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The construction of inorganic porous frameworks from discrete polyoxometalate (POM) units is a major research challenge. Herein, a three-dimensional (3D) all-inorganic porous structure {Mo154}n that consists of classic Mo154 rings connected by Mo-O-Mo covalent bonds was synthesized. Interestingly, the proton conductivity of the 3D-{Mo154}n framework is 1.1×10−2 S cm−1 at 22 °C and 100% relative humidity (RH), which is one of the highest proton conductivities reported thus far for POM-based conductive materials. Compared to the discrete {Mo154} cluster and 1D-{Mo154}n, the enhanced conductivity of 3D-{Mo154}n suggests that assembling POM-based all-inorganic porous frameworks is a promising method for designing proton-conductive materials.

A pure inorganic uranyl phosphate-polyoxometalate of Na17{Na@[(SbW9O33)2(UO2)6(PO3OH)6]}·xH2O (abbreviated as Na@U6P6, with x ≈ 46) featuring a sandwich-type structure was prepared using Keggin-type trilacunary [α-B-SbW9O33]9- units as building blocks, which were formed in situ by SbCl3 and Na2WO4·2H2O. Crystal structural analysis showed that six UO22+ cations and six PO3OH2- anions generated a wheel-like cluster unit with a Na+ center ([Na@(UO2)6(PO3OH)6]+) that is stabilized by two [α-B-SbW9O33]9- units. Na@U6P6 displayed a solid-state photoluminescence quantum yield of 33% at 300 K. The temperature-dependent fluorescence emission spectra showed that Na@U6P6 has temperature-sensitive fluorescence in which its emission intensity decreased by 77% as the temperature increased from 200 to 300 K. These results suggest that such uranyl phosphate-polyoxometalate clusters could serve as potential temperature-sensitive molecular materials.

Cocrystallization of different metal nanoclusters facilitates the preparation of cluster-based nanomaterials with enhanced properties. Herein, two pairs of enantiomeric 3d-4f cocrystallization structures of clusters R/S-[Mn10Ln6] and R/S-[Mn6Ln2] (Ln = Dy for 1R and 1S, Y for 2R and 2S) have been reported. Compounds R/S-[Mn10Ln6][Mn6Ln2] exhibit a large optical activity and magneto-optic effect as verified by natural circular dichroism (NCD) and magnetic circular dichroism (MCD). In addition, alternating current (ac) magnetic measurements show that the chiral R/S-[Mn10Dy6][Mn6Dy2] cocrystallization structure displays slow magnetic relaxation with Ueff = 25.1 K.

To better understand the origin and tectonic evolution of the Paleoproterozoic Jiao-Liao-Ji belt, North China craton, which have long been debated, we have conducted whole-rock geochemical and zircon U-Pb and Hf isotope analyses on Paleoproterozoic monzo(syeno)granitic gneisses and metamafic rocks from eastern Liaoning Province. The results indicate that these monzo(syeno)granitic gneisses and metamafic rocks formed concurrently at ca. 2.2–2.1 Ga. The monzo(syeno)granitic gneisses show geochemical features of A-type granites and were derived from dehydration melting of Archean tonalite-trondhjemite-granodiorite (TTG) with minor involvement of coeval mantle-derived magma in an extensional setting. The metamafic rocks are geochemically similar to mid-ocean-ridge basalt; they were generated by partial melting of isotope-depleted asthenospheric mantle in an intracontinental extensional setting and experienced crustal and continental lithospheric mantle contamination and fractional crystallization. Based on this study and published geological evidence, we propose the following tectonic model for the origin and geodynamic evolution of the Jiao-Liao-Ji belt: (1) Generation of high-density eclogitized lower crust accompanied by formation of voluminous Archean TTGs in the Eastern block; (2) intracontinental extension driven by upwelling of an asthenospheric hotspot along the Jiao-Liao-Ji belt in period of 2.20–2.0 Ga; (3) convergent orogenic processes between the Longgang block and Nangrim block governed by gravity-driven subduction of high-density eclogitized lower crust at ca. 1.95–1.85 Ga; and (4) postorogenic extension caused by delamination of the orogenic root and subsequent hot asthenospheric upwelling. This tectonic model can well explain the origin and geodynamic evolution of the Paleoproterozoic Jiao-Liao-Ji belt.

Incorporating metal clusters within the skeleton of the organic polymers through click reaction can not only effectively prepare cluster-polymer composites, but also effectively avoid the cluster aggregation. Herein, an azide-contatining Lanthanide-Titanium oxo cluster of Eu 8 Ti 10 -N 3 ( Eu 8 Ti 10 -N 3 = [Eu 8 Ti 10 ( µ 3 -O) 14 (H 2 O) 4 (OAc) 2 (tbba) 30 (paza) 4 (THF) 2 ]•4THF•8H 2 O ( 1 ), Htbba = 4-tert-butylbenzoic acid, Hpaza = 4-azidobenzoate, HOAc = acetic acid, THF = Tetrahydrofuran) through in situ solvothermal reaction of 4-Azidobenzoic acid and 4-tert-butylbenzoic acid. Reaction of 1 with PEG ( PEG = Methoxypoly(ethyleneglycol)alkyne, 2000 g/mol) through Cu(I)-catalyzed click chemistry generates a lanthanide-polymer composite of Eu 8 Ti 10 -N 3 @PEG ( 2 ). Investigation on IR, 1 H NMR ICP-OES of 2 indicates that the structural integrity of 1 is maintained in 2 . Study on luminescent properties of 1 and 2 reveals that the quantum yield of 1 itself basically keeps unchanged in 2 . Significantly, the formation of 2 can not only effectively prevent the cluster 1 from aggregation, but also greatly enhance its solubility and adhesion to the substrate. Owing to the solubility and adhesion of luminescent materials being the key to their practical application, present work is thus of great significance for the development of metal cluster-polymer composite luminescent materials.

