irradiation, holes and electrons are generated in the valence band and conduction band of the Co9 S8 , respectively. Part of the charges are transferred to the interface to facilitate the catalytic reaction, while the remaining are transferred by the electrode. When working as a bifunctional catalyst for overall water splitting, the performance can reach 1.33 V at under light conditions, which is significantly better than 1.52 V in a dark environment. Theoretical calculations revealed lowered Gibbs free energy (∆GH *) of the heterojunction with the effect of Fe modification of Co9 S8 . This work sheds a new light in designing novel photoelectrochemical materials to convert solar and electric energy into chemical energy.

Identification of FOXO1 as a geroprotector in human synovium through single-nucleus transcriptomic profiling.

The synovium, a thin layer of tissue that adjacent to the joints and secretes synovial fluid, undergoes changes in aging that contribute to intense shoulder pain and other joint diseases. However, the mechanism underlying human synovial aging remains poorly characterized. Here, we generated a comprehensive profile of synovial cell types present in subacromial synovium from young and aged individuals. By delineating aging-related transcriptomic changes across cell types and their associated regulatory networks, we identified two subsets of mesenchymal stromal cell (MSC) in human synovium, which are lining and sublining MSCs, and found that angiogenesis and fibrosis-associated genes were upregulated whereas genes associated with cell adhesion and cartilage development were downregulated during aging. Moreover, the specific cell-cell communications in aged synovium mirrors that of aging-related inflammation and tissue remodeling, including vascular hyperplasia and tissue fibrosis. In particular, we identified Forkhead box O1 (FOXO1) as one of the major regulons for aging DEGs of synovium MSCs, and validated its downregulation in both lining and sublining MSC populations of the aged synovium. In human FOXO1-depleted MSCs derived from human embryonic stem cells, we recapitulated the senescent phenotype observed in the subacromial synovium of aged donors. These data indicate the important role for FOXO1 in the regulation of human synovial aging. Overall, our study improves upon our understanding of synovial aging during joint degeneration, thereby informing development of new treatments aimed at rejuvenating the aged joint.

Advanced Interface Engineering in Gradient Core/Shell Quantum Dots Enables Efficient Photoelectrochemical Hydrogen Evolution.

Semiconductor core/shell quantum dots (QDs) are considered promising building blocks to fabricate photoelectrochemical (PEC) cells for the direct conversion of solar energy into hydrogen (H2 ). However, the lattice mismatch between core and shell in such QDs results in undesirable defects and severe carrier recombination, limiting photo-induced carrier separation/transfer and solar-to-fuel conversion efficiency. Here, an interface engineering approach is explored to minimize the core-shell lattice mismatch in CdS/CdSex S1-x (x = 0.09-1) core/shell QDs (g-CSG). As a proof-of-concept, PEC cells based on g-CSG QDs yield a remarkable photocurrent density of 13.1 mA cm-2 under AM 1.5 G one-sun illumination (100 mW cm-2 ), which is ≈54.1% and ≈33.7% higher compared to that in CdS/CdSe0.5 S0.5 (g-CSA) and CdS/CdSe QDs (g-CS), respectively. Theoretical calculations and carrier dynamics confirm more efficient carrier separation and charge transfer rate in g-CSG QDs with respect to g-CSA and g-CS QDs. These results are attributed to the minimization of the core-shell lattice mismatch by the cascade gradient shell in g-CSG QDs, which modifies carrier confinement potential and reduces interfacial defects. This work provides fundamental insights into the interface engineering of core/shell QDs and may open up new avenues to boost the performance of PEC cells for H2 evolution and other QDs-based optoelectronic devices.

Concave Structural Carbon Co-Doped with Iron Atom Pairs and Nitrogen as Ultra-High Performance Catalyst Toward Oxygen Reduction.

It is crucial to rationally design and synthesize atomic-scale transition metal-doped carbon catalysts with high electrocatalytic activity to achieve a high-efficient oxygen reduction reaction (ORR). Herein, an electrocatalyst comprised of Fe-Fe dual atom pairs and N-doped concave carbon are reported (N-CC@Fe DA) that achieves ultrahigh electrocatalytic ORR activity. The catalyst is prepared by a gaseous doping approach, with zeolitic imidazolate framework-8 (ZIF-8) as the carbon framework precursor and cyclopentadienyliron dicarbonyl dimer as the Fe-Fe atom pair precursor. The catalyst exhibits high cathodic ORR catalytic performance in an alkaline Zn/air battery and proton exchange membrane fuel cell (PEMFC), yielding peak power densities of 241 mW cm-2 and 724 mW cm-2 , respectively, compared to 127 mW cm-2 and 1.20 W cm-2 with conventional Pt/C catalysts as cathodes. The presence of Fe atom pairs coordinate with N atoms is revealed by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) analysis, and Density Functional Theory (DFT) calculation results show that the Fe-Fe pair structure is beneficial for adsorbing oxygen molecules, activating the O─O bond, and desorbing OH* intermediates formed during oxygen reduction, resulting in a more efficient oxygen reaction. The findings may provide a new pathway for preparing ultra-high-performance doped carbon catalysts with Fe-Fe atom pair structures.

