Construction of a Bifunctional Redox-Site Conjugated Covalent-Organic Framework for Photoinduced Precision Trapping of Uranyl Ions.

The performance of covalent-organic frameworks (COFs) for the photocatalytic extraction of uranium is greatly limited by the number of adsorption sites. Herein, inspired by electronegative redox reactions, we designed a nitrogen-oxygen rich pyrazine connected COF (TQY-COF) with multiple redox sites as a platform for extracting uranium via combining superaffinity and enhanced photoinduction. The preorganized bisnitrogen-bisoxygen donor configuration on TQY-COF is entirely matched with the typical geometric coordination of hexavalent uranyl ions, which demonstrates high affinity (tetra-coordination). In addition, the presence of the carbonyl group and pyrazine ring effectively stores and controls electron flow, which efficaciously facilitates the separation of e-/h+ and enhances photocatalytic performance. The experimental results show that TQY-COF removes up to 99.8% of uranyl ions from actual uranium mine wastewater under the light conditions without a sacrificial agent, and the separation coefficient reaches 1.73 × 106 mL g-1 in the presence of multiple metal ions, which realizes the precise separation in the complex environment. Importantly, DFT calculations further elucidate the coordination mechanism of uranium and demonstrate the necessity of the presence of N/O atoms in the photocatalytic adsorption of uranium.

Six new coumarins from the roots of Toddalia asiatica and their anti-inflammatory activities.

We reported the discovery of six novel coumarins, toddasirins A-F (1-6), each endowed with modified isoprenyl or geranyl side chains, derived from the roots of Toddalia asiatica. Comprehensive structural elucidation was achieved through multispectroscopic analyses, single-crystal X-ray diffraction experiments, and advanced quantum mechanical electronic circular dichroism (ECD) calculations. Furthermore, the anti-inflammatory activity of these compounds was assessed. Notably, compounds 1-3 and 6 demonstrated notable inhibitory effects on nitric oxide (NO) production in lipopolysaccharide (LPS)-induced RAW 264.7 cells, with 50% inhibitory concentration (IC50) values of 3.22, 4.78, 8.90, and 4.31 µmol·L-1, respectively.

MoO2 Pump-Enhanced Flexible TiO2 Nanojungle-Based Chemiresistors for Rapid Room-Temperature Detection of H2S at Parts-per-Billion Levels.

In this study, we developed a gas sensing platform that can sensitively and specifically detect trace H2S in a high-humidity atmosphere at RT. Upon integrating a carbon nitride (C3N4) nanofilm and molybdenum dioxide (MoO2) nanosheets onto nanojungle-like TiO2 nanotube arrays (TiNTs), the fabricated chemiresistor showed rapid response (38 s)/recovery (58 s) abilities and remarkable detection sensitivity for H2S at concentrations down to 2 ppb, with an estimated detection limit of 1.13 ppb at RT and room-environmental light (REL). Importantly, the gas sensor exhibited satisfactory H2S sensing performance even in dark conditions with a response of 1.9 at 200 ppb. In this design, apart from the architectural advantages of the nanojungle-like TiNTs for accelerating the gas flow efficiency and the abundant sensing sites provided by the C3N4 film, the MoO2 nanosheets act as the essential electron pump not only for the H2S response but also for the subsequent recovery process in air. After employing the MoO2 pump onto C3N4/TiNTs, the response time and recovery time of the system are shortened to ∼35 and ∼11%, respectively. Moreover, we demonstrated the good performance of the flexible gas sensor in detecting trace H2S in human exhaled breath with good humidity resistance. These results highlight the possibility of designing chemiresistors operating in RT and REL conditions and to use these environmentally friendly TiO2-based sensors in real applications.

Rational Integration of SnMOF/SnO2 Hybrid on TiO2 Nanotube Arrays: An Effective Strategy for Accelerating Formaldehyde Sensing Performance at Room Temperature.

