Metal–organic frameworks (MOFs) have aroused great interest as lithium-ion battery (LIB) electrode materials. In this work, we first report that a pristine three-dimensional tetrathiafulvalene ...derivatives (TTFs)-based zinc MOF, formulated Zn2(py-TTF-py)2(BDC)2·2DMF·H2O (1) (py-TTF-py = 2,6-bis(4′-pyridyl)tetrathiafulvalene and H2BDC = terephthalic acid), can work as a high-performance electrode material for rechargeable LIBs. The TTFs-Zn-MOF 1 electrode displayed a high discharge specific capacity of 1117.4 mA h g–1 at a current density of 200 mA g–1 after 150 cycles along with good reversibility. After undergoing elevated discharging/charging rates, the electrode showed superior lithium storage performance in the extreme case of 20 A g–1 and could finally recover the capability when the current rate was back to 200 mA g–1. Particularly, specific capacities of 884.2, 513.8, and 327.8 mA h g–1 were reached at high current densities of 5, 10, and 20 A g–1 after 180, 175, and 300 cycles along with good reversibility, respectively. Such an excellent performance is first reported for the LIB anode materials. TTFs-Zn-MOF 2, namely, Zn2(py-TTF-py) (BDC)2·DMF·2H2O (2), was prepared as a contrast to explore the relationship between the structures of the electrode materials and the electrochemical properties. Based on the structural analysis of 1 and 2 and ex situ X-ray photoelectron spectroscopy, the TTF moiety and the twofold TTF pillar play a key role in the excellent electrochemical performance. The full cell of MOF 1 with NMC 622 delivered the capacity of 131.9 mA h g–1 at 100 mA g–1 with the Coulombic efficiency of 99.45% after 70 cycles and exhibited the tolerance to high-current operation.
Most large organic cations in the low-dimensional hybrid halide perovskites deteriorate the photoelectric conversion efficiency of the cells. Integrating electronically active organic components into ...hybrid metal halides is an effective method to improve their photoelectric properties. In this work, a series of compounds obtained by hybridizing redox-active tetrakis(methylthio)tetrathiafulvalene (TMT-TTF) with bismuth chloride, formulated as TMT-TTF4Bi6Cl22 (1 and 1′), TMT-TTF3Bi4Cl16 (2), TMT-TTF2Bi3Cl13 (3), TMT-TTF2Bi2Cl10 (4), and {TMT-TTFBi2Cl8} n (5), were crystallographically characterized. These hybrids exhibit changeable oxidation states of the TTF moiety. The radical cation TTF•+ exists in 1 and 1′, while a mixed-valence TTF•+/TTF2+ appears in 2 that has never been documented in any compounds and the dication TTF2+ exists in 3–5 that has never been introduced into hybrid organic–inorganic materials. The different charged states of the TTF cations lead to various degrees of connectivity of metal chloride anions, which exert a significant effect on the cation–anion arrangement and result in different supramolecular interactions between TMT-TTF and between cations and anions. The changeable oxidation states of the TTF moiety and varying degrees of metal chloride connectivity provide a good comparison among these hybridized bismuth chlorides. The order of conductivity is 2 > 1 > 1′ > 3 ≈ 4 ≫ 5, which results from the synergistic effect of different oxidation states, the packing of TMT-TTF cations, and back charge transfer from the Bi–Cl anion to the TMT-TTF cation. Notably, the electrical conductivity and carrier mobility can be modulated with the fact that compound 2 has the highest performances in the dark, while in light, these properties of 1 and 1′ are in turn higher than that of 2. The order of the photocurrent densities is in accordance with the increase of carrier mobility under irradiation of light. This work is the first systematic study of hybrid metal halides with various oxidation states of TTFs and presents a clear structure–property relationship and offers a fresh view on the design of new perovskite materials at the molecular level.
