Injury Activates Ca2+/Calmodulin-Dependent Phosphorylation of JAV1-JAZ8-WRKY51 Complex for Jasmonate Biosynthesis.

Insect herbivory causes severe damage to plants and threatens the world's food production. During evolutionary adaptation, plants have evolved sophisticated mechanisms to rapidly accumulate a key defense hormone, jasmonate (JA), that triggers plant defense against herbivory. However, little is known about how plants initially activate JA biosynthesis at encounter with herbivory. Here, we uncover that a novel JAV1-JAZ8-WRKY51 (JJW) complex controls JA biosynthesis to defend against insect attack. In healthy plants, the JJW complex represses JA biosynthesis to restrain JA at a low basal level to ensure proper plant growth. When plants are injured by insect attack, injury rapidly triggers calcium influxes to activate calmodulin-dependent phosphorylation of JAV1, which disintegrates JJW complex and activates JA biosynthesis, giving rise to the rapid burst of JA for plant defense. Our findings offer new insights into the highly sophisticated defense systems evolved by plants to defend against herbivory.

Triggered lattice-oxygen oxidation with active-site generation and self-termination of surface reconstruction during water oxidation.

To master the activation law and mechanism of surface lattice oxygen for the oxygen evolution reaction (OER) is critical for the development of efficient water electrolysis. Herein, we propose a strategy for triggering lattice-oxygen oxidation and enabling non-concerted proton-electron transfers during OER conditions by substituting Al in La0.3Sr0.7CoO3-δ. According to our experimental data and density functional theory calculations, the substitution of Al can have a dual effect of promoting surface reconstruction into active Co oxyhydroxides and activating deprotonation on the reconstructed oxyhydroxide, inducing negatively charged oxygen as an active site. This leads to a significant improvement in the OER activity. Additionally, Al dopants facilitate the preoxidation of active cobalt metal, which introduces great structural flexibility due to elevated O 2p levels. As OER progresses, the accumulation of oxygen vacancies and lattice-oxygen oxidation on the catalyst surface leads to the termination of Al3+ leaching, thereby preventing further reconstruction. We have demonstrated a promising approach to achieving tunable electrochemical reconstruction by optimizing the electronic structure and gained a fundamental understanding of the activation mechanism of surface oxygen sites.

Neoadjuvant chemotherapy plus camrelizumab for locally advanced cervical cancer (NACI study): a multicentre, single-arm, phase 2 trial.

BACKGROUND: Locally advanced cervical cancer constitutes around 37% of cervical cancer cases globally and has a poor prognosis due to limited therapeutic options. Immune checkpoint inhibitors in the neoadjuvant setting could address these challenges. We aimed to investigate the efficacy and safety of neoadjuvant chemo-immunotherapy for locally advanced cervical cancer. METHODS: In this single-arm, phase 2 trial, which was done across eight tertiary hospitals in China, we enrolled patients aged 18-70 years with untreated cervical cancer (IB3, IIA2, or IIB/IIIC1r with a tumour diameter ≥4 cm [International Federation of Gynecology and Obstetrics, 2018]) and an Eastern Cooperative Oncology Group performance status of 0 or 1. Eligible patients underwent one cycle of priming doublet chemotherapy (75-80 mg/m2 cisplatin, intravenously, plus 260 mg/m2 nab-paclitaxel, intravenously), followed by two cycles of a combination of chemotherapy (cisplatin plus nab-paclitaxel) on day 1 with camrelizumab (200 mg, intravenously) on day 2, with a 3-week interval between treatment cycles. Patients with stable disease or progressive disease received concurrent chemoradiotherapy, and patients with a complete response or partial response proceeded to radical surgery. The primary endpoint was the objective response rate, by independent central reviewer according to Response Evaluation Criteria in Solid Tumours, version 1.1. Activity and safety were analysed in patients who received at least one dose of camrelizumab. This study is registered with ClinicalTrials.gov, NCT04516616, and is ongoing. FINDINGS: Between Dec 1, 2020, and Feb 10, 2023, 85 patients were enrolled and all received at least one dose of camrelizumab. Median age was 51 years (IQR 46-57) and no data on race or ethnicity were collected. At data cutoff (April 30, 2023), median follow-up was 11·0 months (IQR 6·0-14·5). An objective response was noted in 83 (98% [95% CI 92-100]) patients, including 16 (19%) patients who had a complete response and 67 (79%) who had a partial response. The most common grade 3-4 treatment-related adverse events during neoadjuvant chemo-immunotherapy were lymphopenia (21 [25%] of 85), neutropenia (ten [12%]), and leukopenia (seven [8%]). No serious adverse events or treatment-related deaths occurred. INTERPRETATION: Neoadjuvant chemo-immunotherapy showed promising antitumour activity and a manageable adverse event profile in patients with locally advanced cervical cancer. The combination of neoadjuvant chemo-immunotherapy with radical surgery holds potential as a novel therapeutic approach for locally advanced cervical cancer. FUNDING: National Key Technology Research and Development Program of China and the National Clinical Research Center of Obstetrics and Gynecology.

