Ion diffusion retarded by diverging chemical susceptibility.

For first-order phase transitions, the second derivatives of Gibbs free energy (specific heat and compressibility) diverge at the transition point, resulting in an effect known as super-elasticity along the pressure axis, or super-thermicity along the temperature axis. Here we report a chemical analogy of these singularity effects along the atomic doping axis, where the second derivative of Gibbs free energy (chemical susceptibility) diverges at the transition point, leading to an anomalously high energy barrier for dopant diffusion in co-existing phases, an effect we coin as super-susceptibility. The effect is realized in hydrogen diffusion in vanadium dioxide (VO2) with a metal-insulator transition (MIT). We show that hydrogen faces three times higher energy barrier and over one order of magnitude lower diffusivity when it diffuses across a metal-insulator domain wall in VO2. The additional energy barrier is attributed to a volumetric energy penalty that the diffusers need to pay for the reduction of latent heat. The super-susceptibility and resultant retarded atomic diffusion are expected to exist universally in all phase transformations where the transformation temperature is coupled to chemical composition, and inspires new ways to engineer dopant diffusion in phase-coexisting material systems.

The Non-Denatured Processing of Brasenia schreberi Mucilage-Characteristics of Hydrodynamic Properties and the Effect on In Vivo Functions.

Food non-denatured processes, such as freeze-drying and grinding, are commonly applied to raw materials with good bioactive functions. Although the functional components are maintained, whether structural and physical changes impact the in vivo function is often ignored in practical situations. Brasenia schreberi mucilage (BSM) has a significant alleviation effect on DSS-induced colitis. This work focused on the influence of non-denatured manufacture on the colonic benefits of BSM-based products. First, three forms of products including fresh mucilage (FM), freeze-dried products (FS), and freeze-dried powder (FP) were prepared. Then, their in vitro physiochemical properties were compared, analyzing their influence on the gut inflammation degree, microbial composition, and SCFA production in mice. The results suggested that the water retention rate of FS and FP was decreased to 34.59 ± 3.85%, and 9.93 ± 1.76%. The viscosity of FM, FS, and FP was 20.14 Pa∙s, 4.92 Pa∙s, and 0.41 Pa∙s, respectively. The freeze-drying and grinding process also damaged the lamellar microstructure of BSM. Then, animal tests showed that colitis mice intervened with FM, FS, and FP had disease activity scores of 2.03, 3.95, and 4.62. Meanwhile, FM notably changed the gut microbial composition and significantly increased propionate and butyrate levels. It seemed that the distinct colitis alleviation efficacy of BSM-based products is attributed to different hydrodynamic properties in the gut. FM had relatively higher viscosity and correspondingly high nutritional density in the gut lumen, which stimulates Firmicutes growth and promotes butyrate production, and thereby exhibited the best efficiency on protecting from colitis.

Atomic dynamics of electrified solid-liquid interfaces in liquid-cell TEM.

Electrified solid-liquid interfaces (ESLIs) play a key role in various electrochemical processes relevant to energy1-5, biology6 and geochemistry7. The electron and mass transport at the electrified interfaces may result in structural modifications that markedly influence the reaction pathways. For example, electrocatalyst surface restructuring during reactions can substantially affect the catalysis mechanisms and reaction products1-3. Despite its importance, direct probing the atomic dynamics of solid-liquid interfaces under electric biasing is challenging owing to the nature of being buried in liquid electrolytes and the limited spatial resolution of current techniques for in situ imaging through liquids. Here, with our development of advanced polymer electrochemical liquid cells for transmission electron microscopy (TEM), we are able to directly monitor the atomic dynamics of ESLIs during copper (Cu)-catalysed CO2 electroreduction reactions (CO2ERs). Our observation reveals a fluctuating liquid-like amorphous interphase. It undergoes reversible crystalline-amorphous structural transformations and flows along the electrified Cu surface, thus mediating the crystalline Cu surface restructuring and mass loss through the interphase layer. The combination of real-time observation and theoretical calculations unveils an amorphization-mediated restructuring mechanism resulting from charge-activated surface reactions with the electrolyte. Our results open many opportunities to explore the atomic dynamics and its impact in broad systems involving ESLIs by taking advantage of the in situ imaging capability.

