Ph
3
P is found to be inert to sodium in toluene even on heating. This phenomenon leads to the finding that in toluene Ph
3
PS reacts with sodium efficiently and selectively to produce quantitative ...yields of highly valuable Ph
3
P and anhydrous Na
2
S. By applying this finding, anhydrous Na
2
S can be safely and conveniently prepared using a Ph
3
P-mediated reaction from sodium and sulfur. This finding also leads to the establishment of a feasible alternative strategy (the sulfur method) for the restoration of the Ph
3
PO waste to Ph
3
P that is greener and safer than the currently operating "chlorine method" using phosgene.
Ph
3
P is found to be inert to sodium in toluene even on heating.
Abstract Extracting uranium from real water samples remains a great challenge due to low uranium concentration, concentrated competing ions and volumes of water. The design and preparation of uranium ...adsorbents with high efficiency and affinity are still difficult. Herein, we presented a facile one‐pot strategy to obtain a novel metal organic framework (denoted as Mn‐NDISA) for stable and efficient trapping of low concentration uranium. Mn‐NDISA with a built‐in hydrophobic cavity can boost the absorption affinity to 1.99 × 10 6 mL g −1 through the cooperative capture composed of electrostatic interaction, coordination force and hydrogen binding. Owing to the coordination‐available oxygen sites in flexible framework, a rapid kinetic equilibrium was achieved in just 25 min. Moreover, these exceptional adsorption features enabled Mn‐NDISA to successfully capture the naturally occurring uranium traces (~ppb) in wastewater samples, making it one of the most influential absorbents toward UO 2 2+ ever reported. The experimental and theoretical studies revealed that the electrostatic attraction came from the surface negatively charged Mn‐NDISA and the positively charged UO 2 2+ . The coordination originated from Lewis basic hydroxyl, carbonyl groups, and Lewis acid UO 2 2+ , while hydrogen bonds further reinforced the as‐formed uranium binding complex. This research offered a promising cooperative capture strategy to improve the uranium affinity of the pristine MOF for trace contaminants removal in environmental remediation fields.
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•Triformylphloroglucinol and thiosemicarbazide as precursors for synthesizing TpTsc.•TpTsc with excellent adsorption capacity of gold shows higher than most adsorbents.•Dual functions ...of adsorption and reduction enhance gold adsorption capacity of TpTsc.•TpTsc can selectively extract gold from real electronic waste liquids.
Recovering precious metals from electronic equipment waste involves significant environmental and economic benefits. In this paper, a covalent organic framework, named as TpTsc COF, was synthesized by using flexible alkyl amine thiosemicarbazide (Tsc) and 1,3,5-triformylphloroglucinol (Tp) as precursors for extracting gold from actual electronic waste. The results show that it has favorable selectivity, high recycling and groundbreaking adsorption capacity (4400.23 mg g−1). Such excellent adsorption capacity can be attributed to the improved crystallinity by irreversible enol-to-tautomerism of Tp, the abundant functional group sites in Tsc, and the efficient reduction of gold by thiourea. The adsorption process can be well fitted with the pseudo-second-order kinetic model and Langmuir mode, which is characterized by the coordination between Au (III) and S, N, O atoms in COF, as well as the electrostatic interaction between protonated amino groups and AuCl4− in acidic system. The advantages of this feasible method facilitate effective gold recovery from low-cost electronic waste.
Quantum geometry in condensed-matter physics has two components: the real part quantum metric and the imaginary part Berry curvature. Whereas the effects of Berry curvature have been observed through ...phenomena such as the quantum Hall effect in two-dimensional electron gases and the anomalous Hall effect (AHE) in ferromagnets, the quantum metric has rarely been explored. Here, we report a nonlinear Hall effect induced by the quantum metric dipole by interfacing even-layered MnBi
Te
with black phosphorus. The quantum metric nonlinear Hall effect switches direction upon reversing the antiferromagnetic (AFM) spins and exhibits distinct scaling that is independent of the scattering time. Our results open the door to discovering quantum metric responses predicted theoretically and pave the way for applications that bridge nonlinear electronics with AFM spintronics.