Rare-Earth-Modified NiS2 Improves OH Coverage for an Industrial Alkaline Water Electrolyzer.

The low coverage rate of anode OH adsorption under high current density conditions has become an important factor restricting the development of an industrial alkaline water electrolyzer (AWE). Here, we present our rare earth modification promotion strategy on using the rare earth oxygen-friendly interface to increase the OH coverage of the NiS2 surface for efficient AWE anode catalysis. Density functional theory calculations predict that rare earths can enhance the coverage of surface OH, and the synthesis reaction mechanism is discussed in the synthesis process spectrum. Experimentally, by preparing a series of rare-earth-modified NiS2, the relationship between OH coverage, active site density, and catalytic activity was established by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, time-resolved absorption spectra, and so on. The unique oxygenophilic properties of rare earths enhance OH coverage, thereby increasing the density of active sites for efficient catalysis. Furthermore, Eu2O3/NiS2 was assembled into the AWE equipment and operated stably for over 240 h at a current density of 300 mA cm-2 under industrial conditions of 80 °C and 30% KOH. Rare-earth-modified NiS2 exhibits better catalytic activity than traditional non-noble metal anode catalysts Ni(OH)2 and NiS2, providing a new approach for rare earth promotion to solve the problem of low OH coverage in the AWE anode.

Age-Dependent Female Survival Advantage in Hepatocellular Carcinoma: A Multicenter Cohort Study.

BACKGROUND & AIMS: Hepatocellular carcinoma (HCC) has a higher incidence in males, but the association of sex with survival remains controversial. This study aimed to examine the effect of sex on HCC survival and its association with age. METHODS: Among 33,238 patients with HCC from 12 Chinese tertiary hospitals, 4175 patients who underwent curative-intent hepatectomy or ablation were analyzed. Cancer-specific survival (CSS) was analyzed using Cox regression and Kaplan-Meier methods. Two propensity score methods and multiple mediation analysis were applied to mitigate confounding. To explore the effect of estrogen, a candidate sex-specific factor that changes with age, female participants' history of estrogen use, and survival were analyzed. RESULTS: There were 3321 males and 854 females included. A sex-related disparity of CSS was present and showed a typical age-dependent pattern: a female survival advantage over males appeared at the perimenopausal age of 45 to 54 years (hazard risk [HR], 0.77; 5-year CSS, 85.7% vs 70.6%; P = .018), peaked at the early postmenopausal age of 55 to 59 years (HR, 0.57; 5-year CSS, 89.8% vs 73.5%; P = .015), and was not present in the premenopausal (<45 y) and late postmenopausal groups (≥60 y). Consistent patterns were observed in patients after either ablation or hepatectomy. These results were sustained with propensity score analyses. Confounding or mediation effects accounted for only 19.5% of sex survival disparity. Female estrogen users had significantly longer CSS than nonusers (HR, 0.74; 5-year CSS, 79.6% vs 72.5%; P = .038). CONCLUSIONS: A female survival advantage in HCC depends on age, and this may be associated with age-dependent, sex-specific factors.

Simultaneous Interface Engineering and Phase Tuning of CeO2-Decorated Catalysts for Boosted Oxygen Evolution Reaction.

