Flexible Printed Ultraviolet-to-Near-Infrared Broadband Optoelectronic Carbon Nanotube Synaptic Transistors for Fast and Energy-Efficient Neuromorphic Vision Systems.

To simulate biological visual systems and surpass their functions and performance, it is essential to develop high-performance optoelectronic neuromorphic electronics with broadband response, low power consumption, and fast response speed. Among these, optoelectronic synaptic transistors have emerged as promising candidates for constructing neuromorphic visual systems. In this work, flexible printed broadband (from 275 to 1050 nm) optoelectronic carbon nanotube synaptic transistors with good stability, high response speed (3.14 ms), and low-power consumption (as low as 0.1 fJ per event with the 1050 nm pulse illumination) using PbS quantum dots (QDs) modified semiconducting single-walled carbon nanotubes (sc-SWCNTs) as active layers are developed. In response to optical pulses within the ultraviolet to near-infrared wavelength range, the optoelectronic neuromorphic devices exhibit excitatory postsynaptic current, paired-pulse facilitation, and a transition from short-term plasticity to long-term plasticity, and other optical synaptic behaviors. Furthermore, a simplified neural morphology visual array is developed to simulate integrated functions such as image perception, memory, and preprocessing. More importantly, it can also emulate other complicated bionic functions, such as the infrared perception of salmon eyes and the warning behavior of reindeer in different environments. This work holds immense significance in advancing the development of artificial neural visual systems.

Prognostic and immunological significance of metastasis-associated protein 3 in patients with thymic epithelial tumors.

BACKGROUND: Immune checkpoint inhibitors have shown promising anticancer activity and have recently been proposed as a therapy for thymic epithelial tumors (TETs); however, this treatment is only effective for a subgroup of TET patients. Thus, this study aims to identify the potential genes implicated in the regulation of cancer immunity in TETs. METHODS: The TETs RNA-seq and clinical data were obtained from The Cancer Genome Atlas (TCGA) database. The clinical significance of the tumor microenvironment (TME) in TETs was evaluated. Weighted gene coexpression network analysis (WGCNA) was used to identify the immune response-related hub genes. The expression of metastasis-associated protein 3 (MTA3) in TETs was investigated in public datasets and a patient cohort. Kaplan‒Meier curves were generated to analyze the prognostic value of various factors. The Tumor Immune Estimation Resource (TIMER2.0) was used to estimate the relevance of MTA3 to immune cell infiltration. Gene set enrichment analysis (GSEA) and pathway enrichment analysis were applied to explore the MTA3-related pathways. RESULTS: The TME was found to be clinically significant in TETs. Moreover, MTA3 was identified as a key gene associated with the immune score, and lower MTA3 expression was linked to poor TME and reduced cytotoxic activity in TETs. Furthermore, MTA3 was found to be deregulated in TETs, predictive of poor prognosis. MTA3 was also significantly associated with the infiltration levels of various immune cell types and highly correlated with their corresponding markers. Notably, MTA3 was positively associated with various immune response pathways. CONCLUSION: MTA3 is clinically significant in TETs and correlated with immune cell infiltration. Thus, MTA3 might be a biomarker for predicting the prognosis and immune status of TET patients.

GCF2 mediates nicotine-induced cancer stemness and progression in hepatocellular carcinoma.

Cigarette smoking is one of the most impactful behavior-related risk factors for multiple cancers including hepatocellular carcinoma (HCC). Nicotine, as the principal component of tobacco, is not only responsible for smoking addiction but also a carcinogen; nevertheless, the underlying mechanisms remain unclear. Here we report that nicotine enhances HCC cancer stemness and malignant progression by upregulating the expression of GC-rich binding factor 2 (GCF2), a gene that was revealed to be upregulated in HCC and whose upregulation predicts poor prognosis, and subsequently activating the Wnt/ꞵ-catenin/SOX2 signaling pathway. We found that nicotine significantly increased GCF2 expression and that silencing of GCF2 reduced nicotine-induced cancer stemness and progression. Mechanistically, nicotine could stabilize the protein level of GCF2, and then GCF2 could robustly activate its downstream Wnt/ß-catenin signaling pathway. Taken together, our results thus suggest that GCF2 is a potential target for a therapeutic strategy against nicotine-promoted HCC.

