Dual In Situ Laser Techniques Underpin the Role of Cations in Impacting Electrocatalysts.

Understanding the electrode/electrolyte interface is crucial for optimizing electrocatalytic performances. Here, we demonstrate that the nature of alkali metal cations can profoundly impact the oxygen evolution activity of surface-mounted metal-organic framework (SURMOF) derived electrocatalysts, which are based on NiFe(OOH). In situ Raman spectroscopy results show that Raman shifts of the Ni-O bending vibration are inversely proportional to the mass activities from Cs+ to Li+ . Particularly, a laser-induced current transient technique was introduced to study the cation-dependent electric double layer properties and their effects on the activity. The catalytic trend appeared to be closely related to the potential of maximum entropy of the system, suggesting a strong cation impact on the interfacial water layer structure. Our results highlight how the electrolyte composition can be used to maximize the performance of SURMOF derivatives toward electrochemical water splitting.

CpARF2 and CpEIL1 interact to mediate auxin-ethylene interaction and regulate fruit ripening in papaya.

Papaya (Carica papaya L.) is a commercially important fruit crop. Various phytohormones, particularly ethylene and auxin, control papaya fruit ripening. However, little is known about the interaction between auxin and ethylene signaling during the fruit ripening process. In the present study, we determined that the interaction between the CpARF2 and CpEIL1 mediates the interaction between auxin and ethylene signaling to regulate fruit ripening in papaya. We identified the ethylene-induced auxin response factor CpARF2 and demonstrated that it is essential for fruit ripening in papaya. CpARF2 interacts with an important ethylene signal transcription factor CpEIL1, thus increasing the CpEIL1-mediated transcription of the fruit ripening-associated genes CpACS1, CpACO1, CpXTH12 and CpPE51. Moreover, CpEIL1 is ubiquitinated by CpEBF1 and is degraded through the 26S proteasome pathway. However, CpARF2 weakens the CpEBF1-CpEIL1 interaction and interferes with CpEBF1-mediated degradation of CpEIL1, promoting fruit ripening. Therefore, CpARF2 functions as an integrator in the auxin-ethylene interaction and regulates fruit ripening by stabilizing CpEIL1 protein and promoting the transcriptional activity of CpEIL1. To our knowledge, we have revealed a novel module of CpARF2/CpEIL1/CpEBF1 that fine-tune fruit ripening in papaya. Manipulating this mechanism could help growers tightly control papaya fruit ripening and prolong shelf life.

Surface-Mounted Metal-Organic Frameworks: Past, Present, and Future Perspectives.

Metal-organic frameworks (MOFs) are an emerging class of porous materials composed of organic linkers and metal centers/clusters. The integration of MOFs onto the solid surface as thin films/coatings has spurred great interest, thanks to leveraging control over their morphology (such as size- and shape-regulated crystals) and orientation, flexible processability, and easy recyclability. These aspects, in synergy, promise a wide range of applications, including but not limited to gas/liquid separations, chemical sensing, and electronics. Dozens of innovative methods have been developed to manipulate MOFs on various solid substrates for academic studies and potential industrial applications. Among the developed deposition methods, the liquid-phase epitaxial layer-by-layer (LPE-LbL) method has demonstrated its merits over precise control of the thickness, roughness, homogeneity, and orientations, among others. Herein, we discuss the major developments of surface-mounted MOFs (SURMOFs) in LbL process optimization, summarizing the SURMOFs' performance in different applications, and put forward our perspective on the future of SURMOFs in terms of advances in the formulation, applications, and challenges. Finally, future prospects and challenges with respect to SURMOFs growth will be discussed, keeping the focus on their widening applications.

Porphyrinic MOF Film for Multifaceted Electrochemical Sensing.