Heterogeneous catalysts have attracted extensive attention among various emerging catalysts for their exceptional oxygen evolution reaction (OER) capabilities, outperforming their single-component counterparts. Nonetheless, the synthesis of heterogeneous materials with predictable, precise, and facile control remains a formidable challenge. Herein, a novel strategy involving the decoration of catalysts with CeO2 is introduced to concurrently engineer heterogeneous interfaces and adjust phase composition, thereby enhancing OER performance. Theoretical calculations suggest that the presence of ceria reduces the free energy barrier for the conversion of nitrides into metals. Supporting this, the experimental findings reveal that the incorporation of rare earth oxides enables the controlled phase transition from nitride into metal, with the proportion adjustable by varying the amount of added rare earth. Thanks to the role of CeO2 decoration in promoting the reaction kinetics and fostering the formation of the genuine active phase, the optimized Ni3FeN/Ni3Fe/CeO2-5% nanoparticles heterostructure catalyst exhibits outstanding OER activity, achieving an overpotential of just 249 mV at 10 mA cm-2. This approach offers fresh perspectives for the conception of highly efficient heterogeneous OER catalysts, contributing a strategic avenue for advanced catalytic design in the field of energy conversion.

Interfacing Lanthanide Metal-Organic Frameworks with ZnO Nanowires for Alternating Current Electroluminescence.

Alternating current electroluminescence (ACEL) devices are attractive candidates in cost-effective lighting, sensing, and flexible displays due to their uniform luminescence, stable performance, and outstanding deformability. However, ACEL devices have suffered from limited options for the light-emitting layer, which presents a significant constraint in the progress of utilizing ACEL. Herein, a new class of ACEL phosphors based on lanthanide metal-organic frameworks (Ln-MOFs) is devised. A synthesis of lanthanide-benzenetricarboxylate (Ln-BTC) thin film on a brass grid substrate seeded with ZnO nanowires (NWs) as anchors is developed. The as-synthesized Ln-BTC thin film is employed as the emissive layer and shows visible electroluminescence driven by alternating current (2.9 V µm-1 , 1 kHz) for the first time. Mechanistic investigations reveal that the Ln-based ACEL stems from impact excitation by accelerated electrons from ZnO NWs. Fine-tuning of the ACEL color is also demonstrated by controlling the Ln-MOF compositions and introducing an extra ZnS emitting layer. The advances in these optical materials expand the application of ACEL devices in anti-counterfeiting.

A Coordination-Derived Cerium-Based Amorphous-Crystalline Heterostructure with High Electrocatalytic Oxygen Evolution Activity.

The rational design of heterogeneous catalysts is crucial for achieving optimal physicochemical properties and high electrochemical activity. However, the development of new amorphous-crystalline heterostructures is significantly more challenging than that of the existing crystalline-crystalline heterostructures. To overcome these issues, a coordination-assisted strategy that can help fabricate an amorphous NiO/crystalline NiCeOx (a-NiO/c-NiCeOx ) heterostructure is reported herein. The coordination geometry of the organic ligands plays a pivotal role in permitting the formation of coordination polymers with high Ni contents. This consequently provides an opportunity for enabling the supersaturation of Ni in the NiCeOx structure during annealing, leading to the endogenous spillover of Ni from the depths of NiCeOx to its surface. The resulting heterostructure, featuring strongly coupled amorphous NiO and crystalline NiCeOx , exhibits harmonious interactions in addition to low overpotentials and high catalytic stability in the oxygen evolution reaction (OER). Theoretical calculations prove that the amorphous-crystalline interfaces facilitate charge transfer, which plays a critical role in regulating the local electron density of the Ni sites, thereby promoting the adsorption of oxygen-based intermediates on the Ni sites and lowering the dissociation-related energy barriers. Overall, this study underscores the potential of coordinating different metal ions at the molecular level to advance amorphous-crystalline heterostructure design.

Demographic dynamics and molecular evolution of the rare and endangered subsect. Gerardianae of Pinus: insights from chloroplast genomes and mitochondrial DNA markers.

