Search

Ethylene in principle can be obtained via oxidative coupling of methane (OCM), but it is urgently calling for a low-temperature active and selective catalyst. To accomplish this goal, the CexZr1-xO2 solid solutions with varied Ce/Zr molar ratio were modified with Mn2O3-Na2WO4 to fabricate OCM catalysts. The effects of Ce/Zr ratio and Mn2O3-Na2WO4 doping were investigated on the catalyst reactivity for the OCM, showing that the reaction light-off temperature, activity and selectivity are subject to the Ce/Zr molar ratio and Mn2O3-Na2WO4 doping. The promising catalyst with Ce/Zr molar ratio of 0.15/0.85 achieves 25% CH4 conversion with 67% selectivity to C2-C3 at 660 °C and is stable for at least 100 h. The catalysts were systematically studied by CH4-TPSR, O2-TPO/-TPD, CH4-pulse, in-situ FT-IR, EPR and XPS, showing that the Mn2O3-Na2WO4 doped Ce0.15Zr0.85O2 can generate more O2– species thereby leading to a markedly improved activity and selectivity at much lowered reaction temperature.

To better constrain Ca isotopic fractionation during volcanic magma differentiation, we report Ca isotope data for a series of volcanic glasses from the eastern Manus Basin that represent a continuum of compositions comprising basaltic andesite, andesite, dacite, and rhyolite. Our results show that these volcanic glasses exhibit ~0.25‰ variation in Ca isotopic compositions, with δ44/40Ca ranging from 0.81 ± 0.04 to 1.05 ± 0.04‰. The similar trace element patterns and Sr-Nd isotopic compositions exclude source heterogeneity as the cause of the varied Ca isotopic compositions. Due to their low K/Ca ratios and young age, the Ca isotopic variations cannot be attributed to 40K decay. Instead, the observed Ca isotopic variations are primarily controlled by their lithology. Specifically, δ44/40Ca of basaltic andesite (0.81 ± 0.04) and andesite (0.82 ± 0.01) are similar to the averages of reported mid-ocean ridge basalts (MORBs; 0.84 ± 0.10; 2SD, N = 26) and back-arc basin basalts (BABBs; 0.80 ± 0.08; 2SD, N = 21) in literature, but do not correlate with SiO2 or MgO contents, indicating the Ca isotopic fractionation is insignificant during intermediate-mafic magma evolution. As magma differentiation continues, δ44/40Ca of dacite and rhyolite evolves from 0.85 ± 0.01 to 1.05 ± 0.04‰. Moreover, δ44/40Ca of felsic glasses are negatively correlated with Eu/Eu*, which suggests that the increasing δ44/40Ca of felsic glasses is most likely related to plagioclase (Pl) fractional crystallization. Therefore, we conclude that Ca isotopes can behave differently at different stages of volcanic magma differentiation. Modeling of fractional crystallization using rhyolite-MELTS shows that the relative Ca fractions in crystallized minerals (e.g., Pl vs. Cpx) and the Ca isotopic fractionation factor between the residual melt and crystallized Pl (αmelt-Pl, which is likely related to the An number of Pl, magma temperature and kinetic effects during crystallization), provide a plausible explanation for the behavior of Ca isotopes during volcanic magma differentiation.

Increasing evidence shows that the mantle contributes (directly or indirectly) to Sn-bearing granites worldwide. However, the specific role of mantle in the formation of tin granites and related mineralization remains poorly understood. In the world-class Dachang district, South China, tin mineralization is related to the Longxianggai equigranular/porphyritic biotite granites and tin orebodies are cut by granite porphyry dykes hosting mafic microgranular enclaves (MMEs). A combination of zircon U-Pb dating and Hf-O isotopes, mineral chemistry, and whole-rock elemental and Sr-Nd isotopic compositions—for granitic rocks and MMEs, is employed to constrain the petrogenesis and to unravel the link between tin fertility and mantle upwelling. Laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) zircon U-Pb dating indicates that the biotite granites were emplaced at ca. 93 Ma, and the granite porphyry dykes and MMEs were formed at ca. 86 Ma. The biotite granites are silica- and alkali-enriched with A/CNK ratios of 1.04–1.36, and exhibit elevated concentrations of Li, F, P, Rb, Cs, Ta, Sn, W, and U, showing affinities with highly fractionated S-type granites. Whole-rock geochemical and Nd isotopic (εNd(t) = −10.0 to −7.8) data, and in situ zircon Hf-O (εHf(t) = −9.9 to −3.9, δ18O = 6.2–8.9‰) isotopes indicate that the biotite granites were formed by partial melting of metasedimentary rocks at relatively high temperatures (≥782 °C), possibly with minor input of mantle material. Likewise, the post-ore granite porphyry dykes have similar chemical and mineralogical characteristics as fractionated S-type granites. Zircon Hf-O isotopes (εHf(t) = −9.0 to −4.9, δ18O = 6.5–8.2‰) and whole-rock geochemical data suggest they were derived from a similar source as the biotite granites, whereas elevated εNd(t) values of −5.0 to −3.3 for granite porphyry dykes relative to biotite granites reveal an increasing mantle input. Distinct εNd(t) (−0.4 and −0.3) and zircon Hf-O (εHf(t) = 1.5–5.0, δ18O = 6.5–7.2‰) isotopes of the MMEs, suggest that the mafic melt could be sourced from the asthenospheric mantle, contaminated by subcontinental lithospheric mantle/continental crust during magma ascent, and hybridized by felsic melt at emplacement-level. The magmatic sequence in the Dachang district is indicative of an extensional tectonic setting where mantle-derived magmas are predicted to migrate to shallower crustal levels as the crust progressively becomes thinner and hotter. High-temperature partial melting of mature metasedimentary crust triggered by heat input from the upwelled mantle, may contribute to biotite breakdown, which is important for concentrating tin in melts. Fractional crystallization of initially Sn-rich felsic melts under reduced conditions makes further tin enrichment and produces Sn-bearing granites (the Longxianggai pluton). Prolonged mantle upwelling results in distinct magma mixing and the formation of granite porphyry dykes and MMEs. These dykes are highly fractionated with elevated Sn and W contents, which show great potential to form hydrothermal Sn-W mineralization.

Trace element partitioning between coesite and hydrous silicate melt has been investigated at 5 GPa and 1500−1750°C. High-P experiments successfully produced large coesite crystals in equilibrium with large silicate melt pools (plus kyanite and corundum crystals in some cases). Scanning electron microscopy and micro-Raman spectroscopy were employed to characterize the phases and the textures. Wavelength-dispersive electron microprobe analyses were performed to quantify conventional major elements, and laser ablation-inductively coupled plasma-mass spectrometry analyses were successfully conducted to quantify trace elements. Eventually, high-P partition coefficients were obtained for 33 elements. In general coesite is a very pure phase. With a few possible exceptions like Sc, Ti, and V, nearly all other trace elements are incompatible in coesite. Moreover, the partitioning behaviors of nearly all trace elements except some 4+ cations cannot be readily described by the lattice strain model, presumably implying a minor role for the cation size in the trace-element partitioning. Combining our experimental results with the results in the literature, some T and P effects on the element partitioning behavior have been observed: T seemingly has different effects on different trace elements, but P might negatively correlate with the partition coefficients in all cases. Due to its large modal fraction in some subducted materials such as the continental crustal material, coesite might play an important role in the distributions of some trace elements, Ti for example.

The free-standing Ni-Al2O3 ensemble derived from NiAl-layered double hydroxides (NiAl-LDHs) grown onto a Ni-foam has been developed for the exothermic gas-phase acetone hydrogenation to isopropanol. This approach works effectively and efficiently to achieve a unique combination of high activity/selectivity and enhanced heat/mass transfer stemmed from the Ni-foam. The outstanding catalyst is obtained by direct reduction of the un-calcined NiAl-LDH/Ni-foam, with a high turnover frequency of 0.90 s-1, being capable of converting 90.8% acetone into isopropanol with almost 100% selectivity under stoichiometric H2/acetone molar ratio, atmospheric pressure at 80 °C, and a WHSVacetone of 10 h-1. The catalyst derivation using the un-calcined NiAl-LDH/Ni-foam enables the Ni nanoparticles to be intertwined with Al2O3 to form a large Ni-Al2O3 interface, without interruption of impurities such as irreducible NiO (in the case of calcined NiAl-LDH/Ni-foam samples), which markedly improves the strong acetone adsorption next to the Ni0 hydrogenation sites, thereby leading to a dramatic improvement of catalyst activity.

