Unipolar Solution Flow in Calcium-Organic Frameworks for Seawater-Evaporation-Induced Electricity Generation.

Seawater-flow- and -evaporation-induced electricity generation holds significant promise in advancing next-generation sustainable energy technologies. This method relies on the electrokinetic effect but faces substantial limitations when operating in a highly ion-concentrated environment, for example, natural seawater. We present herein a novel solution using calcium-based metal-organic frameworks (MOFs, C12H6Ca2O19·2H2O) for seawater-evaporation-induced electricity generation. Remarkably, Ca-MOFs show an open-circuit voltage of 0.4 V and a short-circuit current of 14 µA when immersed in seawater under natural conditions. Our experiments and simulations revealed that sodium (Na) ions selectively transport within sub-nanochannels of these synthetic superhydrophilic MOFs. This selective ion transport engenders a unipolar solution flow, which drives the electricity generation behavior in seawater. This work not only showcases an effective Ca-MOF for electricity generation through seawater flow/evaporation but also contributes significantly to our understanding of water-driven energy harvesting technologies and their potential applications beyond this specific context.

Destruction of a Copper Metal-Organic Framework to Induce CuPt Growth as a Heterojunction Catalyst for Hydrogen Peroxide Sensing.

Assembling bimetallic alloys (BAs) with metal-organic frameworks (MOFs) to form heterojunctions has emerged as a promising strategy for the construction of highly active electrocatalysts. However, the current approaches to prepare BA@MOF heterojunctions suffer from poor controllability. In this work, a fascinating method involving partial thermal reduction and galvanic replacement to induce CuPt growth on a CuHHTP MOF (HHTP=2,3,6,7,10,11-hexahydroxytriphenylene) is reported in order to construct a CuPt@CuHHTP heterojunction. The size of the CuPt nanoparticles can be effectively regulated by modifying the reduction temperature. The resultant CuPt NP@CuHHTP heterojunction nanoarrays exhibit high electrocatalytic activity and potential as an electrochemical H2 O2 sensor with a low detection limit (5 nM), high sensitivity (6.942 mA ⋅ mM-1 ⋅ cm-2 ), and outstanding selectivity. This in situ approach provides not only new insights into the preparation of BA@MOF-based heterojunctions but also an effective approach for the optimization of the catalytic performance of MOFs and related materials.

Hierarchical CNTs@CuMn Layered Double Hydroxide Nanohybrid with Enhanced Electrochemical Performance in H2S Detection from Live Cells.

The precise monitoring of H2S has aroused immense research interest in the biological and biomedical fields since it is exposed as a third endogenous gasotransmitter. Hence, there is an urgent requisite to explore an ultrasensitive and economical H2S detection system. Herein, we report a simple strategy to configure an extremely sensitive electrochemical sensor with a 2D nanosheet-shaped layered double hydroxide (LDH) wrapped carbon nanotubes (CNTs) nanohybrid (CNTs@LDH), where a series of CNTs@CuMn-LDH nanohybrids with varied amounts of LDH nanosheets grafted on a conductive CNTs backbone has been synthesized via a facile coprecipitation approach. Taking advantage of the unique core-shell structure, the integrated electrochemically active CuMn-LDH nanosheets on the conductive CNTs scaffold, the maximum interfacial collaboration, and the superior specific surface area with a plethora of surface active sites and ultrathin LDH layers, the as-prepared CNTs@CuMn-LDH nanoarchitectures have exhibited superb electrocatalytic activity toward H2S oxidation. Under the optimum conditions, the electrochemical sensor based on the CNTs@CuMn-LDH nanohybrid shows remarkable sensing performances for H2S determination in terms of a wide linear range and a low detection limit of 0.3 nM (S/N = 3), high selectivity, reproducibility, and durability. With marvelous efficiency achieved, the proposed sensing platform has been practically used in in situ detection of abiotic H2S efflux produced by sulfate reducing bacteria and real-time in vitro tracking of H2S concentrations from live cells after being excreted by a stimulator which in turn might serve as early diseases diagnosis. Thus, our core-shell hybrid nanoarchitectures fabricated via structural integration strategy will open new horizons in material synthesis, biosensing systems, and clinical chemistry.