MAIN CONCLUSION: The divergence of subsect. Gerardianae was likely triggered by the uplift of the Qinghai-Tibetan Plateau and adjacent mountains. Pinus bungeana might have probably experienced expansion since Last Interglacial period. Historical geological and climatic oscillations have profoundly affected patterns of nucleotide variability, evolutionary history, and species divergence in numerous plants of the Northern Hemisphere. However, how long-lived conifers responded to geological and climatic fluctuations in East Asia remain poorly understood. Here, based on paternally inherited chloroplast genomes and maternally inherited mitochondrial DNA markers, we investigated the population demographic history and molecular evolution of subsect. Gerardianae (only including three species, Pinus bungeana, P. gerardiana, and P. squamata) of Pinus. A low level of nucleotide diversity was found in P. bungeana (π was 0.00016 in chloroplast DNA sequences, and 0.00304 in mitochondrial DNAs). The haplotype-based phylogenetic topology and unimodal distributions of demographic analysis suggested that P. bungeana probably originated in the southern Qinling Mountains and experienced rapid population expansion since Last Interglacial period. Phylogenetic analysis revealed that P. gerardiana and P. squamata had closer genetic relationship. The species divergence of subsect. Gerardianae occurred about 27.18 million years ago (Mya) during the middle to late Oligocene, which was significantly associated with the uplift of the Qinghai-Tibetan Plateau and adjacent mountains from the Eocene to the mid-Pliocene. The molecular evolutionary analysis showed that two chloroplast genes (psaI and ycf1) were under positive selection, the genetic lineages of P. bungeana exhibited higher transition and nonsynonymous mutations, which were involved with the strongly environmental adaptation. These findings shed light on the population evolutionary history of white pine species and provide striking insights for comprehension of their species divergence and molecular evolution.

Unusual immunosuppressive pyridine-containing bisnor- (c23), tetranor- (c21) and pentanor- (c20) sesterterpenoids from Tibetan Leucosceptrum canum.

An unusual pyridine-containing sesterterpenoid, leucosceptrodine (1), and five new nor-leucosceptrane sesterterpenoids, including bisnor- (C23, 2), tetranor- (C21, 3) and pentanor- (C20, 4-6) skeletons, were isolated from the leaves of Tibetan Leucosceptrum canum. Their structures including their absolute configurations were determined by extensive spectroscopic analyses and quantum chemical calculations. A single crystal of one epimer (5) was crystallized from a pair of inseparable epimers, and its structure including its absolute configuration was determined by X-ray crystallographic analysis. The immunosuppressive activities of compounds 1-4 with different potencies were evaluated by inhibiting the secretion of cytokines TNF-α and IL-6 in LPS-induced RAW264.7 macrophages.

Modulation of plasmacytoid dendritic cell and CD4+ T cell differentiation accompanied by upregulation of the cholinergic anti-inflammatory pathway induced by enterovirus 71.

Enterovirus 71 (EV71) is a neurotropic enterovirus associated with hand, foot, and mouth disease (HFMD) fatalities. In this study, we investigated the impact of EV71 on plasmacytoid dendritic cells (pDCs) and CD4+ T cells. The results showed that pDCs were promptly activated, secreting interferon (IFN)-α and inducing CD4+ T cell proliferation and differentiation during early EV71 infection. This initiated adaptive immune responses and promoted proinflammatory cytokine production by CD4+ T cells. Over time, viral nucleic acids and proteins were synthesized in pDCs and CD4+ T cells. Concurrently, the cholinergic anti-inflammatory pathway (CAP) was activated, exhibiting an anti-inflammatory role. With constant viral stimulation, pDCs and CD4+ T cells showed reduced differentiation and cytokine secretion. Defects in pDCs were identified as a key factor in CD4+ T cell tolerance. CAP had a more significant regulatory effect on CD4+ T cells than on pDCs and was capable of inhibiting inflammation in these cells.

Atomistically informed hierarchical modeling for revisiting the constituent structures from heredity and nano-micro mechanics of sheath-core carbon fiber.

