Water transport to the core–mantle boundary     

Michael J Walter 《国家科学评论(英文版)》2021,8(4)

Water is transported to Earth''s interior in lithospheric slabs at subduction zones. Shallow dehydration fuels hydrous island arc magmatism but some water is transported deeper in cool slab mantle. Further dehydration at ∼700 km may limit deeper transport but hydrated phases in slab crust have considerable capacity for transporting water to the core-mantle boundary. Quantifying how much remains the challenge.

Water can have remarkable effects when exposed to rocks at high pressures and temperatures. It can form new minerals with unique properties and often profoundly affects the physical, transport and rheological properties of nominally anhydrous mantle minerals. It has the ability to drastically reduce the melting point of mantle rocks to produce inviscid and reactive melts, often with extreme chemical flavors, and these melts can alter surrounding mantle with potential long-term geochemical consequences. At the base of the mantle, water can react with core iron to produce a super-oxidized and hydrated phase, FeO₂H_x, with the potential to profoundly alter the mantle and even the surface and atmosphere redox state, but only if enough water can reach such depths [1].Current estimates for bulk mantle water content based on the average H₂O/Ce ratio of oceanic basalts from melt inclusions and the most un-degassed basalts, coupled with mass balance constraints for Ce, indicate a fraction under one ocean mass [2], a robust estimate as long as the basalts sampled at the surface tap all mantle reservoirs. The mantle likely contains some primordial water but given that the post-accretion Earth was very hot, water has low solubility and readily degasses from magma at low pressures, and its solubility in crystallizing liquidus minerals is also very low, the mantle just after accretion may have been relatively dry. Thus, it is plausible that most or even all of the water in the current mantle is ‘recycled’, added primarily by subduction of hydrated lithospheric plates. If transport of water to the core–mantle boundary is an important geological process with planet-scale implications, then surface water incorporated into subducting slabs and transported to the core–mantle boundary may be a requirement.Water is added to the basaltic oceanic crust and peridotitic mantle in lithospheric plates (hereafter, slab crust and slab mantle, respectively) at mid-ocean ridges, at transform faults, and in bending faults formed at the outer rise prior to subduction [3]. Estimates vary but about 1 × 10¹² kg of water is currently subducted each year into the mantle [4], and at this rate roughly 2–3 ocean masses could have been added to the mantle since subduction began. However, much of this water is returned to the surface through hydrous magmatism at convergent margins, which itself is a response to slab dehydration in an initial, and large, release of water. Meta-basalt and meta-sediments comprising the slab crust lose their water very efficiently beneath the volcanic front because most slab crust geotherms cross mineral dehydration or melting reactions at depths of less than 150 km, and even if some water remains stored in minerals like lawsonite in cooler slabs, nearly complete dehydration is expected by ∼300 km [5].Peridotitic slab mantle may have much greater potential to deliver water deeper into the interior. As shown in Fig. 1a, an initial pulse of dehydration of slab mantle occurs at depths less than ∼200 km in warmer slabs, controlled primarily by breakdown of chlorite and antigorite when slab-therms cross a deep ‘trough’, sometimes referred to as a ‘choke point’, along the dehydration curve (Fig. 1a) [6]. But the slab mantle in cooler subduction zones can skirt beneath the dehydration reactions, and antigorite can transform directly to the hydrated alphabet silicate phases (Phases A, E, superhydrous B, D), delivering perhaps as much as 5 wt% water in locally hydrated regions (e.g. deep faults and fractures in the lithosphere) to transition zone depths [6]. Estimates based on mineral phase relations in the slab crust and the slab mantle coupled with subduction zone thermal models suggest that as much as 30% of subducted water may have been transported past the sub-volcanic dehydration front and into the deeper mantle [4], although this depends on the depth and extent of deep hydration of the slab mantle, which is poorly constrained. Coincidentally, this also amounts to about one ocean mass if water subduction rates have been roughly constant since subduction began, a figure tantalizingly close to the estimated mantle water content based on geochemical arguments [2]. But what is the likely fate of water in the slab mantle in the transition zone and beyond?Open in a separate windowFigure 1.(a) Schematic phase relations in meta-peridotite modified after [6,10,12]. Slab geotherms are after those in [4]. Cold slabs may transport as much as 5 wt% water past ‘choke point 1’ in locally hydrated regions of the slab mantle, whereas slab mantle is dehydrated in warmer slabs. Colder slab mantle that can transport water into the transition zone will undergo dehydration at ‘choke point 2’. How much water can be transported deeper into the mantle and potentially to the core depends on the dynamics of fluid/melt segregation in this region. (b) Schematic showing dehydration in the slab mantle at choke point 2. Migration of fluids within slab mantle will result in water dissolving into bridgmanite and other nominally anhydrous phases with a bulk storage capacity of ∼0.1 wt%, potentially accommodating much or all of the released water. Migration of fluids out of the slab into ambient mantle would also hydrate bridgmanite and other phases and result in net fluid loss from the slab. Conversely, migration of hydrous fluids into the crust could result in extensive hydration of meta-basalt with water accommodated first in nominally anhydrous phases like bridgmanite, Ca-perovskite and NAL phase, but especially in dense SiO₂ phases (stishovite and CaCl₂-type) that can host at least 3 wt% water (∼0.6 wt% in bulk crust).Lithospheric slabs are expected to slow down and deform in the transition zone due to the interplay among the many factors affecting buoyancy and plate rheology, potentially trapping slabs before they descend into the lower mantle [7]. If colder, water-bearing slabs heat up by as little as a few hundred degrees in the transition zone, hydrous phases in the slab mantle will break down to wadsleyite or ringwoodite-bearing