Hydrous minerals in the hybridized zone at the slab-mantle interface play a critical role in retaining and transporting fluid mobile elements in subduction zones. The observed high B and As concentrations and high δ11B values in arc magmas were previously thought to have been resulted from the mechanical transport of forearc serpentinites down to subarc depths by mantle corner flows or through subduction channels because B, As, and Sb are mostly released during early stages of subduction. This study provides new insights into the recycling of B, As, and Sb in subduction zones via an in-situ study on a set of carbonate-bearing serpentinite samples from the Mianlue melange complex in the Qinling Orogen. Petrological observations and bulk-rock Sr-Pb isotopes reveal that the Jianchaling serpentinites were formed by interactions between forearc peridotites and sediment-derived fluids at a shallow depth in the subduction channel. Some Jianchaling serpentinites experienced the lizardite to antigorite transition at 300–400 °C with infiltrations of CO2-rich fluids. In contrast, the Liangyazi antigorite serpentinites were produced at a greater depth. Antigorite grains in the Jianchaling serpentinites have lower Feapfu than those in the Liangyazi serpentinites and most antigorite with geochemical data in the literature. Meanwhile, B, As, and Sb concentrations of Fe-poor antigorite from the Jianchaling serpentines (385–653 ppm B, 198–334 ppm As, and 6.24–8.01 ppm Sb) are not only higher than those of the Fe-rich antigorite from the Liangyazi serpentinites but also 2–3.5 times higher than those of the surrounding lizardite. The lower modal percentage of spinel and ferritchromite in antigorite veinlets, together with the lower bulk-rock FeO content of antigorite-lizardite serpentinites than that of lizardite serpentinites from the Jianchaling region, indicates that some FeO might be lost during the lizardite to antigorite transition. The presence of carbonate minerals in the antigorite veinlets and the remarkably high B, As, and Sb concentrations in the Jianchaling antigorite indicate that the penetrating fluids during the lizardite to antigorite transition are most likely derived from sediment and metabasite decarbonations at

In-situ hydrothermal experiments using diamond-anvil cell show that sulfate and sulfide are the dominant sulfur species under P-T conditions similar to those of porphyry magmas. No sulfite was identified using in-situ Raman spectrometer. This supports that porphyry copper mineralization is controlled by sulfate reduction, rather than sulfite disproportionation.

A series of coesite, coexisting with or without a liquid phase, was synthesized in the nominal system SiO2–H2O at 800–1450 ​°C and 5 ​GPa. Micro-Raman spectroscopy was used to identify the crystalline phase, electron microprobe and LA-ICP-MS were employed to quantify some major and trace elements, and unpolarized FTIR spectroscopy was applied to probe the different types of hydrogen defects, explore water-incorporation mechanisms and quantify water contents. Trace amounts of Al and B were detected in the coesite. Combining our results with the results in the literatures, we have found no positive correlation between the Al contents and the “Al”-based hydrogen concentrations, suggesting that previously proposed hydrogen-incorporation mechanism H+ ​+ ​Al3+ ↔ Si4+ does not function in coesite. In contrast, we have confirmed the positive correlation between the B contents and the B-based hydrogen concentrations. The hydrogen-incorporation mechanism H+ ​+ ​B3+ ↔ Si4+ readily takes place in coesite at different P-T conditions, and significantly increases the water content at both liquid-saturated and liquid-undersaturated conditions. For the SiO2–H2O system, we have found that type-I hydrogarnet substitution plays a dictating role in incorporating water into coesite at liquid-saturated condition, type-II hydrogarnet substitution contributes significantly at nearly dry condition, and both operate at conditions in between. The water solubility of coesite, as dictated by the type-I hydrogarnet substitution, positively correlates with both P and T, c H 2 O ​= ​−105(30) ​+ ​5.2(32) ​× ​P ​+ ​0.112(26) ​× ​T, with c H 2 O in wt ppm, P in GPa and T in °C. Due to its low water solubility and small fraction in subducted slabs, coesite may contribute insignificantly to the vertical water transport in subduction zones. Furthermore, the water solubility of any coesite in exhuming ultra-high pressure metamorphic rocks should be virtually zero as coesite becomes metastable. With an adequately fast water-diffusion rate, this metastable coesite should be completely dry, which may have been the key factor to the partial preservation of most natural Coe. As a byproduct, a new IR experimental protocol for accurate water determination in optically anisotropic nominally anhydrous minerals has been found. Aided with the empirical method of Paterson (1982) it employs multiple unpolarized IR spectra, collected from randomly-orientated mineral grains, to approximate both total integrated absorbance and total integrated molar absorption coefficient. Its success relies on a high-level orientation randomness in the IR analyses.

The Dongguashan deposit is the largest and deepest Cu (Au) deposit in the Tongling region, eastern China. The presence of skarn and stratiform ore bodies in the same system of the Dongguashan deposit has caused much debate as to whether the mineralization was associated with magmatic-hydrothermal or sedimentary origin. In this study, in situ (LA-ICP-MS and EPMA) elemental compositions of medium-to coarse-grained euhedral pyrite from the stratiform and skarn ore bodies, and pyritization marble are investigated in the Dongguashan deposit. The results of the studied pyrite samples have relatively consistent trace element composition characteristics and several genetically significant elemental combinations. Gold and Ag are mainly of lattice bound appearance in pyrite. The Pb, Cu, Sb and Tl elements are mainly incorporated into the pyrite structure as substitutions. The distinctly trace element distribution correlations (e.g., Mn, Se and Tl) of the studied pyrites indicate that they were formed in a high temperature and oxidizing environment. Low Au (1) and Se/Tl (>10) ratios of the studied pyrites imply that the Dongguashan deposit is most likely to be a magmatic-hydrothermal origin.

Seafloor hydrothermal chimneys are significant metal resources and have fundamental effects on marine chemistry balance. Previous studies on growth of the chimneys focused on mineral composition and elemental distribution in chimney walls, but the isotopic composition of different elements and their correlations remain poorly understood. Here, we report lateral Fe and S isotopes from sulfides across a chimney wall in detail from the Deyin-1 hydrothermal field (DHF) on the South Mid-Atlantic Ridge. Pyrite was characterized by increases in both δ34S and δ56Fe from the exterior to the interior within the chimney wall, which is likely related to enhanced S and Fe isotope fractionation between pyrite and fluids derived from the temperature gradient. Furthermore, δ56Fe displayed a well-defined, linear, positive correlation with δ34S in pyrite from the DHF as well as in pyrite from other areas. A model of hydrothermal pyrite formation suggests that, under conditions with uniform hydrothermal fluid, different temperatures and similar pyrite–fluid exchange degrees could result in the observed linear relationships between δ34S and δ56Fe. The regular and coupled Fe–S isotope variations within the chimney wall efficiently constrain the process of hydrothermal sulfide formation.

Supercritical CO2 appearing as bubbles in hydrothermal vents was identified in the south part of the Okinawa Trough using in situ Raman spectroscopy. Significantly, the N2 peak in supercritical CO2 is much larger than those in seawater and vent fluids, indicating that supercritical CO2 enriches N2 from the surrounding environment. Considering that the partial pressures of CO2 and N2 in the Earth’s proto-atmosphere were ~10–20 MPa, supercritical CO2 with high N2 was likely the dominant CO2 phase near the water-air interface in the early history of the Earth, which promoted the synthesis, pre-enrichment and preservation of amino acids and other organic matters that are essential to the origin of life.

