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Primary water and oxygen isotope composition are important tools in tracing magma source and evolution. Metamictization of zircon due to U-Th radioactive decay may introduce external secondary water to the crystal, thereby masking the primary water and oxygen isotope signature. Recently, Raman-based screening has been established to select the low-degree metamict zircons. However, such an approach may not be appropriate for ancient samples, in which nearly all zircons are metamict. It was reported that thermal annealing can potentially heal crystals and retrieve primary water content and δ18O information from metamict zircons, given the weaker hydrogen bond of secondary water than that of primary water. Heating experiments at temperatures of 200–1000 °C over a period of 2–10 h reveal that annealing can effectively recover primary water and oxygen isotopes from metamict zircons. Primary water in crystalline and metamict zircons remains intact when heated at 4 h, which represent the optimal annealing treatment condition. Hydrothermally altered zircon is an exception. It only yields the minimum estimate of its primary water contents at 600 °C over a period of >4 h, probably due to partial primary water loss during metamictization for hydrothermal zircons. Moreover, the proportion of low-δ18O (700 °C. This study therefore provides the basis for applying zircon water and δ18O proxies to geologically ancient samples.

In this study, we developed four clinopyroxene (cpx) and five orthopyroxene (opx) samples as reference materials for SIMS water content analysis.

Eocene mafic magmatism in the Himalaya provides a crucial window for probing the evolution of crustal anatexis processes within the lower plate in a collisional orogen. We report geochemical data from the earliest postcollision ocean-island basalt–like mafic dikes intruding the Tethyan Himalaya near the northern edge of the colliding Indian plate. These dikes occurred coeval, and spatially overlap, with Eocene granitoids in the cores of gneiss domes and were likely derived from interaction between melts from the lithosphere-asthenosphere boundary and the Indian continental lithosphere. We propose that these mafic magmas were emplaced along lithospheric fractures in response to lithospheric flexure during initial subduction of the Indian continent and that the underplating of such mafic magmas resulted in orogen-parallel crustal anatexis within the Indian continent. This mechanism can explain the formation of coeval magmatism and the geologic evolution of a collisional orogen on both sides of the suture zone.

Water in Earth’s deep mantle may have been acquired early1−7, when deep magma oceans that extend to Earth’s lower mantle, possibly to the core-mantle boundary, were prevalent in the aftermath of energetic impacts8,9. However, how early water was retained and distributed during crystallization of magma oceans remains unclear. This is primarily determined by partitioning of water between mantle mineral and silicate melt. Bridgmanite is the first and dominant mineral crystallized from deep magma oceans10. Yet early attempts are restricted to bridgmanite at the topmost lower mantle condition or minerals in the upper mantle and transition zone11. Here we use laser-heated diamond anvil cell to simulate relevant magma ocean conditions and investigate partitioning of water between bridgmanite and melt. Our data show that partitioning of water in bridgmanite over silicate melt is significantly higher than previous estimates and strongly dependent on temperature. Given plausible magma ocean crystallization scenarios, appreciable amounts of water may be retained in the lower mantle following the crystallization of a deep magma ocean. Circulation of such early, deep, and likely primordial water in Earth’s interior could modulate mantle dynamics and facilitate the transition of early Earth to a habitable planet.

Water, in trace amounts, can greatly alter chemical and physical properties of mantle minerals and exert primary control on Earth’s dynamics. Quantifying how water is retained and distributed in Earth’s deep interior is essential to our understanding of Earth’s origin and evolution. While directly sampling Earth’s deep interior remains challenging, the experimental technique using laser-heated diamond anvil cell (LH-DAC) is likely the only method available to synthesize and recover analog specimens throughout Earth’s lower mantle conditions. The recovered samples, however, are typically of micron sizes and require high spatial resolution to analyze their water abundance. Here we use nano-scale secondary ion mass spectrometry (NanoSIMS) to characterize water content in bridgmanite, the most abundant mineral in Earth’s lower mantle. We have established two working standards of natural orthopyroxene that are likely suitable for calibrating water concentration in bridgmanite, i.e., A119(H2O) = 99 ± 13 μg/g (1SD) and A158(H2O) = 293 ± 23 μg/g (1SD). We find that matrix effect among orthopyroxene, olivine, and glass is less than 10%, while that between orthopyroxene and clinopyroxene can be up to 20%. Using our calibration, a bridgmanite synthesized by LH-DAC at 33 ± 1 GPa and 3,690 ± 120 K is measured to contain 1,099 ± 14 μg/g water, with partition coefficient of water between bridgmanite and silicate melt ∼0.025, providing the first measurement at such condition. Applying the unique analytical capability of NanoSIMS to minute samples recovered from LH-DAC opens a new window to probe water and other volatiles in Earth’s deep mantle.