The formation mechanism of ferrihydrite is the key to understand its treatment of pollutants in waste water and purification of surface water and groundwater. Although emerging evidence suggests that formation of the ferrihydrite occurs through the aggregation of prenucleation clusters, rather than classical atom-by-atom growth, its formation mechanism remains unclear. Herein, an iron-oxo anionic cluster of [Fe22 (μ4 -O)8 (μ3 -OH)20 (μ2 -OH)18 (CH3 COO)16 (H2 O)2 ]4- viewed as a dimer of bivacant β-Keggin-Fe13 clusters was for the first time obtained by using lanthanide ions as stabilizers. Upon dissolution in a mixed solution of isopropanol and water, the lacunary β-Keggin-Fe13 cluster can transform into an α-Keggin-Fe13 cluster, distinctly demonstrating that the Keggin-Fe13 cluster rotational isomerization can be realized through the vacant Keggin-Fe13 cluster.

The Wulian complex is located on the northern margin of the Sulu orogenic belt, and was formed by collision between the North China Craton (NCC) to the north and South China Craton (SCC) to the south. It consists of the metasedimentary Wulian Group, gneissic granite and meta-diorite. The U–Pb analyses for the detrital zircons from the Wulian Group exhibit one predominant age population of 2600–2400 Ma with a peak at c. 2.5 Ga and several secondary age populations of > 3000, 3000–2800, 2800–2600, 2200–2000, 1900–1800, 1500–1300 and 1250–950 Ma; some metamorphic zircons have metamorphic ages of c. 2.7, 2.55–2.45, 2.1–2.0 and 1.95–1.80 Ga, which are consistent with magmatic-metamorphic events in the SCC. Additionally, the Wulian Group was intruded by the gneissic granite and meta-diorite at c. 0.76 Ga, attributed to Neoproterozoic syn-rifting bimodal magmatic activity in the SCC and derived from partial melting of Archaean continental crust and depleted mantle, respectively. The Wulian Group therefore has tectonic affinity to the SCC and was mainly sourced from the SCC. The detrital zircons have positive and negative ϵHf(t) values, indicating that their source rocks were derived from reworking of both ancient and juvenile crustal rocks. The major early Precambrian crustal growth took place during c. 3.4–2.5 Ga with a dominant peak at 2.96 Ga and several secondary peaks at 3.27, 2.74 and 2.52 Ga. The two oldest zircons with ages of 3307 and 3347 Ma record the recycling of ancient continental crust (> 3.35 Ga) and crustal growth prior to c. 3.95 Ga in the SCC.

Two high-nuclearity lanthanide-transition metal clusters with the general formula [Ln18CoIICoIII6(OH)14(CO3)9(CH3CH2COO)6(dea)12(H2O)30]·(NO3)8·Cl4·(CH3CH2OH)6·(H2O)12 (Ln18Co7, Ln = Gd (1) and Dy ...

New U- Pb dating and Hf isotope analyses of detrital zircons from the Penglai group occurred in the Jiaobei terrane, NCC have been conducted. The results display age populations of 1000-1300, 1300-1500, 1500-1700, 1700-1800 and >1800 Ma. The Penglai group has identical age spectra, U and Th variations, Th/U ratios and Hf isotopic compositions of detrital zircons, similar litho- and biostratigraphy, and tectonic setting with the Tonian strata of the southeastern NCC, demonstrating that the Penglai group has tectonic affinity of the NCC, and be deposited during Tonian. Given that the detrital zircon age populations are well consistent with the multiple magmatic and metamorphic thermal events in the NCC, especially, 1000-1300 Ma medium-acid and/or acid igneous rocks have been more and more recognized in the Korean Peninsula, we propose that the Penglai group might be mainly sourced from the NCC. The detrital zircon populations of 1000-1300, 1300-1500, 1500-1700 and 1700-1800 Ma exhibit both positive and negative eHf(t) values, combined with late Paleo-Neoproterozoic basic magmatism represented by large volumes of diabase sills in the NCC, suggesting that the NCC experienced strong crust-mantle interactions which might trigger the continuously multi-stage rifting activities of the NCC during late Paleoproterozoic (1.8 Ga)-Neoproterozoic. Supplementary material:https://doi.org/10.6084/m9.figshare.c.4816317

A series of heterometallic Ln-Cr clusters with the formulas [Ln5Cr2(H2L)2(OAc)6(μ3-OH)6(H2O)15](ClO4)7·xH2O (Ln = Gd and x = 33 for 1 and Ln = Dy and x = 21 for 2) and [Ln8Cr4(H2L)4(OAc)8(μ3-OH)16(μ4-O)1(H2O)8](Cl)(ClO4)5·10H2O (Ln = Gd for 3 and Ln = Dy for 4) was obtained through the reaction of the acetate ligands 2,2-dimethylolpropionic acid (H3L) and Ln(ClO4)3 in the presence of chromium salts with different anions under the same high pH conditions. X-ray analysis revealed that compound 1 contained a metal unit [Gd3Cr2] displaying the pentagonal bipyramid configuration and that compound 3 was templated by Cl- and ClO4- as a mixed anion template featuring a quadrangular structure. In compound 3, the 12 metal atoms were arranged in a wheel-shaped metal skeleton [Gd8Cr4], which was produced by 4 tetrahedral metal units [Gd3Cr] sharing vertices. The introduction of the mixed anion template increased the number of metal atoms in the Ln-Cr clusters. Magnetic calculations indicated that there was weak antiferromagnetic Gd···Cr coupling and weak ferromagnetic Gd···Gd coupling in 1, whereas both Gd···Cr and Gd···Gd in 3 exhibited weak antiferromagnetic interactions. Magnetothermal studies showed that compounds 1 and 3 displayed magnetic entropy changes of 25.2 J kg-1 K-1 at 5 K and 7 T and 33.8 J kg-1 K-1 at 2 K and 7 T, respectively.