"Magnus nano-bullets" as T1/T2 based dual-modal for in vitro and in vivo MRI visualization.

Tissue specific T1/T2 dual contrast abilities for magnetic resonance imaging (MRI) have great significance in initial detection of cancer lesions. Herein, we developed a novel kind of Magnus nano-bullets (Mn-DTPA-F-MSNs) distinguished by magnetic (Fe3O4-NPs) head combined with mesoporous (SiO2) persist body, respectively. Subsequently, modify mesoporous SiO2 group and finally loaded with Mn2+. These Magnus nano-bullets have relaxivity value (r1 = 5.12 mM-1 s-1) and relaxivity value (r2 = 265.32 mM-1 s-1); they were > 2 folds in comparison to control at 3.0 T. Meanwhile, Magnus nano-bullets also offered significant enhancements for the detection of Glutathione (GSH), a biomarker that has been showed a redox responsive T1-weighted MRI effect in vitro and in vivo evaluations with good biocompatibility. Therefore, our finding endorses that Magnus nano-bullets offer a "smart" and tremendous strategy for greater GSH responsive T1/T2 dual MRI image probes for future biomedical applications.

Nanocomposites consisting of copper and copper oxide incorporated into MoS4 nanostructures for sensitive voltammetric determination of bisphenol A.

A nanocomposite (NC) of type Cu/Cu2O/CuO@MoS4 was obtained via coprecipitation and a hydrothermal approach from copper oxide nanoparticles and MoS4 nanostructures. A series of nanocomposites has been fabricated with varying fractions of MoS4. The NCs were characterized by XRD, XPS, SEM and TEM. The synergistic effect of enlarged specific surface, high electrocatalytic activity and the presence of mixed valencies strongly enhance the redox response at the interface of a glassy carbon electrode (GCE) modified with the NC. The intercalation properties of MoS4 in the NCs result in outstanding electro-oxidative performance towards bisphenol A (BPA). The modified GCE, best operated at +0.16 V vs. SCE, has a linear response in the 0.0001 µM to 17 µM BPA concentration range (R2 = 0.998) and high sensitivity (1587 mA µM-1 cm-2). The sensor can detect BPA with very good selectivity, enhanced storage stability and a low detection limit of 0.10 nM (S/N = 3). This is the lowest value among the non-enzymatic biosensors reported until now. The sensor was used for real-time in-vitro monitoring of BPA in (spiked) serum samples. Graphical abstract Schematic representation of Cu/Cu2O/CuO@MoS4 hybrid material fabricated by a hydrothermal method for sensitive determination of bisphenol A (BPA) from biological fluids.

Superlattice stacking by hybridizing layered double hydroxide nanosheets with layers of reduced graphene oxide for electrochemical simultaneous determination of dopamine, uric acid and ascorbic acid.

A self-assembled periodic superlattice material was obtained by integrating positively charged semiconductive sheets of a Zn-NiAl layered double hydroxide (LDH) and negatively charged layers of reduced graphene oxide (rGO). The material was used to modify a glassy carbon electrode which then is shown to be a viable sensor for the diagnostic parameters dopamine (DA), uric acid (UA) and ascorbic acid (AA). The modified GCE displays excellent electrocatalytic activity towards these biomolecules. This is assumed to be due to the synergistic effects of (a) excellent interfacial electrical conductivity that is imparted by direct neighboring of conductive rGO to semiconductive channels of LDHs, (b) the superb intercalation feature of LDHs, and (c) the enlarged surface with an enormous number of active sites. The biosensor revealed outstanding electrochemical performances in terms of selectivity, sensitivity, and wide linear ranges. Typically operated at working potentials of -0.10, +0.13 and + 0.27 V vs. saturated calomel electrode, the lower detection limits for AA, DA and UA are 13.5 nM, 0.1 nM, and 0.9 nM, respectively, at a signal-to-noise ratio of 3. The sensor was applied to real-time tracking of dopamine efflux from live human nerve cells. Graphical abstract Schematic of the preparation of a superlattice self-assembled material by integrating positively charged semiconductive sheets of Zn-NiAl layered double hydroxide (LDH) with negatively charged reduced graphene oxide (rGO) layers. It was applied to simultaneous electrochemical detection of dopamine (DA), uric acid and ascorbic acid.