Electrochemical sensors are indispensable in clinical diagnosis, biochemical detection and environmental monitoring, thanks to their ability to detect analytes in real-time with direct electronic readout. However, electrochemical sensors are challenged by sensitivity-the need to detect low concentrations, and selectivity-to detect specific analytes in multicomponent systems. Herein, a porphyrinic metal-organic framework (PP-MOF), Mn-PCN-222 is deposited on a conductive indium tin oxide (ITO) surface. It affords Mn-PCN-222/ITO, a versatile voltammetric sensor able to detect redox-active analytes such as inorganic ions, organic hazardous substances and pollutants, including nitroaromatics, phenolic and quinone-hydroquinone toxins, heavy metal ions, biological species, as well as azo dyes. As a working electrode, the high surface area of Mn-PCN-222/ITO enables high currents, and therefore leverages highly sensitive analysis. The metalloporphyrin centre facilitates analyte-specific redox catalysis to simultaneously detect more than one analyte in binary and ternary systems allowing for detection of a wide array of trace pollutants under real-world conditions, most with high sensitivity.

Advanced Bifunctional Oxygen Reduction and Evolution Electrocatalyst Derived from Surface-Mounted Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) and their derivatives are considered as promising catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), which are important for many energy provision technologies, such as electrolyzers, fuel cells and some types of advanced batteries. In this work, a "strain modulation" approach has been applied through the use of surface-mounted NiFe-MOFs in order to design an advanced bifunctional ORR/OER electrocatalyst. The material exhibits an excellent OER activity in alkaline media, reaching an industrially relevant current density of 200 mA cm-2 at an overpotential of only ≈210 mV. It demonstrates operational long-term stability even at a high current density of 500 mA cm-2 and exhibits the so far narrowest "overpotential window" ΔEORR-OER of 0.69 V in 0.1 m KOH with a mass loading being two orders of magnitude lower than that of benchmark electrocatalysts.

Dual-Function HKUST-1: Templating and Catalyzing Formation of Graphitic Carbon Nitride Quantum Dots Under Mild Conditions.

Graphitic carbon nitride quantum dots (g-CNQDs) are highly promising photoresponsive materials. However, synthesis of monodispersed g-CNQDs remains challenging. Here we report the dual function of MOF [Cu3 BTC2 ] (HKUST-1) as a catalyst and template simultaneously to prepare g-CNQDs under mild conditions. Cyanamide (CA), a graphitic carbon nitride precursor, catalytically dimerized inside the larger MOF cavities at 90 °C and condensed into g-CNQDs at 120 °C in a controlled fashion. The HKUST-1 template was stable under the reaction conditions, leading to uniform g-CNQDs with a particle size of 2.22±0.68 nm. The as prepared g-CNQDs showed photoluminescence emission with a quantum yield of 3.1 %. This concept (MOF dual functionality) for catalyzing CA polycondensation (open metal sites (OMSs) effect) and controlling the produced particle size (pore-templating effect), together with the tunable MOF porosity, is expected to produce unique g-CNQDs with controllable size, morphology, and surface functionality.

Unprecedented High Oxygen Evolution Activity of Electrocatalysts Derived from Surface-Mounted Metal-Organic Frameworks.

The oxygen evolution reaction (OER) is a key process for renewable energy storage. However, developing non-noble metal OER electrocatalysts with high activity, long durability and scalability remains a major challenge. Herein, high OER activity and stability in alkaline solution were discovered for mixed nickel/cobalt hydroxide electrocatalysts, which were derived in one-step procedure from oriented surface-mounted metal-organic framework (SURMOF) thin films that had been directly grown layer-by-layer on macro- and microelectrode substrates. The obtained mass activity of ∼2.5 mA·µg-1 at the defined overpotential of 300 mV is 1 order of magnitude higher than that of the benchmarked IrO2 electrocatalyst and at least 3.5 times higher than the mass activity of any state-of-the-art NiFe-, FeCoW-, or NiCo-based electrocatalysts reported in the literature. The excellent morphology of the SURMOF-derived ultrathin electrocatalyst coating led to a high exposure of the most active Ni- and Co-based sites.

RcPAL, a key gene in lignin biosynthesis in Ricinus communis L.