Efficient Removal of Nitrate in Neutral Solution Using Zero-Valent Al Activated by Soaking.

Nitrate is a contaminant widely found in surface water, and a high concentration of nitrate can pose a serious threat to human health. Zero-valent iron is widely used to reduce nitrate in aqueous solution, but an acidic condition is required. Zero-valent aluminum has a much lower redox potential (E0(Al3+/Al0) = -1.662 V) than zero-valent iron (E0(Fe2+/Fe0) = -0.44 V), making it a better choice for reduction of nitrate. However, a passive oxide film covering on Al surfaces inhibits its electron transfer. In this work, metal Al powder was activated by a soaking procedure in deionized water. It was found that nitrate in neutral solution can be efficiently and completely reduced by soaked Al, even if the concentration of nitrate-N was up to 100 mg L-1. Using an optimal soaking time, the soaked Al can remove >90% of nitrate in aqueous solution within ∼2 h at 50 °C. Furthermore, the nitrate reduction efficiency increased with increasing reaction temperature and dosage of Al powder. After reaction, only ∼50% of pristine N content was left in the form of ammonia ions (NH4+) in aqueous solution. Mechanism analyses showed that after soaking, Al particle surfaces were covered by a layer of loose and fine Al(OH)3 grains, which can shorten the induction time for the beginning of the reaction between inner Al and outside ions or molecules. This is the reason why soaked Al has a high efficiency for nitrate removal. The present results indicate that soaking is an effective way to activate Al to remove nitrate in water.

Synergistic effect and mechanisms of ultrasound and AlOOH suspension on Al hydrolysis for hydrogen production.

Ultrasound can accelerate and change the reaction process and is widely used in the field of hydrogen production and storage. In this study, ultrasound (US) and AlOOH suspension (AH) are used to promote hydrogen production from Al hydrolysis. The results indicate that both US and AH greatly shorten the induction time and enhance the hydrogen production rate and yield. The promoting effect of US and AH on Al hydrolysis originates from the acoustic cavitation effect and catalytic effect, respectively. When AH is used in combination with US, Al hydrolysis has the best hydrogen production performance and the hydrogen yield can reach 96.6 % within 1.2 h, because there is a synergistic effect on Al hydrolysis between AH and US. Mechanism analyses reveal that the micro-jets and local high temperature environment arising from acoustic cavitation improve the catalytic activity of AlOOH, while the suspended AlOOH particles enhance the cavitation effect of US. This work provides a novel and feasible method to promote hydrogen production from Al hydrolysis.

Separation of Excess Fluoride from Water Using Amorphous and Crystalline AlOOH Adsorbents.

Aluminum hydroxide is an effective defluoridation adsorbent; however, the poor defluoridation performance limits its wide application. In this work, amorphous and crystalline AlOOH adsorbents are synthesized through hydrolysis of Al salts, and their defluoridation performances are evaluated in terms of adsorption capacity and rate, sensitivity to pH value, and water quality after defluoridation. The defluoridation performance of AlOOH is closely related to the hydrolysis pH value, but hardly to the type of Al salts. The adsorbent can remove >95% fluoride in the first 2 min and reach adsorption equilibrium within 2 h, and the maximum defluoridation capacity is 41.9 mg/g. Furthermore, the adsorbent exhibits an excellent defluoridation efficiency at a wide pH range of 4.5-10.5. After fluoride removal, the adsorbents prepared at pH values of 6 and 7 exhibit low residual Al concentration. The Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) results confirm that the fluoride removal mechanism is the ligand exchange between fluoride and hydroxyl groups. The excellent defluoridation capacity and low residual Al demonstrate that AlOOH is a potential adsorbent for fluoride separation from water.

A comparative study on high-efficient reduction of bromate in neutral solution using zero-valent Al treated by different procedures.