Formaldehyde is ubiquitously found in the environment, meaning that real-time monitoring of formaldehyde, particularly indoors, can have a significant impact on human health. However, the performance of commercially available interdigital electrode-based sensors is a compromise between active material loading and steric hindrance. In this work, a spaced TiO2 nanotube array (NTA) was exploited as a scaffold and electron collector in a formaldehyde sensor for the first time. A Sn-based metal-organic framework was successfully decorated on the inside and outside of TiO2 nanotube walls by a facile solvothermal decoration strategy. This was followed by regulated calcination, which successfully integrated the preconcentration effect of a porous Sn-based metal-organic framework (SnMOF) structure and highly active SnO2 nanocrystals into the spaced TiO2 NTA to form a Schottky heterojunction-type gas sensor. This SnMOF/SnO2@TiO2 NTA sensor achieved a high room-temperature formaldehyde response (1.7 at 6 ppm) with a fast response (4.0 s) and recovery (2.5 s) times. This work provides a new platform for preparing alternatives to interdigital electrode-based sensors and offers an effective strategy for achieving target preconcentrations for gas sensing processes. The as-prepared SnMOF/SnO2@TiO2 NTA sensor demonstrated excellent sensitivity, stability, reproducibility, flexibility, and convenience, showing excellent potential as a miniaturized device for medical diagnosis, environmental monitoring, and other intelligent sensing systems.

Target-Driven Z-Scheme Heterojunction Formation for ppb H2S Detection from Exhaled Breath at Room Temperature.

As a biomarker of periodontitis, sensitive and timely monitoring of hydrogen sulfide (H2S) in exhaled breath at room temperature (RT) is important for the early intervention of oral diseases. However, the required high operation temperature to achieve high sensitivity is still a technical challenge for directly monitoring exhaled breath. In this study, by integrating metal-organic frameworks (MOFs) into self-aligned TiO2 nanotube arrays (NTs), a chemiresistor gas sensor with outstanding sensitivity and selectivity was constructed for the detection of H2S at RT. The precise regulation of a Co(III)-based MOF CoBDC-NH2 (BDC-NH2 = 2-aminoterephthalic acid) not only induced more active surface for the preconcentration of the target gas but also caused a buildup of Z-scheme heterojunctions in the H2S atmosphere that induced an ultrahigh sensitivity at RT via 365 nm light-emitting diode irradiation. The response and recovery times decreased to ∼50 and ∼28%, respectively, when this system was exposed to UV light. The sensing chips based on the as-prepared TiO2/CoBDC-NH2 NTs exhibited the highest-ranking H2S sensing performance, i.e., a limit of detection of 1.3 ppb and excellent selectivity even to 100 times high concentration of interference gases, owing to the synergistic chemical environment provided by NH2-functionalized Co-MOFs and abundant photogenerated electrons provided by Z-scheme heterojunctions. This sensing chip was also used in a practical application for the timely monitoring of halitosis from direct exhaled breath. This study provides a reliable and sensitive design for clinically aiding the timely detection of H2S in a complex oral environment.

Water Evaporation-Driven Arginine Enantiomer Recognition on a Self-Powered Flexible Chip with High Specificity.

Chiral recognition is a crucial issue in the biomedical and pharmaceutical research communities. Due to the need for expensive equipment, reagents, and external energy, enantiomer identification is difficult to perform outside of a laboratory. Based on water evaporation-induced hydrovoltaic effect, a power-free sensing platform with sensitive chiral recognition capability is proposed for the discrimination of enantiomers. The chiral recognizer was bovine serum albumin (BSA), a naturally occurring protein. Using arginine (Arg) enantiomers as the sensing targets, the difference in enantioselectivity between l-Arg and d-Arg on a BSA-modified porous carbon substrate can be measured directly from the output voltage. By combining the cyclization reaction between NO and O-phenylenediamine (OPD), it has been discovered that the sensitivity and specificity of enantioselective identification can be significantly enhanced based on the surface charges. The limit of detection (LOD) could be as low as 76.0 nM. In addition, the proposed chips are extremely flexible and can function under deformation without sacrificing output performance. This self-powered chiral recognition chip paves a new path for the detection of chiral molecules at any time, any place, and it also has excellent potential for use in flexible wearable technology.