To better understand the heterogeneous anisotropic nanocomposite features and provide reliable underlying constitutive parameters of carbon fiber for continuum-level simulations, hierarchical modeling approaches combining quantum chemistry, molecular dynamics, numerical and analytical micromechanics are employed for studying the structure-performance relationships of the precursor-inherited sheath-core carbon fiber layers. A robust debonding force field is derived from energy matching protocols, including bond dissociation enthalpy calculations and rigid-constraint potential energy surface scan. Logistic long range bond stretching curves with exponential parameters and shifted force vdW curves are designed to diminish energy perturbations. The pseudo-crystalline microstructure is proposed and validated using virtual wide angle X-ray diffraction patterns and bond-orientational order parameters. The distribution or alignment features of the nanocomposite microstructures are collected from quantum chemical topology analysis and normal vector extractions. Non-equilibrium tensile loading simulation predicts the decomposed strain energy contributions, principal-axis modulus, strength limit, localized stress, and fracture morphologies of the model. Finally, an atomistically-informed stiffness prediction model combining numerical homogenization and analytical self-consistent Eshelby-Mori-Tanaka-type effective mean field micromechanics theory is proposed, giving a successful estimation of the overall stiffness matrix of the sheath-core carbon fiber system. The hierarchical models in combination with the carbonization reaction template will help in providing efficient and feasible schemes for the synergistic process-performance control of distinct types of carbon fiber.

Exploring the interplay of liquid crystal orientation and spherical elastic shell deformation in spatial confinement.

The application of liquid crystal technology typically relies on the precise control of molecular orientation at a surface or interface. This control can be achieved through a combination of morphological and chemical methods. Consequently, variations in constrained boundary flexibility can result in a diverse range of phase behaviors. In this study, we delve into the self-assembly of liquid crystals within elastic spatial confinement by using the Gay-Berne model with the aid of molecular dynamics simulations. Our findings reveal that a spherical elastic shell promotes a more regular and orderly alignment of liquid crystals compared to a hard shell. Moreover, during the cooling process, the hard-shell confined system undergoes an isotropic-smectic phase transition. In contrast, the phase behavior within the spherical elastic shell closely mirrors the isotropic-nematic-smectic phase transition observed in bulk systems. This indicates that the orientational arrangement of liquid crystals and the deformations induced by a flexible interface engage in a competitive interplay during the self-assembly process. Importantly, we found that phase behavior could be manipulated by altering the flexibility of the confined boundaries. This insight offers a fresh perspective for the design of innovative materials, particularly in the realm of liquid crystal/polymer composites.

Percutaneous microwave ablation versus sclerotherapy for large hepatic hemangioma: a multi-center cohort study.

OBJECTIVE: The study aimed to compare the effectiveness and safety of ultrasound-guided microwave ablation (MWA) and percutaneous sclerotherapy (PS) for the treatment of large hepatic hemangioma (LHH). METHODS: This retrospective study included 96 patients who underwent MWA (n = 54) and PS (n = 42) as first-line treatment for LHH in three tertiary hospitals from January 2016 to December 2021. Primary outcomes were technique efficacy rate (volume reduction rate [VRR] > 50% at 12 months), symptom relief rate at 12 months and local tumor progression (LTP). Secondary outcomes included procedure time, major complications, treatment sessions, cost and one-, two-, three-year VRR. RESULTS: During a median follow-up of 36 months, the MWA group showed a higher technique efficacy rate (100% vs. 90.4%, p = .018) and symptom relief rate (100% vs. 80%, p = .123) than the PS group. The MWA group had fewer treatment sessions, higher one-, two- and three-year VRR, lower LTP rate (all p < .05), longer procedure time and higher treatment costs than the PS group (both p < .001). MWA shared a comparable major complications rate (1.8% vs. 2.4%, p = .432) with PS. After multivariate analysis, the lesion's heterogeneity and maximum diameter >8.1 cm were independent risk factors for LTP (all p < .05). In the PS group, lesions with a cumulative dose of bleomycin > 0.115 mg/cm3 had a lower risk of LTP (p = .006). CONCLUSIONS: Both MWA and PS treatments for large hepatic hemangioma are safe and effective, with MWA being superior in terms of efficacy.