Coffee Ring-Inspired Approach toward Oriented Self-Assembly of Biomimetic Murray MOFs as Sweat Biosensor.

The emergence of metal-organic frameworks (MOFs) has sparked intensive attention and opened up the possibility of "crystal engineering." However, low conductivity, slow diffusion of guest molecules, as well as powder forms always hinder the development of MOF application, especially for biosensors and bioelectronics. Herein, a coffee ring-inspired strategy toward oriented self-assembly of a biomimetic MOF film following Murray's law is proposed, which can effectively reduce the transfer resistance. The approach includes two types of self-assembly, evaporation-driven and heteroepitaxy self-assembly, and endows the centimeter-expanded MOF film with oriented macropores, mesopores, and micropores. The Murray MOF network enables greatly enhanced electrons and mass transfer efficiency for electrochemical sensing. Also, the newly discovered lactate and glucose sensing abilities in a wide pH hold striking potential in new generation of wearable sweat biosensors, miniature bioelectronics, and lab-on-a-chip devices.

Graphene paper supported MoS2 nanocrystals monolayer with Cu submicron-buds: High-performance flexible platform for sensing in sweat.

Flexible sweat biosensors are of considerable current interest for the development of wearable smart miniature devices. In this work, we report a novel type of flexible and electrochemical sweat platform fabricated by depositing Cu submicron buds on freestanding graphene paper (GP) carrying MoS2 nanocrystals monolayer for bio-functional detection of glucose and lactate. Quantitative analysis of glucose and lactate was carried out by using amperometric i-t method. Linear ranges were obtained between 5 and 1775 µM for glucose and 0.01-18.4 mM for lactate, and their corresponding limits of detection were 500 nM and 0.1 µM, respectively. The platform demonstrates fast response, good selectivity, superb reproducibility and outstanding flexibility, which enable its use for monitoring glucose and lactate in human perspiration. The strategy of structurally integrating 3D transition metal, 0D transition metal sulfide and 2D graphene will provide new insight into the design of flexible electrodes for sweat glucose and lactate monitoring and a wider range of applications in biosensing, bioelectronics, and lab-on-a-chip devices.

CCL2/CCR2-dependent recruitment of Th17 cells but not Tc17 cells to the lung in a murine asthma model.

BACKGROUND: Interleukin (IL)-17 has been implicated in the pathogenesis of asthma and the progression of airway inflammation. Here, we used a model of allergic asthma and found that the frequencies of IL-17-secreting T helper (Th)17 and CD8 (Tc)17 cells were both significantly increased, as was the expression of the CC chemokine receptor (CCR2) on the surface of these cells. CC chemokine ligand 2 (CCL2) has been shown to mediate the activation and recruitment of inflammatory cells in asthma, which are also skewed after ovalbumin (OVA) challenge. However, the role of CCL2 on Th17 cells and Tc17 cells in asthma has not been illuminated. METHODS: Mice that were sensitized and challenged with OVA received anti-CCL2 antibody (Ab; 5 µg/day intratracheally) or CCR2 antagonist (RS504393, 2 mg/kg/day intraperitoneally) prior to the challenge. Some mice received an isotype control Ab or vehicle alone. We then assessed the effects of allergic asthma and anti-CCL2 Ab or CCR2 antagonist treatment on the levels of IL-17 and CCL2, the Th17 and Tc17 cell frequencies and lung tissue inflammation. RESULTS: We demonstrated that CCL2 and IL-17 levels and the frequency of Th17 and Tc17 cells in lung tissues and bronchoalveolar lavage fluid increased in the asthma group compared with the normal control mice. Blocking the CCL2/CCR2 axis greatly reduced the Th17 but not the Tc17 cell frequency, and revealed a suppressive effect on airway inflammation. CONCLUSION: These findings indicate a role for the CCL2/CCR2 axis in mediating Th17 but not Tc17 cell migration during acute allergic airway inflammation.

Plasmon-Switched Kinetics for Formic Acid Dehydrogenation: Selective Adsorption Driven by Local Field and Hot Carriers.

