Wind Aggregation Enhanced Triboelectric-Electromagnetic Hybrid Generator with Slit Effect.

It is of great significance to establish a low-cost, high-efficiency, self-powered micrometeorological monitoring system for agriculture, animal husbandry, and transportation. However, each additional detection element in the meteorological monitoring system increases the power consumption of the whole system by about 0.7 W. As a renewable energy technology, a triboelectric nanogenerator has the advantages of low price and self-powered sensing. To reduce the power consumption of the micrometeorological monitoring system, this work introduces an innovative solution: the wind-gathering enhanced triboelectric-electromagnetic hybrid generator (WGE-TEHG). Coupling the thin-film vibrating triboelectric nanogenerator (TENG) and electromagnetic generator (EMG), the TENG is used to monitor wind direction and the EMG is used to monitor wind speed and provide energy needed by the system. In particular, the TENG can be used as a self-powered sensor to reduce the power consumption of the sensing system. Besides, the TENG is used to produce slit effect to enhance the output performance of EMG. The experimental results show that the WGE-TEHG can build a self-powered natural environment micrometeorological sensing system. It can monitor the wind direction, wind speed, temperature, and relative humidity. This research has great application value for the self-powered sensing implementation of a hybrid TENG and EMG.

Janus Polyurethane Adhesive Patch with Antibacterial Properties for Wound Healing.

Despite the rapid development of tissue adhesives, flaws including allergies, poor stability, and indiscriminate double-sided adhesive properties limit their application in the medical field. In this work, Janus polyurethane patches were spontaneously prepared by adjusting the difference in the functional group distribution between the top and bottom sides of the patch during emulsion drying. Consequently, poor adhesion was exhibited on the bottom surface, while the top surface can easily adhere to metals, polymers, glasses, and tissues. The difference in adhesive strength to pork skin between the two surfaces is more than 5 times. The quaternary ammonium salt and hydrophilic components on the surface of the polyurethane patch enable the rapid removal and absorption of water from the tissue surface to achieve wet adhesion. Animal experiments have demonstrated that this multifunctional Janus polyurethane patch can promote skin wound closure and healing of infected wounds. This facile and effective strategy to construct Janus polyurethane patch provides a promising method for the development of functional tissue-adhesives.

A non-peptide-based fluorescent probe capable of sensitively visualizing asparagine endopeptidase.

The non-peptide-based fluorescent probe QMC11 is capable of specifically targeting asparagine endopeptidase (AEP) and imaging cellular endogenous AEP. The motion of the probe can be restricted by AEP to activate fluorescence while keeping a low background signal.

Tunable Thermal Conductivity of Sustainable Geopolymers by the Si/Al Ratio and Moisture Content: Insights from Atomistic Simulations.

In this work, the effects of the Si/Al ratio and moisture content on thermal transport in sustainable geopolymers have been comprehensively investigated by using the molecular dynamics simulation. The thermal conductivity of geopolymer systems increases with the increase of Si/Al ratio, and the phonon vibration frequency region, which plays a major role in the main increase of its thermal conductivity, is 8-25 THz, while the rest of the frequency interval contributes less. With the increase of moisture content, the thermal conductivity of geopolymer systems decreases at first, then increases, and finally stabilizes, which is contrary to the changing trend of the porosity of the system. This is mainly because the existence of pores leads to phonon scattering during thermal transport, which, in turn, affects the thermal conductivity of the system. When the moisture content is 5%, the thermal conductivity reaches a minimum value of about 1.103 W/(m·K), which is 40.2% lower than the thermal conductivity of the system without a water molecule. This work will help to enhance the physical level understanding of the relationship between the geopolymer structures and thermal transport properties.

Improvements in the Appearance and Nutritional Quality of Tomato Fruits Resulting from Foliar Spraying with Silicon.