In order to investigate the behavior of potassium (K) isotopes during metamorphic dehydration and to further constrain its implications for K recycling in the subduction zone, we measured K isotopic compositions of whole-rocks and separated minerals (phengite, omphacite, amphibole) from Sumdo eclogites, Tibet, using a recently established high-precision analysis method. Our data reveal that the δ41K (‰) of the whole-rock eclogites (−1.64 to −0.24) displays dramatically lower values than observed in fresh mid-ocean ridge basalts (MORB) (−0.43 ± 0.17) and altered MORB (−0.76 to −0.11). In addition, the δ41K values of eclogites show a positive correlation with both K2O contents and K/Nb ratios, which suggests that the low δ41K values were most likely caused by dehydration during subduction. Thus, isotopically heavy K may be released into the mantle wedge, while the light component is subducted into the deep mantle. Therefore, the K isotope systems have the potential to trace subducted crustal materials and to create heterogeneity within the mantle. Mineral separates from Sumdo eclogites are highly heterogeneous in K isotopic compositions, ranging from −0.98 to +0.23 in phengite, from −1.25 to −1.10 in omphacite and from −1.16 to −0.09 in amphibole. The K isotope fractionations between amphibole and phengite and between amphibole and omphacite vary from −0.30 to +0.25 and from −0.04 to +0.63, respectively, indicating K isotopic disequilibrium between amphibole and omphacite/phengite, which might result from the multistage growth of minerals during subduction metamorphism. However, generally phengites show heavier K isotopic compositions than the coexisting omphacite (Δ41Kphengite-amphibole = +0.25) and amphibole (Δ41Kphengite-amphibole = +0.03 ∼ +0.30, except TB193 is −0.25), which may imply that the K isotopic fractionation is controlled by the difference in coordination numbers of K between phengite (6) and omphacite (7 to 8)/amphibole (8).

Calcium isotopes can potentially be used to trace many geological processes. Characterizing the Ca isotopic compositions of marine sediments is a precondition for using Ca isotopes to trace the recycling of marine sediments into the mantle and mantle-derived rocks. The best way to achieve this goal is to investigate different types of marine sediments that are adjacent to subduction zones and would undergo subduction in the future. Here, we present high-precision Ca isotopic data for marine sediments from the Deep Sea Drilling Project (DSDP) Sites 543 and 144 along the Lesser Antilles forearc region, to constrain the Ca isotope signatures of marine sediments with various components and assess their possible effects on δ44/40Ca of the local mantle and arc lavas via subduction. Our results show that the δ44/40Ca values of these marine sediments vary from 0.10 to 1.21‰ and depend on lithology. Carbonate-rich sediments from Site 144 exhibit δ44/40Ca values in the range of 0.10–0.58‰ with a weighted average value of 0.36‰, which is ∼0.6‰ lower than that of the mantle. In comparison, δ44/40Ca of clay-rich sediments from Site 543 range from 0.79 to 1.21‰ with a mantle-like mean value of 0.96‰. The data obtained here suggest that carbonate- and clay-rich marine sediments differ significantly both in Ca isotopic compositions and CaO contents. Recycling of these sediments will result in different effects on the isotopic compositions of the local mantle and probably affect the local arc lavas. Specifically, carbonate-rich sediments from Site 144 with high CaO contents and light Ca isotopic compositions can alter the local mantle to lower δ44/40Ca signatures, which is expected in the southern Lesser Antilles arc lavas.

Levulinic acid (LA) is an important biomass-based chemical. The preparation of LA from bagasse is of great practical significance for the comprehensive and efficient utilization of biomass. Biomass bagasse is mainly composed of cellulose, hemicellulose, and lignin. The cellulose is mainly degraded to glucose, and hemicellulose is mainly degraded to xylose, with dilute acid treatment at high temperature. In this research, we produced the LA from bagasse with dilute acid treatment at high temperature. The influences of residence time (10–60 min), reaction temperature (170–240 °C), liquid-to-solid ratio (5:1–25:1 mL/g), and acid concentration (1–5%) on the synthesis of LA were investigated by statistical methods, achieving a maximum LA yield of 16.25%. Additionally, LA was isolated and extracted from bagasses hydrolysate by ion exchange and vacuum distillation. The adsorption capacity of different resins was determined and compared. The optimal resin to acquire better adsorption capacity was determined. The better adsorption capacity was obtained when the D301 resin was selected as the filter for ion exchange. The height-to-diameter rate, eluent flow rate, elution volume of ion exchange column were 10, 0.84 BV/h, 56.4 mL, respectively. The eluent was then distilled under vacuum, collecting the components at 130–140 °C. The total yield and purity of LA were 67.1% and 78%, respectively.

We report a Ni-foam-structured MoNi4-MoOx nanocomposite catalyst derived from NiMoO4 spinel in situ grown on Ni-foam, which is highly active, selective (>93%) and stable for the gas-phase hydrogenation of dimethyl oxalate to ethanol. Such a reaction proceeds mainly through ethylene glycol formation, whereas a pathway through methyl acetate (MA) formation also occurs. Catalyst activity and selectivity are primarily governed by the MoNi4 nanoalloy but can be further improved by an MoOx modifier, due to the synergistic MoNi4-MoOx interaction that markedly promotes the MA hydrogenation to EtOH.

The photophysical properties of two previously synthesized, highly efficient, bright red emitting complexes [Eu(btfa)3DPEPO] (CIE, 0.672; 0.326) (Eu-1) and [Eu(nta)3DPEPO] (CIE, 0.673; 0.326) (Eu-2) (btfa = 4,4,4-trifluoro-1-phenyl-1,3-butanedione, nta = 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione and DPEPO = bis(2-(diphenylphosphino)phenyl)ether oxide) are reported. The complexes have been used as dopants to fabricate several single and double emitting layer (EML) electroluminescent (EL) devices. At the optimum doping concentration of 4 wt%, the single EML device of Eu-1 exhibited a pure red color with an external quantum efficiency (EQE) of 2.9% and a maximum brightness (B) = 1320 cd m−2, maximum current efficiency (ηc) = 4.08 cd A−1, maximum power efficiency (ηp) = 3.37 lm W−1 with a very low turn-on voltage (Vturn-on) = 3.8 V. Importantly, the single EML device of Eu-2 at the optimum doping concentration exhibited pure red EL with EQE of 6.0% with the best EL performance: B = 2108 cd m−2, ηc = 8.45 cd A−1, and ηp = 6.98 lm W−1 at a very low Vturn-on = 3.5 V. The performances of this device are among the best reported for devices incorporating a europium complex as a red emitter. Furthermore, the EL performances were achieved at the current density of 10 mA cm−2, thereby alleviating a serious efficiency roll-off as a major obstacle to the development of Eu-complex based EL devices.

A new homodinuclear complex [Eu(btfa)3]2bpm (1) was synthesized incorporating 4,4,4-trifluoro-1-phenyl-1,3-butanedione (btfa) as the primary and 2,2′-bipyrimidine (bpm) as the auxiliary ligand. The complex was characterized by analytical and spectroscopic techniques, with special emphasis on the crystal structure and photoluminescence (PL) properties, both experimentally and theoretically. Single crystal X-ray diffraction (SCXRD) analysis reveals that the two Eu(III) ions in 1 are eight coordinate, where the bpm behaves as a N4 donor linking the two Eu(III) ions symmetrically. Each Eu(III) ion displays a distorted square antiprismatic (DSAP, D4d) coordination geometry. Complex 1 displayed bright red emission with (CIE)x,y color coordinates = 0.670; 0.330 and an absolute photoluminescence quantum yield (PLQY) of 54.4%. The theoretical intensity parameters (Ω2 and Ω4), radiative (AR) and non-radiative (ANR) decay rates, intrinsic quantum yield (QEuEu), sensitization efficiency (ηsen) and PLQY were assessed using the LUMPAC software and showed very good agreement with the experimental values. Based on these, an energy transfer (ET) mechanism is proposed and discussed. Moreover, 1 was used as an emitter to fabricate single- and double-emitting layer (EML) red-emitting electroluminescent devices. Double-EML device at the optimum doping concentration of 4.0 wt% displayed impressive EL performances, brightness (B) = 812 cd m−2, maximum current efficiency (ηc) = 3.97 cd A−1, maximum power efficiency (ηp) = 3.89 lm W−1, and external quantum efficiency (EQE) = 2.8% at very low Vturn-on = 3.2 V with (CIE)x,y = 0.662, 0.321 which is close to the standard red color recommended by NTSC (0.67, 0.33).

In this study, an efficient device design strategy in improving the performances of blue fluorescent electroluminescence was demonstrated by co-doping 9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole (CzSi) into a light-emitting layer (EML) as an electron transport ladder. 9,10-Bis[4-(6-methylbenzothiazol-2-yl)phenyl]anthracene (DBzA) and 4,4′,4′′-tris(carbazol-9-yl)triphenylamine (TcTa) were utilized as the emitter and the main host material, respectively. Compared with the device without CzSi, the performances of the co-doped device were improved effectively because of the well-matched energy levels and excellent electron transport ability of CzSi, which facilitated the injection of electrons and thus balanced the distribution of carriers. The feasibility of this device design strategy was demonstrated by investigating single-carrier devices, transient electroluminescent (EL) spectra and normalized EL spectra. Finally, the optimal pure blue fluorescent device realized a maximum brightness, current efficiency, power efficiency and external quantum efficiency (EQE) of up to 28 009 cd m−2, 7.51 cd A−1, 7.60 lm W−1 and 6.8%, respectively. Even at a high brightness of 1000 cd m−2, current efficiency and EQE as high as 6.21 cd A−1 and 5.6%, respectively, can still be retained by the same device.