assemblages, and a hydrous fluid (Fig. 1a). Wadselyite and ringwoodite can themselves accommodate significant amounts of water and so hydrated portions of the slab mantle would retain ∼1 wt% water. A hydrous ringwoodite inclusion in a sublithospheric diamond with ∼1.5 wt% H₂O may provide direct evidence for this process [8].But no matter if slabs heat up or not in the transition zone, as they penetrate into the lower mantle phase D, superhydrous phase B or ringwoodite in the slab mantle will dehydrate at ∼700–800 km due to another deep trough, or second ‘choke point’, transforming into an assemblage of nominally anhydrous minerals dominated by bridgmanite (∼75 wt%) with, relatively, a much lower bulk water storage capacity (< ∼0.1 wt%) [9] (Fig. 1a). Water released from the slab mantle should lead to melting at the top of the lower mantle [10], and indeed, low shear-wave velocity anomalies at ∼700–800 km below North America may be capturing such dehydration melting in real time [11].The fate of the hydrous fluids/melts released from the slab in the deep transition zone and shallow lower mantle determines how much water slabs can carry deeper into the lower mantle. Presumably water is released from regions of the slab mantle where it was originally deposited, like the fractures and faults that formed in the slab near the surface [3]. If hydrous melts can migrate into surrounding water-undersaturated peridotite within the slab, then water should dissolve into bridgmanite and coexisting nominally anhydrous phases (Ca-perovskite and ferropericlase) until they are saturated (Fig. 1b). And because bridgmanite (water capacity ∼0.1 wt%) dominates the phase assemblage, the slab mantle can potentially accommodate much or all of the released water depending on details of how the hydrous fluids migrate, react and disperse. If released water is simply re-dissolved into the slab mantle in this way then it could be transported deeper into the mantle mainly in bridgmanite, possibly to the core–mantle boundary. Water solubility in bridgmanite throughout the mantle pressure-temperature range is not known, so whether water would partially exsolve as the slab moves deeper stabilizing a melt or another hydrous phase, or remains stable in bridgmanite as a dispersed, minor component, remains to be discovered.Another possibility is that the hydrous fluids/melts produced at the second choke point in the slab mantle at ∼700 km migrate out of the slab mantle, perhaps along the pre-existing fractures and faults where bridgmanite-rich mantle should already be saturated, and into either oceanic crust or ambient mantle (Fig. 1b). If the hydrous melts move into ambient mantle, water would be consumed by water-undersaturated bridgmanite, leading to net loss of water from the slab to the upper part of the lower mantle, perhaps severely diminishing the slab’s capacity to transport water to the deeper mantle and core. But what if the water released from slab mantle migrates into the subducting, previously dehydrated, slab crust?Although slab crust is expected to be largely dehydrated in the upper mantle, changes in its mineralogy at higher pressures gives it the potential to host and carry significant quantities of water to the core–mantle boundary. Studies have identified a number of hydrous phases with CaCl₂-type structures, including δ-AlOOH, ϵ-FeOOH and MgSiO₂(OH)₂ (phase H), that can potentially stabilize in the slab crust in the transition zone or lower mantle. Indeed, these phases likely form extensive solid solutions such that an iron-bearing, alumina-rich, δ-H solid solution should stabilize at ∼50 GPa in the slab crust [12], but only after the nominally anhydrous phases in the crust, (aluminous bridgmanite, stishovite, Ca-perovskite and NAL phase) saturate in water. Once formed, the δ-H solid solution in the slab crust may remain stable all the way to the core mantle boundary if the slab temperature remains well below the mantle geotherm otherwise a hydrous melt may form instead [12] (Fig. 1a). But phase δ-H solid solution and the other potential hydrated oxide phases, intriguing as they are as potential hosts for water, may not be the likely primary host for water in slab crust. Recent studies suggest a new potential host for water—stishovite and post-stishovite dense SiO₂ phases [13,14].SiO₂ minerals make up about a fifth of the slab crust by weight in the transition zone and lower mantle [15] and recent experiments indicate that the dense SiO₂ phases, stishovite (rutile structure—very similar to CaCl₂ structure) and CaCl₂-type SiO₂, structures that are akin to phase H and other hydrated oxides, can host at least 3 wt% water, which is much more than previously considered. More importantly, these dense SiO₂ phases apparently remain stable and hydrated even at temperatures as high as the lower mantle geotherm, unlike other hydrous phases [13,14]. And as a major mineral in the slab crust, SiO₂ phases would have to saturate with water first before other hydrous phases, like δ-H solid solution, would stabilize. If the hydrous melts released from the slab mantle in the transition zone or lower mantle migrate into slab crust the water would dissolve into the undersaturated dense SiO₂ phase (Fig. 1b). Thus, hydrated dense SiO₂ phases are possibly the best candidate hosts for water transport in slab crust all the way to the core mantle boundary due to their high water storage capacity, high modal abundance and high-pressure-temperature stability.Once a slab makes it to the core–mantle boundary region, water held in the slab crust or the slab mantle may be released due to the high geothermal gradient. Heating of slabs at the core–mantle boundary, where temperatures may exceed 3000°C, may ultimately dehydrate SiO₂ phases in the slab crust or bridgmanite (or δ-H) in the slab mantle, with released water initiating melting in the mantle and/or reaction with the core to form hydrated iron metal and super oxides, phases that may potentially explain ultra-low seismic velocities in this region [1,10]. How much water can be released in this region from subducted lithosphere remains a question that is hard to quantify and depends on dynamic processes of dehydration and rehydration in the shallower mantle, specifically at the two ‘choke points’ in the slab mantle, processes that are as yet poorly understood. What is clear is that subducting slabs have the capacity to carry surface water all the way to the core in a number of phases, and possibly in a phase that has previously seemed quite unlikely, dense SiO₂.  相似文献   