Research on silicon (Si), an element considered beneficial for plant growth, has focused on abiotic and biotic stress mitigation. However, the effect of Si on tomato fruit quality under normal growth conditions remains unclear. This study investigated the effects of applying different levels of Si (0 mmol·L-1 [CK], 0.6 mmol·L-1 [T1], 1.2 mmol·L-1 [T2], and 1.8 mmol·L-1 [T3]) in foliar sprays on tomato fruit quality cultivated in substrates, and the most beneficial Si level was found. Compared to CK, exogenous Si treatments had a positive influence on the appearance and nutritional quality of tomato fruits at the mature green, breaker, and red ripening stages. Of these, T2 treatment significantly increased peel firmness and single-fruit weight in tomato fruits. The contents of soluble sugars, soluble solids, soluble proteins, and vitamin C were significantly higher, and the nitrate content was significantly lower in the T2 treatment than in the CK treatment. Cluster analysis showed that T2 produced results that were significantly different from those of the CK, T1, and T3 treatments. During the red ripening stage, the a* values of fruits in the T2 treatment tomato were significantly higher than those in the other three treatments. Moreover, the lycopene and lutein contents of the T2 treatment increased by 12.90% and 17.14%, respectively, compared to CK. T2 treatment significantly upregulated the relative gene expression levels of the phytoene desaturase gene (PDS), the lycopene ε-cyclase gene (LCY-E), and the zeaxanthin cyclooxygenase gene (ZEP) in the carotenoid key genes. The total amino acid content in tomato fruits in the T2 treatment was also significantly higher than that of CK. In summary, foliar spraying of 1.2 mmol·L-1 exogenous Si was effective in improving the appearance and nutritional quality of tomato fruits under normal growth conditions. This study provides new approaches to further elucidate the application of exogenous silicon to improve tomato fruit quality under normal conditions.

Micro-Droplets Parameters Monitoring in a Microfluidic Chip via Liquid-Solid Triboelectric Nanogenerator.

The monitoring of micro-droplets parameters is significant to the development of droplet microfluidics. However, existing monitoring methods have drawbacks such as high cost, interference with droplet movement, and even the potential for cross-contamination. Herein, a micro-droplets monitoring method (MDMM) based on liquid-solid triboelectric nanogenerator (LS-TENG) is proposed, which can realize non-invasive and self-powered monitoring of micro-droplets in a microfluidic chip. The droplet frequency is monitored by voltage pulse frequency and a mathematical model is established to monitor the droplet length and velocity. Furthermore, this work constructs micro-droplets sensor (MDS) based on the MDMM to carry out the experiment. The coefficients of determination (R2 ) of the fitting curves of the micro-droplets frequency, length, and velocity monitoring are 0.998, 0.997, and 0.995, respectively. To prove the universal applicability of the MDMM, the micro-droplets generated by different liquid media and channel structures are monitored. Eventually, a micro-droplet monitoring system is built, which can realize the counting of micro-droplets and the monitoring of droplet frequency and length. This work provides a novel approach for monitoring micro-droplets parameters, which holds the potential to advance developments in the field of microfluidics.

COAP-Pd Catalyzed Asymmetric Allylic Alkylation of Azlactones with MBH Carbonates: Access to Unnatural α-Quaternary Stereogenic Glutamic Acid Derivatives.

A palladium-catalyzed regioselective and asymmetric allylic alkylation of azlactones with MBH carbonates has been developed with chiral oxalamide-phosphine ligands. The corresponding reaction afforded a range of optically active γ-arylidenyl glutamic acid derivatives bearing an α-chiral quaternary stereocenter in good yields with excellent linear regio- and high enantioselectivity. This protocol furnishes an alternative approach for the construction of enantio-enriched unnatural α-amino acid derivatives.

Protective effects and mechanisms of N-acetylcysteine on indomethacin-induced intestinal injury in a porcine model.