BACKGROUND: Castor (Ricinus communis L.) is an important seed oil crop. Castor oil is a highly demanded oil for several industrial uses. Current castor bean varieties suffer from low productivity and high risk of insect pests and diseases. High productive and pest/disease resistance varieties are needed. Lignin has been associated to the resistance for pest, disease and lodging. Lignin is produced from several metabolites of the phenylpropanoid pathway. PAL is the key enzyme of the phenylpropanoid pathway. The gene PAL may assist in the improvement of resistance of castor bean. RESULTS: The RcPAL CDs was amplified and its function was examined by transgenic overexpression and antisense expression, lignin histochemical staining, real-time PCR, lignin content measurement and morphological investigation. Its full length was 2145 bp, encoding 714 amino acids. The overexpression of RcPAL (7.2 times) increased significantly the PAL activity, dyeing depth of xylem cells and lignin content (14.44%), resulting in a significantly lower plant height, deeper and thicker blade, more green leaves, shorter internode, thicker stem diameter, and opposite in antisense expression plants (lignin content lowered by 27.1%), demonstrated that the gene RcPAL was a key gene in castor lignin biosynthesis. CONCLUSIONS: The gene RcPAL is a key gene in castor lignin biosynthesis and can be induced to express under mechanical damage stress. When up-regulated, it increased the lignin content significantly and dwarfed the plant height, and opposite when down-regulated. The gene RcPAL may assist in the improvement of resistance and plant type of castor bean.

A positive-feedback loop between tumour infiltrating activated Treg cells and type 2-skewed macrophages is essential for progression of laryngeal squamous cell carcinoma.

BACKGROUND: Foxp3+ regulatory T (Treg) cells and M2 macrophages are associated with increased tumour progression. However, the interaction between Treg cells and M2 macrophages remains unclear. METHODS: The expression of FoxP3 and CD163 was detected by immunohistochemistry in 65 cases of laryngeal squamous cell carcinoma (LSCC). In vitro, the generation of activated Treg (aTreg) cells and M2 macrophages by interactions with their precursor cells were analysed by flow cytometry and ELISA. In vivo, the antitumour effects were assessed by combined targeting aTreg cells and M2 macrophages, and intratumoural immunocytes were analysed by flow cytometry. RESULTS: In LSCC tissue, accumulation of aTreg cells and M2 macrophages predicted a poor prognosis and were positively associated with each other. In vitro, aTreg cells were induced from CD4+CD25- T cells by cancer cell-activated M2-like macrophages. Consequently, these aTreg cells skewed the differentiation of monocytes towards an M2-like phenotype, thereby forming a positive-feedback loop. Combined targeting aTreg cells and M2 macrophages led to potent antitumour immunity in vivo. CONCLUSIONS: The positive-feedback loop between aTreg cells and M2 macrophages is essential to maintain or promote immunosuppression in the tumour microenvironment and may be a potential therapeutic target to inhibit tumour progression.

Comparative transcriptomic analyses of normal and malformed flowers in sugar apple (Annona squamosa L.) to identify the differential expressed genes between normal and malformed flowers.

BACKGROUND: Sugar apple (Annona squamosa L.), a popular fruit with high medicinal and nutritional properties, is widely cultivated in tropical South Asia and America. The malformed flower is a major cause for a reduction in production of sugar apple. However, little information is available on the differences between normal and malformed flowers of sugar apple. RESULTS: To gain a comprehensive perspective on the differences between normal and malformed flowers of sugar apple, cDNA libraries from normal and malformation flowers were prepared independently for Illumina sequencing. The data generated a total of 70,189,896 reads that were integrated and assembled into 55,097 unigenes with a mean length of 783 bp. A large number of differentially expressed genes (DEGs) were identified. Among these DEGs, 701 flower development-associated transcript factor encoding genes were included. Furthermore, a large number of flowering- and hormone-related DEGs were also identified, and most of these genes were down-regulated expressed in the malformation flowers. The expression levels of 15 selected genes were validated using quantitative-PCR. The contents of several endogenous hormones were measured. The malformed flowers displayed lower endogenous hormone levels compared to the normal flowers. CONCLUSIONS: The expression data as well as hormone levels in our study will serve as a comprehensive resource for investigating the regulation mechanism involved in floral organ development in sugar apple.