We report the fabrication of amorphous (In x Ga 1-x ) 2 O 3 metal-semiconductor-metal ultraviolet (UV) photodetectors on glass substrate by co-sputtering. It was found that, we could change the ...cutoff wavelength of the fabricated photodetectors by changing the RF sputtering power of the In 2 O 3 target. With 5 V applied bias, it was found that the measured dark currents were 2 × 10 -12 , 1 × 10 -11 , and 2.3 × 10 -11 A for sample A prepared with 40 W In 2 O 3 sputtering power, sample B prepared with 50 W In 2 O 3 sputtering power, and sample C prepared with 60 W In 2 O 3 sputtering power, respectively. It was also found that the UV-to-visible rejection ratios were 3 × 10 3 , 5 × 10 3 , and 1.5 × 10 4 for samples A, B, and C, respectively. Furthermore, it was found that the response speeds of the fabricated devices were good.
The electrical performance of amorphous indium gallium oxide (a-IGO) thin-film transistors applied as deep-ultraviolet (DUV) phototransistors is investigated. It was found that the bandgap of a-IGO ...can be engineered by altering its chemical composition. The performance of the phototransistors depended strongly on In 2 O 3 content in the IGO film. When the indium content increases from 21% to 31%, the phototransistor cutoff red-shifted from 280 to 320 nm. The DUV-to-visible rejection ratio and photoresponsivity of the fabricated phototransistors were ~10 5 and 0.18 A/W.
We characterized the heterogeneity and risk factors of cognitive decline in euthymic bipolar disorder (BD), and their magnitude of associations with subjective daily functions. In this retrospective ...cohort, BD type I patients (
= 128) were followed for an average of 6.5 years. Intelligence quotient (IQ) at index date was recorded, and premorbid IQ was estimated. We used Brief Assessment of Cognition in Affective Disorders (BAC-A) to assess cognition at follow-up. We evaluated current functions with World Health Organization Disability Assessment Schedule 2.0. Clinical and sociodemographic factors were examined for their independent effects on longitudinal cognitive decline. In addition, we employed multivariate adaptive regression spline to detect inflection points for the nature of slope changes in cognitive decline among BD patients. During follow-up years, 21 BD patients (16.4%) showed longitudinal cognitive decline. In cognitive decline group, all cognitive domains of BAC-A were significantly worsened. We found that density of episodes with psychotic features was an independent risk factor for cognitive decline after adjusted for age, gender and dose of mood stabilizer. After the age of 42 years, a steeper cognitive change was observed in the cognitive decline group. The correlation pattern between cognitive domains and functional outcomes differed between patients with and without cognitive decline. The present study characterized cognitive heterogeneity longitudinally in BD patients. As density of episodes play roles for cognitive decline, our results emphasize the importance of relapse prevention. Our findings provide hints for future personalized interventions and facilitating genetic and biological studies for dissecting the heterogeneity of bipolar illness.
Inorganic CuSCN and organic tetrathiafulvalene derivatives (TTFs) have been exploited as hole-transport materials (HTM) in hybrid perovskite solar cells. To develop new HTM, we herein report two ...hybrid materials incorporating redox-active TTFs with CuSCN framework (TTFs-CuSCN). Single-crystal analysis showed that compound Cu2(py-TTF-py)(SCN)2 (1) is three-dimensional (3D) and compound Cu(py-TTF-py)(SCN) (2) is two-dimensional (2D) (py-TTF-py = 2,6-bis(4′-pyridyl)tetrathiafulvalene). There are covalent coordination interactions between CuSCN and py-TTF-py and short S···S contacts between the py-TTF-py ligands for both compounds. Besides, C···S contacts exist between py-TTF-py ligands of the neighboring 2D networks in 2, which facilitate the charge transfer and supply efficient multidimensional pathways for carrier migration. As a result, 2 presented better semiconductor performance in comparison with that of 1. The performance of 2 related to the HTMs could be significantly improved by modulating the electronic state of the TTFs-CuSCN framework via oxidative doping. The iodine-doped 2D material (2-I 2 ) gives the most excellent conductivity and carrier mobility, which might be a potential new HTM.