This study aimed to investigate the effect of N-acetylcysteine (NAC) on indomethacin (IDMT)-induced intestinal injury in a piglet model and explore the underlying molecular mechanisms. Piglets were randomly divided into 3 treatment groups: (1) control group; (2) IDMT group; (3) NAC+IDMT group. The results showed that NAC administration significantly increased the average daily gain of piglets, attenuated the intestine hyperemia, and restored normal jejunal morphology. Further studies indicated that NAC administration significantly increased plasma citrulline concentration and jejunal villin expression, but decreased the content of proinflammatory cytokines in plasma and jejunum of IDMT-stimulated piglets. NAC administration selectively decreased the proportion of eosinophils but not neutrophils in plasma. Furthermore, NAC administration significantly increased the activities of superoxide dismutase and catalase in plasma but decreased the concentrations of hydrogen peroxide (plasma) and malondialdehyde (plasma and jejunum), as well as the activity of myeloperoxidase (jejunum) when comparing NAC+IDMT group with IDMT group. Gene Ontology analysis showed that the significantly enriched molecular function term was "ubiquitin-like protein ligase binding" for NAC+IDMT versus IDMT differentially regulated genes. In the biological process category, differentially regulated genes of NAC+IDMT versus IDMT were mainly enriched in immune-related terms. The major enrichments for differentially regulated proteins (DRPs) of NAC+IDMT versus IDMT were terms involved in lipid metabolism and immune response. KEGG pathway enrichment analysis showed that "arginine biosynthesis" was a significant enrichment term for the DRPs of NAC+IDMT versus IDMT. Further studies demonstrated that NAC administration up-regulated argininosuccinate synthase 1 mRNA expression and down-regulated arginase mRNA expression in the jejunum of IDMT-stimulated piglets. Moreover, the content of nitric oxide was restored to a normal level with the reduction of nitric oxide synthase activity. NAC administration ameliorated intestinal injury in IDMT-challenged piglets by enhancing antioxidant and anti-inflammatory functions and modulating arginine metabolism in the small intestine.

Construct of qualitative diagnostic biomarkers specific for glioma by pairing serum microRNAs.

BACKGROUND: Serum microRNAs (miRNAs) are promising non-invasive biomarkers for diagnosing glioma. However, most reported predictive models are constructed without a large enough sample size, and quantitative expression levels of their constituent serum miRNAs are susceptible to batch effects, decreasing their clinical applicability. METHODS: We propose a general method for detecting qualitative serum predictive biomarkers using a large cohort of miRNA-profiled serum samples (n = 15,460) based on the within-sample relative expression orderings of miRNAs. RESULTS: Two panels of miRNA pairs (miRPairs) were developed. The first was composed of five serum miRPairs (5-miRPairs), reaching 100% diagnostic accuracy in three validation sets for distinguishing glioma and non-cancer controls (n = 436: glioma = 236, non-cancers = 200). An additional validation set without glioma samples (non-cancers = 2611) showed a predictive accuracy of 95.9%. The second panel included 32 serum miRPairs (32-miRPairs), reaching 100% diagnostic performance in training set on specifically discriminating glioma from other cancer types (sensitivity = 100%, specificity = 100%, accuracy = 100%), which was reproducible in five validation datasets (n = 3387: glioma = 236, non-glioma cancers = 3151, sensitivity> 97.9%, specificity> 99.5%, accuracy> 95.7%). In other brain diseases, the 5-miRPairs classified all non-neoplastic samples as non-cancer, including stroke (n = 165), Alzheimer's disease (n = 973), and healthy samples (n = 1820), and all neoplastic samples as cancer, including meningioma (n = 16), and primary central nervous system lymphoma samples (n = 39). The 32-miRPairs predicted 82.2 and 92.3% of the two kinds of neoplastic samples as positive, respectively. Based on the Human miRNA tissue atlas database, the glioma-specific 32-miRPairs were significantly enriched in the spinal cord (p = 0.013) and brain (p = 0.015). CONCLUSIONS: The identified 5-miRPairs and 32-miRPairs provide potential population screening and cancer-specific biomarkers for glioma clinical practice.

Microscopic Mechanism of Tunable Thermal Conductivity in Carbon Nanotube-Geopolymer Nanocomposites.

Geopolymer has been considered as a green and low-carbon material with great potential application due to its simple synthesis process, environmental protection, excellent mechanical properties, good chemical resistance, and durability. In this work, the molecular dynamics simulation is employed to investigate the effect of the size, content, and distribution of carbon nanotubes on the thermal conductivity of geopolymer nanocomposites, and the microscopic mechanism is analyzed by the phonon density of states, phonon participation ratio, spectral thermal conductivity, etc. The results show that there is a significant size effect in the geopolymer nanocomposites system due to the carbon nanotubes. In addition, when the content of carbon nanotubes is 16.5%, the thermal conductivity in carbon nanotubes vertical axial direction (4.85 W/(m k)) increases by 125.6% compared with the system without carbon nanotubes (2.15 W/(m k)). However, the thermal conductivity in carbon nanotubes vertical axial direction (1.25 W/(m k)) decreases by 41.9%, which is mainly due to the interfacial thermal resistance and phonon scattering at the interfaces. The above results provide theoretical guidance for the tunable thermal conductivity in carbon nanotube-geopolymer nanocomposites.