Arnequinol A (1), featuring an unprecedented 6/6/3 tricyclic carbon skeleton fused with a heptatomic oxo-bridge, together with arnequinone A (2) bearing a highly conjugated methyl-shifting benzogeijerene skeleton, were isolated from Arnebia euchroma. Their structures were elucidated by extensive spectroscopic methods and quantum chemical calculations of the 13C nuclear magnetic resonance (NMR) data and electronic circular dichroism (ECD) spectra. The plausible biosynthetic pathways for 1 and 2 were presented. In an in vitro test, compound 2 showed potent neuroprotective activity against serum-deprivation induced PC12 cell damage at a concentration of 10 μmol/L.

Water content and oxygen isotopes in zircon provide crucial constraints on magma source and process, yet they can be significantly modified by zircon metamictization, which causes secondary water absorption into the zircon crystal and the concomitant oxygen isotope changes. Therefore, it is imperative to develop a screening scheme to select the least-metamict zircons for the analyses. We propose a screening scheme based on our study on the Suzhou A-type granite (South China) through integrating Raman spectroscopy, water and trace element measurements, and oxygen isotope analysis. The results show that the primary water content is retained in zircon when the full-width at half maximum (FWHM) is 1007 cm−1 of ν3(SiO4) vibration band, while the primary δ18O is preserved at 1005.5 cm−1 Raman shift. Changes in trace element concentrations in Suzhou zircons are different from previous observations in metamict zircons but most likely related to magma evolution, which implies that trace elements are insensitive to metamictization. Primary δ18O in Suzhou zircons (4.5–6.0‰) fall into the mantle range, indicating a dominant mantle contribution to Suzhou granites. Primary water content was estimated at ca. 650–1400 ppm, significantly higher than those of typical I-type granite (400–736 ppm) and upper mantle-derived zircons (81–177 ppm). The high primary zircon water content was not controlled by the sub-solidus process, temperature, pressure, and cation charge balance but considered to reflect the high-water content in melts. This suggests a hydrous origin for the Suzhou A-type granite, which challenges the conventional view of anhydrous petrogenesis for A-type granites.

The topographic transition of central–northern Tibet since the early Miocene has created a consistently high and flat plateau similar to that of today. However, to date, the associated deep crust and/or /mantle events are poorly understood, mainly due to an early Miocene metamorphic–magmatic lull within the Qiangtang Block. To address this issue, we undertook a study of crustal xenoliths and zircon xenocrysts in 6.0–2.3 Ma lavas in the Qiangtang Block. The occurrence of 22.6–12.9 Ma high-temperature–low-pressure granulite xenoliths implies that the middle crust of the block has been very hot since that time. Zircon xenocrysts and granitic xenoliths from 6.0–2.3 Ma lavas were studied and shown to have high δ18O values, which supports Miocene crustal melting and the formation of unexposed, coeval felsic plutons. Combined with paleoelevation data from the Tibetan Plateau, our results suggest that the early Miocene cold–hot thermal transition of the middle–lower crust was near-synchronous with topographic evolution from high-relief mountains to a flat plateau, which supports crustal flow as the main topographic smoothing mechanism for central–northern Tibet.

Difurofuranoids A–F (1–6), six novel furofuran lignan dimers that were polymerized through the unusual connection of C5–C5′′, were isolated from the fruits of Forsythia suspensa.

Three matrine-derived alkaloids, alopecuroidine A (1), alopecuroidine B (2a) and alopecuroidine C (2b) were isolated from the seeds of Sophora alopecuroides. Their structures were elucidated by extensive spectroscopic analyses and X-ray diffraction. Three compounds possess an unprecedented rearranged fused 7/6/5/6 tetracyclic skeleton with a diazacycloheptane structure. Their plausible biosynthetic pathway was also proposed. The anti-proliferative activities of compounds 1 and 2a were examined by the MTT assay. Compound 1 inhibited the viability of human lung cancer A549 cells, having a half maximal inhibitory concentration (IC50) of 7.58 ± 2.47 μmol/L at 72 h. The flow cytometric analysis suggested that 1 inhibited A549 cell growth by inducing apoptosis and cell-cycle arrest. Additionally, 1 induced the loss of mitochondrial membrane potential, elevated intracellular reactive oxygen species, increased the Bax/Bcl-2 ratio, stimulated cleaved-caspase-3 and P53 protein levels, and suppressed the pro-caspase-3 level. Thus, 1 appeared to induce A549 cells apoptosis through a mitochondria-mediated apoptotic pathway.