Bromate, a toxic by-product of bromide-containing drinking water after disinfecting with ozone, has attracted much attention in the past two decades. Traditional methods to activate zero-valent metals for reducing bromate are to eliminate their surface oxide layer by acid washing. In this work, for the first time, zero-valent Al (ZVAl) was surface treated by the following procedures including soaking, soaking and freeze-drying, soaking and heat-treating, and γ-Al2O3 covering Al particle surfaces (GCAP). It was found that all of above surface treated ZVAls have an obvious high efficiency for bromate reduction relative to pristine ZVAl. The bromate reduction rate is GCAP > soaking Al > freeze-drying Al > soaking and heat-treating Al > pristine Al, and using GCAP just 30 min is taken to completely reduce bromate to bromide in neutral solution. Mechanism analyses revealed that Al surface treating or covered by fine γ-Al2O3 phase can promote the hydration and breakage of Al surface passive oxide layer, resulting in a fast contact of inner Al with outside ions, leading to a high reduction rate of bromate in neutral solution. XPS analyses indicated that there are no bromate or bromide ions adsorbed on Al particle surfaces, implying that there is a high direct donating efficiency of electrons from inner Al to bromate ions in solution. Furthermore, GCAP has a good reusability and >90% bromate can be reduced even it was reused up to 4 cycles.

Filtrates with Hydroxyl Radicals Prepared using Al + Acid + H2O2 for Removing Organic Pollutants.

In this work, for the first time, high-activity filtrates were prepared by the reaction of aluminum (Al) powder with hydrogen peroxide (H2O2) in acidic solution and then filtration, which were used to degrade various organic pollutants such as phenol, methyl orange, and bisphenol A. It was found that the filtrates can effectively degrade and mineralize various organic pollutants and have a high efficiency comparable to their parent Al + acid + H2O2 suspensions. The filtrates can keep their high activity for several weeks under ambient conditions, and the activity depends on their initial pH value. At a pH value of ∼3.5, the reaction activity of filtrates is the best. Electron spin resonance spectroscopy (ESR) analyses indicated that there is a large quantity of stable hydroxyl radicals (OH•) existing in the filtrates, which are responsible for the removal of organic pollutants. Furthermore, the related factors are discussed.

Relative Order of Acidity among Hydroxyl Groups of Oxyluciferin and Emission Light Colors in Aqueous Solution.

The magnitude of the acidity of the oxyluciferin in water in the ground and excited state is investigated, and it is found for the first time using computational approach that the enol group of the phenol-enol species is the most acidic in the ground state, but the deprotonation of the phenol of the phenol-keto form is the most favored in the excited state. The relative order of the acidity among the hydroxyl groups in the oxyluciferin is attributed to the sequence of the O-H bond lengths in the enol and phenol group of the phenol-enol form, and the phenol group of the phenol-keto species. The mechanism of determining the dominant emissive species in the excited state is proposed, and the dependence of emission light colors on the photoexcitation energy is elucidated by the high relative concentration of six chemical forms in the ground state and the absorption efficiency.

Oxide modified aluminum for removal of methyl orange and methyl blue in aqueous solution.

In this work, pristine aluminum (Al) powder was soaked in deionized water for a time period and then it was dried and heat-treated at 400 °C such that a layer of fine Al2O3 grains covered the Al particle surfaces, forming oxide modified Al powder (OM-Al). It was found that OM-Al greatly enhanced the efficiency in removing methyl orange (M-orange) and methyl blue (M-blue) in aqueous solution. The time to completely degrade M-orange and M-blue by OM-Al is about one third of that by pristine Al powder, and decreases with increasing dosage of OM-Al. The enhancement in dye removal rate by oxide modification is much better than that with ultrasonic assistance, especially for M-blue. LC/MS spectrum analyses revealed that large dye molecules are broken into small biodegradable organic molecules after reaction with OM-Al. It is deduced that the promotion of fine Al2O3 on the hydration process of Al surface passive oxide film is the main mechanism responsible for the enhancement of dye removal by OM-Al. Furthermore, OM-Al has a good recyclability and 80% of M-orange and M-blue can be removed even when it was reused for up to three cycles. These results indicate that oxide modification is an effective way to activate Al for the removal of organic dyes.