Engineering CuMOF in TiO2 Nanochannels as Flexible Gas Sensor for High-Performance NO Detection at Room Temperature.

As a marker molecule in respiratory gases for the pulmonary disease asthma, nitric oxide (NO) has attracted much attention for real-time gas monitoring. However, low sensitivity, poor selectivity, and high operating temperature limit the practical applications of metal oxide semiconductor (MOS) based chemiresistor gas sensors. Herein, by deliberately introducing metal-organic frameworks (MOFs) in free-standing TiO2 nanochannels (NCs), a chemiresistor gas sensor with excellent detection ability and outstanding selective traits is developed for sensing NO at room temperature (RT). The precisely engineered Cu(II)-based MOF Cu-TCA (H3TCA = tricarboxytriphenyl amine) induces more active surface in the NCs, causing the buildup of CuTCA/TiO2 p-n heterojunctions that improve the sensing response at RT just via a simple UV irradiation (λ = 365 nm). Importantly, the specialized reductive reaction of Cu(II) by NO enables a remarkable selectivity toward NO analysis. Owing to the synergistic large active surface and chemical sensitization effects from Cu-TCA, the resulting Cu-TCA/TiO2 NCs show outstanding sensing performance; i.e., the response ((Rgas - Rair)/Rair) reaches 124% at 50 ppm of NO with a detection limit of 140 ppb at RT. In addition, the response time decreases to 25.6% if the system is subjected to UV irradiation. The as-formed sensing membrane is also demonstrated to be practically effective for flexible and wearable sensing devices for quantitative NO analysis. This study facilitates the use of MOFs to achieve synergistically enhanced selectivity and sensitivity to develop high-performance gas sensors.

Acronyrones A-C, unusual prenylated acetophenones from Acronychia pedunculata.

Two novel prenylated acetophenones with new carbon skeletons, acronyrones A and B (1 and 2), and a new analogue, acronyrone C (3), together with two known compounds (4 and 5) were isolated from the leaves of Acronychia pedunculata. Their structures with absolute configurations were identified by interpretation of spectroscopic data, single crystal X-ray diffraction, and electronic circular dichroism (ECD) calculations. Compounds 1 and 2 represent the first example of prenylated acetophenones possessed a C7 (1) and a C6 (2) side chain, forming a 4-isobutylchroman-2-one unit and a 3-(2-methylpropylidene)benzofuran-2(3H)-one moiety with the acetophenone core, respectively. In addition, compound 4 exhibited significant dose-dependent transcriptional activation effect against retinoid X receptor-α (RXRα), and could be regarded as a new type of non-classical RXR ligand.

Exploiting Free-Standing p-CuO/n-TiO2 Nanochannels as a Flexible Gas Sensor with High Sensitivity for H2S at Room Temperature.

Hydrogen sulfide (H2S) is an extremely hazardous gas and is harmful to human health and the environment. Here, we developed a flexible H2S gas-sensing device operated at room temperature (25 °C) based on CuO nanoparticles coated with free-standing TiO2-nanochannel membranes that were prepared by simple electrochemical anodization. Benefiting from the modulated conductivity of the CuO/TiO2 p-n heterojunction and a unique nanochannel architecture, the traditional thermal energy was innovatively replaced with UV irradiation (λ = 365 nm) to provide the required energy for triggering the sensing reactions of H2S. Importantly, upon exposure to H2S, the p-n heterojunction is destroyed and the newly formed ohmic contact forms an antiblocking layer at the interface of CuS and TiO2, thus making the sensing device active at room temperature. The resulting CuO/TiO2 membrane exhibited a notable detection sensitivity for H2S featuring a minimum detection limit of 3.0 ppm, a response value of 46.81% against 100 ppm H2S gas, and a rapid response and recovery time. This sensing membrane also demonstrated excellent durability, long-term stability, and wide-range response to a concentration of up to 400 ppm in the presence of 40% humidity as well as outstanding flexibility and negligible change in electrical measurements under various mechanical stability tests. This study not only provides a new strategy to design a gas sensor but also paves a universal platform for sensitive gas sensing.