Evidence for oxygenation of Fe-Mg oxides at mid-mantle conditions and the rise of deep oxygen     

Jin Liu  Chenxu Wang  Chaojia Lv  Xiaowan Su  Yijin Liu  Ruilian Tang  Jiuhua Chen  Qingyang Hu  Ho-Kwang Mao  Wendy L Mao 《国家科学评论(英文版)》2021,8(4)

As the reaction product of subducted water and the iron core, FeO₂ with more oxygen than hematite (Fe₂O₃) has been recently recognized as an important component in the D” layer just above the Earth''s core-mantle boundary. Here, we report a new oxygen-excess phase (Mg, Fe)₂O_3+δ (0 < δ < 1, denoted as ‘OE-phase’). It forms at pressures greater than 40 gigapascal when (Mg, Fe)-bearing hydrous materials are heated over 1500 kelvin. The OE-phase is fully recoverable to ambient conditions for ex situ investigation using transmission electron microscopy, which indicates that the OE-phase contains ferric iron (Fe³⁺) as in Fe₂O₃ but holds excess oxygen through interactions between oxygen atoms. The new OE-phase provides strong evidence that H₂O has extraordinary oxidation power at high pressure. Unlike the formation of pyrite-type FeO₂Hx which usually requires saturated water, the OE-phase can be formed with under-saturated water at mid-mantle conditions, and is expected to be more ubiquitous at depths greater than 1000 km in the Earth''s mantle. The emergence of oxygen-excess reservoirs out of primordial or subducted (Mg, Fe)-bearing hydrous materials may revise our view on the deep-mantle redox chemistry.  相似文献   

Experiments on Cu-isotope fractionation between chlorine-bearing fluid and silicate magma: implications for fluid exsolution and porphyry Cu deposits     

Haihao Guo  Ying Xia  Ruixia Bai  Xingchao Zhang  Fang Huang 《国家科学评论(英文版)》2020,7(8):1319

Hydrothermal fluid is essential for transporting metals in the crust and mantle. To explore the potential of Cu isotopes as a tracer of hydrothermal-fluid activity, Cu-isotope fractionation factors between Cl-bearing aqueous fluids and silicate magmas (andesite, dacite, rhyolite dacite, rhyolite and haplogranite) were experimentally calibrated. Fluids containing 1.75–14 wt.% Cl were mixed together with rock powders in Au₉₅Cu₅ alloy capsules, which were equilibrated in cold-seal pressure vessels for 5–13 days at 800–850°C and 2 kbar. The elemental and Cu-isotopic compositions of the recovered aqueous fluid and solid phases were analyzed by (LA-) ICP–MS and multi-collector inductively coupled plasma mass spectrometry, respectively. Our experimental results show that the fluid phases are consistently enriched in heavy Cu isotope (⁶⁵Cu) relative to the coexisting silicates. The Cu-isotope fractionation factor (Δ⁶⁵Cu_FLUID-MELT) ranges from 0.08 ± 0.01‰ to 0.69 ± 0.02‰. The experimental results show that the Cu-isotopic fractionation factors between aqueous fluids and silicates strongly depend on the Cu speciation in the fluids (e.g. CuCl(H₂O), CuCl₂^– and CuCl₃²⁻) and silicate melts (CuO_1/2), suggesting that the exsolved fluids may have higher δ⁶⁵Cu than the residual magmas. Our results suggest the elevated δ⁶⁵Cu values in Cu-enriched rocks could be produced by addition of aqueous fluids exsolved from magmas. Together with previous studies on Cu isotopes in the brine and vapor phases of porphyry deposits, our results are helpful for better understanding Cu-mineralization processes.  相似文献   

Mineralogy of the deep lower mantle in the presence of H2O     

Qingyang Hu  Jin Liu  Jiuhua Chen  Bingmin Yan  Yue Meng  Vitali B Prakapenka  Wendy L Mao  Ho-Kwang Mao 《国家科学评论(英文版)》2021,8(4)