Atomically precise molecular metal-oxo clusters provide ideal models to understand metal oxide surfaces, self-assembly, and form-function relationships. Devising strategies for synthesis and isolation of these molecular forms remains a challenge. Here, the synthesis of four Ln-Fe oxo clusters that feature the ϵ-{Fe13 } Keggin cluster in their core is reported. The {Fe13 } metal-oxo cluster motif is the building block of two important iron oxyhydroxyide phases in nature and technology, ferrihydrite (as the δ-isomer) and magnetite (the ϵ-isomer). The reported ϵ-{Fe13 } Keggin isomer as an isolated molecule provides the opportunity to study the formation of ferrihydrite and magnetite from this building unit. The four currently reported isostructural lanthanide-iron-oxo clusters are fully formulated [Y12 Fe33 (TEOA)12 (Hyp)6 (μ3 -OH)20 (μ4 -O)28 (H2 O)12 ](ClO4 )23 ⋅50 H2 O (1, Y12 Fe33 ), [Gd12 Fe33 (TEOA)12 (Hyp)6 (μ3 -OH)20 (μ4 -O)32 (H2 O)12 ](ClO4 )15 ⋅50 H2 O (2, Gd12 Fe33 ) and [Ln16 Fe29 (TEOA)12 (Hyp)6 (μ3 -OH)24 (μ4 -O)28 (H2 O)16 ](ClO4 )16 (NO3 )3 ⋅n H2 O (Ln=Y for 3, Y16 Fe29 , n=37 and Ln=Gd for 4, Gd16 Fe29 n=25; Hyp=trans-4-Hydroxyl-l-proline and TEOA=triethanolamine). The next metal layer surrounding the ϵ-{Fe13 } core within these clusters exhibits a similar arrangement as the magnetite lattice, and Fe and Ln can occupy the same positions. This provides the opportunity to construct a family of compounds and optimize magnetic exchange in these molecules through composition tuning. Small-angle X-ray scattering (SAXS) and high-resolution electrospray ionization mass spectrometry (HRESI-MS) show that these clusters are stable upon dissolution in both water and organic solvents, as a first step to performing further chemistry towards building magnetic arrays or investigating ferrihydrite and magnetite assembly from pre-nucleation clusters.

Two pairs of enantiomeric 3d–4f metal clusters, [Co2Ln[(R)/(S)-L]4]·Cl5·(H2O)2·CH3OH·CH3CH2OH [Co2Ln; Ln = Gd (1S and 1R), Dy (2S and 2R)], were synthesized by the reaction of chiral Schiff-base li...

Two lanthanide-titanium oxo clusters (LTOCs), formulated as [Eu3Ti3(μ3-O)2(μ3-OH)(CH3O)2(Ac)2(CH3OH)(tbba)12]·CH3OH (1) and [Eu6Ti8(μ3-O)13(μ2-OH)(μ3-OCH3)2(μ2-OCH3)2(H2O)(CH3OH)2(tbba)19]·Htbba·10H2O (2), were synthesized through the solvothermal reaction of 4-tert-butylbenzoate ligand, Eu(Ac)3·3H2O, and Ti(OiPr)4 in methanol. Single-crystal structural analysis reveals that 1 crystallized in the orthorhombic space group Pnn2, and 2 crystallized in the triclinic space group P1. Structurally, the core of 1 can be viewed as a coplanar unit of [Eu3Ti3(μ3-O)2(μ3-OH)]16+ formed through each μ3-O2- and μ3-OH- bridging one Ti4+ and two Eu3+ ions, while that of 2 can be viewed as two units of [Eu3Ti3(μ3-O)3(μ2-O)4(μ2-OCH3)2(CH3OH)]5+ and [Eu3Ti5(μ3-O)6(μ2-OH)(μ3-OCH3)2(H2O)(CH3OH)]14+ connected through four μ2-O units from the [Eu3Ti3(μ3-O)3(μ2-O)4(μ2-OCH3)2(CH3OH)]5+ unit to respectively coordinate two Eu3+ and two Ti4+ ions from the [Eu3Ti5(μ3-O)6(μ2-OH)(μ3-OCH3)2(H2O)(CH3OH)]14+ unit. Measurement of their luminescence properties shows that the luminescence lifetime and quantum yield are 1212 μs and 69.6% for 1 and 857 μs and 56.2% for 2. When F- was introduced into 1 in a molar ratio of F- to 1 of 1:3, its quantum yield was increased 1.3 times, and the lifetime increased from 1.2 to 1.4 ms. However, no obvious enhancement in the emission intensity was observed in 2; even the molar ratio of F- to 2 is in the range from 2 to 1/4. Investigation on the structures of 1 and 2 reveals that the luminescence lifetime and quantum yield in 1 is significantly larger than that in 2 are attributed to the vibration of the nonradiative O-H vibration groups in 1 being significantly smaller than that in 2.

High-nuclearity lanthanide clusters have attracted much attention in different fields because of their unique physical and chemical properties and their potential applications. In this review, the synthetic strategy and building blocks for the assembly of high-nuclearity lanthanide clusters are outlined based on recently reported high-nuclearity lanthanide clusters. Perspectives for future studies on high-nuclearity lanthanide clusters are also discussed. We hope this review will provide insight into future research on high-nuclearity lanthanide clusters.