Understanding illumination-mediated kinetics is essential for catalyst design in plasmon catalysis. Here we prepare Pd-based plasmonic catalysts with tunable electronic structures to reveal the underlying illumination-enhanced kinetic mechanisms for formic acid (HCOOH) dehydrogenation. We demonstrate a kinetic switch from a competitive Langmuir-Hinshelwood adsorption mode in dark to a non-competitive type under irradiation triggered by local field and hot carriers. Specifically, the electromagnetic field induces a spatial-temporal separation of dehydrogenation-favorable configurations of reactant molecule HCOOH and HCOO- due to their natural different polarities. Meanwhile, the generated energetic carriers can serve as active sites for selective molecular adsorption. The hot electrons act as adsorption sites for HCOOH, while holes prefer to adsorb HCOO-. Such unique non-competitive adsorption kinetics induced by plasmon effects serves as another typical characteristic of plasmonic catalysis that remarkably differs from thermocatalysis. This work unravels unique adsorption transformations and a kinetic switching driven by plasmon nonthermal effects.

Modulation of copper sites in porphyrin metal-organic frameworks for electrochemical ascorbic acid sensing.

Two metal-organic frameworks (MOFs) with different Cu-centered coordination structures were synthesized. By introducing 4,4-bipyridine as a linker in the Cu-MOFs, we have discovered that Cu-O, instead of Cu-N, is the active site with higher electrocatalytical activity towards ascorbic acid, which is essential to understand and develop Cu-based ascorbic acid sensors.

The study of the ratio and distribution of Th17 cells and Tc17 cells in asthmatic patients and the mouse model.

BACKGROUND: Whether CD8+ IL-17-producing T cells, namely Tc17 cells, play a role in asthma has not been determined. The aim of this study was to evaluate and compare the frequency of peripheral blood Th17 cells and Tc17 cells in asthmatic patients. In addition, the number, ratio and distribution of Th17 cells and Tc17 cells in the lung tissue and splenocytes of asthmatic mice were also investigated. METHODS: Th17 and Tc17 cells in the peripheral blood samples of asthmatic patients and in murine spleens were detected by flow cytometric analysis. Th17 and Tc17 cells in murine lung tissues were detected by double immuno-fluorescence stain. IL-17A levels in murine bronchoalveolar lavage were detected by ELISA. RESULTS: The result of the flow cytometric analysis showed the percentage of Th17 cells among CD3+ T cell populations in patients with asthma was higher than that in healthy controls (P < 0.01), The percentage of Tc17 cells was also higher (P < 0.05). The percentages of Th17 and Tc17 cells in asthmatic mice were both much higher than that in control animals (P < 0.01). Frozen sections of lung tissue showed that the number of Th17 cells and Tc17 cells in the asthma group were all significantly higher than in the control group (P < 0.01). CONCLUSIONS: Our findings suggest a functional disequilibrium of Th17 and Tc17 cell subsets in asthma that may contribute to the inflammatory process and provide novel insights into a hypothetical driving role of those cells in disease pathogenesis.

Cobalt Nanoparticles Anchored on N-Doped Porous Carbon Derived from Yeast for Enhanced Electrocatalytic Oxygen Reduction Reaction.

Biomass-derived carbon materials have received extensive attention for use in high-performance electrocatalysts. In this study, a highly efficient electrocatalyst is developed with Co nanoparticles anchored on N-doped porous carbon material (CoNC) by using yeast as a biomass precursor through a facial activation and pyrolysis process. CoNC exhibits comparable catalytic activity with commercial 20 % Pt/C for the oxygen reduction reaction (ORR) with a half-wave potential of 0.854 V. A home-made primary Zn-air battery exhibited an open circuit potential of 1.45 V and a peak power density of 188 mW cm-2 . Moreover, the discharge voltage of the primary battery maintained at a stable value up to 9 days. The enhanced performance of CoNC was probably ascribed to its high content of pyridinic-N and graphitic-N species, extra Co loading and porous structure, which provided sufficient active sites and channels to promote mass/electron transfer for ORR. This work provides a promising strategy to develop an efficient non-noble metal carbon-based electrocatalyst for fuel cells and metal-air batteries.

Enhanced Proton Transfer in Proton-Exchange Membranes with Interconnected and Zwitterion-Functionalized Covalent Porous Material Structures.