Rational Design of Coordination Polymers Composited Hollow Multishelled Structures for Drug Delivery.

Multifunctional drug delivery systems (DDS) are in high demand for effectively targeting specific cells, necessitating excellent biocompatibility, precise release mechanisms, and sustained release capabilities. The hollow multishelled structure (HoMS) presents a promising solution, integrating structural and compositional design for efficient DDS development amidst complex cellular environments. Herein, starting from a Fe-based metal-organic framework (MOF), amorphous coordination polymers (CP) composited HoMS with controlled shell numbers are fabricated by balancing the rate of MOF decomposition and shell formation. Fe-CP HoMS loaded with DOX is utilized for synergistic chemotherapy and chemodynamic therapy, offering excellent responsive drug release capability (excellent pH-triggered drug release 82% within 72 h at pH 5.0 solution with doxorubicin (DOX) loading capacity of 284 mg g-1). In addition to its potent chemotherapy attributes, Fe-CP-HoMS possesses chemodynamic therapy potential by continuously catalyzing H2O2 to generate ·OH species within cancer cells, thus effectively inhibiting cancer cell proliferation. DOX@3S-Fe-CP-HoMS, at a concentration of 12.5 µg mL-1, demonstrates significant inhibitory effects on cancer cells while maintaining minimal cytotoxicity toward normal cells. It is envisioned that CP-HoMS could serve as an effective and biocompatible platform for the advancement of intelligent drug delivery systems in the realm of cancer therapy.

Proteomics Analysis Reveals the Underlying Factors of Mucilage Disappearance in Brasenia schreberi and Its Influence on Nutrient Accumulation.

Brasenia schreberi J.F. Gmel (BS) is rich in mucilage, which has diverse biological activities, and is utilized in the food and pharmaceutical industries due to its nutritional value. Proteomics analysis was employed to investigate the cause of mucilage disappearance in BS and its effect on nutrient accumulation. Among the 2892 proteins identified, 840 differentially expressed proteins (DEPs) were found to be involved in mucilage development. By comparing the expression patterns and functions and pathway enrichment, the DEPs mainly contributed to carbon and energy metabolism, polysaccharide metabolism, and photosynthesis. Our study also revealed positive correlations between mucilage accumulation and tryptophan metabolism, with high levels of indole-3-acetic (IAA) contributing to mucilage accumulation. Furthermore, environmental changes and particularly excessive nutrients were found to be detrimental to mucilage synthesis. Overall, in the absence of various stimuli in the growing environment, BS accumulates more nutrients within the plant itself instead of producing mucilage.

Number of denatured rigor cross-bridges determines the intracellular volume shrinkage in porcine muscle fibre under PSE-inducing condition.

Earlier onset of rigor mortis is a critical physiological progress occurring in the development of pale soft and exudative (PSE) meat. However, how rigor cross-bridges denature under different physiological conditions and their impacts on water-holding capacity remains unclear. To address this scientific question, we firstly established a method to quantify the extent of rigor cross-bridge denaturation using skinned fibres prepared from porcine longissimus thoracis et lumborum muscle. Effects of pH and temperature on the kinetics of rigor cross-bridge denaturation, actomyosin denaturation and shrinkage of muscle fibre were studied. We then manipulated the number of rigor cross-bridges before the denaturation condition was initiated (pH 5.5, 38 °C). Results suggested that the loss of water-holding capacity in PSE meat is determined by the number of denatured rigor cross-bridges. Physiochemical analysis on myofibrils demonstrated that increase in protein oxidation, surface hydrophobicity and loss of electrostatic repulsive force between myofibrils may be involved in the mechanism.

Atomically synergistic Zn-Cr catalyst for iso-stoichiometric co-conversion of ethane and CO2 to ethylene and CO.