Guided by TNF-α secretion inhibitory activity assay, four taraxastane-type triterpenoids, including two new ones, 22-oxo-20-taraxasten-3β, 30-diol (1) and 22α-hydroxy-20-taraxasten-30β, 30-triol (2), have been obtained from an active fraction of the petroleum ether-soluble extract of the the medicinal and edible plant Cirsium setosum. Their structures were elucidated by spectroscopic data and CD data analysis. In the TNF-α secretion inhibitory activity assay, compounds 1 and 2 were active with the IC50 of 2.6 and 3.8 μmol·L-1, respectively. In addition, compounds 1 and 2 showed moderately selective cytotoxicity against the human ovarian cancer (A2780) and colon cancer (HCT-8) cell lines.

Herein, a fluorescent probe based on the FRET mechanism was designed and synthesized for sensing trace water in acetonitrile and tetrahydrofuran. When this probe was titrated with water, excellent linearity and low detection limit were obtained; in addition, theoretical calculations were used to optimize the transition state of the probe towards the sensing of water. Moreover, the observed vibration between the probe and the water molecule supported the proposed sensing mechanism.

Access to Super H-mode is demonstrated for moderately shaped plasmas in agreement with EPED [Snyder et al., Phys. Plasmas 16, 056118 (2009)] predictions. In particular, Super H-mode is realized in a DIII-D shape that is accessible to the JET tokamak. The reduced triangularity of the JET-compatible shape compared to previous Super H-mode plasma shapes does not prevent deep ascension into the so-called Super H-mode "channel."Operationally, access is enabled and optimized by delaying the neutral beam power injection and, thus, protracting the L-H transition. In highly shaped DIII-D plasmas, the injection of nitrogen sufficient for the establishment of a radiative divertor is shown to be possible during Super H-mode without pedestal degradation. Due to its increased stored energy and radiative divertor integration capabilities, Super H-mode is a promising candidate as operating regime for JET, ITER, and future fusion reactors.

A luminescent lanthanide-titanium oxo cluster of Eu2Ti4(μ2-O)2(μ3-O)4(phen)2(tbza)10·4CH3CN (1, Eu2Ti4-phen-tbza, phen = 1,10-phenanthroline, Htbza = 4-tert-butylbenzoic acid) was prepared through ...

Gymnadenia conopsea R. Br. is a traditional Tibetan medicinal plant that grows at altitudes above 3000 m, which is used to treat neurasthenia, asthma, coughs, and chronic hepatitis. However, a comprehensive configuration of the chemical profile of this plant has not been reported because of the complexity of its chemical constituents. In this study, a rapid and precise method based on ultra-high performance liquid chromatography (UPLC) combined with an Orbitrap mass spectrometer (UPLC&ndash, Orbitrap&ndash, MS/MS) was established in both positive- and negative-ion modes to rapidly identify various chemical components in the tubers of G. conopsea for the first time. Finally, a total of 91 compounds, including 17 succinic acid ester glycosides, 9 stilbenes, 6 phenanthrenes, 19 alkaloids, 11 terpenoids and steroids, 20 phenolic acid derivatives, and 9 others, were identified in the tubers of G. conopsea based on the accurate mass within 3 ppm error. Furthermore, many alkaloids, phenolic acid derivates, and terpenes were reported from G. conopsea for the first time. This rapid method provides an important scientific basis for further study on the cultivation, clinical application, and functional food of G. conopsea.

Five new secoiridoid glycosides, cornusphenosides E-I (1–5), were isolated and characterized from an active fraction of ethanol extract of the fruits of Cornus officinalis. Their structures were determined by extensive spectroscopic data analysis, including 2 D NMR and HRESIMS experiments. In the preliminary assay, compound 5 (when evaluated at 10 μM) showed the neuroprotective effect against H2O2-induced SH-SY5Y cell damage.

Searching for PD-1/PD-L1 inhibitor from medicinal plants has become a potential method to discover small molecular cancer immunotherapy drugs. Using PD-1/PD-L1 inhibitory activity assay in vitro, a bioactive fraction was obtained from the ethanol extract of Gymnadenia conopsea. A sensitive UPLC-HRMS/MS method was established for the rapid screening and identification of compositions from bioactive fraction. Based on the characteristic fragmentation patterns of standards analysis and extracted ion chromatogram (EIC) method, 46 compounds were rapidly screened and identified (including 35 succinic acid ester glycosides and 11 other compounds), among which 17 compounds were tentatively identified as new compounds.

Heterometallic lanthanide-transition-metal (4f-3d) clusters with well-defined crystal structures integrate multiple metal centers and provide a platform for achieving synergistic catalytic effects. Herein, we present a strategy for enhanced hydrogen evolution by loading atomically precise 4f-3d clusters Ln52 Ni56 on a CdS photoabsorber surface. Interestingly, some Ni2+ ions in the clusters Ln52 Ni56 were exchanged by the Cd2+ to form Ln52 Ni56-x Cdx /CdS composites. Photocatalytic studies show that the efficient synergistic multipath charge separation and transfer from CdS to the Eu52 Ni56-x Cdx cluster enable high visible-light-driven hydrogen evolution at 25 353 μmol h-1 g-1 . This work provides the strategy to design highly active photocatalytic hydrogen evolution catalysts by assembling heterometallic 4f-3d clusters on semiconductor materials.

We report the rational design of coordination-driven self-assembly metal-organic nanostructures for multifunctional nanotheranostics. Zinc(II) coordination-based nano-formulations capable of loading indocyanine green (ICG) and therapeutic genes were prepared to achieve a fluorescence/photoacoustic imaging-guided combination photo/gene therapy strategy. We showed the enhanced theranostic capability of zinc(II)-dipicolylamine-assisted assembly of ICG, as well as simultaneous targeted gene delivery in an experimental mouse model of cancer. Such a co-assembly strategy provides a facile way to achieve combined therapeutic functions for personalized nanomedicine.