Arnebinones B, E, and D (1-3) have been found to be sensitive to light, generating complex and diverse proton transfer products when triggered by light. A unique two-step irreversible intramolecular proton transfer of 1 produced five scalemic mixtures, of which four possessed intriguing dual planar chirality. The unprecedented orientation epimerization equilibrium of the intra-annular double bond was first observed and researched in the homologous meroterpenoids by HPLC monitoring and DFT calculations. A "p-benzoquinone-CH2/CH-π" moiety in the structure was the common key feature for the occurrence of this type of photoenolization reaction. The product transformation processes and universality of this photoinduced irreversible proton transfer reaction were analyzed together with the cytotoxic activities of arnebinones B, D, and E, and their photoreaction products.

OBJECTIVE The present study was designed to evaluate the effects of adjuvant chemotherapy (CT) vs. radiotherapy (RT, alone or combined with CT) on the prognosis of patients with high-risk, early-stage (stage I and stage II) endometrioid endometrial carcinoma. METHODS This single-center retrospective clinical study was conducted in Union Hospital, Tongji Medical College, Huazhong University of Science and Technology between 2010 and 2019. In the present study, endometrioid endometrial carcinoma patients, who underwent total hysterectomy and bilateral salpingo-oophorectomy followed by postoperative adjuvant CT or RT (alone or combined with CT), and were diagnosed with stage IA grade 2/3 with lymph-vascular space invasion (LVSI), and stage IB with two or more uterine risks, including old age, histological grade 2 or 3, LVSI and stage II, were included. According to the postoperative adjuvant therapy, all eligible patients were divided into two groups: CT group and RT (RT±CT) group. The primary objective was to investigate overall survival (OS) and disease-free survival (DFS) between the CT and RT groups. Grade 3 or worse adverse events were also presented in the present study. RESULTS A total of 145 eligible patients were included. Among these patients, 97 patients underwent adjuvant CT and 48 patients underwent adjuvant RT (RT±CT). The median follow-up was 47.2 months, and the five-year OS rate was 92.7% in the CT group and 88.6 % in the RT group [hazard ratio (HR): 0.81, 95% confidence interval (CI): 0.22-2.99). The 5-year DFS rate for the two groups was 85.7% and 80.2%, respectively (HR: 0.82, 95% CI: 0.33-2.05). The cumulative incidence of local-regional disease recurrence at 60 months of follow-up was 6.2% in the CT group and 6.3% in the RT group (HR=1.11; 95%CI: 0.28-4.35). The cumulative incidence of distant recurrence at 60 months of follow-up was 5.2% in the CT group and 10.4% in the RT group (HR=0.65; 95%CI: 0.19-2.24). Both groups of patients were well-tolerant, and the only grade 3 or worse adverse events were neutropenia and thrombocytopenia. CONCLUSION There was no difference in efficacy for adjuvant CT or adjuvant RT (RT±CT) in high-risk, early-stage endometrioid endometrial carcinoma. CT exhibited a trend of reducing the distant relapse, although there was no significant difference, when compared with adjuvant RT (RT±CT).

The formation of post-collisional mantle-derived rocks in the Tibetan Plateau has been linked to the deep geodynamic processes that cause surface uplift. Co-existing silica-oversaturated to silica-undersaturated mantle-derived rocks have been identified in the northern Qiangtang Terrane (NQT). However, the origins of silica-undersaturated magmas are controversial, and the mechanisms responsible for variable silica activity in the mantle-derived rocks are unclear. Here, we present 40Ar/39Ar chronology, mineral chemistry, and whole-rock geochemical data for the Bamaoqiongzong (BMQZ) volcanic rocks of the NQT. The BMQZ volcanic rocks consist of olivine leucitites, trachybasalts, and phonolites and were erupted at ca. 29 Ma. All samples are unsaturated in silica and characterized by enrichment in light rare earth elements and large-ion lithophile elements, depletion in high-field-strength elements, and the presence of negative Nb–Ta–Ti anomalies and positive Pb anomalies. All samples show limited variation in (87Sr/86Sr)i (0.7079–0.7085) and εNd(t) values (−6.9 to −5.3). The geochemical compositions of the BMQZ volcanic rocks indicate that they were produced by partial melting of carbonated phlogopite–lherzolite within the lithospheric mantle. The formation of the olivine leucitites-trachybasalts-phonolites suite was controlled by fractional crystallization and magma mixing in a magmatic plumbing system. This plumbing system included several independent reservoirs and conduits within the crust. The enriched mantle sources of the BMQZ volcanic rocks were formed by the addition of carbonate-rich melts released from the southward-subducted Songpan–Ganzi Terrane after the Late Cretaceous. Our new results, together with published data, reveal systematic variations in geochemical compositions between silica-undersaturated and silica-oversaturated rocks in the NQT, which are ascribed to variations in the nature of the subducted continental materials added during intracontinental subduction. Carbonate-rich melts that were formed by the breakdown of carbonate minerals helped to generate the mantle sources of silica-undersaturated rocks, whereas silicate melts produced by the partial melting of sediment diapirs contributed to the generation of the silica-oversaturated rocks. On the basis of published numerical modelling of continental subduction and crustal deformation records in the NQT, we suggest that intracontinental subduction and lithospheric thinning together contributed to the generation of post-collisional mantle-derived rocks in the Tibetan Plateau.