Multi-Scale Dispersion Engineering on Biomass-Derived Materials for Ultra-Wideband and Wide-Angle Microwave Absorption.

Efficient electromagnetic waves (EMWs) absorbing materials play a vital role in the electronic era. In traditional research on microwave absorbing (MA) materials, the synergistic modulation of material dispersion and structural dispersion of EMWs by incorporating multi-scale effects has frequently been overlooked, resulting in an untapped absorption potential. In this study, the material dispersion customization method based on biomass carbon is determined by quantitative analysis. The study carries out thermodynamic modulation of carbon skeleton, micro-nano porous engineering, and phosphorus atom donor doping in turn. The dielectric properties are improved step by step. In terms of structural dispersion design, inspired by the theory of antenna reciprocity, a Vivaldi antenna-like absorber is innovatively proposed. With the effective combination of material dispersion and structural dispersion engineering by 3D printing technology, the ultra-wideband absorption of 36.8 GHz and the angular stability of close to 60 ° under dual polarization are successfully realized. The work breaks the deadlock of mutual constraints between wave impedance and attenuation rate through the dispersion modulation methods on multiple scales, unlocking the potential for designing next-generation broadband wide-angle absorbers.

In situ growth of metal-organic framework thin films with gas sensing and molecule storage properties.

New porous metal-organic framework (MOF) films based on the flexible ligand 1,3,5-tris[4-(carboxyphenyl)oxamethyl]-2,4,6-trimethylbenzene (H3TBTC) were fabricated on α-Al2O3 substrates under solvent thermal conditions. The factors affecting the fabrication of films, such as the temperature of pre-activation and the dosage of the reagents, were investigated. Tuning the subtle factors on film fabrications, a series of MOF thin films with different morphologies and grain sizes were prepared. The morphology and grain size of the films are monitored by scanning electron microscopy (SEM). X-ray diffraction (XRD) and attenuated total reflection infrared (ATR-IR) were also used to characterize the MOF films. The results indicate that the temperature of pre-activation and the dosage of the reagents are the key parameters during the process of film formation. The properties of the films, especially the sensing and sorption behavior, have been studied by an optical digital cameral and ultraviolet-visible (UV-vis) spectra. The evidence shows that the films are sensitive to small organic molecules, such as methanol and pyridine. Meanwhile, the films can adsorb small dye molecules. Thus, the films may have potential applications in either organic vapor sensing or storage of small dye molecules.

Intramolecular-Catalyzed Vitrimers with White-Light Emission for Light-Emitting Diode Encapsulation.

Currently available encapsulating materials for white light-emitting diodes (WLEDs) have certain limitations, such as the toxicity of phosphors and the non-recyclable nature of the encapsulating materials. In this study, relatively promising encapsulating materials with two significant advantages are developed. First, the chips can be directly encapsulated without phosphors using luminescent encapsulating materials. Second, the encapsulating materials can be reprocessed for recycling via intramolecular catalysis. To this end, blue-light-emitting vitrimers (BEVs) are prepared by the reaction of epoxy resin with amines and are found to exhibit strong blue emission and fast stress relaxation via internal catalysis. To obtain white-light emission, a well-designed yellow component, perylenetetracarboxylic dianhydride, is grafted into the BEVs to generate white-light-emitting vitrimers (WEVs). A rare synergy of blue- and yellow-light emission affords white-light emission. When the WEV is used as an encapsulating adhesive for 365 nm LED chips without inorganic phosphors, stable white light with CIE coordinates (0.30, 0.32) is successfully achieved, indicating a promising future for WLED encapsulation.

Bionic electroluminescent perovskite light-emitting device.