Summary Large-scale shale gas exploitation greatly enriches ethane resources, making the oxidative dehydrogenation of ethane to ethylene quite fascinating, but the qualified catalyst with unique combination of enhanced activity/selectivity, enhanced heat transfer, and low pressure drop presents a grand challenge. Herein, a high-performance Nb2O5-NiO/Ni-foam catalyst engineered from nano- to macroscale for this reaction is tailored by finely tuning the performance-relevant Nb2O5-NiO interaction that is strongly dependent on NiO-precursor morphology. Three NiO-precursors of different morphologies (clump, rod, and nanosheet) were directly grown onto Ni-foam followed by Nb2O5 modification to obtain the catalyst products. Notably, the one from the NiO-precursor of nanosheet achieves the highest ethylene yield, in nature, because of markedly diminished unselective oxygen species due to enhanced interaction between Nb2O5 and NiO nanosheet. An advanced catalyst is developed by further thinning the NiO-precursor nanosheet, which achieves 60% conversion with 80% selectivity and is stable for at least 240 h., Graphical Abstract, Highlights • A series of Nb2O5-NiO/Ni-foam catalysts are developed for the ODE reaction • Catalysts are obtained by Nb2O5 modification of NiO-precursors grown onto Ni-foam • Thinning NiO-precursors dramatically improves the ethylene selectivity • Non-selective O2- species are markedly reduced with enhanced Nb2O5-NiO interaction, Catalysis; Organic Reaction; Nanomaterials; Nanostructure

Methyl glycolate (MG) is a versatile platform molecule to produce numerous important chemicals and materials, especially new-generation biocompatible and biodegradable poly(glycolic acid). In principle, it can be massively produced from syngas (CO + H2) via gas-phase hydrogenation of CO-derived dimethyl oxalate (DMO), but the groundbreaking catalyst represents a grand challenge. Here, we report the discovery of a Ni-foam-structured nanoporous Ni3P catalyst, evolutionarily transformed from a Ni2P/Ni-foam engineered from nano- to macro-scale, being capable of nearly fully converting DMO into MG at >95% selectivity and stable for at least 1000 h without any sign of deactivation. As revealed by kinetic experiments and theoretical calculations, in comparison with Ni2P, Ni3P achieves a higher surface electron density that is favorable for MG adsorption in a molecular manner rather than in a dissociative manner and has much higher activation energy for MG hydrogenation to ethylene glycol (EG), thereby markedly suppressing its overhydrogenation to EG.

Enrichments in light REE without concomitant enrichments in high-field-strength elements in mantle peridotites are usually attributed to inputs from carbonate-rich melts and referred to as ‘carbonatite’ metasomatism as opposed to interaction with evolved silicate melts. Alternatively, both enrichment types are ascribed to percolating volatile-bearing mafic liquids whose chemical signatures evolve from ‘silicate’ to ‘carbonatite’. Here we compare these models for peridotites in which these enrichment types are combined, as may be common in the mantle. We report new Ca-Sr-Nd isotope and chemical data for lherzolite and harzburgite xenoliths from Spitsbergen that were metasomatized, first, by silicate, then by carbonate-rich melts that formed carbonate-bearing pockets replacing earlier minerals. Seven crushed samples were treated with acetic acid that dissolved carbonates formed in the latest event, but not silicates. The leachates (acid-removed carbonates making up 0.6–1.4% of total sample mass) contain much more Sr than the residues after leaching (277–2923 vs. 16–60 ppm), have a greater overall 87Sr/86Sr range (0.7049–0.7141 vs. 0.7036–0.7055) and higher 87Sr/86Sr in each sample than the residues. The leachates have lower δ44/40Ca range (0.17–0.68‰) than the residues (0.78–1.00‰), as well as lower δ44/40Ca than the residues in all samples but one. By and large, the carbonates are out of Ca-Sr isotope equilibrium with the host peridotites implying that the older silicate and younger carbonatite metasomatism were produced by different parental melts, thus supporting the existence of distinctive carbonate-rich metasomatic media in the lithospheric mantle, possibly including recycled materials. The δ44/40Ca in the leachates (i.e. carbonates, 0.17–0.68‰) are well below bulk silicate Earth (BSE) estimates (0.94 ± 0.05‰) and δ44/40Ca in non-metasomatized melt-depleted mantle. Yet, δ44/40Ca in the non-leached whole rock (WR) carbonate-bearing samples (0.75–0.95‰) fall within, or are only slightly lower than, the BSE range. The 87Sr/86Sr range in these WR samples (0.7030–0.7112) includes very high values for peridotites with large aggregates of dolomite and Mg-calcite. It appears that both carbonatite and silicate metasomatism may produce δ44/40Ca values lower than the BSE such that Ca-isotope data cannot robustly tell apart these two enrichment types, yet carbonatite metasomatism may yield the lowest δ44/40Ca. Carbonates, even at small mass fractions, are significant hosts of Sr in the WR Spitsbergen peridotites (8–51 wt.% of Sr mass) because of very high Sr concentrations, but add little to WR Ca balance (3–12 wt.%). As a result, high Sr content and 87Sr/86Sr ratios may be indices (though not definitive proofs) of carbonatite metasomatism in mantle rocks.

Scheelite has been analyzed from the Shizhuyuan and the Xianglushan world-class W deposits from the Nanling W–Sn region and Jiangnan W belt, respectively. The Shizhuyuan deposit consists of proximal skarn and greisen W–Sn–Mo–Bi and distal Pb–Zn–Ag veins. The Xianglushan deposit, contains layer-like sulfide–scheelite and skarn W orebodies on granite cupolas overprinted by W greisen veins. Scheelite in skarn ores from the Shizhuyuan contains higher concentrations of Mo than those in the sulfide–scheelite and skarn ores from the Xianglushan deposit, reflecting differences between oxidizing and reducing magmatic-hydrothermal fluids. Under oxidizing conditions, W is accompanied by Mo partitions into exsolved fluids to form W–Mo garnet skarns, whereas under reducing conditions, little Mo is carried by exsolved fluids to form W pyroxene skarns. Trace element patterns of scheelite from both deposits show negative Ba, Sr, Zr, and Ti, and positive Ta anomalies. Rare earth element (REE)patterns of scheelite within skarns from the Shizhuyuan deposit have negatively inclined and flat M-type tetrad patterns, and scheelite from the greisens displays flat and positively inclined M-type tetrad patterns. We infer that the fluids formed scheelite within the W skarns and greisens inherited parental magma trace element and REE characteristics (depleted Ba, Sr, Zr, and Ti, enriched Ta, negative Eu anomalies, and tetrad effects). Whereas, scheelite from sulfide–scheelite veins and skarns of the Xianglushan deposit also has W- and MW-type tetrad REE patterns. The W-type tetrad REE patterns are complementary to REE patterns from the Renjiashan granite, and the MW-type tetrad REE patterns occur during a single evolutionary stage within a complex hydrothermal environment. Sulfide mineralization can form after or before W skarns (the former like Shizhuyuan deposit and the latter like Xianglushan deposit). The formation conditions of the latter included reducing conditions and sulfide firstly supersaturated in the melt, resulting in sulfide drops which carried W aggregated on the cupolas. W skarns and greisens in both deposits underwent generally successive processes related to water supersaturation in the melt. Following a temperature decrease and crystallization, bubbles carried material changing from Si and metal to Si oxide complexes.