PERSISTENT SUBRETINAL FLUID AFTER VITRECTOMY FOR MACULAR HOLE-ASSOCIATED RETINAL DETACHMENT.

PURPOSE: To evaluate the incidence, associated factors, and outcome of persistent subretinal fluid (SRF) after vitrectomy for macular hole-associated retinal detachment (MHRD). METHODS: A total of 158 eyes from 156 patients with MHRD who achieved macular hole closure after primary vitrectomy were included in the analysis; persistent SRF was defined as the presence of SRF for more than 1 month after first surgery. Preoperative and postoperative parameters were analyzed for their relationship with SRF development. RESULTS: Persistent SRF was observed in 19 eyes (12.0% of 158) postoperatively. Seven eyes (36.8% of 19) with persistent SRF eventually displayed complete absorption during follow-up. Univariate analysis revealed that eyes with persistent SRF were statistically associated with internal limiting membrane inverted flap, duration of symptoms, tamponade (perfluoropropane/silicone oil: 14/5 vs. 35/104, P < 0.001), and MHRD subtype (Type 1/Type 2/Type 3: 15/4/0 vs. 60/40/39, P = 0.003). In multivariate analysis, only internal limiting membrane inverted flap (odds ratio, 15.778, 95% confidence interval, 3.170-78.523; P = 0.001) was positively associated with persistent SRF. There were no significant differences in best-corrected visual acuity improvement ( P = 0.425) between the SRF involved foveal and without involved foveal groups and no significant differences between the SRF complete absorption and incomplete absorption groups. CONCLUSION: Absorption of persistent SRF may be more difficult in MHRD eyes than in ordinary rhegmatogenous retinal detachment eyes. The internal limiting membrane inverted flap in MHRD was associated with a greater likelihood of persistent SRF. The location and incomplete absorption of persistent SRF did not seem to be associated with the final visual outcome.

Progress on CRISPR/Cas9 system in the genetic improvement of livestock and poultry.

CRISPR/Cas9 gene editing technology, as a highly efficient genome editing method, has been extensively employed in the realm of animal husbandry for genetic improvement. With its remarkable efficiency and precision, this technology has revolutionized the field of animal husbandry. Currently, CRISPR/Cas9-based gene knockout, gene knock-in and gene modification techniques are widely employed to achieve precise enhancements in crucial production traits of livestock and poultry species. In this review, we summarize the operational principle and development history of CRISPR/Cas9 technology. Additionally, we highlight the research advancements utilizing this technology in muscle growth and development, fiber growth, milk quality composition, disease resistance breeding, and animal welfare within the livestock and poultry sectors. Our aim is to provide a more comprehensive understanding of the application of CRISPR/Cas9 technology in gene editing for livestock and poultry.

Stabilizing Sulfur Sites in Tetraoxygen Tetrahedral Coordination Structure for Efficient Electrochemical Water Oxidation.

Ion regulation strategy is regarded as a promising pathway for designing transition metal oxide-based electrocatalysts for oxygen evolution reaction (OER) with improved activity and stability. Precise anion conditioning can accurately change the anionic environment so that the acid radical ions (SO4 2- , PO3 2- , SeO4 2- , etc.), regardless of their state (inside the catalyst, on the catalyst surface, or in the electrolyte), can optimize the electronic structure of the cationic active site and further increase the catalytic activity. Herein, we report a new approach to encapsulate S atoms at the tetrahedral sites of the NaCl-type oxide NiO to form a tetraoxo-tetrahedral coordination structure (S-O4 ) inside the NiO (S-NiO -I). Density functional theory (DFT) calculations and operando vibrational spectroscopy proves that this kind of unique structure could achieve the S-O4 and Ni-S stable structure in S-NiO-I. Combining mass spectroscopy characterization, it could be confirmed that the S-O4 structure is the key factor for triggering the lattice oxygen exchange to participate in the OER process. This work demonstrates that the formation of tetraoxygen tetrahedral structure is a generalized key for boosting the OER performances of transition metal oxides.

Stabilizing Lattice Oxygen through Mn Doping in NiCo2O4-δ Spinel Electrocatalysts for Efficient and Durable Acid Oxygen Evolution.