Wireless Battery-Free Generation of Electric Fields on One-Dimensional Asymmetric Au/ZnO Nanorods for Enhanced Raman Sensing.

Wearable electronics have great potential in enhancing health monitoring, disease diagnosis, and environmental pollution tracking. Development of wearable surface-enhanced Raman spectroscopy (SERS) substrates with target sampling and sensitive sensing functions is a promising way to obtain physical and chemical information. This study describes a facile and effective approach for constructing an electrically modulated SERS (E-SERS) substrate as a wearable and wireless battery-free substrate with improved sensitivity. By integrating zinc oxide nanorods (ZnO NRs) with asymmetric gold decoration, controllable enhanced piezoelectric potentials were achieved using magnets to supply the adjustable pressure force. Owing to spatially oriented electron-hole pair separation on the asymmetric NRs, the local hotspot intensity at the Au tips is significantly improved, increasing the SERS signal by 6.7 times. This mechanism was quantitatively analyzed using Raman spectra by in situ formation of Prussian blue (PB). As a proof-of-concept, the E-SERS substrate was further used as a wearable flexible device to directly collect the sweat on a runner's skin and then monitor the lactate status of the runner. This study offers new insight into the development of E-SERS substrates and provides new design options for the construction of wearable sampling and sensing devices for the noninvasive monitoring of metabolites in healthcare and biomedical fields.

Cobalt-Tungsten Bimetallic Carbide Nanoparticles as Efficient Catalytic Material for High-Performance Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are promising candidates for next-generation energy storage devices owing to their advantages such as high theoretical specific capacity and energy density. However, the shuttle effect of polysulfide intermediates and the slow electrochemical kinetics have a severe passive effect on the cycling stability and rate performance. A Co3 W3 C@C composite was prepared through a simple one-pot pyrolysis method and used as a modifying layer on a commercial separator. The obtained modified separator not only prevented the shuttle effect through both strong chemical interaction and a physical barrier toward polysulfides, but also acted as a catalytic membrane to catalyze the electrochemical redox of active sulfur species. By employing the coated separator, the cathode with 60 wt % sulfur delivered a high initial capacity of 1345 mAh g-1 at 0.1 A g-1 , excellent rate performance with a high capacity of 670 mAh g-1 even at 7 A g-1 , and outstanding cycle performance with a low decay rate of 0.06 % per cycle and an average Coulombic efficiency of 99.3 % within 500 cycles at 1 A g-1 . Even at a sulfur loading of 3 mg cm-1 , a high initial capacity of 869 mAh g-1 and 632 mAh g-1 after 200 cycles at 1 A g-1 were obtained. The results demonstrate the advantages of Co-W bimetallic carbide in preventing the shuttle effect and promoting the redox kinetics for high performance Li-S batteries.

A water-evaporation-induced self-charging hybrid power unit for application in the Internet of Things.

A self-charging hybrid power unit has been developed by integrating a water-evaporation-induced nanogenerator with a flexible nano-patterned supercapacitor. The nanogenerator can harvest environmental thermal energy and mechanical energy through the water evaporation process, and the supercapacitor can be charged simultaneously. The former offers stable electrical power as output, whereas the Ppy-based supercapacitor shows a capacitance of 12.497 mF/cm2 with 96.42% retention after 4,000 cycles. After filling the power unit with water as the fuel, it can be fully charged in about 20 min. The power unit can be flexibly integrated with electronic devices such as sensor nodes and wireless transmitters employing the Internet of Things. This new approach can offer new possibilities in continuous future operation of randomly distributed electronic devices incorporated in the Internet of Things.

A Self-Powered Breath Analyzer Based on PANI/PVDF Piezo-Gas-Sensing Arrays for Potential Diagnostics Application.