The property theory is a unique principle instructing traditional Chinese doctors to prescribe proper medicines against diseases. As an essential part of it, the five-flavor theory catalogs various Chinese materia medicas (CMMs) into five flavors (sweet, bitter, sour, salty, and pungent) based on their taste and medical functions. Although CMM has been successfully applied in China for thousands of years, it is still a big challenge to interpret CMM flavor via modern biomarkers, further deepening its elusiveness. Herein, to identify the correlation between gut microbiota and CMM flavor, we selected 14 CMMs with different flavors to prepare their aqueous extracts, quantified the contained major chemical components, and then performed full-length 16S rRNA sequencing to analyze the gut microbiota of C57BL/6 mice administrated with CMM extracts. We found that flavones, alkaloids, and saponins were the richest components for sweet-, bitter-, and pungent-flavored CMMs, respectively. Medicines with merged flavors (bitter-pungent and sweet-pungent) displayed mixed profiles of components. According to gut microbial analysis, modulation of CMMs belonging to the same flavor on the taxonomic classification was inconsistent to an extent, while the functional sets of gut microbiota, co-abundance gene groups (CAGs), strongly and differentially responded to distinct flavors. Moreover, these correlations were in line with their pharmacological actions. Therefore, the gut microbial functional sets (CAGs) could act as the possible indicator to reflect CMM flavor, rather than the composition of microbial community.

Berberine (BBR) is an effective cholesterol-lowering drug. Although gut microbiota has been implicated in the pharmacological activities of BBR, little evidence exists on the specific species of gut microbiota involved in its therapeutic effects, nor on linking gut bacteria to its recognized hypercholesterolemia-alleviating mechanism-upregulation of the low-density lipoprotein receptor (LDLR) in the liver. The present study was performed to identify the specific species of gut microbiota involved in the anti-hyperlipdemic effect of BBR, and interpret its mechanism through linking the gut microbiota and LDLR. The BBR-enriched gut bacterial species were identified by whole genome shotgun sequencing. Pure cultured B. producta was orally administered to C57BL/6 mice to evaluate its anti-hyperlipdemic effect. The LDLR-upregulating effect of B. producta was evaluated both in vitro and in vivo. Orally administration of BBR (200 mg/kg) decreased serum and liver lipid levels in HFD-induced hyperlipidemic mice. Microbiome analysis indicated that Blautia was closely associated with BBR's lipid-modulating activities. Further analysis revealed that BBR selectively promoted the growth of Blautia producta. Orally treatment of HFD mice with live B. producta reduced obesity and alleviated hyperlipidemia. Notably, the B. producta significantly increased LDLR expression in the liver, and its spent culture supernatant upregulated the LDLR level and promoted LDL uptake by HepG2 cells. Simultaneously, B. producta also linked butyrate-producing and bile salt hydrolase (BSH)-inhibiting effect of BBR. The gut microbiota, especially B. producta, may confers the hypercholesterolemia-alleviating effects of berberine. B. producta represents a novel probiotic that may be used for the treatment of dyslipidemia.

Eight new arnebinol B-based meroterpenoids ((-)-1, 2, 3, (-)-5, and 7-10) with a constrained 6/10/5 tricyclic backbone were isolated from the roots of Arnebia euchroma. The planar and steric structures of these new compounds were unambiguously elucidated by extensive spectroscopic analyses, X-ray diffraction crystallography, and ECD calculations. The predominant relative orientation between H-7 and the Z double bond with a methyl substituent in the rigid 10-membered carbocycle, along with the planar chirality of the Z double bond was analyzed and discussed for the first time. The illustration of the planar chirality derived from the Z double bond should be paid great importance during the structure elucidation on these homologous meroterpenoids. All the isolated meroterpenoids were screened for their cytotoxicities against the HCT-8, PANC-1, HGC-27, HepG2, and PC9 cell lines, and compounds (+)-5 and (-)-5 exhibited the most potent cytotoxicity.