A Class of Enantiomerically Pure Bis-oxamide Palladium Complexes: Modular Synthesis via Domino C(sp2)-H Bond Arylation and Photophysical Property.

A one-pot, five-step domino reaction was developed for the arylation of bis-oxamides derived from optically pure 1,2-diphenylethylenediamine, leading to the formation of a series of chiral bis-oxalamide palladium(II) complexes bearing tetraaryl-conjugated substituents in good yields. In addition, these palladium(II) complexes exhibited perceptible blue fluorescence under ultraviolet light irradiation.

Carrier-Free ATP-Activated Nanoparticles for Combined Photodynamic Therapy and Chemotherapy under Near-Infrared Light.

The combination of photodynamic therapy (PDT) and chemotherapy (chemo-photodynamic therapy) for enhancing cancer therapeutic efficiency has attracted tremendous attention in the recent years. However, limitations, such as low local concentration, non-suitable treatment light source, and uncontrollable release of therapeutic agents, result in reduced combined treatment efficacy. This study considered adenosine triphosphate (ATP), which is highly upregulated in tumor cells, as a biomarker and developed ingenious ATP-activated nanoparticles (CDNPs) that are directly self-assembled from near-infrared photosensitizer (Cy-I) and amphiphilic Cd(II) complex (DPA-Cd). After selective entry into tumor cells, the positively charged CDNPs would escape from lysosomes and be disintegrated by the high ATP concentration in the cytoplasm. The released Cy-I is capable of producing single oxygen (1 O2 ) for PDT with 808 nm irradiation and DPA-Cd can concurrently function for chemotherapy. Irradiation with 808 nm light can lead to tumor ablation in tumor-bearing mice after intravenous injection of CDNPs. This carrier-free nanoparticle offers a new platform for chemo-photodynamic therapy.

COAP/Pd-Catalyzed Linear Asymmetric Allylic Alkylation for Optically Active 3,3-Disubstituted Oxindole Derivatives with a Four-Carbon Amino Side Chain.

An asymmetric linear selective allylic alkylation of vinylaziridines with 3-aryl oxindoles has been developed by using a chiral oxamide-phosphine (COAP-Bn-OMe-p)/palladium complex in methanol, which furnished a wide variety of 3,3-disubstituted oxindole derivatives in good yields with excellent regio- and enantioselectivities.

Shape memory polyurethane potentially used for vascular stents with water-induced stiffening and improved hemocompatibility.

Shape memory polymers (SMPs) with multiple functionalities have great potential in implantable biomedical devices, especially vascular stents. However, stents made of SMPs are generally faced with the problem of insufficient radial support due to the sharp decline of the modulus after shape recovery. Therefore, it is necessary to improve the modulus of SMPs after opening the narrow part by other means. In this study, the novel SMPs available for vascular stents were developed with impressive water-induced stiffening when shape recovered in a physiological environment. Herein, a series of shape memory polyurethanes (SMPUs) containing full hard segments on the main chains and bearing hydrophilic tertiary amine soft segments on the side chains were synthesized. When immersed in water, the soft segments were dramatically separated from the hard segments, which were aggregated more to form densely packed hard domains with stronger hydrogen bonding and higher crystallinity. Both Young's modulus and the shape recovery ratio were thus promoted due to the segmental rearrangement in water. At the same time, hydrophilic side chains migrated to the surface driven by the segmental rearrangement in water, which promotes the adhesion and growth of vascular endothelial cells and inhibits the activation of the coagulation system. The ingenious structural design provided SMPUs with adequate mechanical strength and hemocompatibility to qualify for potential applications in self-expanding vascular stents.

Effects of UV/Fe(II)/sulfite pre-treatment on NOM-enhanced Ca2+ scaling during nanofiltration treatment: Fouling mitigation, mechanisms, and correlation analysis of membrane resistance.