Developing atomically synergistic bifunctional catalysts relies on the creation of colocalized active atoms to facilitate distinct elementary steps in catalytic cycles. Herein, we show that the atomically-synergistic binuclear-site catalyst (ABC) consisting of [Formula: see text]-O-Cr6+ on zeolite SSZ-13 displays unique catalytic properties for iso-stoichiometric co-conversion of ethane and CO2. Ethylene selectivity and utilization of converted CO2 can reach 100 % and 99.0% under 500 °C at ethane conversion of 9.6%, respectively. In-situ/ex-situ spectroscopic studies and DFT calculations reveal atomic synergies between acidic Zn and redox Cr sites. [Formula: see text] ([Formula: see text]) sites facilitate ß-C-H bond cleavage in ethane and the formation of Zn-Hδ- hydride, thereby the enhanced basicity promotes CO2 adsorption/activation and prevents ethane C-C bond scission. The redox Cr site accelerates CO2 dissociation by replenishing lattice oxygen and facilitates H2O formation/desorption. This study presents the advantages of the ABC concept, paving the way for the rational design of novel advanced catalysts.

Visualizing Facets Asymmetry Induced Directional Movement of Cadmium Chloride Nanomotor.

Nanomotors in solution have many potential applications. However, it has been a significant challenge to realize the directional motion of nanomotors. Here, we report cadmium chloride tetrahydrate (CdCl2·4H2O) nanomotors with remarkable directional movement under electron beam irradiation. Using in situ liquid phase transmission electron microscopy, we show that the CdCl2·4H2O nanoparticle with asymmetric surface facets moves through the liquid with the flat end in the direction of motion. As the nanomotor morphology changes, the speed of movement also changes. Finite element simulation of the electric field and fluid velocity distribution around the nanomotor assists the understanding of ionic self-diffusiophoresis as a driving force for the nanomotor movement; the nanomotor generates its own local ion concentration gradient due to different chemical reactivities on different facets.

Impact of environmental education on environmental quality under the background of low-carbon economy.

Introduction: How does environmental education affect environmental quality? There is no consensus among theorists. This paper is devoted to exploring the influence mechanism of environmental education and environmental quality under the background of a low-carbon economy from a theoretical model and empirical analysis. Methods: The research method of this paper includes two aspects. First, from the consideration of the central planner, this paper draws on and improves the Ramsey Model to explore the interaction mechanism among environmental education, environmental quality and green growth. Second, this paper uses provincial panel data from China from 2011 to 2017 for empirical analysis, which mainly verifies the impact mechanism of environmental education on environmental quality. Results and discussion: The theoretical model shows that environmental education enhances green consumption intention through residents' environmental awareness and enhances enterprises' cleaner production motivation through environmental pressure. Correspondingly, the pressure to improve environmental quality will also promote the economy's endogenous growth through the digital economy's transformation and the accumulation of human capital. The empirical analysis confirms that environmental education can improve environmental quality through green consumption and pollution control. Still, the effect of improving environmental quality only through pollution control is not apparent, and pollution control needs to be combined with environmental education, especially in high-pollution areas. Finally, this paper puts forward some suggestions for optimizing environmental education.

A special polysaccharide hydrogel coated on Brasenia schreberi: preventive effects against ulcerative colitis via modulation of gut microbiota.

Ulcerative colitis (UC) is a growing health concern in humans, but it can be prevented by using special dietary strategies. Young stems and leaves of Brasenia schreberi (BS) are coated with a special polysaccharide hydrogel (BS mucilage) which can be beneficial for colon health. The aim of this study was to investigate the preventive effects of BS mucilage against UC in a DSS-treated mouse model. Although containing only 0.3% solid content, our research showed that BS mucilage effectively attenuated the disease activity index (DAI) and the spleen index and downregulated IL-1ß, IL-18, IL-6 and CAT mRNA levels in DSS-treated mice, which is a promising UC alleviation function. Additionally, BS mucilage also improved the propionate and butyrate levels in mouse feces and alleviated the imbalanced gut microbiota induced by DSS. The abundance of pro-inflammatory and colorectal cancer related bacteria, such as Prevotella, Ruminococcus, Acutalibacter and Christensenella, was decreased by BS mucilage feeding, whereas the abundance of anti-inflammatory and SCFA-producing bacteria including Alistipes and Odoribacter was increased. In conclusion, the current study shows that the daily consumption of BS mucilage could be an effective way to prevent UC in mice, via modulation of gut microbiota.