The increasing morbidity of internal diseases poses serious threats to human health and quality of life. Exhaled breath analysis is a noninvasive and convenient diagnostic method to improve the cure rate of patients. In this study, a self-powered breath analyzer based on polyaniline/polyvinylidene fluoride (PANI/PVDF) piezo-gas-sensing arrays has been developed for potential detection of several internal diseases. The device works by converting exhaled breath energy into piezoelectric gas-sensing signals without any external power sources. The five sensing units in the device have different sensitivities to various gas markers with concentrations ranging from 0 to 600 ppm. The working principle can be attributed to the coupling of the in-pipe gas-flow-induced piezoelectric effect of PVDF and gas-sensing properties of PANI electrodes. In addition, the device demonstrates its use as an ethanol analyzer to roughly mimic fatty liver diagnosis. This new approach can be applied to fabricating new exhaled breath analyzers and promoting the development of self-powered systems.

A self-powered brain-linked biosensing electronic-skin for actively tasting beverage and its potential application in artificial gustation.

A new self-powered brain-linked biosensing electronic-skin (e-skin) for detecting pH value and alcoholicity of beverages has been realized based on polydimethysiloxane/polypyrrole (PDMS/Ppy) nanostructures. This e-skin (linking brain and transmitting signal to the specific encephalic region) can work as an artificial gustation system for gustatory perception substitution without an external electricity source. The sensing units on the e-skin can efficiently convert mechanical energy (human motion) into triboelectric impulse. The triboelectric output can be influenced by pH value and alcohol concentration in common beverages (acidic, alkaline or alcoholic drinks), which can be treated as the bio-chemical sensing signal. The bio-chemical sensing behavior arises from the triboelectrification/bio-chemical-sensing coupling effect. The biosensing e-skin is simply linked to the brain of a mouse at the primary motor cortex area, and the inputting signal can take part in the mouse perception, thus realizing behavior interventions, e.g., shaking of legs. This study provides a novel approach for developing artificial gustation e-skin and self-powered brain-machine interaction system with low cost.

Self-powered wearable sensing-textiles for real-time detecting environmental atmosphere and body motion based on surface-triboelectric coupling effect.

Self-powered wearable sensing-textiles for real-time detecting environmental atmosphere and body motion have been presented. The textile is based on highly-stretchable conductive ecoflex fiber modified with multiwall carbon nanotube and polyaniline (PANI) derivatives (acting as one electrode). The surface of the fiber is twined with varnished wire (acting as the other electrode). Upon applied deformation of stretching or bending, the sensing-textile can harvest the mechanical energy and output electric signals through the triboelectrification effect between PANI and varnished wire. After being attached on the human body, the triboelectric output of the sensing-textile can be used to monitor body motion, including finger bending and body stretching. Interestingly, the triboelectric output of the sensing-textile is significantly dependent on the atmosphere, which can actively distinguish different gas species in the environment. The sensitivity, stability and selectivity against ethanol, ammonia, acetone and formaldehyde are high. The response against 400 ppm ethanol vapor at room temperature is up to 54.73%. The current density is 2.1 × 10-4 A m-2, and the power density is 4.2 × 10-5 W m-2. During both the motion detecting and gas sensing processes, no external electricity power is needed. The triboelectric signal can be treated as not only the sensing signal but also the power source for driving the device. The working mechanism is based on surface-triboelectric coupling effect. The present results can promote the development of self-powered wearable electronics.

Self-powered vision electronic-skin basing on piezo-photodetecting Ppy/PVDF pixel-patterned matrix for mimicking vision.

The development of multifunctional electronic-skin that establishes human-machine interfaces, enhances perception abilities or has other distinct biomedical applications is the key to the realization of artificial intelligence. In this paper, a new self-powered (battery-free) flexible vision electronic-skin has been realized from pixel-patterned matrix of piezo-photodetecting PVDF/Ppy film. The electronic-skin under applied deformation can actively output piezoelectric voltage, and the outputting signal can be significantly influenced by UV illumination. The piezoelectric output can act as both the photodetecting signal and electricity power. The reliability is demonstrated over 200 light on-off cycles. The sensing unit matrix of 6 × 6 pixels on the electronic-skin can realize image recognition through mapping multi-point UV stimuli. This self-powered vision electronic-skin that simply mimics human retina may have potential application in vision substitution.

Self-powered gustation electronic skin for mimicking taste buds based on piezoelectric-enzymatic reaction coupling process.