Arsenic removal from water by metal-organic framework MIL-88A microrods.

Fe-based metal-organic framework MIL-88A microrods were synthesized by hydrothermal method, which were used to adsorb As(V) in water for the first time. The experimental results indicated that MIL-88A has a very fast adsorption rate towards arsenic in water. The kinetic and isothermal data for arsenic removal were better fitted to the pseudo-second-order kinetic model and Langmuir model, respectively, implying a chemical and monolayer adsorption for As(V) on MIL-88A microrods. Two rate-controlling processes during adsorption were revealed by the intraparticle diffusion model. The maximum adsorption capacity of MIL-88A reached 145 mg g-1, higher than those of Fe-based MIL adsorbents reported previously, which probably originates from its unique microstructure with abundant OH- groups and an unusual large swelling towards water. These show that Fe-based MIL-88A is a good candidate for arsenic removal.

Electrostatic Catalysis Induced by Luciferases in the Decomposition of the Firefly Dioxetanone and Its Analogue.

The variations of the barrier heights in the decomposition of the firefly dioxetanone and its analogues with the electrostatic field produced by the active site amino acid residues in the firefly luciferase are examined by a density functional theory study of the high-energy intermediates of the three luciferins. The positive electric field along the long-axis direction of the luciferins lowers the activation energy and acts as an electrostatic catalyst in the thermolysis process. The calculated barrier heights for the firefly dioxetanone and its analogues surrounded by the firefly Photinus pyralis luciferase show that the energy barrier of the firefly dioxetanone is lowered by the luciferase but is raised for the other analogue. Thus, the thermolysis rate is enhanced for the natural d-luciferin and reduced for the other analogue by the firefly luciferase, which elucidates why the luciferase acts as a catalyst for the natural d-luciferin but makes some luciferins emit weaker light signals.

New insight into magneto-structural phase transitions in layered TbMn2Ge2-based compounds.

The Tb1-xYxMn2Ge2 series (x = 0, 0.1, 0.2) compounds are found to exhibit two magnetic phase transitions with decreasing temperature: from the paramagnetic state to the antiferromagnetic interlayer state at TNinter and from an antiferromagnetic interlayer structure to a collinear ferrimagnetic interlayer structure at TCinter. Compared with the slight change of TNinter (409 K, 410 K and 417 K for x = 0, 0.1 and 0.2 respectively), the replacement of Y for Tb leads to a significant decrease in TCinter from 97.5 K for x = 0 to 74.6 K for x = 0.2. The variation in TCinter can be ascribed to the combination of two effects: (1) chemical pressure and (2) magnetic dilution effect by Y substitution for Tb. Besides, a strong anisotropic magnet-volume effect has been detected around TCinter in all compounds with Δa/a = 0.125%, 0.124% and 0.130% for x = 0, 0.1 and 0.2, respectively while no obvious effect is detected along the c-axis. The maximum magnetic entropy change were found to be -ΔSmax = 9.1 J kg-1 K-1, 11.9 J kg-1 K-1 and 6.3 J kg-1 K-1 with a field change from 0 T to 5 T for x = 0, 0.1, 0.2 respectively.

How Does the Local Electrostatic Field Influence Emitted Wavelengths and Bioluminescent Intensities of Modified Heteroaromatic Luciferins?

The firefly chromophore, oxyluciferin, is in the pocket of the firefly luciferase and is surrounded by the side-chains of some amino acid residues. The charged residues produce the local electrostatic field (LEF) around the oxyluciferin. The emitted wavelengths and intensities of the oxyluciferin and its heterocyclic analogs under the LEF are examined. The common overlapping volumes of the HOMO and LUMO explain why the oscillator strengths vary under the LEF. Three average Ex change rates of the first excited energy are introduced to measure what luciferins are more sensitive to the LEF. The first excited energies and intensities in two enzymatic-like microenvironments are simulated via the LEF. The oscillator strengths and the net electric charges of the O6' and the O4 are applied to explain the experimental bioluminescent intensities.