A perovskite light-emitting-diode (PeLED) displaying green color is combined with a brown fluorescent coating (FC) layer to form a hybrid FC-PeLED system. The FC-PeLED system can simulate the natural process of bionics of plant colors from green to brown through a low energy (<0.6 mW) input, promoting the development of future low-cost and low-power consumption bionics technology.

In Situ Tracking of Wetting-Front Transient Heat Release on a Surface-Mounted Metal-Organic Framework.

Transient heat generation during guest adsorption and host-guest interactions is a natural phenomenon in metal-organic framework (MOF) chemistry. However, in situ tracking of such MOF released heat is an insufficiently researched field due to the fast heat dissipation to the surroundings. Herein, a facile capillary-driven liquid-imbibition approach is developed for in situ tracking of transient heat release at the wetting front of surface-mounted MOFs (SURMOFs) on cellulosic fiber substrates. Spatiotemporal temperature distributions are obtained with infrared thermal imaging for a range of MOF-based substrates and imbibed liquids. Temperature rises at the wetting front of water and binary mixtures with organic solvents are found to be over 10 K with an ultrafast and distinguishable thermal signal response (<1 s) with a detectable concentration limit ≤1 wt%. As an advancement to the state-of-the-art in trace-solvent detection technologies, this study shows great prospects for the integration of SURMOFs in future sensor devices. Inspired by this prototypal study, SURMOF-based transient heat signal transduction is likely to be extended to an ever-expanding library of SURMOFs and other classes of surface-grafted porous materials, translating into a wide range of convenient, portable, and ubiquitous sensor devices.

Metamorphosis of Heterostructured Surface-Mounted Metal-Organic Frameworks Yielding Record Oxygen Evolution Mass Activities.

Materials derived from surface-mounted metal-organic frameworks (SURMOFs) are promising electrocatalysts for the oxygen evolution reaction (OER). A series of mixed-metal, heterostructured SURMOFs is fabricated by the facile layer-by-layer deposition method. The obtained materials reveal record-high electrocatalyst mass activities of ≈2.90 kA g-1 at an overpotential of 300 mV in 0.1 m KOH, superior to the benchmarking precious and nonprecious metal electrocatalysts. This property is assigned to the particular in situ self-reconstruction and self-activation of the SURMOFs during the immersion and the electrochemical treatment in alkaline aqueous electrolytes, which allows for the generation of NiFe (oxy)hydroxide electrocatalyst materials of specific morphology and microstructure.

Biological nitrogen removal and metabolic characteristics in a full-scale two-staged anoxic-oxic (A/O) system to treat optoelectronic wastewater.

In order to explore the treatment efficiency of optoelectronic wastewater and pollutant degradation mechanism of full-scale two-stage AO process, 160 d monitoring was conducted in this study. The results showed that the two-stage AO process owned relatively stable nitrogen and organic matter removal performance. The average concentration of COD, NH4+-N, and TN in effluent was 54, 3.78 and 13.77 mg L-1, respectively, and the removal rate was over 80%. The results of high-throughput sequencing demonstrated that the dominant microorganism was Proteobacteria, Bacteroidetes, Firmicutes, Chlorofeli, and Acidobacteria, and differences of interaction networks exited between aerobic and anoxic units. Meanwhile, the microorganism metabolism in aerobic units was significantly different from that in anoxic unit, and the metabolism of the microbial community for treating optoelectronic wastewater was significantly different from that for treating urban domestic sewage.

Characterization of human peripheral blood γδ T cells in patients with sepsis.