Decoding aging-dependent regenerative decline across tissues at single-cell resolution.

Regeneration across tissues and organs exhibits significant variation throughout the body and undergoes a progressive decline with age. To decode the relationships between aging and regenerative capacity, we conducted a comprehensive single-cell transcriptome analysis of regeneration in eight tissues from young and aged mice. We employed diverse analytical models to study tissue regeneration and unveiled the intricate cellular and molecular mechanisms underlying the attenuated regenerative processes observed in aged tissues. Specifically, we identified compromised stem cell mobility and inadequate angiogenesis as prominent contributors to this age-associated decline in regenerative capacity. Moreover, we discovered a unique subset of Arg1+ macrophages that were activated in young tissues but suppressed in aged regenerating tissues, suggesting their important role in age-related immune response disparities during regeneration. This study provides a comprehensive single-cell resource for identifying potential targets for interventions aimed at enhancing regenerative outcomes in the aging population.

CHIT1-positive microglia drive motor neuron ageing in the primate spinal cord.

Ageing is a critical factor in spinal-cord-associated disorders1, yet the ageing-specific mechanisms underlying this relationship remain poorly understood. Here, to address this knowledge gap, we combined single-nucleus RNA-sequencing analysis with behavioural and neurophysiological analysis in non-human primates (NHPs). We identified motor neuron senescence and neuroinflammation with microglial hyperactivation as intertwined hallmarks of spinal cord ageing. As an underlying mechanism, we identified a neurotoxic microglial state demarcated by elevated expression of CHIT1 (a secreted mammalian chitinase) specific to the aged spinal cords in NHP and human biopsies. In the aged spinal cord, CHIT1-positive microglia preferentially localize around motor neurons, and they have the ability to trigger senescence, partly by activating SMAD signalling. We further validated the driving role of secreted CHIT1 on MN senescence using multimodal experiments both in vivo, using the NHP spinal cord as a model, and in vitro, using a sophisticated system modelling the human motor-neuron-microenvironment interplay. Moreover, we demonstrated that ascorbic acid, a geroprotective compound, counteracted the pro-senescent effect of CHIT1 and mitigated motor neuron senescence in aged monkeys. Our findings provide the single-cell resolution cellular and molecular landscape of the aged primate spinal cord and identify a new biomarker and intervention target for spinal cord degeneration.

Editorial: Focus on green nanomaterials for a sustainable internet of things.

In the dynamic landscape of the Internet of Things (IoT), where smart devices are reshaping our world, nanomaterials can play a pivotal role in ensuring the IoT's sustainability. These materials are poised to redefine the development of smart devices, not only enabling cost-effective fabrication but also unlocking novel functionalities. As the IoT is set to encompass an astounding number of interconnected devices, the demand for environmentally friendly nanomaterials takes center stage. ThisFocus Issuespotlights cutting-edge research that explores the intersection of nanomaterials and sustainability. The collection delves deep into this critical nexus, encompassing a wide range of topics, from fundamental properties to applications in devices (e.g. sensors, optoelectronic synapses, energy harvesters, memory components, energy storage devices, and batteries), aspects concerning circularity and green synthesis, and an array of materials comprising organic semiconductors, perovskites, quantum dots, nanocellulose, graphene, and two-dimensional semiconductors. Authors not only showcase advancements but also delve into the sustainability profile of these materials, fostering a responsible endeavour toward a green IoT future.

Engineering Fe-N4 Electronic Structure with Adjacent Co-N2C2 and Co Nanoclusters on Carbon Nanotubes for Efficient Oxygen Electrocatalysis.

Regulating the local configuration of atomically dispersed transition-metal atom catalysts is the key to oxygen electrocatalysis performance enhancement. Unlike the previously reported single-atom or dual-atom configurations, we designed a new type of binary-atom catalyst, through engineering Fe-N4 electronic structure with adjacent Co-N2C2 and nitrogen-coordinated Co nanoclusters, as oxygen electrocatalysts. The resultant optimized electronic structure of the Fe-N4 active center favors the binding capability of intermediates and enhances oxygen reduction reaction (ORR) activity in both alkaline and acid conditions. In addition, anchoring M-N-C atomic sites on highly graphitized carbon supports guarantees of efficient charge- and mass-transports, and escorts the high bifunctional catalytic activity of the entire catalyst. Further, through the combination of electrochemical studies and in-situ X-ray absorption spectroscopy analyses, the ORR degradation mechanisms under highly oxidative conditions during oxygen evolution reaction processes were revealed. This work developed a new binary-atom catalyst and systematically investigates the effect of highly oxidative environments on ORR electrochemical behavior. It demonstrates the strategy for facilitating oxygen electrocatalytic activity and stability of the atomically dispersed M-N-C catalysts.