Research on Alfven waves and Alfven eigenmodes is of importance in tokamak plasma physics, such as investigation of interaction between energetic particles and AEs, turbulence and anomalous transport due to AEs, and so on. An Alfven antennas system is designed for J-TEXT tokamak in order to study the Alfven eigenmode excitation, damping features and so on. For a typical J-TEXT plasma, the computed gaps in the Alfven continua range from 300 to 500 kHz, with respect to the Alfven waves dispersion relation. Three pairs of antennas are designed at different toroidal angels respectively on the low field side. Each pair consisting of two coils installed with angles of ±45 off the mid-plane along the poloidal direction. With this system, strong magnetic field components of different mode number can be produced.

P-type molecular sieve antimicrobial agents, which were grafted with potassium diformate using chitosan as an intermediat, were synthesized from hydrothermal process. The effects of hydrothermal process conditions (pH, reaction time, reaction temperature and mass ration of P-type molecular sieves: chitosan: potassium diformate) were investigated in detail. XRD, FTIR spectroscopy and SEM were applied to characterized the P-type molecular sieve antimicrobial agents. The antimicrobial performance of P-type molecular sieve antimicrobial agents were evaluated with the OD value and growth curve of Staphylococcus aureus. Atomic absorption spectrophotometer was introduced to measure the K+ concentration. Under the optimum synthesis condition of P-type molecular sieve antimicrobial agents (reaction temperature=50 °C, reaction time=3 h, and the mass ratio=3:1:2), the inhibitory rate of P-type molecular sieve antimicrobial agents was as high as 89%.

Titanium oxo clusters (TOCs) are the well-defined molecular modes for TiO2 materials and provide the opportunity to clarify the relationships between the structures and properties of TiO2. Here, we...

A building blocks strategy is an effective approach for constructing the large molecular systems. Herein, we demonstrate that high-resolution electro-spray ionization mass spectrometry (HRESI-MS) provides an effective chance to insight the assemble process of the building blocks and guides the construction of high-nuclearity metal clusters on the basis of the reaction of Ti(Oi Pr)4 , Eu(acac)3 , and salicylic acid. The time-dependent HRESI-MS indicates that not only a Eu3 Ti building block can be formed, but that it can further assemble into a Eu24 Ti8 compound. Temperature-dependent HRESI-MS reveals that increase of the reaction temperature favors the formation and crystallization of the stable Eu24 Ti8 structure. Single-crystal structural analysis demonstrates that the Eu24 Ti8 has a wheel-like structure with diameter of ca. 4.1 nm and is the highest nuclearity lanthanide-titanium oxo cluster reported to date.

Although many high-nuclearity lanthanide-containing clusters with aesthetical topological nanoarchitectures and unique magnetic properties have been synthesized, there was a big time lag to develop functional soft materials and devices on the basis of these clusters, because of their stability and processability. Herein, we report a universal strategy to fabricate lanthanide cluster based magnetic soft materials under ambient conditions. The prototypical cluster [Gd52Ni56(IDA)48(OH)154(H2O)38]18+ was encapsulated as an inorganic core by polymeric shells of sulfonate end functionalized poly(ethylene glycol) monoalkyl ethers through electrostatic interaction. The thickness of the shell was readily controlled by precisely tuning length of the polymer chain, leading to controllably reduced antiferromagnetic interactions between the clusters. The encapsulated hybrids can self-assemble to form vesicles in solution and can be used as an excellent agent for in vivo magnetic resonance imaging.

The Chinese Fusion Engineering Testing Reactor (CFETR) is a next fusion device proposed in China. The ability to exhaust the plasma power loss is a critical issue for the successful production of a fusion power reactor. For Phase II of CFETR with fusion power ~1 GW, the extremely large divertor heat load would be a severe challenge to achieve steady-state operation. In this paper, we have simulated the divertor performance by using SOLPS5.0 (B2.5-EIRENE) code package for a lower single null divertor configuration based on a core self-consistent steady-state scenario with Ar seeding. The core self-consistent steady-state scenario is calculated by a 1.5-D modeling workflow utilizing the One Modeling Framework for Integrated Tasks (OMFIT) framework. The modeling shows that Ar puffing from the lower divertor region together with D2 puffing from upstream is highly effective in mitigation of the divertor peak heat flux and temperature for the whole outer target and near strike point on the inner divertor target, however, electron and ion temperature ( $T_{e}$ and $T_{i})$ at far scrape-off layer on inner divertor is still higher than the erosion mitigation. In addition, comparison simulation of different divertor geometries has been performed in this paper. Further work on self-consistent core-edge coupling to estimate the effect of impurity seeding on core performance as well as the optimization of divertor geometry and operations will be studied.