This study was aimed to evaluate the effects of a pre-treatment involving sulfite (S(IV)) synergistically activated by ultraviolet (UV)/Fe(II) on natural organic matter (NOM)-enhanced Ca2+ scaling during nanofiltration treatment. Based on the variations in the physicochemical properties and correlation analyses of irreversible resistance, the intrinsic fouling mechanisms were revealed from two aspects: bulk crystallization (interaction between NOM and inorganic ions) and surface crystallization (morphology of surface crystallization and a change in the Ca2+ concentration in the scaling layer). Furthermore, the degradation contribution rates of different free radicals during the UV/Fe(II)/S(IV) (UFS) treatment process were evaluated. During the reactions in the UFS, three free radicals (SO·-4, OH·- and e- aq) were generated, and in-situ Fe(III) was formed in-situ. The carboxyl groups of the NOM were attacked by the free radicals, resulting in decreased of carboxyl concentration and density. In addition, the bond between Ca2+ and NOM weakened, and hydrophobic (HPO) substances were mineralized. However, the Fe(III) formed in-situ was active and electropositive, competing with Ca2+ for the complexation active sites on the NOM. The synergy effect of bulk crystallization and surface crystallization led to a significant decrease in the particle size of feed solution. The crystal size and roughness of membrane surface also decreased, which was conducive to reducing the membrane irreversible resistance. Correlation analysis revealed that the HPO ratio, carboxyl density and particle size (> 100 nm) ratio were effective characterization parameters for predicting irreversible resistance. This study not only provides guidance for alleviating membrane fouling caused by NOM-enhanced Ca2+ scaling during the nanofiltration process, but also presents the rationality of irreversible resistance during nanofiltration process and various indicators with strong linear correlation.

UV/Fe(II) synergistically activated S(IV) per-treatment on HA-enhanced Ca2+ scaling in NF filtration: Fouling mitigation, mechanisms and correlation analysis of membrane resistance in different filtration stage.

The aim of this study was to investigate the feasibility and fouling mitigation mechanisms of UV/Fe(II) synergistically activated sulfite (S(IV)) (UFS) pretreatment to alleviate membrane fouling caused by HA-enhanced Ca2+ scaling. After UFS treatment, hydrophobic substances and carboxyl groups structure were destroyed by the in-situ-generated SO•-4, resulted in a significant reduction of hydrophobic substances ratio and carboxyl group concentration. Due to the formation of more electropositive in-situ-generated Fe(III), the complexation between Ca2+ and carboxyl groups was weakened so that the bulk crystallization size on the membrane surface was greatly reduced. The filter cake enhanced osmotic pressure effect (CEOP) and concentration polarization effect were hence alleviated, as well as the surface roughness. At the microcosmic perspective, as the energy barrier between the membrane and foulants was increased significantly after pretreatment, the anti-foulants adsorption ability of the membrane was enhanced. Correlation analysis showed that the carboxyl concentration and density, HPO ratio, larger particle size (>100 nm) ratio, the Ca2+ concentration in the scaling layer and energy barrier all had a good correlation with the membrane resistance. This research not only provides an advanced oxidation technology that can effectively alleviate the synergistically-fouling effect of HA and Ca2+ of nanofiltration process, but also proposes a guidance for the UV/Fe(II) synergistically activated sulfite.

NIR Photothermal-Responsive Shape Memory Polyurethane with Protein-Inspired Aggregated Chymotrypsin-Sensitive Degradable Domains.

Biodegradable shape memory polymers are promising biomaterials for stents used in minimally invasive surgical procedures such as intestinal stents. Herein, a series of biodegradable shape memory polyurethanes (SMPUs) containing a novel phenylalanine-derived chain extender (PHP) are synthesized. Inspired by the fact that the function of biomacromolecules such as proteins is rich and varied because of the multiple combinations of the amino acid in highly evolved biosystems, this study finds that the sequence distribution of PHP in SMPU will also have a great influence on the phase structure and degradation behavior, especially the difference of surface morphology caused by degradation. Considering that the transition temperature (Ttrans ) of SMPU obtained is higher than physiological temperature, oxidized carbon black (OCB) with the ability of photothermal conversion is introduced into SMPU, which can not only endow SMPU with near-infrared response shape recovery characteristics, but also enhance phase separation degree and mechanical properties of them. SMPU/OCB composites show excellent shape memory effect and rapid photothermal response, and they can be degraded by chymotrypsin with an adjustable degradation rate. These SMPU/OCB composites show broad potential for application as intestinal stents.

