The hierarchical aggregation of molecular nanostructures from multiple components is a grand synthetic challenge, which requires highly selective linkage control. We demonstrate how two orthogonal ...linkage groups, that is, organotin and lanthanide cations, can be used to drive the aggregation of a giant molecular metal oxide superstructure. The title compound {(Sn(CH3)2)2O4{CeW5O18 TeW4O16CeSn(CH3)24TeW8O314}2}46− (1 a) features dimensions of ca. 2.2×2.3×3.4 nm3 and a molecular weight of ca. 25 kDa. Structural analysis shows the hierarchical aggregation from several independent subunits. Initial biomedical tests show that 1 features an inhibitory effect on the proliferation of HeLa cells based on an apoptosis pathway. In vivo experiments in mice reveal the antiproliferative activity of 1 and open new paths for further development of this new compound class.
Hierarchical assembly of a giant heterometallic polyoxotungstate supercluster with a molecular weight of ca. 25 kDa is reported. Geometrically unrestricted cerium(III) and geometrically restricted dimethyl tin cation linkers are used to gain access to a giant molecular species featuring three different polyoxometalate building units. The compound demonstrates in vitro and in vivo antiproliferative activity against HeLa cervical cancer cell lines.
The fabrication of transparent, conductive, and uniform silver nanowire films using the scalable rod-coating technique is described in this study. Properties of the transparent conductive thin films ...are investigated, as well as the approaches to improve the performance of transparent silver nanowire electrodes. It is found that silver nanowires are oxidized during the coating process. Incubation in hydrogen chloride (HCl) vapor can eliminate oxidized surface, and consequently, reduce largely the resistivity of silver nanowire thin films. After HCl treatment, 175 Ω/sq and approximately 75% transmittance are achieved. The sheet resistivity drops remarkably with the rise of the film thickness or with the decrease of transparency. The thin film electrodes also demonstrated excellent flexible stability, showing < 2% resistance change after over 100 bending cycles.
The exploration of high nuclearity molecular metal oxide clusters and their reactivity is a challenge for chemistry and materials science. Herein, we report an unprecedented giant molecular ...cerium–bismuth tungstate superstructure formed by self‐assembly from simple metal oxide precursors in aqueous solution. The compound, {W14CeIV6O61(W3Bi6CeIII3(H2O)3O14B‐α‐BiW9O333)2}34− was identified by single‐crystal X‐ray diffraction and features 104 metal centers, a relative molar mass of ca. 24 000 and is ca. 3.0×2.0×1.7 nm3 in size. The cluster anion is assembled around a central {Ce6} octahedron which is stabilized by several molecular metal oxide shells. Six trilacunary Keggin anions (B‐α‐BiW9O339−) cap the superstructure and limit its growth. In the crystal lattice, water‐filled channels with diameters of ca. 0.5 nm are observed, and electrochemical impedance spectroscopy shows pronounced proton conductivity even at low temperature.
A giant cerium–bismuth tungstate cluster featuring more than 100 metal ions and a relative molar mass of approximately 24 000 is structurally characterized. The cluster anions form a highly 3D‐porous crystalline lattice featuring water‐filled channels. Proton conductivity measurements show high proton mobility within the framework.
CD8
T cell-mediated cancer clearance is often suppressed by the interaction between inhibitory molecules like PD-1 and PD-L1, an interaction acts like brakes to prevent T cell overreaction under ...normal conditions but is exploited by tumor cells to escape the immune surveillance. Immune checkpoint inhibitors have revolutionized cancer therapeutics by removing such brakes. Unfortunately, only a minority of cancer patients respond to immunotherapies presumably due to inadequate immunity. Antitumor immunity depends on the activation of the cGAS-STING pathway, as STING-deficient mice fail to stimulate tumor-infiltrating dendritic cells (DCs) to activate CD8
T cells. STING agonists also enhance natural killer (NK) cells to mediate the clearance of CD8
T cell-resistant tumors. Therefore STING agonists have been intensively sought after. We previously discovered that manganese (Mn) is indispensable for the host defense against cytosolic dsDNA by activating cGAS-STING. Here we report that Mn is also essential in innate immune sensing of tumors and enhances adaptive immune responses against tumors. Mn-insufficient mice had significantly enhanced tumor growth and metastasis, with greatly reduced tumor-infiltrating CD8
T cells. Mechanically, Mn
promoted DC and macrophage maturation and tumor-specific antigen presentation, augmented CD8
T cell differentiation, activation and NK cell activation, and increased memory CD8
T cells. Combining Mn
with immune checkpoint inhibition synergistically boosted antitumor efficacies and reduced the anti-PD-1 antibody dosage required in mice. Importantly, a completed phase 1 clinical trial with the combined regimen of Mn
and anti-PD-1 antibody showed promising efficacy, exhibiting type I IFN induction, manageable safety and revived responses to immunotherapy in most patients with advanced metastatic solid tumors. We propose that this combination strategy warrants further clinical translation.
•Ground glass opacities in subpleural regions are the main CT features of COVID-19.•Pulmonary consolidation mostly occurs in critical patient.•Imaging features vary according to disease severity.•CT ...imaging can evaluate the severity and treatment outcome.
To report CT features of coronavirus disease-2019 (COVID-19) in patients with various disease severity.
The CT manifestations and clinical data of 73 patients with COVID-19 were retrospectively collected in 6 hospitals from Jan 21 to Feb 3, 2020. We analyzed the initial and follow-up CT features of patients with disease severity, according to the Guidelines for the Diagnosis and Treatment of New Coronavirus Pneumonia.