Mesenchymal stromal cells (MSCs) based therapy is a promising approach to treat inflammatory disorders. However, therapeutic effect is not always achieved. Thus the mechanism involved in inflammation ...requires further elucidation. To explore the mechanisms by which MSCs respond to inflammatory stimuli, we investigated whether MSCs employed inflammasomes to participate in inflammation. Using in vitro and in vivo models, we found that canonical NLRP3 and non-canonical caspase-11 inflammasomes were activated in bone-associated MSCs (BA-MSCs) to promote the inflammatory response. The NLRP3 inflammasome was activated to mainly elicit IL-1β/18 release, whereas the caspase-11 inflammasome managed pyroptosis. Furthermore, we sought a small molecule component (66PR) to inhibit the activation of inflammasomes in BA-MSCs, which consequently improved their survival and therapeutic potential in inflammation bowel diseases. These current findings indicated that MSCs themselves could directly promote the inflammatory response by an inflammasome-dependent pathway. Our observations suggested that inhibition of the proinflammatory property may improve MSCs utilization in inflammatory disorders.
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•NLRP3 and caspase-11 inflammasomes were activated in bone associated MSCs after stimulation.•NLRP3 inflammasome mainly secreted IL-1β/18, whereas caspase-11 inflammasome managed pyroptosis in bone associated MSCs.•Inhibition of inflammasomes in bone associated MSCs benefits their utilization for inflammatory diseases therapy.
Abnormal inflammations cause currently high incidence of diseases worldwide, such as sepsis, allergic reactions, and even cancer. But the therapy of inflammatory diseases is far from satisfaction heretofore. MSCs are great interest to treat inflammatory disorders. However, many studies found their therapeutic effects were not always achieved. Further studies on the molecular mechanisms by which MSCs respond to the inflammatory microenvironment will undoubtedly promote applications in clinic. Here, we observed that MSCs promoted the inflammatory response by an inflammasome-dependent pathway. Regulation of this pathway improved MSCs to counter against inflammatory disorders.
Microbiota dysbiosis and mucosa-associated bacteria are involved in colorectal cancer progression. We hypothesize that an interaction between virulent pathobionts and epithelial defense promotes ...tumorigenesis.
Chemical-induced CRC mouse model was treated with antibiotics at various phases. Colonic tissues and fecal samples were collected in a time-serial mode and analyzed by gene microarray and 16S rRNA sequencing. Intraepithelial bacteria were isolated using a gentamicin resistance assay, and challenged in epithelial cultures.
Our study showed that antibiotic treatment at midphase but not early or late phase reduced mouse tumor burden, suggesting a time-specific host–microbe interplay. A unique antimicrobial transcriptome profile showing an inverse relationship between autophagy and oxidative stress genes was correlated with a transient surge in microbial diversity and virulence emergence in mouse stool during cancer initiation. Gavage with fimA/fimH/htrA-expressing invasive Escherichia coli isolated from colonocytes increased tumor burden in recipient mice, whereas inoculation of bacteria deleted of htrA or triple genes did not. The invasive E.coli suppressed epithelial autophagy activity through reduction of microtubule-associated protein 1 light-chain 3 transcripts and caused dual oxidase 2–dependent free radical overproduction and tumor cell hyperproliferation. A novel alternating spheroid culture model was developed for sequential bacterial challenge to address the long-term changes in host–microbe interaction for chronic tumor growth. Epithelial cells with single bacterial encounter showed a reduction in transcript levels of autophagy genes while those sequentially challenged with invasive E.coli showed heightened autophagy gene expression to eliminate intracellular microbes, implicating that bacteria-dependent cell hyperproliferation could be terminated at late phases. Finally, the presence of bacterial htrA and altered antimicrobial gene expression were observed in human colorectal cancer specimens.
Invasive pathobionts contribute to cancer initiation during a key time frame by counterbalancing autophagy and oxidative stress in the colonic epithelium. Monitoring gut microbiota and antimicrobial patterns may help identify the window of opportunity for intervention with bacterium-targeted precision medicine.
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In this letter, a Ta 2 O 5 /a-IGZO thin film transistor (TFT) was directly stacked on a crystalline-Si interdigitated back contact (IBC) photovoltaic (PV) cell to create a self-powered solar switch. ...The a-IGZO TFT and IBC PV cell were integrated into a single chip without an external circuit. This device exhibits switching property induced by illumination. The results show that it can be switched even under a low solar illumination of 300 W/m 2 due to the low threshold voltage of the a-IGZO TFT (0.25 V). The ON/OFF current contrast ratio was measured to be ~20 under 1-sun illumination. The fabrication process and characteristics of this device make it suitable and practicable for use as a self-powered solar switch.
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