A new self-powered wearable gustation electronic skin for mimicking taste buds has been realized based on enzyme-modified/ZnO nanowire arrays on patterned-electrode flexible substrate. The e-skin can actively taste beverages or fruits without any external electric power. Through the piezoelectric-enzymatic reaction coupling effect, the nanowires can harvest the mechanical energy of body movement and output piezoelectric signal. The piezoelectric output is significantly dependent on the concentration of target analyte. The response for detecting 2 × 10-2 M ascorbic acid (ascorbate acid oxidase@ZnO) is up to 171.747, and the selectivity is high. The response for detecting 50% alcohol (alcohol oxidase@ZnO) is up to 45.867. Our results provide a new research direction for the development of multifunctional e-skin and expand the study scope for self-powered bionic systems.

A Self-Powered Wearable Noninvasive Electronic-Skin for Perspiration Analysis Based on Piezo-Biosensing Unit Matrix of Enzyme/ZnO Nanoarrays.

The emerging multifunctional flexible electronic-skin for establishing body-electric interaction can enable real-time monitoring of personal health status as a new personalized medicine technique. A key difficulty in the device design is the flexible power supply. Here a self-powered wearable noninvasive electronic-skin for perspiration analysis has been realized on the basis of a piezo-biosensing unit matrix of enzyme/ZnO nanoarrays. The electronic-skin can detect lactate, glucose, uric acid, and urea in the perspiration, and no outside electrical power supply or battery is used in the biosensing process. The piezoelectric impulse of the piezo-biosensing units serves as the power supply and the data biosensor. The working mechanism can be ascribed to the piezoelectric-enzymatic-reaction coupling effect of enzyme/ZnO nanowires. The electronic-skin can real-time/continuously monitor the physiological state of a runner through analyzing the perspiration on his skin. This approach can promote the development of a new-type of body electric and self-powered biosensing electronic-skin.

High-efficiency sono-solar-induced degradation of organic dye by the piezophototronic/photocatalytic coupling effect of FeS/ZnO nanoarrays.

Highly-efficient sono-solar-induced degradation of organic dye by the piezophototronic/photocatalytic coupling effect of FeS/ZnO nanoarrays was achieved. A steel screen was used as the substrate for supporting FeS/ZnO nanoarrays, and the nanoarrays were vertically and uniformly grown on the substrate via a wet-chemical route. Under ultrasonic and solar irradiation, FeS/ZnO nanoarrays have high sono-photocatalytic activity for degrading methylene blue in water. The photogenerated carriers can be separated by a piezoelectric field and a built-in electric field, resulting in a low recombination rate and high photocatalytic efficiency. The piezophototronic and photocatalytic effects were coupled together. The experimental/theoretical data indicate that this novel wastewater treatment can co-use mechanical and solar energy in nature, and so is a promising technology for environment improvement.

High Piezo-photocatalytic Efficiency of CuS/ZnO Nanowires Using Both Solar and Mechanical Energy for Degrading Organic Dye.

High piezo-photocatalytic efficiency of degrading organic pollutants has been realized from CuS/ZnO nanowires using both solar and mechanical energy. CuS/ZnO heterostructured nanowire arrays are compactly/vertically aligned on stainless steel mesh by a simple two-step wet-chemical method. The mesh-supported nanocomposites can facilitate an efficient light harvesting due to the large surface area and can also be easily removed from the treated solution. Under both solar and ultrasonic irradiation, CuS/ZnO nanowires can rapidly degrade methylene blue (MB) in aqueous solution, and the recyclability is investigated. In this process, the ultrasonic assistance can greatly enhance the photocatalytic activity. Such a performance can be attributed to the coupling of the built-in electric field of heterostructures and the piezoelectric field of ZnO nanowires. The built-in electric field of the heterostructure can effectively separate the photogenerated electrons/holes and facilitate the carrier transportation. The CuS component can improve the visible light utilization. The piezoelectric field created by ZnO nanowires can further separate the photogenerated electrons/holes through driving them to migrate along opposite directions. The present results demonstrate a new water-pollution solution in green technologies for the environmental remediation at the industrial level.