The food source of hadal endemic fauna provides an insight into the carbon cycle in trenches and a biological adaptation to the impoverished and harsh trench environment. Here, we present the first Delta C-14 results of hadal amphipods from three trenches in the Pacific to define the organic matter source in these remote ecosystems. Amphipod muscle tissues contain a bomb C-14 signature (Delta C-14 from 10 +/- 2 parts per thousand to 65 +/- 2 parts per thousand), thereby revealing a dietary preference for labile and fresh organic matter derived from the surface water. Thus, the carbon cycle in the deepest ocean trench has a tight linkage with the surface ocean via the food chain. The bomb C-14 dating result suggests that hadal amphipods have a low tissue turnover rate and an unexpectedly long lifetime (>10 years), at more than 4 times higher than the common longevity (similar to 2 years) of amphipods in shallow waters. Plain Language Summary Hadal trenches (depth > 6,000 m) are the remotest and the least explored places on our planet, with characteristics of low temperatures, high pressure, limited food, and frequent geological activity. Knowing the source of organic matter for hadal life is key in understanding the ocean carbon cycle and the biological adaptation in trenches. We report the first C-14 results of hadal amphipods from three trenches in the West Pacific, including the deepest ocean trench, Mariana, which indicates that the organic matter for amphipods is mostly from the surface water. This tight linkage between the organic matter within the hadal fauna and in surface water points out that the anthropogenic pollution can reach the deepest ocean trench rapidly via the food chain. Moreover, the bomb C-14 dating method can be applied to hadal amphipods, thereby suggesting a low tissue turnover rate and an unexpectedly long lifetime, which might be a result of an adaptation to the impoverished and harsh environment.

The Dongyuan deposit, in the recently identified world-class porphyry–skarn W metallogenic belt, east Jiangnan Orogen, China, is characterized by a set of nearly parallel and horizontal multi-cycle orebodies within cupolas of porphyritic granodiorite. Almost every orebody from the top to the bottom shows similar vertical changes in vein morphology and mineral assemblage from ≤1 cm quartz–feldspar–scheelite–calcite veins to 1–2 cm quartz–feldspar–muscovite–scheelite veins to 2–5 cm quartz–feldspar–muscovite–scheelite veins to ≥5 cm quartz veins. From the bottom to the top of each orebody in every cycle, the mole number of AlIV in K-feldspar decreases, the concentrations of Mn2+ in calcite increases, and the mole number of OH− in muscovite decreases. These changes reflect repetitive fluctuations in the concentrations of major elements that were involved in the precipitation of minerals as well as the physicochemical conditions of fluids during vein formation in the multi-cycle orebodies. The concentrations of Mo are obviously lower in pyrite from the middle orebodies than in the top and bottom orebodies. Our data indicate that the ore-forming fluids were sourced from multi-batch fluids that were exsolved from magma. The ΣLREE/ΣHREE ratios in the scheelite decrease from the upper to lower orebodies. Similar trends are found within a single orebody from the top to the bottom of veins. These trends were due to feldspar fractionation in the magmas and ore-forming fluids, respectively, because the crystallization of feldspar tends to capture LREEs. Therefore, the following model is proposed for the formation of the Dongyuan porphyry W deposit: the magma crystallized first at the roof of the intrusion, causing the underlying magmas to become oversaturated in H2O; the exsolved H2O then accumulated at the boundary between the crystallized upper part and the underlying magmas; as fluid pressures increased, cracks formed in the overlying crystallized granodiorite, and as a consequence the first cycle of vein networks was formed. This process was repeated as the interface between magma and crystallized rock moved downwards, thus forming the multi-cycle W orebodies that are embedded in the pluton.

Dihydroartemisinin (DHA) has been shown to be capable of inhibiting cancer growth, whereas it remains largely elusive that the underlying molecular mechanism of DHA induced acute myeloid leukemia (AML) cell death. In the present study, we examined the effects of DHA on the proliferation and ferroptosis of AML cells as well as to elucidate the underlying molecular mechanisms. We found that DHA strongly inhibited the viability of AML cell lines and arrest cell cycle at G0/G1 phase. Further studies found that DHA effectively induced AML cells ferroptosis, which was iron-dependent and accompanied by mitochondrial dysfunction. Mechanistically, DHA induced autophagy by regulating the activity of AMPK/mTOR/p70S6k signaling pathway, which accelerated the degradation of ferritin, increased the labile iron pool, promoted the accumulation of cellular ROS and eventually led to ferroptotic cell death. Over expression of ISCU (Iron-sulfur cluster assembly enzyme, a mitochondrial protein) significantly attenuated DHA induced ferroptosis by regulating iron metabolism, rescuing the mitochondrial function and increasing the level of GSH. Meanwhile, FTH reconstituted AML cells also exhibited the reduced lipid peroxides content and restored the DHA-induced ferroptosis. In summary, these results provide experimental evidences on the detailed mechanism of DHA-induced ferroptosis and reveal that DHA might represent a promising therapeutic agent to preferentially target AML cells.

Two new mixed ligand complexes [Eu(tfac)3(DPEPO)] (Eu-1) and [Tb(tfac)3(DPEPO)] (Tb-2) incorporating trifluoroacetylacetone (Htfac) and bis(2-(diphenylphosphino)phenyl)ether oxide (DPEPO) were synthesized in gram-scale quantities and used as emitters to fabricate single- and double-EML (light-emitting layer) electroluminescence (EL) devices. The single-EML device with the structure: ITO/HAT-CN (6 nm)/HAT-CN (0.2 wt%):TAPC (50 nm)/Eu-1 (1–6 wt%): 26DCzPPy (10 nm)/Tm3PyP26PyB (50 nm)/LiF (1 nm)/Al (100 nm) showed light red (CIE, x: 0.574; y: 0.275) emission for the Eu-1 based EL devices due to the presence of a host emission with a brightness of 1274 cd m−2, current efficiency (ηc), power efficiency (ηp) and external quantum efficiency (EQE) of 0.58 cd A−1, 0.68 lm W−1, and 0.70%, respectively. The single-EML device for the Tb-2 complex with the same device structure displayed white-light emission. The optimized single-EML device of Tb-2 with 14.0 wt% doping concentration showed an impressive EL performance with brightness of 1637 cd m−2, ηc ≈ 3.05 cd A−1, ηp ≈ 2.80 lm W−1, EQE ≈ 1.4%, Vturn-on ≈ 3.1 V, respectively. This is the first report of single component white organic light emitting diode (W-OLED) fabricated from an organo-Tb(III) complex. The W-OLEDs show low turn-on voltages (Vturn-on) ≈ 3.1 V and are thus advantageous in lowering the power consumption of the OLED display.

Chemical looping concept paves way toward intrinsically safe and efficient oxidative coupling of methane (CL-OCM) process, because it permits the reaction to proceed via repeating reduction-oxidation cycle in two reactors. It is calling for a ground-breaking catalyst with enough high selective CH4-converting lattice-oxygen carrying capacity but represents a grand challenge. Herein, we report an efficient catalyst obtainable by decorating an oxygen carrier FeMnO3 with Na2WO4, with good cycling performance, achieving a high space time yield of 29.8 gC2-C3 kgcat.-1 h-1 with 20% CH4 conversion and 80% C2-C3 selectivity at 800 oC and a low catalyst/CH4 weight ratio of 13.5. CL-OCM process is established by “FeMnO3↔[MnFe2O4 + MnO]” red-ox cycle. Na2WO4-decoration gets lattice oxygen stored in FeMnO3 transformed from non-selective to selective due to mitigation of lattice-oxygen evolution. Scaled up CL-OCM testing with 10-gram catalyst also yields comparable results seen in the case of using 1-gram catalyst, validating great application potential.

The MnOx-Na2WO4 catalyst for oxidative coupling of methane (OCM) is highly attractive but its high light-off temperature (>800 °C) is a major obstacle for commercialization. In-depth understanding of reaction light-off relevant chemistry is particularly desirable. We explored the OCM light-off over several metal-oxide-supported MnOx-Na2WO4 catalysts. As CH4 conversion above 15% with acceptable C2-3 selectivity is considered as the sign of OCM light-off, support-dependent OCM light-off is clearly observed over MnOx-Na2WO4 supported on SnO2 (660 °C), TiO2 (670 °C), MgO (690 °C), and ZnO (720 °C), being tightly linked with the redox rate of Mn3+(or Mn4+) ↔ Mn2+ cycle governed by support oxides.

Fullerene molecules have attracted considerable interest because of the unique curved aromatic π-conjugated systems. However, the complicated and costly technologies for purification of highly pure fullerenes hamper easy access to these attractive molecules and consequently limit most of the fullerene applications. Here, we report the discovery of a carcerand-like cage acting as a stand-alone host for efficient separation and purification of C60 and C70 from fullerene soot. The cage, built through the self-assembly of metal coordination, is capable of quantitatively encapsulating fullerenes C60 and C70. The fullerene complexes are highly stable at high temperatures because of the small crevices with precisely defined sizes, multiple favorable CH−π interactions, and concave–convex aromatic interaction between fullerenes and corannulenes. Importantly, the carcerand-like cage shows a temperature-dependent selective binding preference for C60 over C70, which allows us to develop an efficient and green procedu...