A series of 4-thiosubstituted flavan derivatives (1-44) were designed and synthesized. The target compounds were assayed for inhibitory activity against α-glucosidase in vitro, and the results indicated that all compounds displayed significant effects in the range of IC

Understanding the subduction and recycling of continental crust is crucial for reconstructing the long-term evolutionary history of Earth's mantle and crust. The Himalaya-Tibet orogen is arguably the world's best natural laboratory for investigating these processes. Cenozoic post-collisional ultrapotassic volcanic rocks are common in the Lhasa block of southern Tibet and they can provide important clues to crust-mantle interaction in a well-characterized continental collision zone. Understanding the sources and processes that generated these lavas can contribute to our understanding of the thermal and compositional characteristics of the deep mantle and geodynamic processes in this region, including Indian continental subduction. In this contribution, we report Sr-Nd-Pb-O-B isotope and elemental chemistry data for post-collisional (13-11 Ma) ultrapotassic rocks from the TangraYumco-Xuruco rift (TYXR) in the Lhasa block. The arc-like trace-element signatures and markedly enriched Sr-Nd-Pb-O isotope compositions indicate that these mafic rocks originate from a mantle source containing recycled crustal components. Unlike pre-collisional (∼64 Ma) ultrapotassic rocks in the Lhasa block with arc-like B/Nb (0.85-1.89) and B (−9.0 to −2.5‰) values, the TYXR post-collisional ultrapotassic rocks with much lower B/Nb (0.05-0.85) and B (down to −20.5‰) values resemble Miocene K-rich volcanic rocks from western Anatolia. These western Anatolian rocks have been formed by either progressive dehydration of a stalled slab or deep-subducted continental crust. However, some TYXR samples have lower B/Nb ratios than MORB, consistent with a fluid-starved source. These markedly negative B in conjunction with low B/Nb cannot be explained by the addition of melts from oceanic sediments, which generally yield lower B/Nb but higher B values than MORB (e.g., the Armenia post-collisional mafic rocks). Given the low B of Indian upper continental crust and its similar Sr-Nd-Pb isotopic signatures to the post-collisional lavas, it is clear that the post-collisional ultrapotassic rocks in the Lhasa block contain a significant component derived from subducted Indian continental crust. Combined with the temporal evolution of regional magmatism, tectonics and geophysical data, we propose that the break-off and tearing of subducted Indian continental slab induced post-collisional magmatism in the Lhasa block. Our case study provides evidence that continental subduction contributes to very light B isotope compositions of post-collisional magmas, which suggests that B isotopes have the potential to discriminate between oceanic subduction and continental subduction.

BackgroundThe effects of metabolic syndrome (MS) on premature myocardial infarction (PMI) are not clear to date. This study aimed to investigate the impact of MS and its components on clinical severity and long-term prognosis in patients with PMI.MethodsWe enrolled 772 patients aged ≤45 years old who were diagnosed with acute myocardial infarction (AMI) at our hospital consecutively between 2015 and 2020. The patients were divided into an MS group and non-MS group. The parameters of clinical severity were compared using regression analysis. Patients were followed for median of 42 months for major adverse cardiovascular events (MACE).ResultsHyperglycemia was associated with multi-vessel disease [odds ratio(OR)=1.700, 95% confidence interval (CI)=1.172-2.464, P=0.005] and Syntax score ≥33 (OR=2.736, 95% CI=1.241-6.032, P=0.013). Increased MACE were observed in the MS group(17.9% vs 10.3%, P=0.004).The Kaplan-Meier curve also showed significant differences (P< 0.001). MS was an independent risk factor for MACE. Of each component of MS, BMI ≥28 kg/m2 (hazard ratio [HR]=2.022, 95% CI =1.213-3.369, P=0.007] and hyperglycemia (HR=2.904, 95% CI=1.847-4.567, P) were independent risk factors for MACE.ConclusionsIn patients with PMI, 1) hyperglycemia usually indicates more severe lesions; 2) MS as a whole was an independent risk factor for MACE; 3) BMI ≥28.0 kg/m2 and hyperglycemia were associated with MACE.