Understanding the mineralogy of the Earth''s interior is a prerequisite for unravelling the evolution and dynamics of our planet. Here, we conducted high pressure-temperature experiments mimicking the conditions of the deep lower mantle (DLM, 1800–2890 km in depth) and observed surprising mineralogical transformations in the presence of water. Ferropericlase, (Mg, Fe)O, which is the most abundant oxide mineral in Earth, reacts with H₂O to form a previously unknown (Mg, Fe)O₂H_x (x ≤ 1) phase. The (Mg, Fe)O₂H_x has a pyrite structure and it coexists with the dominant silicate phases, bridgmanite and post-perovskite. Depending on Mg content and geotherm temperatures, the transformation may occur at 1800 km for (Mg_0.6Fe_0.4)O or beyond 2300 km for (Mg_0.7Fe_0.3)O. The (Mg, Fe)O₂H_x is an oxygen excess phase that stores an excessive amount of oxygen beyond the charge balance of maximum cation valences (Mg²⁺, Fe³⁺ and H⁺). This important phase has a number of far-reaching implications including extreme redox inhomogeneity, deep-oxygen reservoirs in the DLM and an internal source for modulating oxygen in the atmosphere.  相似文献   

Free Radical Scavenging Properties of Skin and Pulp Extracts of Different Grape Cultivars In Vitro and Attenuation of H2O2-Induced Oxidative Stress in Liver Tissue Ex Vivo     

Indrani Singha  Subir Kumar Das 《Indian journal of clinical biochemistry : IJCB》2015,30(3):305-312

Grapes are the richest source of antioxidants due to the presence of potent bioactive phytochemicals. In this study, the phytochemical contents, scavenging activities and protective role against H₂O₂-induced oxidative stress in liver tissue ex vivo of four grape (Vitis vinifera) cultivars extracts, namely Flame seedless (black), Kishmish chorni (black with reddish brown), Red globe (red) and Thompson seedless mutant (green), were evaluated. The total phenolics and flavonoids content in pulp or skin fractions of different grape cultivars were in the range of 47.6–310 mg gallic acid equivalent/g fresh weight (fw), and 46.6–733.3 µg catechin equivalent/g fw respectively. The scavenging activities in skin of different grape varieties against 2,2-diphenyl-1-picrylhydrazyl (44–58 %), hydrogen peroxide (15.3–18.6 %), and hydroxyl radicals (50–85 %), were higher than pulp of the corresponding cultivars. These scavenging activities of grape extracts were found to be significantly (p < 0.01) correlated with the levels of total phenols, flavonoids and ascorbic acid. Liver tissues from goat treated with H₂O₂ (500 μM) showed significantly decreased GSH content by 42.9 % and activities of catalase by 50 % and glutathione reductase by 66.6 %; while increased thiobarbituric acid reactive substances and nitric oxide level by 2.53- and 0.86-fold, respectively, and activity of glutathione S-transferase by 0.96-fold. Grape skin extracts showed the stronger protective activity against H₂O₂-induced oxidative stress in liver tissue ex vivo, than its pulp of any cultivar; and the Flame seedless (black) cultivar showed the highest potential. In conclusion, our study suggested that the higher antioxidant potential, phytochemical contents and significant scavenging capacities in pulp and skin of grape extracts showed the protective action of grape extracts against H₂O₂-induced oxidative stress in liver tissue ex vivo.  相似文献   

Water in the upper mantle and deep crust of eastern China: concentration,distribution and implications     

Qun-Ke Xia  Jia Liu  Istvn Kovcs  Yan-Tao Hao  Pei Li  Xiao-Zhi Yang  Huan Chen  Ying-Ming Sheng 《国家科学评论(英文版)》2019,6(1):125

Understanding the concentration and distribution of water in the Earth''s mantle plays a substantial role in studying its chemical, physical and dynamic processes. After a decade of research, a comprehensive dataset of water content in upper-mantle samples has been built for eastern China, which is now the only place with water-content data from such diverse types of natural samples, and provides an integrated picture of the water content and its distribution in the upper mantle at a continental scale. The main findings include the following: (i) the temporal heterogeneity of the water content in the lithospheric mantle from early Cretaceous (∼120 Ma) to Cenozoic (<40 Ma) was tightly connected with the stability of the North China Craton (from its destruction to its consolidation); (ii) the heterogeneous water content in the Cenozoic lithospheric mantle beneath different blocks of eastern China was not only inherited from tectonic settings from which they came, but was also affected later by geological processes they experienced; (iii) the distinct water content between the lowermost crust and lithospheric mantle of eastern China and its induced rheological contrast at the base of the crust indicate that the continental crust–mantle boundary could behave either in a coupled or decoupled manner beneath different areas and/or at different stages; (iv) the alkali basalts of eastern China demonstrate a heterogeneous distribution of water content in the mantle; local and regional comparisons of the water content between the lithospheric mantle and basalts'' source indicate that the Cenozoic alkali basalts in eastern China were not sourced from the lithospheric mantle. Instead, the inferred high water contents in the mantle sources suggest that the Cenozoic eastern China basalts were likely sourced from the mantle transition zone (MTZ); and (v) both oceanic and continental crusts may carry a certain amount of water back into the deep mantle of eastern China by plate subduction. Such recycled crustal materials have not only created a local water-rich zone, but have also introduced crustal geochemical signatures into the mantle, both accounting for crustal geochemical imprints in the intra-plate magmatic rocks of eastern China.  相似文献   