Hepatocellular carcinoma (HCC) is one of the most prevalent malignancies worldwide because of rapid progression and high incidence of metastasis or recurrence. Accumulating evidence shows that ...CD73-expressing tumor cell is implicated in development of several types of cancer. However, the role of CD73 in HCC cell has not been systematically investigated and its underlying mechanism remains elusive.
CD73 expression in HCC cell was determined by RT-PCR, Western blot, and immunohistochemistry staining. Clinical significance of CD73 was evaluated by Cox regression analysis. Cell counting kit-8 and colony formation assays were used for proliferation evaluation. Transwell assays were used for motility evaluations. Co-immunoprecipitation, cytosolic and plasma membrane fractionation separation, and ELISA were applied for evaluating membrane localization of P110β and its catalytic activity. NOD/SCID/γc(null) (NOG) mice model was used to investigate the in vivo functions of CD73.
In the present study, we demonstrate that CD73 was crucial for epithelial-mesenchymal transition (EMT), progression and metastasis in HCC. CD73 expression is increased in HCC cells and correlated with aggressive clinicopathological characteristics. Clinically, CD73 is identified as an independent poor prognostic indicator for both time to recurrence and overall survival. CD73 knockdown dramatically inhibits HCC cells proliferation, migration, invasion, and EMT in vitro and hinders tumor growth and metastasis in vivo. Opposite results could be observed when CD73 is overexpressed. Mechanistically, adenosine produced by CD73 binds to adenosine A2A receptor (A2AR) and activates Rap1, which recruits P110β to the plasma membrane and triggers PIP3 production, thereby promoting AKT phosphorylation in HCC cells. Notably, a combination of anti-CD73 and anti-A2AR achieves synergistic depression effects on HCC growth and metastasis than single agent alone.
CD73 promotes progression and metastasis through activating PI3K/AKT signaling, indicating a novel prognostic biomarker for HCC. Our data demonstrate the importance of CD73 in HCC in addition to its immunosuppressive functions and revealed that co-targeting CD73 and A2AR strategy may be a promising novel therapeutic strategy for future HCC management.
Triphenylphosphine oxide is a well-known industrial waste byproduct, and thousands of tons of it are generated every year. Due to its chemical stability and limited applications, settlement of this ...waste issue has drawn extensive attention from chemists. The reduction of triphenylphosphine oxide to triphenylphosphine is heretofore the most employed solution, and is well reviewed. In view of our recent studies on the selective and efficient conversion of Ph3P(O) to other valuable organophosphorus chemicals by using sodium, the present perspective mainly highlights the advances on the utilization of Ph3P(O) to prepare a diverse range of functional organophosphorus compounds, except Ph3P, via selective P–C, C–H, and P–O bond cleavages.
This study reports a novel and convenient bimodal method for label-free and signal-off detection of arsenate in environmental samples. Cobalt oxyhydroxide (CoOOH) nanoflakes with facile preparation ...and intrinsic peroxidase-like activity as nanozyme can efficiently catalyze the conversion of chromogenic substrate such as 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) with the presence of H2O2 into green-colored oxidation products. CoOOH nanoflakes can specifically bind with arsenate via electrostatic attraction and As–O bond interaction, which gives rise to inhibition of the peroxidase-like activity of CoOOH. Thus, through arsenate specific inhibition of CoOOH nanozyme toward ABTS catalysis, a simple colorimetric method was developed for arsenate detection with a detection limit of 3.72 ppb. Based on the system of CoOOH nanozyme and ABTS substrate, this colorimetric method can be converted into an electrochemical sensor for arsenate assay by the utilization of CoOOH nanoflake-modified electrode. The electrochemical measurement can be realized by chronoamperometry, which showed more sensitive and a lower limit of detection as low as 56.1 ppt. The applicability of this bimodal method was demonstrated by measuring arsenate and total arsenic in different real samples such as natural waters and soil extracted solutions, and the results are of satisfactory accuracy as confirmed by inductively coupled plasma mass spectrometry analysis. The bimodal strategy offers obvious advantages including a label-free step, convenient operation, on-site assay, low cost, and high sensitivity, which is promising for reliable detection of arsenate and total arsenic in environmental samples.
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•Reductive transformation of Ph3P(O) to Ph2PR.•Selective TMSO-P bond cleavage.•Easy preparation of chiral-phosphines.