High-nuclearity cluster-type metal complexes are a unique class of compounds, many of which have aesthetically pleasing molecular structures. Their interesting physical and chemical properties arise primarily from the electronic and/or magnetic interplay between the component metal ions. Among the extensive studies in the past two decades, those on lanthanide-containing clusters, lanthanide-exclusive or heterometallic with transition metal elements, are most notable. The research was driven by both the synthetic challenges for these generally elusive species and their intriguing magnetic properties, which are useful for the development of energy-efficient and environmentally friendly magnetic cooling technologies. Our efforts in this vein have been concentrated on developing rational synthetic methods for high-nuclearity lanthanide-containing clusters. By means of the now widely adopted approach of "ligand-controlled hydrolysis" of lanthanide ions, a great variety of cluster-type lanthanide hydroxide complexes had been prepared in the first half of this developing period (1999-2006). In this Account, our efforts since 2007 are summarized. These include (1) further development of synthetic strategies in order to expand the ligand scope and/or to increase the nuclearity (25) of the cluster species and (2) magnetic studies pertinent to the pursuit of materials with a large magnetocaloric effect (MCE). Specifically, with the hope of expanding the family of ligands and producing clusters of previously unknown structures, we tested under hydrothermal or solvothermal conditions the use of readily available yet not commonly used ligands for controlling lanthanide hydrolysis; such ligands, carboxylates as mundane examples, tend to form insoluble complexes prior to any possible hydrolysis. We have also validated the use of preformed transition metal complexes as metalloligands for subsequent control of lanthanide hydrolysis toward heterometallic 3d-4f clusters. Furthermore, we demonstrated using ample examples that the presence of small anions as templates is essential to the assembly of high-nuclearity lanthanide-containing clusters and that maintaining a low concentration of the anion template(s) is a key to such success. It has been found that slow production/release of such anion templates by in situ ligand decomposition or absorption of atmospheric CO

Four high-nuclearity lanthanide–transition metal clusters, formulated as [Ln45M7(OH)68(CO3)12(CH3COO)26(CH3CH2COO)6(H2O)70]·(ClO4)25·(H2O)x (abbreviated as Ln45M7: 1, Gd45Co7; 2, Gd45Ni7; 3, Dy45Co7; 4, Dy45Ni7; x ≈ 50), were obtained with the mixed protecting ligands acetate and propionate. Structural analysis shows that the cluster cationic core contains 52 metal ions featuring a bowl-like structure. 12 CO32− and 3 ClO4− anions play the role of mixed anion templates. Magnetic studies reveal that the two isotropic Gd-containing clusters Gd45Co7 and Gd45Ni7 exhibit a large magnetocaloric effect (MCE), while the anisotropic Dy-containing clusters Dy45Co7 and Dy45Ni7 show slow relaxation of magnetization.

Nanoscale inorganic wheel-shaped structures are one of the most striking types of molecular aggregations. Here, we report the synthesis of a gigantic lanthanide wheel cluster containing 140 Gd3+ atoms. As the largest lanthanide cluster reported thus far, {Gd140} features an attractive wheel-like structure with 10-fold symmetry. The nanoscopic molecular wheel possesses the largest diameter of 6.0 nm and displays high stability in solution, which allows direct visualization by scanning transmission electron microscopy. The newly discovered lanthanide {Gd140} cluster represents a new member of the molecular wheel family.

The ramp up scenario design, which considers of both physics and engineering constrains, plays an important part in fusion device design. A workflow of ramp up design, which includes Tokamak Simulation Code (TSC), ONETWO and ANSYS, has been developed on CFETR Integrated Design Platform. According to the 0-D design, the 1.5 D code TSC is used to build a ramp up scenario describing all parameters evolutions, targeting the design goals and attempting to remain in all constrains. In TSC simulation, the deposited power and driven current of auxiliary heating are calculated by ONETWO. The plasma current and PF coil currents are then used as input of ANSYS, to analysis the 3D eddy current and electromagnetic force in the main structural components. An example case of CFETR ramp up, with ohmic heating during the current ramp up phase and 57 MW of neutral beam and 10 MW of electron cyclotron at the flattop, is given in this article to show the function of the workflow. Under the unified environment for both physics and engineering design provided by CFETR integrated design platform, the present workflow will make the ramp up design more efficient.

The largest Ln-Fe metal cluster [Gd12 Fe14 (μ3 -OH)12 (μ4 -OH)6 (μ4 -O)12 (TEOA)6 (CH3 COO)16 (H2 O)8 ]⋅(CH3 COO)2 (CH3 CN)2 ⋅(H2 O)20 (1) and the core-shell monodisperse metal cluster of 1 a@SiO2 (1 a=[Gd12 Fe14 (μ3 -OH)12 (μ4 -OH)6 (μ4 -O)12 (TEOA)6 (CH3 COO)16 (H2 O)8 ]2+ ) were prepared. Experimental and theoretical studies on the magnetic properties of 1 and 1 a@SiO2 reveal that encapsulation of one cluster into one silica nanosphere not only effectively decreases intermolecular magnetic interactions but also significantly increases the zero-field splitting effect of the outer layer Fe3+ ions.

A series of heterometallic 3d–4f clusters, formulated as Na17[Ln3(H2O)5NiII(H2O)3(Sb4O4)(SbW9O33)3(NiIIW6O24)(WO2)3(CH3COO)]·(H2O)65 [abbreviated as Ln3Ni2, where Ln = La3+ (1), Pr3+ (2), and Nd3+ (3)], K5Na11[Ln3(H2O)3NiII3(H2O)6(SbW9O33)3(WO4)(CO3)]·(H2O)40 [abbreviated as Ln3Ni3, where Ln = La3+ (4), Pr3+ (5), and Nd3+ (6)], and K3Na27[Ln3NiII9(μ3-OH)9(SbW9O33)2(PW9O34)3(CH3COO)3]·(H2O)80 [abbreviated as Ln3Ni9, where Ln = Dy3+ (7) and Er3+ (8)], were obtained through the reaction of the lacunary {SbW9O33} precursor with Ln(NO3)3·6H2O and NiCl2·6H2O in a NaAc/HAc buffer in the presence of different anions. Single-crystal X-ray structure analysis revealed that compounds 1–3 possessed tetrameric architectures featuring three Keggin-type {SbW9O33} and one Anderson-type {NiIIW6O24} building blocks encapsulating one {Sb4O4} cluster, three WO2 units, three Ln3+ metal ions, and two Ni2+ metal ions. Compounds 4–6 displayed cyclic trimeric aggregates of three {SbW9O33} units enveloping one CO32–-templated trinu...