Excellent proton-conductive accelerators are indispensable for efficient proton-exchange membranes (PEMs). Covalent porous materials (CPMs), with adjustable functionalities and well-ordered porosities, show much promise as effective proton-conductive accelerators. In this study, an interconnected and zwitterion-functionalized CPM structure based on carbon nanotubes and a Schiff-base network (CNT@ZSNW-1) is constructed as a highly efficient proton-conducting accelerator by in situ growth of SNW-1 onto carbon nanotubes (CNTs) and subsequent zwitterion functionalization. A composite PEM with enhanced proton conduction is acquired by integrating CNT@ZSNW-1 with Nafion. Zwitterion functionalization offers additional proton-conducting sites and promotes the water retention capacity. Moreover, the interconnected structure of CNT@ZSNW-1 induces a more consecutive arrangement of ionic clusters, which significantly relieves the proton transfer barrier of the composite PEM and increases its proton conductivity to 0.287 S cm-1 under 95 % RH at 90 °C (about 2.2 times that of the recast Nafion, 0.131 S cm-1 ). Furthermore, the composite PEM displays a peak power density of 39.6 mW cm-2 in a direct methanol fuel cell, which is significantly higher than that of the recast Nafion (19.9 mW cm-2 ). This study affords a potential reference for devising and preparing functionalized CPMs with optimized structures to expedite proton transfer in PEMs.

Photo-enhanced dehydrogenation of formic acid on Pd-based hybrid plasmonic nanostructures.

Coupling visible light with Pd-based hybrid plasmonic nanostructures has effectively enhanced formic acid (FA) dehydrogenation at room temperature. Unlike conventional heating to achieve higher product yield, the plasmonic effect supplies a unique surface environment through the local electromagnetic field and hot charge carriers, avoiding unfavorable energy consumption and attenuated selectivity. In this minireview, we summarized the latest advances in plasmon-enhanced FA dehydrogenation, including geometry/size-dependent dehydrogenation activities, and further catalytic enhancement by coupling local surface plasmon resonance (LSPR) with Fermi level engineering or alloying effect. Furthermore, some representative cases were taken to interpret the mechanisms of hot charge carriers and the local electromagnetic field on molecular adsorption/activation. Finally, a summary of current limitations and future directions was outlined from the perspectives of mechanism and materials design for the field of plasmon-enhanced FA decomposition.

Synergistic Combination of Fermi Level Equilibrium and Plasmonic Effect for Formic Acid Dehydrogenation.

Developing an efficient catalyst for formic acid (FA) dehydrogenation is a promising strategy for safe hydrogen storage and transportation. Herein, we successfully developed trimetallic NiAuPd heterogeneous catalysts through a galvanic replacement reaction and a subsequent chemical reduction process to boost hydrogen generation from FA decomposition at room temperature by coupling Fermi level engineering with plasmonic effect. We demonstrated that Ni worked as an electron reservoir to donate electrons to Au and Pd driven by Fermi level equilibrium whereas plasmonic Au served as an optical absorber to generate energetic hot electrons and a charge-redistribution mediator. Ni and Au worked cooperatively to promote the charge heterogeneity of surface-active Pd sites, leading to enhanced chemisorption of formate-related intermediates and eventually outstanding activity (342 mmol g-1 h-1 ) compared with bimetallic counterpart. This work offers excellent insight into the rational design of efficient catalysts for practical hydrogen energy exploitation.

Natural oxidase-mimicking copper-organic frameworks for targeted identification of ascorbate in sensitive sweat sensing.

Sweat sensors play a significant role in personalized healthcare by dynamically monitoring biochemical markers to detect individual physiological status. The specific response to the target biomolecules usually depends on natural oxidase, but it is susceptible to external interference. In this work, we report tryptophan- and histidine-treated copper metal-organic frameworks (Cu-MOFs). This amino-functionalized copper-organic framework shows highly selective activity for ascorbate oxidation and can serve as an efficient ascorbate oxidase-mimicking material in sensitive sweat sensors. Experiments and calculation results elucidate that the introduced tryptophan/histidine fundamentally regulates the adsorption behaviors of biomolecules, enabling ascorbate to be selectively captured from complex sweat and further efficiently electrooxidized. This work provides not only a paradigm for specifically sweat sensing but also a significant understanding of natural oxidase-inspired MOF nanoenzymes for sensing technologies and beyond.