The Dunde iron–zinc deposit is a typical submarine volcanogenic iron oxide deposit in the eastern Awulale Metallogenic Belt of the western Tianshan. We report new petrography, rare earth elements (REE), and fluid inclusion microthermometry and C–O–Sr isotopes of the calcite from the skarn and the magnetite ores from the Dunde deposit. Calcite from both the skarn and magnetite ores displays high LREE/HREE (44–172), implying significant REE fractionation. We infer that the complexation of Cl (± F) during the fluid circulation and mineralogical control of calcite at the depositional sites were important for the LREE enrichment in the Dunde calcite. The restricted Y/Ho (26.7–32.1) suggests that calcite in the skarn and magnetite ores was co-genetic and the superchondritic Y/Ho may have resulted from the preferential incorporation of Y over Ho in calcite. Positive Eu anomaly (1.23–1.63) of the skarn calcite may have been inherited from the parental fluids, while the negative or slightly positive anomaly (0.65–1.04) of the magnetite ore calcite may have been resulted from the high Sr2 + content that suppressed Eu2 + in calcite. Fluid inclusion microthermometric results exhibit a wide range of homogenization temperatures (106 °C–364 °C) and salinities (0.2 wt.%–41.5 wt.% NaCl equiv.). Three kinds of ore-forming fluids can be distinguished, i.e., high-salinity (> 35 wt.% NaCl equiv.), medium-salinity (10 wt.%–35 wt.% NaCl equiv.) and low-salinity (< 10 wt.% NaCl equiv.) fluids. The high-salinity fluid was likely to be magma-derived and occurred in both the skarn- and magnetite ore calcite. The low-salinity fluid, possibly seawater-derived, was found only in the skarn calcite. The medium-salinity fluid, mainly of CaCl2–H2O aqueous- and brine-featured fluids, may have been the product of the fluid–rock interactions as the magmatic fluids and seawater circulated through the strata. The Dunde calcite has δ13C comparable to marine carbonates, but δ18O substantially lower, suggesting possibly a result of limestone dissolution. Calculated δ18O of the fluids in equilibrium with calcite vary from − 0.78‰ to 5.46‰ (− 0.78‰–1.85‰ and 2.15‰–5.46‰ for skarn calcite and magnetite ore calcite, respectively), implying magmatic fluids and seawater mixing. The Dunde calcite 87Sr/86Sr (0.7071 to 0.7078) correlate positively with 1/Sr, implying that two sources, i.e., basaltic/andesitic volcanic wall rocks (87Sr/86Sr: 0.7056–0.7066) and limestones/seawater (87Sr/86Sr: 0.7075–0.7089), may have been involved in the mineralization. Mass-balance calculation between fresh basaltic tuff and its neighboring skarn showed that extra Ca, Mg and Fe were added to the basaltic tuff during the hydrothermal alteration. The limestone dissolution during the fluid–rock interactions may have added Ca to the ore-forming fluids, while Fe and Mg may have been introduced from the deep-seated magmatic system via the heated Cl-rich fluid circulation.

Objective: This study aims to analyze the effect of lyophilized recombinant human brain natriuretic peptide on the endothelial function of patients with acute myocardial infarction. Methods: One hundred and thirty-six patients with acute myocardial infarction in our hospital were randomly divided into a control group and an experimental group (68 cases each). The patients in the control group were treated by conventional treatment. The patients in the experimental group were treated with lyophilized recombinant human brain natriuretic peptide besides the conventional treatment. The levels of flow-mediated dilatation (FMD), serum nitric oxide (NO), and endothelin-1 were compared between the two groups before and after treatment. Results: Before treatment, there was no significant difference between the two groups in the level of FMD (P>0.05); after treatment, the level of FMD in the experimental group was higher than that in the control group, and the difference was statistically significant (P0.05); after treatment, the levels of serum NO and endothelin-1 in the experimental group significantly improved, which were better than those in the control group (P

Diffuse large B-cell lymphoma (DLBCL) is the most common subtype of lymphoma, accounting for approximately 30% to 40% of non-Hodgkin’s lymphomas (NHL). The administration of rituximab significantly improved the outcomes of DLBCL; however, the unavoidable development of resistance limits the long-term efficacy. Therefore, a new generation of less toxic drugs with higher chemotherapy response is required to prevent or reverse chemoresistance. TEOA is a pentacyclic triterpenoid compound isolated from the roots of Actinidia eriantha. Studies have confirmed that TEOA has significant cytotoxicity on gastrointestinal cancer cells. However, there are no relevant reports on DLBCL cells. In this study, we investigated the potential molecular mechanism of the anticancer activity of TEOA in DLBCL cells. The results demonstrated that TEOA inhibited proliferation and induced apoptosis in time-and dose-dependent manners. TEOA induced reactive oxygen species (ROS) generation, which was reversed by N-acetyl cysteine (NAC). TEOA induced DNA damage, increased the level of γ-H2AX, and the phosphorylation of CHK1 and CHK2. In addition, TEOA induced the activation of the p38 MAPK pathway and pretreated with p38 inhibitor SB20358 or ROS scavenger could block TEOA-induced DNA damage. Taken together, these results suggest that ROS mediated activation of the p38 MAPK signal pathway plays an important role in initiating TEOA-induced DNA damage.

The kinetics of serpentinization were investigated at 400–500 °C and 3.0–20 kbar using natural olivine and peridotite for run durations of 9–38 days. The serpentine varieties were lizardite for all the experiments. The serpentinization kinetics at 400 °C and 3.0 kbar and at 500 °C and 20 kbar displayed a sigmoidal kinetic behavior, with very sluggish reaction rates at the early stage of serpentinization, followed by a sudden increase in the reaction rates. They were 1–2 orders of magnitude faster than serpentinization kinetics commonly used for modeling serpentinization-related processes. Pressure greatly increases the rates of peridotite serpentinization at 500 °C, e.g., 19% of reaction extent was achieved within 20 days for experiments at 500 °C and 3.0 kbar with starting grain sizes of

Phosphorescent organic light emitting diodes (PHOLEDs) have been fabricated with structure of indium tin oxide/MoO3 doped 4,4′-N,N'-dicarbazole-biphenyl (CBP) 30 nm/tris(4-carbazoyl-9-ylphenyl)amine 10 nm/CBP doped with tris(2-phenylpyridine)iridium(III) (CBP:Ir(ppy)3) x/bathocuproine 50 nm/LiF 1 nm/Al, where x = 2.5, 5, 10, and 20 nm, respectively. The current efficiency (CE) of device with x = 10 nm is higher than those with x = 2.5 and 5 nm, mostly because the width of exciton formation zone (5.7 nm) with x = 10 nm is larger than those (2.5 and 5 nm) with x = 2.5 and 5 nm. However, the current density with x = 10 nm decreases than those with x = 2.5 and 5 nm at a certain driving voltage, since the ~ 4.3 nm CBP:Ir(ppy)3 accommodating no exciton formation with x = 10 nm plays a role of transporting holes, raising ohmic loss of hole and thereby increasing driving voltage. When x increases from 10 to 20 nm, the width of exciton formation zone rises from 5.7 to 6.8 nm with CE almost unchanged, and the current density decreases as a result of increased ohmic loss of hole. The current research is useful to develop high-efficiency and low-driving voltage PHOLEDs.

Application of microbial fermentation of xylose to produce xylitol can not only turn waste into useful products and conserve resources, but also protect the environment. Currently, more than 100 kinds of microorganisms are known to ferment xylose, among which Candida tropicalis has strong xylose conversion ability and high tolerance to inhibitors such as furfural, acetate, and phenolics in xylose mother liquor. The present study focused on fermenting xylose hydrolysate from sugarcane bagasse to produce xylitol using C. tropicalis strain 31949. The effects of inoculum age, inoculum quantity, and initial xylose concentration on xylitol fermentation by C. tropicalis 31949 were discussed. The following optimum fermentation conditions were determined: inoculum quantity, 10%; inoculum age, 26 h; and initial xylose concentration, 100 g/L. Under these optimal fermentation conditions, C. tropicalis 31949 could ferment sugarcane bagasse hydrolysate, which was pretreated by vacuum concentration and activated carbon detoxification decoloration, to produce 62.9800 g/L xylitol.