Design the electrocatalysts without noble metal is still a challenge for oxygen evolution reaction (OER) in acid media. Herein, we reported the manganese (Mn) doping method to decrease the concentration of oxygen vacancy (VO) and form the Mn-O structure adjacent octahedral sites in spinel NiCo2O4-δ (NiMn1.5Co3O4-δ), which highly enhanced the activity and stability of spinel NiCo2O4-δ with a low overpotential (η) of 280 mV at j=10 mA cm-2 and long-term stability of 80 h in acid media. The isotopic labelling experiment based on differential electrochemical mass spectrometry (DEMS) clearly demonstrated the lattice oxygen in NiMn1.5Co3O4-δ is more stable due to strong Mn-O bond and shows synergetic adsorbate evolution mechanism (SAEM) for acid OER. Density functional theory (DFT) calculations reveal highly increased oxygen vacancy formation energy (EVO) of NiCo2O4-δ after Mn doping. More importantly, the highly hydrogen bonding between Mn-O and *OOH adsorbed on adjacent Co octahedral sites promote the formation of *OO from *OOH due to the greatly enhanced charge density of O in Mn substituted sites.

Promoting Molecular Exchange on Rare-Earth Oxycarbonate Surfaces to Catalyze the Water-Gas Shift Reaction.

It is highly desirable to fabricate an accessible catalyst surface that can efficiently activate reactants and desorb products to promote the local surface reaction equilibrium in heterogeneous catalysis. Herein, rare-earth oxycarbonates (Ln2O2CO3, where Ln = La and Sm), which have molecular-exchangeable (H2O and CO2) surface structures according to the ordered layered arrangement of Ln2O22+ and CO32- ions, are unearthed. On this basis, a series of Ln2O2CO3-supported Cu catalysts are prepared through the deposition precipitation method, which provides excellent catalytic activity and stability for the water-gas shift (WGS) reaction. Density functional theory calculations combined with systematic experimental characterizations verify that H2O spontaneously dissociates on the surface of Ln2O2CO3 to form hydroxyl by eliminating the carbonate through the release of CO2. This interchange efficiently promotes the WGS reaction equilibrium shift on the local surface and prevents the carbonate accumulation from hindering the active sites. The discovery of the unique layered structure provides a so-called "self-cleaning" active surface for the WGS reaction and opens new perspectives about the application of rare-earth oxycarbonate nanomaterials in C1 chemistry.

Novel risk factors for craniofacial microsomia and assessment of their utility in clinic diagnosis.

Craniofacial microsomia (CFM, OMIM%164 210) is one of the most common congenital facial abnormalities worldwide, but it's genetic risk factors and environmental threats are poorly investigated, as well as their interaction, making the diagnosis and prenatal screening of CFM impossible. We perform a comprehensive association study on the largest CFM cohort of 6074 samples. We identify 15 significant (P < 5 × 10-8) associated genomic loci (including eight previously reported) and decipher 107 candidates based on multi-omics data. Gene Ontology term enrichment found that these candidates are mainly enriched in neural crest cell (NCC) development and hypoxic environment. Single-cell RNA-seq data of mouse embryo demonstrate that nine of them show dramatic expression change during early cranial NCC development whose dysplasia is involved in pathogeny of CFM. Furthermore, we construct a well-performed CFM risk-predicting model based on polygenic risk score (PRS) method and estimate seven environmental risk factors that interacting with PRS. Single-nucleotide polymorphism-based PRS is significantly associated with CFM [P = 7.22 × 10-58, odds ratio = 3.15, 95% confidence interval (CI) 2.74-3.63], and the top fifth percentile has a 6.8-fold CFM risk comparing with the 10th percentile. Father's smoking increases CFM risk as evidenced by interaction parameter of -0.324 (95% CI -0.578 to -0.070, P = 0.011) with PRS. In conclusion, the newly identified risk loci will significantly improve our understandings of genetics contribution to CFM. The risk prediction model is promising for CFM prediction, and father's smoking is a key environmental risk factor for CFM through interacting with genetic factors.