Diverse rock types and contrasting geochemical compositions of post-collisional mafic rocks across the Tibetan Plateau indicate that the underlying enriched lithospheric mantle is heterogeneous; however, how these enriched mantle sources were formed is still debated. The accreted terranes within the Tibetan Plateau experienced multiple stages of evolution. To track the geochemical characteristics of their associated lithospheric mantle through time, we can use mantle-derived magmas to constrain the mechanism of mantle enrichment. We report zircon U-Pb ages, major and trace element contents, and Sr-Nd isotopic compositions for Early Cretaceous and late Eocene mafic rocks in the southern Qiangtang terrane. The Early Cretaceous Baishagang basalts (107.3 Ma) are characterized by low K2O/Na2O (

We aimed to explore the utility of multiple biomarkers with GRACE risk stratification for non-ST-elevation myocardial infarction (NSTEMI). A total of 1,357 patients diagnosed with NSTEMI were enrolled in this study at multiple medical centers in Tianjin, China. The outcomes were 1-year all-cause death and major adverse cardiac events (MACE: all-cause death, hospital admission for unstable angina, hospital admission for heart failure, nonfatal recurrent myocardial infarction, and stroke). C-index, net reclassification improvement (NRI), and integrated discrimination improvement (IDI) were calculated to verify that the biomarkers improve the predictive accuracy of the GRACE score. A total of 57 participants died, while 211 participants experienced 231 MACEs during follow-up (mean: 339 days). For all-cause death, the combination of N-terminal pro-B-type natriuretic peptide (NT-proBNP) and D-dimer improved the predictive accuracy of GRACE the most, with C-index, IDI, and NRI values of 0.88, 0.085, and 1.223, respectively. For MACE, trigeminal combination of NT-proBNP, fibrinogen, and D-dimer resulted in C-index, IDI, and NRI values of 0.80, 0.079, and 0.647, respectively. As a result, NT-proBNP, D-dimer, fibrinogen, and GRACE comprise a new scoring system for assessing 1-year clinical events. Kaplan-Meier analysis revealed a significant increase in 1-year mortality (score ≥3.85 vs

One pair of new amides enantiomers (1a and 1b) and two known amides were isolated from the rhizomes of Polygonum cuspidatum. Their structures were established using UV, IR, HRESIMS, and NMR data. Notably, compound 1 possesses unique C-C connection between feruloyltyramine and resveratrol. Their absolute configurations were determined by the ECD method. All compounds were evaluated for their α-glucosidase inhibitory activity and compounds 2 and 3 showed significant inhibitory activity with IC50 values of 2.82 and 13.06 μmol/L, respectively (positive control acarbose, IC50 385 μmol/L).

Oxygen isotopic analysis of aragonite by secondary ion mass spectrometry (SIMS) is of significance to reveal the high spatial resolution information correlated with microstructure which could not be achieved by conventional methods. Appropriate reference materials to calibrate instrumental mass fractionation of SIMS are vital to acquire accurate values. However, the scarcity of standards (as far as we know, there were just two in-house laboratory-based potential reference materials reported) limits the development of this field. Herein, an inorganically precipitated aragonite vein sample (VS001/1-A) being evaluated through several hundred SIMS oxygen isotopic analyses was ascertained to have homogeneous oxygen isotopic composition with an external reproducibility of 0.3‰ (1σ) and to be a potential SIMS reference material. The instrumental bias evident in the series of aragonites, decreased by ∼3.4‰ with decreasing aragonite Ca content. Corals, as biogenic carbonates, were used as examples for evaluating the application of the in situ SIMS analysis method, and processes involved in “vital effects” are described. The development of in situ oxygen isotopic microanalysis of aragonite is significant for the application of revealing possible biocarbonate mineralization mechanisms.

A concise method was established to determine the relative and absolute configurations of aryl-glycerols that depend on the chemical shift differences (Δδ) of the diastereotopic methylene protons (H-3) by 1H NMR spectroscopy. When using DMSO-d6 as the preferred solvent, the threo configuration corresponded to a larger ΔδH3a–H3b value (>0.15 ppm), whereas the erythro configuration ( 0.20 ppm. In the erythro enantiomers, the Δδ value of 1R,2S was >0.09 ppm, and that of 1S,2R was

New phloroglucinol glycosides, aglycones, and oxidative dearomatized products of aglycones were discovered from Agrimonia pilosa, and the mechanism of the auto oxidative dearomatization was disclosed as a free radical chain reaction with 3O2.