In total, 30 cases of patients undergoing health check-ups with the diagnostic criteria of sepsis were included in the present study. The clinical data of each patient with sepsis were recorded at admission. In the present study, the association between the proportion of T cells in patients with sepsis and those in a healthy condition were observed. The expression of immunosuppressive molecules on the surface of Vδ1 T cells were examined, as well as studying the secretion of inflammatory cytokines in Vδ2 T cells, and the ability of the Vδ1 T cells to inhibit the secretory level of interferon-γ (IFN-γ) and the inflammatory function of Vδ2 T cells were monitored. The inhibition of proliferation of naïve CD4 T cells by Vδ1 T cells and inflammatory function of Vδ2 T cells were examined. The number of Vδ1 T cells in the peripheral blood of patients with sepsis was significantly increased compared with healthy controls (P<0.01); the proportion of Vδ2 T cells was opposite to that of Vδ1 T cells. The Sequential Organ Failure Assessment score, survival and survival time were positively associated with Vδ1 T cell ratio (P<0.05) and negatively correlated with Vδ2 T cells. The expression of cytotoxic T-lymphocyte protein 4 and T cell immunoglobulin and mucin domain-containing protein 3 on the surface of Vδ1 T cells in the peripheral blood of patients with sepsis was significantly increased compared with the healthy controls (P<0.01), and the levels of IFN-γ and tumor necrosis factor-α secreted by Vδ2 T cells were significantly decreased (P<0.01). The immunosuppressive function of Vδ1 T cells was significantly higher, and the function of Vδ2 T cells was significantly reduced (P<0.01). The phosphorylation level of Erk1/2 in Vδ2 T cells was significantly lower (P<0.01). The present results suggested that the imbalance and functional changes of different γδ T cell subtypes in the peripheral blood of patients with sepsis are associated with sepsis, and may be involved in sepsis progression.

Recent Approaches to Design Electrocatalysts Based on Metal-Organic Frameworks and Their Derivatives.

Rational design and synthesis of efficient electrocatalysts are important constituents in addressing the currently growing provision issues. Typical reactions, which are important to catalyze in this respect, include CO2 reduction, the hydrogen and oxygen evolution reactions as well as the oxygen reduction reaction. The most efficient catalysts known up-to-date for these processes usually contain expensive and scarce elements, substantially impeding implementation of such electrocatalysts at a larger scale. Metal-organic frameworks (MOFs) and their derivatives containing affordable components and building blocks, as an emerging class of porous functional materials, have been recently attracting a great attention thanks to their tunable structure and composition together with high surface area, just to name a few. Up to now, several MOFs and MOF-derivatives have been reported as electrode materials for the energy-related electrocatalytic application. In this review article, we summarize and analyze current approaches to design such materials. The design strategies to improve the Faradaic efficiency and selectivity of these catalysts are discussed. Last but not least, we discuss some novel strategies to enhance the conductivity, chemical stability and efficiency of MOF-derived electrocatalysts.

Top-Down Synthesis of Nanostructured Platinum-Lanthanide Alloy Oxygen Reduction Reaction Catalysts: Pt xPr/C as an Example.

The oxygen reduction reaction (ORR) is of great interest for future sustainable energy conversion and storage, especially concerning fuel cell applications. The preparation of active, affordable, and scalable electrocatalysts and their application in fuel cell engines of hydrogen cars is a prominent step toward the reduction of air pollution, especially in urban areas. Alloying nanostructured Pt with lanthanides is a promising approach to enhance its catalytic ORR activity, whereby the development of a simple synthetic route turned out to be a nontrivial endeavor. Herein, for the first time, we present a successful single-step, scalable top-down synthetic route for Pt-lanthanide alloy nanoparticles, as witnessed by the example of Pr-alloyed Pt nanoparticles. The catalyst was characterized by high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and photoelectron spectroscopy, and its electrocatalytic oxygen reduction activity was investigated using a rotating disk electrode technique. Pt xPr/C showed ∼3.5 times higher [1.96 mA/cm2Pt, 0.9 V vs reversible hydrogen electrode (RHE)] specific activity and ∼1.7 times higher (0.7 A/mgPt, 0.9 V vs RHE) mass activity compared to commercial Pt/C catalysts. On the basis of previous findings and characterization of the Pt xPr/C catalyst, the activity improvement over commercial Pt/C originates from a lattice strain introduced by the alloying process.