Precisely synthesized segmented polyurethanes toward block sequence-controlled drug delivery.

The construction of polyurethanes (PUs) with sequence-controlled block structures remains a serious challenge. Here, we report the precise synthesis of PUs with desirable molecular weight, narrow molecular weight distribution, and controlled block sequences from commercially available monomers. The synthetic procedure is derived from a liquid-phase synthetic methodology, which involves diisocyanate-based iterative protocols in combination with a convergent strategy. Furthermore, a pair of multifunctional PUs with different sequence orders of cationic and anion segments were prepared. We show that the sequence order of functional segments presents an impact on the self-assembly behavior and results in unexpected surface charges of assembled micelles, thereby affecting the protein absorption, cell internalization, biodistribution and antitumor effect of the nanocarriers in vitro and in vivo. This work provides a versatile platform for the development of precise multiblock PUs with structural complexity and functional diversity, and will greatly facilitate the clinical translation of PUs in biomedicine.

Water-Triggered Stiffening of Shape-Memory Polyurethanes Composed of Hard Backbone Dangling PEG Soft Segments.

Shape-memory polymers (SMPs) induced by heat or water are commonly used candidates for biomedical applications. Shape recovery inevitably leads to a dramatic decrease of Young's modulus due to the enhanced flexibility of polymer chains at the transition temperature. Herein, the principle of phase-transition-induced stiffening of shape-memory metallic alloys (SMAs) is introduced to the design of molecular structures for shape-memory polyurethane (SMPUs), featuring all-hard segments composed of main chains that are attached with poly(ethylene glycol) (PEG) dangling side chains. Different from conventional SMPs, they achieve a soft-to-stiff transition when shape recovers. The stiffening process is driven by water-triggered segmental rearrangement due to the incompatibility between the hard segments and the soft PEG segments. Upon hydration, the extent of microphase separation is enhanced and the hard domains are transformed to a more continuous morphology to realize more effective stress transfer. Meanwhile, such segmental rearrangement facilitates the shape-recovery process in the hydrated state despite the final increased glass transition temperature (Tg ). This work represents a novel paradigm of simultaneously integrating balanced mechanics, shape-memory property, and biocompatibility for SMPUs as materials for minimally invasive surgery such as endoluminal stents.

Recombinant adeno-associated virus serotype 9 AAV-RABVG expressing a Rabies Virus G protein confers long-lasting immune responses in mice and non-human primates.

Three or four intramuscular doses of the inactivated human rabies virus vaccines are needed for pre- or post-exposure prophylaxis in humans. This procedure has made a great contribution to prevent human rabies deaths, which bring huge economic burdens in developing countries. Herein, a recombinant adeno-associated virus serotype 9, AAV9-RABVG, harbouring a RABV G gene, was generated to serve as a single dose rabies vaccine candidate. The RABV G protein was stably expressed in the 293T cells infected with AAV9-RABVG. A single dose of 2 × 1011 v.p. of AAV9-RABVG induced robust and long-term positive seroconversions in BALB/c mice with a 100% survival from a lethal RABV challenge. In Cynomolgus Macaques vaccinated with a single dose of 1 × 1013 v.p. of AAV9-RABVG, the titres of rabies VNAs increased remarkably from 2 weeks after immunity, and maintained over 31.525 IU/ml at 52 weeks. More DCs were activated significantly for efficient antigen presentations of RABV G protein, and more B cells were activated to be responsible for antibody responses. Significantly more RABV G specific IFN-γ-secreting CD4+ and CD8+ T cells, and IL-4-secreting CD4+ T cells were activated, and significantly higher levels of IL-2, IFN-γ, IL-4, and IL-10 were secreted to aid immune responses. Overall, the AAV9-RABVG was a single dose rabies vaccine candidate with great promising by inducing robust, long-term humoral responses and both Th1 and Th2 cell-mediated immune responses in mice and non-human primates.