By introducing trimethylsilyl chloride (TMSCl), the pentavalent ...phosphoryl P(V) compounds such as triphenylphosphine oxides, secondary phosphine oxides etc., were readily converted to the corresponding R2P(OTMS) intermediates, that can further react efficiently with an electrophile R’X or with a nucleophile R’Li to produce the corresponding trivalent phosphines R2PR’. Chiral phosphines could also be obtained stereospecifically by this strategy.
The origin of mafic enclaves in granitoid plutons has long been a matter of debate. In this paper, we present detailed petrographic, mineralogical, geochemical, and SrNdHf isotopic data, UPb zircon ...dates, and field and petrological observations, for mafic microgranular enclaves (MMEs) and their host quartz monzonites from the Muchen pluton in Southeast China to evaluate their origins. LA–ICP–MS UPb dating of zircon yields crystallisation ages of 112.4±1.2Ma and 112.1±1.0Ma for the MMEs and host quartz monzonites, respectively, indicating their coeval formation during the late Early Cretaceous. Field and petrological observations, such as spheroidal shapes, back-veining, double enclaves, xenocrysts, acicular apatites, and oscillatory zoning with repeated resorption surfaces in plagioclases, suggest that the MMEs are globules of a more mafic magma that was injected into and mingled with the host felsic magma. Geochemically, the host monzonites are intermediate-acidic, metaluminous, alkaline, and K-rich. In contrast, the MMEs are relatively poor in Si and K. The host monzonites are enriched in Rb, Th and U, and depleted in Sr, P, Nb, Ta and Ti, and show moderate to strong europium depletions (δEu=0.12–0.60). These mineralogical and geochemical features classify the quartz monzonites as belonging to the I-type granitoids. The MMEs have broadly similar trace element signatures to those of the host monzonite, but are distinct in having relatively enriched Sr and P, more depleted Zr and Hf, and weak to moderate Eu depletions (δEu=0.43–0.93). Major and trace element data plotted versus isotopic data for the MMEs and the host quartz monzonites yield covariant arrays that result from magma mixing during their petrogenesis. The MMEs and the host quartz monzonites have similar initial 87Sr/86Sr ratios (ISr) of 0.7058–0.7070 and 0.7062–0.7065, respectively, and both have high εNd(t) values (−2.6 to +0.6 for MMEs; −3.2 to −2.4 for quartz monzonites). However, zircons from the MMEs have different εHf(t) values (−0.4 to +6.2) than the host quartz monzonites (−1.0 to +1.8), indicating that the MMEs and host granitoids largely crystallised from different magmas, providing direct evidence for mafic–felsic magma mixing processes. The zircon saturation geothermometer and Al-in-hornblende geobarometer show that the Muchen pluton crystallised at temperatures of 797–851°C and depths of 6–7km. The integrated petrology, and elemental and isotopic compositions suggest that the MMEs and host quartz monzonites were generated by mixing of depleted, mantle-derived, mafic magmas and felsic magmas produced by partial melting of crustal materials in an extensional setting.
► Mafic microgranular enclaves are commonly present in Muchen pluton, South China. ► The consistency of ages implies the quartz monzonites and MMEs were coeval. ► Mafic magmas from which the MMEs crystallised likely had a depleted mantle source. ► Quartz monzonites were derived from a hybrid magma due to crust–mantle interaction. ► The Muchen pluton was most likely generated in an extensional setting.
The Scaly-foot Snail, Chrysomallon squamiferum, presents a combination of biomineralised features, reminiscent of enigmatic early fossil taxa with complex shells and sclerites such as sachtids, but ...in a recently-diverged living species which even has iron-infused hard parts. Thus the Scaly-foot Snail is an ideal model to study the genomic mechanisms underlying the evolutionary diversification of biomineralised armour. Here, we present a high-quality whole-genome assembly and tissue-specific transcriptomic data, and show that scale and shell formation in the Scaly-foot Snail employ independent subsets of 25 highly-expressed transcription factors. Comparisons with other lophotrochozoan genomes imply that this biomineralisation toolkit is ancient, though expression patterns differ across major lineages. We suggest that the ability of lophotrochozoan lineages to generate a wide range of hard parts, exemplified by the remarkable morphological disparity in Mollusca, draws on a capacity for dynamic modification of the expression and positioning of toolkit elements across the genome.
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