The newly discovered giant Dahutang W–Cu–Mo deposit in the central part of the Jiangnan Orogen hosts an estimated resource of 1.1 million tons (Mt) of WO3, plus a proven resource of 0.65 Mt Cu and 0.08 Mt Mo. The Dahutang deposit is temporally and spatially associated with the Late Mesozoic S-type granites emplaced into the Neoproterozoic Jiuling granodiorite batholith and the Shuangqiaoshan Group. Based on petrographic observations, eight hydrothermal alteration/mineralization stages have been recognized, comprising pegmatitic (Stage I), potassic alteration (Stage II), albite alteration (Stage III), greisenization and main mineralization (Stage IV), polymetallic sulfide mineralization (Stage V), late scheelite mineralization (Stage VI), carbonate alteration (Stage VII) and supergene alteration (Stage VIII). Stage IV can be further divided into the early greisenization (Stage IV-A), the main wolframite mineralization (Stage IV-B) and the main scheelite mineralization (Stage IV-C). Fluid inclusion and H–O isotope analyses on nine Stage IV to VII ore/gangue minerals (wolframite, cassiterite, scheelite, sphalerite, fluorapatite, fluorite, quartz, calcite and chlorite) suggest the presence of an early W and a late Cu–Mo ore-forming fluid system. The early ore-forming fluids belong to a medium to high temperature (200°–420 °C), low salinity H2O–NaCl–CaCl2 system. This primary magmatic-hydrothermal fluid (δ18Ofluid = 5.4 to 8.8‰ and δD = −102 to −75‰) was likely exsolved from the Late Jurassic granites at Dahutang. Wolframite and scheelite coexist closely with fluorapatite and fluorite, respectively, indicating that the volatile-rich fluids at Dahutang were also rich in tungsten, fluorine and phosphorous. Tungsten was likely transported as tungstate species (e.g., WO42− and HWO4−), oxygen fluorine complexes (e.g., [WO2F4]2−, [WO3F2]2−) and phosphorous heteropolytungstate (e.g., [P(W12O40)]3−) in the fluids. Fluorapatite and wolframite may have precipitated first when the temperature dropped from 400° to 320 °C (along with pH increase) at an estimated depth of 7.8 km. This was likely followed by the extensive scheelite mineralization (with fluorite precipitation) that formed huge disseminated/veinlet-type W orebodies when the temperature further dropped to 200 °C (along with pH increase). After the W mineralization, extensive Cu–Mo polymetallic mineralization and the associated sericite-chlorite alterations may have formed by the granite porphyry and/or muscovite granite emplacement. The late ore-forming fluids belong to a medium to high temperature (200°–360 °C), low salinity H2O–NaCl–CaCl2 system. Molybdenum was likely transported mainly as Mo complexes (e.g., H2MoO4/MoO42−), and copper as Cu–Cl complexes. Molybdenite and chalcopyrite may have begun to precipitate when the fluids ascended and the temperature dropped to 330 °C. Meteoric water incursion may have then occurred (δ18Ofluid = 1.9–6.9‰ and δD = −99 to −68‰) and further cooled the fluid system to 250 °C, forming large Cu–Mo orebodies.

Magnesite (MgCO3) is a likely main host of carbonates in the mantle and plays an important role in the transport and storage of carbon in the Earth's mantle. Its physical properties at high pressure and high temperature (PT) are crucial for understanding the deep carbon cycle. Here we investigated thermodynamic and elastic properties of magnesite under the mantle PT conditions using first-principles calculations with local density approximation (LDA). Magnesite has the seismic velocities close to those of forsterite. The effect of the magnesite on seismic velocity of the carbonated peridotite and eclogite is subtle in the upper mantle. However, magnesite has much smaller seismic velocities and far larger elastic anisotropy than major minerals in the transition zone and lower mantle. The enrichment of magnesite in the transition zone and lower mantle will likely produce seismically detectable low-velocity zone and velocity anisotropy.

Ethnopharmacological relevance The root of Rosa roxburghii Tratt (Ci Li Gen) is a kind of Chinese ethnomedicine in Gui Zhou province, used for the treatment of abdominal pain, acute bacillary dysentery, gastroenteritis and other diseases in human and livestock. Aim of the study The aim of this study was to isolate and identify the effective antimicrobial components from the ethyl acetate extract of the Ci Li Gen and to investigate its antimicrobial mechanism afterwards. Materials and methods The effective antimicrobial components in the ethyl acetate extract from the Ci Li Gen were isolated by high-performance liquid chromatography (HPLC) and identified by high-resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR). The antibacterial activity was evaluated by the minimum inhibition concentration (MIC) measured by microdilution technique. The antibacterial mechanism was investigated by the time-kill curve, sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) combined with NanoLC-ESI-MS/MS, intracellular esterase activity detected by Flow cytometry, and the ultrastructural changes of the Escherichia coli ATCC 25922 observed by scanning electron microscope (SEM). Results The effective antimicrobial component (peak 4) was identified as strictinin isomers by HRMS and NMR. The MIC of strictinin isomers against E. coli was 0.125 mg/mL. With respect to the negative control group, the results of SDS-PAGE and NanoLC-ESI-MS/MS showed that the up-regulated proteins of the strictinin isomers treated group were Metal-binding protein ZinT, 30S ribosomal protein S4 and 50S ribosomal protein L4, while the down-regulated protein was hydroperoxide reductase subunit C. Moreover, in the strictinin isomers treated group, the esterase activity in the E. coli cells was reduced and the bacteria E. coli became atrophied, pitted and contorted, and the surface of E. coli was rough and blurred. Conclusions According to the above results, the antimicrobial mechanism of strictinin isomers against E. coli were oxidative stress and protein synthesis disorder, which inhibited the activity of the enzymes required for bacterial growth and metabolism. These findings reflected the pleiotropic effects of strictinin isomers, making it a promising antimicrobial agent for pharmaceutical research.

Introduction: Coronary artery disease originates from the blockage of the inner walls of the coronary arteries due to a plaque buildup. Accumulating studies have highlighted the role of microRNAs (miRs) delivered by exosomes in the progression of coronary artery disease. Thus, the current study was to elucidate the role and mechanism by which miR-25-3p influences oxidized low density lipoprotein (ox-LDL)-induced coronary vascular endothelial cell (CVEC) inflammation. Methods: Primarily isolated CVECs were treated with ox-LDL to induce inflammation. Atherosclerosis models were induced in ApoE−/− mice and the peripheral blood platelet exosomes (PLT-Exo) were extracted and induced by thrombin, followed by co-culture with CVECs. The relationship between miR-25-3p and A disintegrin and metalloprotease 10 (Adam10) as well as the involvement of the NF-κB signaling pathway was evaluated. In order to evaluate the effect of PLT-Exo containing miR-25-3p on ox-LDL-induced CVEC inflammation, lipid accumulation and fibrosis, miR-25-3p mimic/inhibitor (in vitro), miR-25-3p agomir (in vivo), and si-Adam10 were delivered. Results: MiR-25-3p was expressed poorly in ox-LDL-induced CVECs and vascular tissues but exhibited high levels of expression in thrombin-induced PLT-Exo of atherosclerosis models of ApoE−/− mice. CVECs endocytosed PLT-Exo upregulated the miR-25-3p expression. Adam10 was identified as a target gene of miR-25-3p. The thrombin-induced activated PLT-Exo carrying miR-25-3p reduced Adam10 expression to inhibit ox-LDL-induced CVEC inflammation and lipid deposition through downregulating levels of α-smooth muscle actin, Collagen I a1, Collagen III a1, triglycerides, total cholesterol, interleukin (IL)-1β, IL-6, and tumor necrosis factor-α. Furthermore, the NF-κB signaling pathway participated in the inhibitory effect of PLT-Exo carrying miR-25-3p. Conclusion: Collectively, PLT-Exo overexpressing miR-25-3p attenuates ox-LDL-induced CVEC inflammation in ApoE−/− mouse models of atherosclerosis.