Sepsis is identified as a severe inflammatory disease. Epigallocatechin-3-gallate (EGCG) has been reported to be a powerful anti-inflammatory chemical substance in numerous diseases. However, the underlying mechanism of the anti-inflammatory effects of EGCG in sepsis remains to be elucidated.The surgery for cecal ligation and puncture (CLP) was performed on male C57BL/6J mice aged 8 weeks. THP-1 cells were treated with 1 μg/ml lipopolysaccharide (LPS) for 24 h to imitate sepsis in vitro. Haematoxylene-Eosin (HE) staining of the sections of liver, lung and kidney was performed to evaluate the pathological changes. The inflammatory cytokines were quantitated by ELISA. qRT-PCR was performed to measure the expression levels of PVT1, miR-16-5p, and TLR4. The protein level of TLR4 was also assessed by Western blotting. Double luciferase reporter assay and RIP assay were performed to validate the interactions among PVT1, miR-16-5p, and TLR4.EGCG inhibited the expression levels of PVT1 and TLR4 and enhanced miR-16-5p expression in CLP-operated mice and LPS-treated THP-1 cells. EGCG reduced the levels of inflammatory cytokines, which were restored by PVT1 overexpression. Mechanistically, PVT1 bound with miR-16-5p to activate TLR4 signaling. Further experiments demonstrated that miR-16-5p silencing or TLR4 overexpression antagonized sh-PVT1 or miR-16-5p mimics-mediated inhibitory effects on inflammatory cytokines, respectively. Knockdown of PVT1 alleviated inflammatory injury in CLP-induced sepsis in mice.EGCG may effectively lower the levels of sepsis-induced inflammatory cytokines by targeting the PVT1/miR-16-5p/TLR4 axis.

Three new monocyclic monoterpenoid containing β-D-apiofuranosyl-(1→2)-O-β-D-glucopyranosyl moieties, together with three other known monocyclic monoterpenoid O-glycosides, were obtained from the roots of Glycyrrhiza uralensis for the first time. Their structures were determined by UV, IR, HRESIMS, and 1D and 2D NMR data.

Lithium garnets have been widely studied as promising electrolytes that could enable the next-generation all-solid-state lithium batteries. However, upon exposure to atmospheric moisture and carbon dioxide, insulating lithium carbonate forms on the surface and deteriorates the interfaces within electrodes. Here, we report a scalable solid sintering method, defined by lithium donor reaction that allows for complete decarbonation of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) and yields an active LiCoO2 layer for each garnet particle. The obtained LiCoO2 coated garnets composite is stable against air without any Li2CO3. Once working in a solid-state lithium battery, the LiCoO2-LLZTO@LiCoO2 composite cathode maintains 81% of the initial capacity after 180 cycles at 0.1 C. Eliminating CO2 evolution above 4.0 V is confirmed experimentally after transforming Li2CO3 into LiCoO2. These results indicate that Li2CO3 is no longer an obstacle, but a trigger of the intimate solid-solid interface. This strategy has been extended to develop a series of LLZTO@active layer materials., Formation of insulating lithium carbonate on surface of lithium garnets hinders their application as solid electrolyte in lithium ion batteries. Here the authors explore a scalable sintering approach to utilize the undesired Li2CO3 and improve the active material-electrolyte interface within cathodes.

Seven new phenolic acids, 7, 8-epiblechnic acid (1), 8-epiblechnic acid 9-ehthyl-9'-methyl ester (2), 9'-ehyl-isolithospermate (3), 9''-methyl-isolithospermate (4), 9'-ethyl-9''-methyl-isolithospermate (5), 9', 9''-dimethyl-isolithospermate (6), sebesteniod E (7), were isolated from the roots of Salvia miltiorrhiza. Their structures were elucidated by detailed spectroscopic means including UV, IR, HRESIMS, and NMR data spectra. The bioactive assays of compounds 1-7 against neuroprotection activities were determined. The results suggested that compound 4 exhibited a moderate glutamate-induced neuroprotective activity and the cell survival rate was 24.0% (10

Phytochemical investigation of the rhizome of Ligusticum chuanxiong Hort led to the isolation and identification of three new compounds, chuanxiongoside A, (2E,4E)-8-(6-O-inositolyl)-8-oxo-2,7-dimethyl-octadienoic acid (2), chuanxiongoside C (3). The structures of these compounds were unambiguously established by HR-ESI-MS, UV, IR, CD, NMR spectral data and comparison to reported data. All the isolated compounds (1-3) were investigated for their inhibitory effects on nitric oxide (NO) production in LPS-induced RAW 264.7 cells. All compounds showed excellent inhibition of NO production stronger than curcumin. [Formula: see text].