Shadow glass transition as a thermodynamic signature of β relaxation in hyper-quenched metallic glasses     

Qun Yang  Si-Xu Peng  Zheng Wang  Hai-Bin Yu 《国家科学评论(英文版)》2020,7(12):1896

One puzzling phenomenon in glass physics is the so-called ‘shadow glass transition’ which is an anomalous heat-absorbing process below the real glass transition and influences glass properties. However, it has yet to be entirely characterized, let alone fundamentally understood. Conventional calorimetry detects it in limited heating rates. Here, with the chip-based fast scanning calorimetry, we study the dynamics of the shadow glass transition over four orders of magnitude in heating rates for 24 different hyper-quenched metallic glasses. We present evidence that the shadow glass transition correlates with the secondary (β) relaxation: (i) The shadow glass transition and the β relaxation follow the same temperature–time dependence, and both merge with the primary relaxation at high temperature. (ii) The shadow glass transition is more obvious in glasses with pronounced β relaxation, and vice versa; their magnitudes are proportional to each other. Our findings suggest that the shadow glass transition signals the thermodynamics of β relaxation in hyper-quenched metallic glasses.  相似文献   

Au23(CR)14 nanocluster restores fibril Aβ’s unfolded state with abolished cytotoxicity and dissolves endogenous Aβ plaques     

Wenkang Zhang  Guanbin Gao  Zhongjie Ma  Zhuoying Luo  Meng He  Taolei Sun 《国家科学评论(英文版)》2020,7(4):763

The misfolding of amyloid-β (Aβ) peptides from the natural unfolded state to β-sheet structure is a critical step, leading to abnormal fibrillation and formation of endogenous Aβ plaques in Alzheimer''s disease (AD). Previous studies have reported inhibition of Aβ fibrillation or disassembly of exogenous Aβ fibrils in vitro. However, soluble Aβ oligomers have been reported with increased cytotoxicity; this might partly explain why current clinical trials targeting disassembly of Aβ fibrils by anti-Aβ antibodies have failed so far. Here we show that Au₂₃(CR)₁₄ (a new Au nanocluster modified by Cys-Arg (CR) dipeptide) is able to completely dissolve exogenous mature Aβ fibrils into monomers and restore the natural unfolded state of Aβ peptides from misfolded β-sheets. Furthermore, the cytotoxicity of Aβ₄₀ fibrils when dissolved by Au₂₃(CR)₁₄ is fully abolished. More importantly, Au₂₃(CR)₁₄ is able to completely dissolve endogenous Aβ plaques in brain slices from transgenic AD model mice. In addition, Au₂₃(CR)₁₄ has good biocompatibility and infiltration ability across the blood–brain barrier. Taken together, this work presents a promising therapeutics candidate for AD treatment, and manifests the potential of nanotechnological approaches in the development of nanomedicines.  相似文献   

Correlating the electronic structures of metallic/semiconducting MoTe2 interface to its atomic structures     

Bo Han  Chen Yang  Xiaolong Xu  Yuehui Li  Ruochen Shi  Kaihui Liu  Haicheng Wang  Yu Ye  Jing Lu  Dapeng Yu  Peng Gao 《国家科学评论(英文版)》2021,8(2)

Contact interface properties are important in determining the performances of devices that are based on atomically thin two-dimensional (2D) materials, especially for those with short channels. Understanding the contact interface is therefore important to design better devices. Herein, we use scanning transmission electron microscopy, electron energy loss spectroscopy, and first-principles calculations to reveal the electronic structures within the metallic (1T^′)-semiconducting (2H) MoTe₂ coplanar phase boundary across a wide spectral range and correlate its properties to atomic structures. We find that the 2H-MoTe₂ excitonic peaks cross the phase boundary into the 1T^′ phase within a range of approximately 150 nm. The 1T^′-MoTe₂ crystal field can penetrate the boundary and extend into the 2H phase by approximately two unit-cells. The plasmonic oscillations exhibit strong angle dependence, that is a red-shift of π+σ (approximately 0.3–1.2 eV) occurs within 4 nm at 1T^′/2H-MoTe₂ boundaries with large tilt angles, but there is no shift at zero-tilted boundaries. These atomic-scale measurements reveal the structure–property relationships of the 1T^′/2H-MoTe₂ boundary, providing useful information for phase boundary engineering and device development based on 2D materials.  相似文献   

Stoichiometric evolutions of PH3 under high pressure: implication for high-Tc superconducting hydrides     

Ye Yuan  Yinwei Li  Guoyong Fang  Guangtao Liu  Cuiying Pei  Xin Li  Haiyan Zheng  Ke Yang  Lin Wang 《国家科学评论(英文版)》2019,6(3):524