In situ electrochemical reductive construction of metal oxide/metal-organic framework heterojunction nanoarrays for hydrogen peroxide sensing.

Transition metal oxide/metal-organic framework heterojunctions (TMO@MOF) that combine the large specific surface area of MOFs with TMOs' high catalytic activity and multifunctionality, show excellent performances in various catalytic reactions. Nevertheless, the present preparation approaches of TMO@MOF heterojunctions are too complex to control, stimulating interests in developing simple and highly controllable methods for preparing such heterojunction. In this study, we propose an in situ electrochemical reduction approach to fabricating Cu2O nanoparticle (NP)@CuHHTP heterojunction nanoarrays with a graphene-like conductive MOF CuHHTP (HHTP is 2,3,6,7,10,11-hexahydroxytriphenylene). We have discovered that size-controlled Cu2O nanoparticles could be in situ grown on CuHHTP by applying different electrochemical reduction potentials. Also, the obtained Cu2O NP@CuHHTP heterojunction nanoarrays show high H2O2 sensitivity of 8150.6 µA·mM-1·cm2 and satisfactory detection performances in application of measuring H2O2 concentrations in urine and serum samples. This study offers promising guidance for the synthesis of MOF-based heterojunctions for early cancer diagnosis.

Increased expression of aryl hydrocarbon receptor and interleukin 22 in patients with allergic asthma.

OBJECTIVES: We sought to determine whether the aryl hydrocarbon receptor (AhR) and interleukin (IL)-22 may be involved in the pathogenesis of the peripheral blood mononuclear cells (PBMCs) in allergic asthmatic patients and whether their expression may be related to the severity of the disease. METHODS: Blood samples were obtained from each subject with allergic asthma (n =18), controlled asthma (n = 17) and healthy controls (n = 12) respectively. The PBMCs were collected for AhR mRNA detection by real-time quantitative polymerase chain reaction (PCR). The plasma was collected for IL-22 protein detection by enzyme-linked immunosorbent assay (ELISA). RESULTS: The expression of AhR mRNA in PBMCs and IL-22 protein in plasma of patients with allergic asthma were higher than those in controlled asthma cases and healthy controls. The plasma concentrations of IL-22 had negative correlation with the predicted percentage of forced expiratory volume in the first second (FEV1%) and the percentage of FEV1 and forced vital capacity (FEV1/FVC%) and it was positively correlated with the asthma severity score (ASS) of the asthmatics. CONCLUSION: Our results suggested that both AhR and IL-22 might be involved in the pathogenesis of allergic asthma in human and the level of IL-22 might have some relationship with the severity of the disease.

Effect of integrated medical and nursing intervention model on quality of life and unhealthy emotion of patients with esophageal cancer undergoing radiotherapy.

OBJECTIVE: To explore the application of integrated medical and nursing intervention model in radiotherapy for patients with esophageal cancer. METHODS: A total of 78 patients with esophageal cancer undergoing radiotherapy were randomly divided into two groups: control group (n=39, receiving traditional separate medical and nursing management) and study group (n=39, receiving integrated medical and nursing intervention mode). Before and after intervention, the mental state, nutritional index, quality of life and self-efficacy were compared between the two groups, and the adverse reactions were recorded during radiotherapy. RESULTS: Compared with those before intervention, the scores of hamilton anxiety rating scale (HAMA) and hamilton depression scale (HAMD) were lower in both groups when they were discharged from hospital, and the study group was lower than the control group (all P<0.05). The scores of comprehensive quality of life assessment questionnaire (GQOLI-74) and self-management efficacy scale (SUPPH) were increased in both groups, and the study group was higher than the control group (all P<0.05). After intervention for 3 weeks, the levels of Hb, TP and Alb in the two groups were higher than those before intervention, and the study group was higher than the control group (all P<0.05). During radiotherapy, the total incidence of adverse reactions in the study group was lower than that in the control group (P<0.05). CONCLUSION: Integrated medical and nursing intervention can obviously relieve the unhealthy emotion and improve the nutritional status, quality of life and self-efficacy for patients with esophageal cancer undergoing radiotherapy.