Apatite is ubiquitous in A-type granites, and can be used to elucidate the volatile contents of the silicate melt, which reflect its source characteristics. A-type granites have been recognized as a distinct group of granites. A1- and A2-type subgroups are produced under different extensional settings. However, the details of the mechanisms behind the distinctive geochemical characteristics of A1- and A2-type granites remain obscure. Belts of Cretaceous A1- and A2-type granites occur along the Lower Yangtze River Belt in eastern China. Here we investigated the major and trace element compositions of apatites from contemporary A1- and A2-type granites at different localities along the Lower Yangtze River Belt, in order to decipher their discrepant source processes. Apatites from A1- and A2-type granites show similar major and trace elements, but differ in their F and Cl concentrations. Apatites from A1-type granites in the eastern part of the Lower Yangtze River Belt have much lower F and higher Cl concentrations compared to A2-type granites in the western part. Moreover, from the east to the west, the F concentrations of apatites from A1-type granites increase, while the Cl concentrations decline. In a subducted plate, F is retained by amphibole, chlorite, serpentine and mica minerals through the amphibolite stage, and finally by phengite and lawsonite during the eclogite stage, whereas, Cl is controlled by amphibole, chlorite and serpentine. The high and varied Cl concentrations in A1 subgroup apatites, therefore, may be attributed to the breakdown of amphibole, chlorite and/or serpentine decomposition during partial melting of subducted oceanic crust releasing a large amount of Cl at shallower depth. In contrast, F is transported to deeper depths in the subducted oceanic crust, and released through breakdown of phengite and lawsonite, making an important contribution to the formation of A2-type granites. Apatites from A1- and A2-type granite samples show regular changes in LREE/HREE, LREE/MREE and MREE/HREE ratios with increasing distance from the location of the subduction zone, probably as the result of nonsynchronous dehydration of the serpentine and phengite at different stages during subduction. We propose that A1- and A2-type granites on the Lower Yangtze River Belt were derived from sources metasomatised by fluids originating from the breakdown of amphibole, chlorite and/or serpentine with higher Cl, lower F, and from phengite and/or lawsonite with relatively higher F but lower Cl, respectively.

The Dachang tin-dominant polymetallic district in western South China, hosts a total reserve of 110 Mt ore @ 1% Sn, 3–5% by-products of Zn, Pb, Sb, In and Cu, and 100 to 300 g/t Ag. Economic tin orebodies in the district mainly developed in Devonian limestone, black shale and siliceous rocks, as massive/stratiform and vein/stockwork mineralization. LA-ICP-MS U–Pb dating on seven cassiterite samples from the Tongkeng-Changpo and Gaofeng Sn–Zn–Pb deposits, and the Dafulou, Huile and Kangma Sn–Zn deposits, yields weighted mean 206Pb/238U ages ranging from 90.3 ± 1.8 Ma to 95.4 ± 4.9 Ma. These dates are significantly younger than the Devonian ore-hosted strata, but agree well with the previously published zircon U–Pb ages of 96.6–93.9 Ma for the Longxianggai biotite granite within analytical uncertainties, showing a close temporal link between the granitic magmatism and tin mineralization. Cassiterite grains from various ore types in the Dachang district show clear growth zonations as reflected from their cathodoluminescence images. LA-ICP-MS trace element analyses of cassiterite grains indicate that they have relatively high Ti, Fe and W but low Nb and Ta contents, which corresponds to the clear luminescencing. Chemical variations of cassiterite from different ore types, i.e. cassiterite-sulfide ores and cassiterite-bearing quartz veins, are indistinguishable, except for more enriched Fe in cassiterite from cassiterite-quartz veins. Combined with Cretaceous U–Pb ages, elevated Fe and W contents of cassiterite suggest tin-dominant polymetallic deposits in the Dachang district were formed in a granite-related magmatic-hydrothermal system controlled by the Longxianggai biotite granite, precluding their syngenetic origin.

Mantle peridotites show that Ca is isotopically heterogeneous in Earth's mantle, but the mechanism for such heterogeneity remains obscure. To investigate the effect of partial melting on Ca isotopic fractionation and the mechanism for Ca isotopic heterogeneity in the mantle, we report high-precision Ca isotopic compositions of the normal Mid-Ocean Ridge Basalts (N-MORB) from the southern Juan de Fuca Ridge. Ca-44/40 of these N-MORB samples display a small variation ranging from 0.750.05 to 0.860.03 (relative to NIST SRM 915a, a standard reference material produced by the National Institute of Standards and Technology), which are slightly lower than the estimated Upper Mantle value of 1.050.04 parts per thousand and the Bulk Silicate Earth (BSE) value of 0.94 +/- 0.05 parts per thousand. This phenomenon cannot be explained by fractional crystallization, because olivine and orthopyroxene fractional crystallization has limited influence on Ca-44/40 of N-MORB due to their low CaO contents, while plagioclase fractional crystallization cannot lead to light Ca isotopic compositions of the residue magma. Instead, the lower Ca-44/40 of N-MORB samples compared to their mantle source is most likely caused by partial melting. The offset in Ca-44/40 between N-MORB and BSE indicates that at least 0.1-0.2 parts per thousand fractionation would occur during partial melting and light Ca isotopes are preferred to be enriched in magma melt, which is in accordance with the fact that Ca-44/40 of melt-depleted peridotites are higher than fertile peridotites in literature. Therefore, partial melting is an important process that can decrease Ca-44/40 in basalts and induce Ca isotopic heterogeneity in Earth's mantle.

Applications for l-lactic acid are increasing. Recent studies have investigated inexpensive raw materials for producing l-lactic acid and have explored technical principles. We optimized fermentation conditions for enzymatic hydrolysis of sugarcane bagasse as a substrate for l-lactic acid production, and to achieve a high conversion rate of bagasse to l-lactic acid using Rhizopus oryzae. The maximum conversion rate of l-lactic acid was 28.45% in the conditions of 48-h fermentation time and 200 r/min rotary shaking in 50 mL liquid medium with 10% inoculum. The kinetics of fermentation were worked out. Logistic equations, Luedeking–Piret equations and Luedeking–Piret-like equations were chosen as kinetic models. Three kinetic models were constructed which reflected microbial growth, product synthesis and substrate consumption; R2 of three kinetics model equations, respectively, were 0.9799, 0.9869, 0.9911, which indicated that the predicted values fit the experimental data and the equations accurately describe the fermentation process of R. oryzae Gim3.129 for producing l-lactic acid. The models described the fermentation process of R. oryzae Gim3.129 successfully and provided a theoretical foundation for the industrialization of l-lactic acid from sugarcane bagasse.

The Gaosong Sn–Cu deposit in the Gejiu ore district, SW China, is a large cassiterite–sulfide deposit, hosting total ore reserves of 67.4 Mt @1.3% Sn and 19.0 Mt @1.1% Cu. Two types of mineralization developed in the deposit, i.e. cassiterite-sulfide ore within the proximal skarn in contact with the Gaofengshan biotite granite, and fault-controlled stratiform-like cassiterite–iron oxide ± sulfide ore in the distal carbonate country rock. Cassiterite grains are disseminated in both ores. In situ U–Pb dating of one cassiterite sample from the cassiterite-sulfide ore and two from the cassiterite–iron oxide ± sulfide ore yielded weighted mean 206Pb/238U ages of 84.3 ± 1.4 Ma, 85.1 ± 1.0 Ma and 83.5 ± 2.1 Ma, respectively. The three mineralization ages are consistent with the emplacement age of the Gaofengshan granite (85.8 ± 0.6 Ma) within error, suggesting a close temporal link between tin mineralization and granitic magmatism. Cassiterite grains can be divided into two types based on cathodoluminescence (CL) illustrations, namely euhedral Cst I and veinlet-like Cst II. In the cassiterite–sulfide ore, Cst I has clear oscillatory zonation and is dull luminescing. In the cassiterite–iron oxide ± sulfide ore, Cst I core is dull luminescing (blue in OM−CL) and surrounded by a bright luminescing Cst I rim (yellow in OM−CL). Cst I is replaced by Cst II veinlets with bright luminescing (yellow in OM−CL). The SEM−CL luminescing intensity of cassiterite is mainly controlled by Ti content. Elevated W and Fe but low Nb, Ta, Zr and Hf concentrations of cassiterites from the Gaosong deposit, are distinctly different from those of cassiterites in VMS/SEDEX tin deposits, but similar to those from granite-related tin deposits. The Late Cretaceous crystallization ages and trace element characteristics demonstrate that cassiterites from both ores were formed in a magmatic-hydrothermal system associated with the Gaofengshan granite, and preclude the SEDEX origin of the stratiform-like cassiterite–iron oxide ± sulfide ore.