The superconductivity of hydrides under high pressure has attracted a great deal of attention since the recent observation of the superconducting transition at 203 K in strongly compressed H₂S. It has been realized that the stoichiometry of hydrides might change under high pressure, which is crucial in understanding the superconducting mechanism. In this study, PH₃ was studied to understand its superconducting transition and stoichiometry under high pressure using Raman, IR and X-ray diffraction measurements, as well as theoretical calculations. PH₃ is stable below 11.7 GPa and then it starts to dehydrogenate through two dimerization processes at room temperature and pressures up to 25 GPa. Two resulting phosphorus hydrides, P₂H₄ and P₄H₆, were verified experimentally and can be recovered to ambient pressure. Under further compression above 35 GPa, the P₄H₆ directly decomposed into elemental phosphorus. Low temperature can greatly hinder polymerization/decomposition under high pressure and retains P₄H₆ up to at least 205 GPa. The superconductivity transition temperature of P₄H₆ is predicted to be 67 K at 200 GPa, which agrees with the reported result, suggesting that it might be responsible for superconductivity at higher pressures. Our results clearly show that P₂H₄ and P₄H₆ are the only stable P–H compounds between PH₃ and elemental phosphorus, which is helpful for shedding light on the superconducting mechanism.  相似文献   

Olivine-norite rock detected by the lunar rover Yutu-2 likely crystallized from the SPA-impact melt pool     

Honglei Lin  Zhiping He  Wei Yang  Yangting Lin  Rui Xu  Chi Zhang  Meng-Hua Zhu  Rui Chang  Jinhai Zhang  Chunlai Li  Hongyu Lin  Yang Liu  Sheng Gou  Yong Wei  Sen Hu  Changbin Xue  Jianfeng Yang  Jie Zhong  Xiaohui Fu  Weixing Wan  Yongliao Zou 《国家科学评论(英文版)》2020,7(5):913

Chang’E-4 landed in the South Pole-Aitken (SPA) basin, providing a unique chance to probe the composition of the lunar interior. Its landing site is located on ejecta strips in Von Kármán crater that possibly originate from the neighboring Finsen crater. A surface rock and the lunar regolith at 10 sites along the rover Yutu-2 track were measured by the onboard Visible and Near-Infrared Imaging Spectrometer in the first three lunar days of mission operations. In situ spectra of the regolith have peak band positions at 1 and 2 μm, similar to the spectral data of Finsen ejecta from the Moon Mineralogy Mapper, which confirms that the regolith''s composition of the landing area is mostly similar to that of Finsen ejecta. The rock spectrum shows similar band peak positions, but stronger absorptions, suggesting relatively fresh exposure. The rock may consist of 38.1 ± 5.4% low-Ca pyroxene, 13.9 ± 5.1% olivine and 48.0 ± 3.1% plagioclase, referred to as olivine-norite. The plagioclase-abundant and olivine-poor modal composition of the rock is inconsistent with the origin of the mantle, but representative of the lunar lower crust. Alternatively, the rock crystallized from the impact-derived melt pool formed by the SPA-impact event via mixing the lunar crust and mantle materials. This scenario is consistent with fast-cooling thermal conditions of a shallow melt pool, indicated by the fine to medium-sized texture (<3 mm) of the rock and the SPA-impact melting model [Icarus 2012; 220: 730–43].  相似文献   

Charmonium and charmoniumlike states at the BESIII experiment     

Chang-Zheng Yuan 《国家科学评论(英文版)》2021,8(11)

Charmonium is a bound state of a charmed quark and a charmed antiquark, and a charmoniumlike state is a resonant structure that contains a charmed quark and antiquark pair but has properties that are incompatible with a conventional charmonium state. While operating at center-of-mass energies from 2 to 5 GeV, the BESIII experiment can access a wide mass range of charmonium and charmoniumlike states, and has contributed significantly in this field. We review BESIII results involving conventional charmonium states, including the first observation of the M1 transition ψ(2S) → γη_c(2S) and the discovery of the ψ₂(3823) state; and report on studies of charmoniumlike states, including the discoveries of the Z_c(3900) and Z_c(4020) tetraquark candidates, the resolution of the fine structure of the Y(4260) state, the discovery of the new production process e⁺e⁻ → γX(3872) and the uncovering of strong evidence for the commonality among the X(3872), Y(4260) and Z_c(3900) states. The prospects for further research at BESIII and proposed future facilities are also presented.  相似文献   

Large-scale multiferroic complex oxide epitaxy with magnetically switched polarization enabled by solution processing     

Cong Liu  Feng An  Paria S M Gharavi  Qinwen Lu  Junkun Zha  Chao Chen  Liming Wang  Xiaozhi Zhan  Zedong Xu  Yuan Zhang  Ke Qu  Junxiang Yao  Yun Ou  Zhiming Zhao  Xiangli Zhong  Dongwen Zhang  Nagarajan Valanoor  Lang Chen  Tao Zhu  Deyang Chen  Xiaofang Zhai  Peng Gao  Tingting Jia  Shuhong Xie  Gaokuo Zhong  Jiangyu Li 《国家科学评论(英文版)》2020,7(1):84

Complex oxides with tunable structures have many fascinating properties, though high-quality complex oxide epitaxy with precisely controlled composition is still out of reach. Here we have successfully developed solution-based single-crystalline epitaxy for multiferroic (1-x)BiTi_(1-y)/2Fe_yMg_(1-y)/2O₃–(x)CaTiO₃ (BTFM–CTO) solid solution in large area, confirming its ferroelectricity at the atomic scale with strong spontaneous polarization. Careful compositional tuning leads to a bulk magnetization of 0.07 ± 0.035 μ_B/Fe at room temperature, enabling magnetically induced polarization switching exhibiting a large magnetoelectric coefficient of 2.7–3.0 × 10⁻⁷ s/m. This work demonstrates the great potential of solution processing in large-scale complex oxide epitaxy and establishes novel room-temperature magnetoelectric coupling in epitaxial BTFM–CTO film, making it possible to explore a much wider space of composition, phase, and structure that can be easily scaled up for industrial applications.  相似文献   