Six patients (8%) were diagnosed as mild type pneumonia; these patients had no obvious abnormal CT findings or manifested mild changes of lung infection. All 43 patients (59 %) with common type presented unique or multiple ground-glass opacities (GGO) in the periphery of the lungs, with or without interlobular septal thickening. In the 21 patients (29 %) with severe type, extensive GGO and pulmonary consolidation were found in 16 cases (16/21, 76 %) and 5 cases (24 %), respectively. An extensive "white lung", with atelectasis and pleural effusion were found in critical type patients (3, 4%). On the resolutive phase of the disease, CT abnormalities showed complete resolution, or demonstrated residual linear opacities.
Different CT features are seen according to disease severity, which can help COVID-19 stratification.
Tin‐based halide perovskite materials have been successfully employed in lead‐free perovskite solar cells, but the overall power conversion efficiencies (PCEs) have been limited by the high carrier ...concentration from the facile oxidation of Sn2+ to Sn4+. Now a chemical route is developed for fabrication of high‐quality methylammonium tin iodide perovskite (MASnI3) films: hydrazinium tin iodide (HASnI3) perovskite film is first solution‐deposited using presursors hydrazinium iodide (HAI) and tin iodide (SnI2), and then transformed into MASnI3 via a cation displacement approach. With the two‐step process, a dense and uniform MASnI3 film is obtained with large grain sizes and high crystallization. Detrimental oxidation is suppressed by the hydrazine released from the film during the transformation. With the MASnI3 as light harvester, mesoporous perovskite solar cells were prepared, and a maximum power conversion efficiency (PCE) of 7.13 % is delivered with good reproducibility.
High‐quality, pinhole‐free CH3NH3SnI3 films are achieved from pristine NH2NH3SnI3 perovskite, and the oxidation of Sn2+ to Sn4+ can be efficiently suppressed owing to the reduction agent hydrazine generated inside the films in the conversion. With the CH3NH3SnI3 film as light absorber, mesoporous MASnI3 perovskite solar cells were fabricated with a maximum PCE of 7.13 %.
A hybrid organic–inorganic compound, (pyrrolidinium)MnBr3
, distinguished from rare earth (RE)‐doped inorganic perovskites, is discovered as a new member of the ferroelectrics family, having ...excellent luminescent properties and relatively large spontaneous polarization of 6 μC cm−2, as well as a weak ferromagnetism at about 2.4 K. With a quantum yield of >28% and emission lifetime >0.1 ms, such multiferroic photoluminescence is a suitable candidate for future applications in luminescence materials, photovoltaics, and magneto‐optoelectronic devices.
Primordial follicle assembly in the mouse occurs during perinatal ages and largely determines the ovarian reserve that will be available to support the reproductive life span. The development of ...primordial follicles is controlled by a complex network of interactions between oocytes and ovarian somatic cells that remain poorly understood. In the present research, using single-cell RNA sequencing performed over a time series on murine ovaries, coupled with several bioinformatics analyses, the complete dynamic genetic programs of germ and granulosa cells from E16.5 to postnatal day (PD) 3 were reported. Along with confirming the previously reported expression of genes by germ cells and granulosa cells, our analyses identified 5 distinct cell clusters associated with germ cells and 6 with granulosa cells. Consequently, several new genes expressed at significant levels at each investigated stage were assigned. By building single-cell pseudotemporal trajectories, 3 states and 1 branch point of fate transition for the germ cells were revealed, as well as for the granulosa cells. Moreover, Gene Ontology (GO) term enrichment enabled identification of the biological process most represented in germ cells and granulosa cells or common to both cell types at each specific stage, and the interactions of germ cells and granulosa cells basing on known and novel pathway were presented. Finally, by using single-cell regulatory network inference and clustering (SCENIC) algorithm, we were able to establish a network of regulons that can be postulated as likely candidates for sustaining germ cell-specific transcription programs throughout the period of investigation. Above all, this study provides the whole transcriptome landscape of ovarian cells and unearths new insights during primordial follicle assembly in mice.
Seismic anisotropy records past and present tectonic deformations and provides important constraints for understanding the structure and dynamics of the Earth's interior. In this work, we use ...tremendous amounts of high‐quality P wave arrival times from local and regional earthquakes to determine a high‐resolution tomographic model of 3‐D P wave azimuthal anisotropy down to 1,000‐km depth beneath East Asia. Our results show that trench‐parallel fast‐velocity directions (FVDs) are visible in the shallow portion of the subducting Pacific slab (<80 km), whereas the deeper portion of the Pacific slab mainly exhibits trench‐normal FVDs, except for the stagnant slab in the mantle transition zone (MTZ) where obvious NE‐SW FVDs are revealed. The FVDs in the subslab mantle change from a subduction‐parallel trend at depths of 80–400 km to a subduction‐normal trend in the MTZ. Large‐scale low‐velocity anomalies are revealed beneath the Philippine Sea plate where the FVD is NE‐SW. The FVDs along the Izu‐Bonin arc and in a slab gap exhibit a striking anticlockwise toroidal trend. All these features may reflect complex 3‐D flows in the mantle wedge due to tearing and dehydration processes of the subducting Pacific slab. The subducting Pacific slab is split at ~300‐km depth under the Bonin arc and then penetrates into the lower mantle, whereas under East Asia the Pacific slab becomes stagnant in the MTZ and reaches the North‐South Gravity Lineament in China. The intraplate volcanoes in East Asia are caused by hot and wet upwelling flows in the big mantle wedge above the stagnant Pacific slab.
Key Points
Depth‐varying azimuthal anisotropy is revealed in the Pacific slab and subslab mantle
Toroidal anisotropy indicates complex mantle flows induced by the Pacific slab tearing under the Izu‐Bonin arc
The results shed new light on intraplate volcanism and mantle dynamics in Western Pacific and East Asia
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