Developing a widely-used reactive force field is meaningful to explore the fundamental reaction mechanism on gas-surface chemical reaction dynamics due to its very high computational efficiency. We here present a study of hydrogen and its deuterated molecules dissociation on Pd surfaces based on a full-dimensional potential energy surface (PES) constructed by using a simple second moment approximation reactive force field (SMA RFF). Although the descriptions of the adsorbate-substrate interaction contain only the dissociation reaction of H2/Pd(111) system, a good transferability of SMA potential energy surface (PES) is shown to investigate the hydrogen dissociation on Pd(100). Our simulation results show that, the dissociation probabilities of H2 and its deuterated molecules on Pd(111) and Pd(100) surfaces keep non-monotonous variations with respect to the incident energy Ei, which is in good agreement with the previous ab initio molecular dynamics. Furthermore, for the oriented molecules, the dissociation probabilities of the oriented H2 (D2 and T2) molecule have the same orientation dependence behavior as those oriented HD (HT and DT) molecules.

Three homometallic high-nuclearity clusters, formulated as [(CO3)2@Ln37(LH3)8(CH3COO)21(CO3)12(μ3-OH)41(μ2-H2O)5(H2O)40]·(ClO4)21·(H2O)100 (abbreviated as Ln37, Ln = Gd (1); Tb (2); Eu (3), LH3 = 1,2,3-cyclohexanetriol) and featuring a double cage-like structure, were obtained through the reaction of 1,2,3-cyclohexanetriol, acetate ligand, and Ln(ClO4)3. The largest odd-numbered lanthanide cluster Gd37 exhibits an entropy change (−ΔSm) of 38.7 J kg–1 K–1.

A series of lanthanide–titanium oxo clusters (LnTOCs), Ln2Ti8-Ac, Ln2Ti8-p-Toluic, and Ln2Ti8-Anthra (Ln = Eu and Tb), were prepared based on acetic acid (HAc), p-toluic acid (Hp-Toluic), and anthr...

Sparassis crispa is a kind of edible fungus widely grows in the north temperate zone, which shows various medicinal properties. Due to the complexity of chemical constitutes of this species, few investigations have acquired a comprehensive configuration for the chemical profile of it. In this study, a strategy based on ultra-high performance liquid chromatography (UPLC) combined with Orbitrap mass spectrometer (MS) was established for rapidly characterizing various chemical components in S. crispa. Through the summarized MS/MS fragmentation patterns of reference compounds and systematic identification strategy, a total of 110 components attributed to six categories were identified for the first time. Moreover, allergic rhinitis (AR) is a worldwide inflammatory disease seriously affecting human health, and the development of drugs to treat AR has been a topic of interest. It has been reported that the extracts of S. crispa showed obvious inhibitory effects on degranulation of mast cell- and allergen-induced IgE and proinflammatory mediators, but the active components and specific mechanism were still not clear. Src family kinases (SFKs) participate in the initial stage of allergy occurrence, which are considered the targets of AR treatment. Herein, on the basis of that self-built chemical database, virtual screening was applied to predict the potential SFKs inhibitors in S. crispa, using known crystal structures of Hck, Lyn, Fyn, and Syk as receptors, followed by the anti-inflammatory activity evaluation for screened hits by intracellular calcium mobilization assay. As results, sparoside A was directly confirmed to have strong anti-inflammatory activity with an IC50 value of 5.06 &plusmn, 0.60 &mu, M. This study provides a useful elucidation for the chemical composition of S. crispa, and demonstrated its potential inhibitory effects on AR, which could promote the research and development of effective agents from natural resources.

Three previously undescribed iridoids, cornusfurals A&ndash, C, were isolated from the ethanolic extracts of fruits of Cornus officinalis. Their structures were elucidated by spectroscopic methods, including one-dimensional and two-dimensional nuclear magnetic resonance, ultraviolet spectroscopy, infrared spectroscopy, and mass spectrometry. The neuroprotective activity was evaluated by measuring corticosterone-induced damage in PC12 cells. The results showed that cornusfural B decreased corticosterone-induced PC12 cell damage compared with that in model cells.

Excellent confinement has been routinely observed in DIII-D (J. L. Luxon, Nucl. Fusion 2002) high β p discharges, which are characterized by a strong large-radius internal transport barrier (ITB) in almost all kinetic channels. Typically, the ion thermal transport is neoclassical with conventional long-wavelength turbulence instabilities suppressed by α stabilization, while the mechanism for the anomalous electron thermal transport remains unclear [Garofalo et al., Nucl. Fusion 55(12), 123025 (2015)]. A new gyrokinetic analysis shows that while the large values of α in the ITB can stabilize all local electrostatic drift wave (ES-DW) instabilities as well as the kinetic ballooning mode, a new slab-like microtearing mode (MTM) with its eigenfunction mainly peaking on the high field slide is destabilized. This destabilization is shown to be more likely to happen in discharges with high safety factors. Nonlinear gyrokinetic simulations demonstrate that this MTM branch can reproduce the experimentally inferred electron thermal flux in the ITB region and, therefore, provide convincing evidence that the electron temperature profile in the ITB is regulated by the MTM. Extrapolations to the future scenarios, like ITER high β p plasmas, show that the dominant instability is likely to come back to ES-DW due to the lower density gradient and collisionality. However, even in this regime, some unusual features associated with MTMs predicted for DIII-D parameters, such as the high-field-side peaking and slab nature, may remain for the reactor ES-DW.