Cracking the superheavy pyrite enigma: possible roles of volatile organosulfur compound emission     

Xianguo Lang  Zhouqiao Zhao  Haoran Ma  Kangjun Huang  Songzhuo Li  Chuanming Zhou  Shuhai Xiao  Yongbo Peng  Yonggang Liu  Wenbo Tang  Bing Shen 《国家科学评论(英文版)》2021,8(10)

The global deposition of superheavy pyrite (pyrite isotopically heavier than coeval seawater sulfate in the Neoproterozoic Era and particularly in the Cryogenian Period) defies explanation using the canonical marine sulfur cycle system. Here we report petrographic and sulfur isotopic data (δ³⁴S_py) of superheavy pyrite from the Cryogenian Datangpo Formation (660–650 Ma) in South China. Our data indicate a syndepositional/early diagenetic origin of the Datangpo superheavy pyrite, with ³⁴S-enriched H₂S supplied from sulfidic (H₂S rich) seawater. Instructed by a novel sulfur-cycling model, we propose that the emission of ³⁴S-depleted volatile organosulfur compounds (VOSC) that were generated via sulfide methylation may have contributed to the formation of ³⁴S-enriched sulfidic seawater and superheavy pyrite. The global emission of VOSC may be attributed to enhanced organic matter production after the Sturtian glaciation in the context of widespread sulfidic conditions. These findings demonstrate that VOSC cycling is an important component of the sulfur cycle in Proterozoic oceans.  相似文献   

Cytotoxicity and Apoptosis Inducing Activities of 2-Amino-4H-chromene-3-carbonitrile Derivatives Loaded on Gold Nanoparticles Against Human Breast Cancer Cell Line T47D     

Zahra Saffari  Maryam Farahnak Zarabi  Hasan Aryapour  Alireza Foroumadi  Ali Farhangi  Soheil Ghassemi  Azim Akbarzadeh 《Indian journal of clinical biochemistry : IJCB》2015,30(2):140-149

Chemotherapy drugs, used for prevention of uncontrolled cell proliferation in certain tissues as well as inducing apoptosis in tumor cells, are important candidates for treatment of cancer. The synthesized 2-amino-4H-chromene-3-carbonitrile derivatives effective on cancerous cells resistant to other drugs such as Paclitaxel were used due to their ability in induction of apoptosis. The growth inhibitory and inducing apoptosis activities were determined. In order to make it target-oriented, the best compound was conjugated with gold nanoparticles (NPs) by aspartic acid with chemical reduction method. Cytotoxicity effect of 2-amino-4H-chromene-3-carbonitrile derivatives against the T47D breast cancer cell line was determined by MTT assay. The synthesis of gold NPs was confirmed by transmission electron microscopy, UV–Vis and dynamic light scattering. To assess the effects of compounds on the process of apoptosis, staining methods with acridine orange–ethidium bromide and Hoechst staining by fluorescence microscopy and DNA fragmentation by the diphenylamine method were used. The synthesized compounds containing two NH₂ groups on benzene rings, demonstrated more cytotoxicity effect. The effect of conjugation with gold NPs and the induction of apoptosis were studied with the best compound. The cytotoxicity effects of the synthesized 2-amino-4H-chromene-3-carbonitrile compounds were changed by replacement of NO₂ group on thiol ring with different chemical groups on the benzene ring. Analyses of treated cell lines by conjugated and non-conjugated forms of compounds verified their ability in inducing apoptosis while conjugated form demonstrated higher apoptosis.  相似文献   

Interaction of hemoglobin Grey Lynn (Vientiane) with a non-deletional α+-thalassemia in an adult Thai proband     

Kritsada Singha  Goonnapa Fucharoen  Supan Fucharoen 《Biochemia medica : ?asopis Hrvatskoga dru?tva medicinskih biokemi?ara / HDMB》2014,24(1):167-174

Hemoglobin (Hb) Grey Lynn is a Hb variant caused by a substitution of Phe for Leu at position 91 of α1-globin chain, originally described in individual of unknown ethnic background. This article addresses the interaction of Hb Grey Lynn with a non-deletional α⁺-thalassemia found in Thailand, a hitherto un-described condition. The proband was adult Thai woman referred for investigation of mild anemia with Hb 90 g/L. Hb analyses using low pressure liquid chromatography raised a suspicion of abnormal Hb presence, which was failed to demonstrate by cellulose acetate electrophoresis and capillary electrophoresis. DNA sequencing identified a CTT (Leu) to TTT (Phe) mutation at codon 91 corresponding to the Hb Grey Lynn (Vientiane) [α91(FG3)Leu>Phe (α1) on α1-globin gene and a C deletion between codons 36 and 37 on α2-globin gene causing α⁺-thalassemia. As compared to those observed in a compound heterozygote for Hb Grey Lynn / α⁰-thalassemia reported previously, higher MCV (81.7 fL) and MCH (26.3 pg) values with a lower level of Hb Grey Lynn (19.7%) were observed in the proband. The normochromic normocytic anemia observed could be due to the interaction of Hb Grey Lynn with α⁺-thalassemia. The two mutations could be identified using PCR-RFLP and allele-specific PCR assays developed.  相似文献   