Dense and submicron-sized polycrystalline β-Si3N4 bulk samples with average grain size of 263 ± 68 nm have been synthesized using micron-sized α-Si3N4 powder (2 μm) as the starting material by simultaneously tuning the pressure and temperature conditions. The measured Vickers hardness HV of the submicron-sized polycrystalline β-Si3N4 could reach up to about 20 GPa, approaching the upper limit of the single crystal β-Si3N4. The measured fracture toughness KIC of the polycrystalline β-Si3N4 has been enhanced from 3.0 to 4.1 MPa m1/2, as much as 36%, while without sacrificing the hardness. This study demonstrates that using micron-sized powder as the starting material to synthesize submicron-sized polycrystalline bulks by phase transformation under extreme pressure conditions is an efficient pathway to break through the old paradigm—the higher the fracture toughness of a material, the lower the hardness.

Significance Reconstructing past extreme weather events, such as tropical cyclones and cold surges, using natural paleoclimate archives can lengthen the instrumental data and help us have a broader understanding of the range of weather variability not evident in instrumental record. However, the time resolution of current paleoarchives, from millennial to monthly at best, is usually too low to explore past weather events. Here we found that the Tridacna shells from South China Sea, western Pacific, have continuous daily growth bands, and several daily to hourly resolution biogeochemical proxy records were developed. Our results demonstrate that these records can record nearby tropical cyclones and cold surges, indicating that Tridacna shells have the potential to be an unprecedented ultra-high-resolution archive for paleoweather reconstructions., Paleoclimate research has built a framework for Earth’s climate changes over the past 65 million years or even longer. However, our knowledge of weather-timescale extreme events (WEEs, also named paleoweather), which usually occur over several days or hours, under different climate regimes is almost blank because current paleoclimatic records rarely provide information with temporal resolution shorter than monthly scale. Here we show that giant clam shells (Tridacna spp.) from the tropical western Pacific have clear daily growth bands, and several 2-y-long (from January 29, 2012 to December 9, 2013) daily to hourly resolution biological and geochemical records, including daily growth rate, hourly elements/Ca ratios, and fluorescence intensity, were obtained. We found that the pulsed changes of these ultra-high-resolution proxy records clearly matched with the typical instrumental WEEs, for example, tropical cyclones during the summer−autumn and cold surges during the winter. When a tropical cyclone passes through or approaches the sampling site, the growth rate of Tridacna shell decreases abruptly due to the bad weather. Meanwhile, enhanced vertical mixing brings nutrient-enriched subsurface water to the surface, resulting in a high Fe/Ca ratio and strong fluorescence intensity (induced by phytoplankton bloom) in the shell. Our results demonstrate that Tridacna shell has the potential to be used as an ultra-high-resolution archive for paleoweather reconstructions. The fossil shells living in different geological times can be built as a Geological Weather Station network to lengthen the modern instrumental data and investigate the WEEs under various climate conditions.

The 1,2-dibromoethane- and KI-mediated α-acyloxylation of ketones is reported in moderate to good yield without the use of transition metals and strong oxidants. Various acids are well tolerated with wide functional group compatibility. An 1,2-dibromoethane- and KI-catalysed reaction mechanism is proposed based on the results of control experiments.

The determination of the original boron (B) isotopic composition in altered basaltic glass is important to characterize magma generation and evolution in the mantle. Traditional whole-rock analysis of the B isotopic composition of basaltic glass requires time-consuming pretreatment for removing the altered section. Here, a protocol of in situ B isotopic analysis of basaltic glass by secondary ion mass spectrometry was developed using an accessible reference material BCR-2G which was first ascertained as a standard material for in situ B-isotopic analysis, whose B isotopic value (δ11B = −5.44‰; 2σ = 0.55‰) was determined by solution-based multi-collector-inductively coupled plasma-mass spectrometry in this study. Trans-sectional analysis of both slightly and extensively altered grains was performed from the cores outward to the rims (palagonite) by this in situ method to verify its ability in rapidly extracting information of the original (unaltered) B composition from natural samples. The δ11B values of the pristine (unaltered) melt ranging from −8.99‰ to −12.00‰ could be rapidly determined from the slightly altered grain, which is distinguishable from those of its transition (−3.14‰ to +9.56‰) and palagonite (+5.04‰ to +8.56‰) sections. Compared with the slightly altered one, the extensively altered grain has just the transition and palagonite sections without the pristine section. Therefore, in situ B isotopic profiling analysis of basaltic glass is beneficial for rapidly obtaining original magma B information from a single natural altered grain.