Internal magnetic fluctuation measurements are utilized to identify turbulence associated with micro-tearing modes (MTM) in the DIII-D Edge-Localized-Mode (ELM)-y H-mode pedestal. Using a Faraday-effect polarimeter, magnetic turbulence (150–500 kHz) is directly observed with a typical line-averaged fluctuation amplitude of ∼0.8 G at peak frequency (250 kHz) and ∼15 G integrated over the spectrum from 150 to 500 kHz. Frequency, poloidal wavenumber, and propagation direction of the magnetic turbulence all serve to identify as MTM. Magnetic turbulence amplitude non-monotonically correlates with collision frequency, peaks off mid-plane, and correlates with electron temperature gradient evolution between ELMs, consistent with MTM features identified from theory and gyro-kinetic simulation. The magnetic turbulence growth correlates with confinement degradation in ELMy H-mode plasmas during a slow density ramp. These internal measurements provide unique constraints toward developing physics understanding and validating models of the H-mode pedestal for future devices.

We report two nonanuclear lanthanide complexes, [Ln9(μ4-O)(μ3-OH)8(LH)4(OAc)4(H2O)12]·5ClO4·24H2O (Ln = Gd, 1; Dy, 2), where LH2– is the doubly deprotonated chiral ligand Chromogen I (2-acetamido-2,3-dideoxy-D-erythro-hex-2-enofuranose), one of the many products from the dehydration of N-acetyl-D-glucosamine (GlcNAc). Mass spectroscopic studies established the solution stability of these clusters. Through hydrogen bonding, the cluster complex self-organizes into a nanostructured 54-metal cagelike assembly featuring six of its units occupying the vertices of an octahedron. Free Chromogen I can be obtained in pure form and high yield by a straightforward workup of the cluster complex. This is the first report of dehydrating GlcNAc without the need of a catalyst or forcing conditions.

We propose a design method for all-optical multi-level regenerators by mimicking the normalized power transfer function (PTF) in the first-order approximation to the ideal step-like PTF, in which a key step is to appropriately select the amplitude and phase conditions of Mach–Zehnder-interferometer (MZI)-based regenerators. As an example, we describe the design process of the self-phase-modulation (SPM)-based MZI regenerator constructed by a section of nonlinear fiber and an optical phase shifter (OPS). It is shown that the parameter of reference power level (RPL) can be regarded as the upper limit of input power, which is useful for the measure of the multi-level regeneration performance. The number of regenerative power levels increases with the RPL parameter. For 4-level pulse amplitude modulated (4PAM) optical signals degraded by the Gaussian noises with the standard deviation of 0.02, the SPM-based MZI regenerator has an average noise reduction ratio (NRR) of 6.5 dB, better than that of 1st-order regenerator by about 5 dB.

The EFIT program is integrated with the high resolution laser polarimeter interferometer system (POLARIS), the soft X-ray imaging diagnostic system (SXR) and the electron cyclotron emission radiometer (ECE) in the J-TEXT tokamak. Then some internal information about Faraday angle and the position of safety factor q=1 can be obtained as a constraint to EFIT. The modified EFIT code is used to calculate the internal parameters such as flux function, safety factor q, pressure and current density.

The China Fusion Engineering Test Reactor (CFETR) integrated system code contains three parts: a zero dimensional code, a physics platform and an engineering platform. We use the zero dimensional code to identify a set of preliminary physics and engineering parameters for CFETR, which is used as input to initiate multi-dimension studies using the physics and engineering platform for design, verification and validation. Effective data exchange between the zero dimensional code and the physical platform is critical for the optimization of CFETR design. For example, in evaluating the impact of impurity radiation on core performance, an open field line code is used to calculate the impurity transport from the first-wall boundary to the pedestal. The impurity particle in the pedestal are used as boundary conditions in a transport code for calculating impurity transport in the core plasma and the impact of core radiation on core performance. Comparison of the results from the multi-dimensional study to those from the zero dimensional code is used to further refine the controlled radiation model. The data transfer between the zero dimensional code and the physical platform, including data iteration and validation, and justification for performance parameters will be presented in this paper.

We have developed a ratiometric fluorescent probe based on ICT mechanism for imaging intracellular sulfite (SO 3 2− ) in HeLa cells. The probe could selectively stain cells with scarce cytotoxicity and excellent photostability. The probe displayed a high selectivity for sulfite over other anions and active small biological molecules including cysteine (Cys), homocysteine (Hcy) and glutathione (GSH) at room temperature. The reaction could complete within 30 s and detection limit was as low as 76 nM, which is superior to some reported probes. The detecting mechanism was proved by MS, 1 H NMR and theoretical calculation. The probe can also detect endogenous sulfite in HepG2 cells.

The equilibrium fitting code (EFIT) and its application in the J-TEXT tokamak are integrated by the Matlab language. The function of analysis and visualization to the results is added. In addition, the experiment data measured by soft X-ray (SXR) are used to calculate plasma equilibrium as a constraint condition. The improved EFIT code is used for J-TEXT discharge and the profiles of plasma parameters such as flux function, safety factor q, pressure and current density are obtained from the reconstructed configurations.

NBDlyso with lysosome-locating morpholine moiety has been developed as a high selective and sensitive fluorescent pH probe. This probe can respond to acidic pH (2.0-7.0) in a short time (less than 1 min) and not almost change after continuously illuminated for an extended period by ultraviolet light. The fluorescence intensity of NBDlyso enhanced 100-fold in acidic solution, with very good linear relationship (R(2) = 0.996). The pKa of probe NBDlyso is 4.10. Therefore, NBDlyso was used to detect lysosomal pH changes successfully. Besides, X-ray crystallography was used to verify the structure of NBDlyso, and the recognition mechanism involving photo-induced electron transfer was interpreted theoretically by means of DFT and TDDFT calculations skillfully when NBDlyso comes into play under the acidic condition. This probe showed good ability to sense pH change in living cell image.