An accurate single descriptor for ion–π interactions     

Zhangyun Liu  Zheng Chen  Jinyang Xi  Xin Xu 《国家科学评论(英文版)》2020,7(6):1036

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A highly alkaline-stable metal oxide@metal–organic framework composite for high-performance electrochemical energy storage     

Shasha Zheng  Qing Li  Huaiguo Xue  Huan Pang  Qiang Xu 《国家科学评论(英文版)》2020,7(2):305

Most metal–organic frameworks (MOFs) hardly maintain their physical and chemical properties after exposure to alkaline aqueous solutions, thus precluding their use as potential electrode materials for electrochemical energy storage devices. Here, we present the design and synthesis of a highly alkaline-stable metal oxide@MOF composite, Co₃O₄ nanocube@Co-MOF (Co₃O₄@Co-MOF), via a controllable and facile one-pot hydrothermal method under highly alkaline conditions. The obtained composite possesses exceptional alkaline stability, retaining its original structure in 3.0 M KOH for at least 15 days. Benefitting from the exceptional alkaline stability, unique structure, and larger surface area, the Co₃O₄@Co-MOF composite shows a specific capacitance as high as 1020 F g⁻¹ at 0.5 A  g⁻¹ and a high cycling stability with only 3.3% decay after 5000 cycles at 5 A g⁻¹. The as-constructed solid-state flexible device exhibits a maximum energy density of 21.6 mWh cm⁻³.  相似文献   

Alloimmunization to Red Cells and the Association of Alloantibodies Formation with Splenectomy Among Transfusion-Dependent β-Thalassemia Major/HbE Patients     

Suteenee Jansuwan  Orathai Tangvarasittichai  Surapon Tangvarasittichai 《Indian journal of clinical biochemistry : IJCB》2015,30(2):198-203

Severe hemolytic anemia in β-thalassemia major and β-thalassemias/HbE (β-TM) patients requires giving blood transfusions. Chronic blood transfusions lead to iron overload consequence with organs damage and risk of alloantibody-formation. This study evaluates the prevalence of red cell alloimmunization and estimates the risk of alloantibody-formation in chronic transfusion-dependent β-TM patients. This cross sectional study was conducted on 143 β-TM patients receiving regular transfusions. We tried to determine the frequency, types and factors influencing red cell alloimmunization in these transfusion-dependent β-TM patients. Median age of 25 (17.5 %) alloantibody-formation β-TM patients was 19.0 years (inter quartile 15.5–24.0 years). The alloantibodies were Anti-Rh (E) (13.1 %), Anti-Rh (D) (0.7 %). Thirty-four patients (23.8 %) of the sample had splenectomies of which 10 (29.4 %) had alloantibody-formation. The interval from first transfusion to antibody development varied from 1.5 to 14 years. Alloantibody-formation correlated with splenectomy and splenectomy correlated with number of transfusion (p < 0.005). In multiple logistic regression used to estimate the risk of alloantibodies formation with splenectomy; OR and 95 % CI were 2.88 (1.07–7.80), p = 0.037 after adjusting for other co-variates. The rate of red cell alloimmunization was 17.5 % and splenectomy associated with increased alloantibody-formation in these transfusion-dependent β-TM patients.  相似文献   

Encapsulating metal organic framework into hollow mesoporous carbon sphere as efficient oxygen bifunctional electrocatalyst     

Wanfeng Xiong  Hongfang Li  Hanhui You  Minna Cao  Rong Cao 《国家科学评论(英文版)》2020,7(3):609

Applying metal organic frameworks (MOFs) in electrochemical systems is a currently emerging field owing to the rich metal nodes and highly specific surface area of MOFs. However, the problems for MOFs that need to be solved urgently are poor electrical conductivity and low ion transport. Here we present a facile in situ growth method for the rational synthesis of MOFs@hollow mesoporous carbon spheres (HMCS) yolk–shell-structured hybrid material for the first time. The size of the encapsulated Zeolitic Imidazolate Framework-67 (ZIF-67) is well controlled to 100 nm due to the spatial confinement effect of HMCS, and the electrical conductivity of ZIF-67 is also increased significantly. The ZIF@HMCS-25% hybrid material obtained exhibits a highly efficient oxygen reduction reaction activity with 0.823 V (vs. reversible hydrogen electrode) half-wave potential and an even higher kinetic current density (J_K = 13.8 mA cm⁻²) than commercial Pt/C. ZIF@HMCS-25% also displays excellent oxygen evolution reaction performance and the overpotential of ZIF@HMCS-25% at 10 mA cm⁻² is 407 mV. In addition, ZIF@HMCS-25% is further employed as an air electrode for a rechargeable Zn–air battery, exhibiting a high power density (120.2 mW cm⁻² at 171.4 mA cm⁻²) and long-term charge/discharge stability (80 h at 5 mA cm⁻²). This MOFs@HMCS yolk–shell design provides a versatile method for the application of MOFs as electrocatalysts directly.  相似文献