Revealing the Mechanism of sp-N Doping in Graphdiyne for Developing Site-Defined Metal-Free Catalysts.

Due to the limited reserves of metals, scientists are devoted to exploring high-performance metal-free catalysts based on carbon materials to solve environment-related issues. Doping would build up inhomogeneous charge distribution on surface, which is an efficient approach for boosting the catalytic performance. However, doping sites are difficult to control in traditional carbon materials, thus hindering their development. Taking the advantage of unique sp-C in graphdiyne (GDY), a new N doping configuration of sp-hybridized nitrogen (sp-N), bringing a Pt-comparable catalytic activity in oxygen reduction reaction is site-defined introduced. However, the reaction intermediate of this process is never captured, hindering the understanding of the mechanism and the precise synthesis of metal-free catalysts. After the four-year study, the fabrication of intermediate-like molecule is realized, and finally sp-N doped GDY via the pericyclic reaction is obtained. Compared with GDY doped with other N configurations, the designed sp-N GDY shows much higher catalytic activity in electroreduction of CO2 toward CH4 production, owing to the unique electronic structure introduced by sp-N, which is more favorable in stabilizing the intermediate. Thus, besides opening the black-box for the site-defined doping, this work reveals the relationship between doping configuration and products of CO2 reduction.

Strong Structural and Electronic Coupling in Metavalent PbS Moiré Superlattices.

Moiré superlattices are twisted bilayer materials in which the tunable interlayer quantum confinement offers access to new physics and novel device functionalities. Previously, moiré superlattices were built exclusively using materials with weak van der Waals interactions, and synthesizing moiré superlattices with strong interlayer chemical bonding was considered to be impractical. Here, using lead sulfide (PbS) as an example, we report a strategy for synthesizing moiré superlattices coupled by strong chemical bonding. We use water-soluble ligands as a removable template to obtain free-standing ultrathin PbS nanosheets and assemble them into direct-contact bilayers with various twist angles. Atomic-resolution imaging shows the moiré periodic structural reconstruction at the superlattice interface due to the strong metavalent coupling. Electron energy loss spectroscopy and theoretical calculations collectively reveal the twist-angle-dependent electronic structure, especially the emergent separation of flat bands at small twist angles. The localized states of flat bands are similar to well-arranged quantum dots, promising an application in devices. This study opens a new door to the exploration of deep energy modulations within moiré superlattices alternative to van der Waals twistronics.

Composition of major quinochalcone hydroxysafflor yellow A and anhydrosafflor yellow B is associated with colour of safflower (Carthamus tinctorius) during colour-transition but not with overall antioxidant capacity: A study on 144 cultivars.

Yellow pigments in the water-extract of safflower (Carthamus tinctorius L.) belong to quinochalcone flavonoid family and are widely used as food colourants. The aim of the study was to characterize the main quinochalcone compounds in safflower water-extract during blooming period when floret changed colour. Mass-spectrometry results showed that hydroxysafflor yellow A (HSYA) and anhydrosafflor yellow B (AHSYB) were the most abundant. Based on 370 florets samples collected from 144 cultivars, the contents of HSYA and AHSYB were determined, which showed that only AHSYB content had relatively strong positive association with colour indexes. The ratio of HSYA/AHSYB and visual colour exhibited certain patterns: yellow = 2, orange = 3-4, red = more dispersed, mostly falling 5-6. Most of the florets had HSYA increased first and decreased, while AHSYB decreased all the time when floret changed colour as yellow â†’ orange â†’ red. Regardless of the composition of HSYA/AHSYB in florets, the antioxidant capacities of safflower petal water-extracts were the same.

Swap motion-directed twinning of nanocrystals.

Twinning frequently occurs in nanocrystals during various thermal, chemical, or mechanical processes. However, the nucleation and propagation mechanisms of twinning in nanocrystals remain poorly understood. Through in situ atomic resolution transmission electron microscopy observation at millisecond temporal resolution, we show the twinning in Pb individual nanocrystals via a double-layer swap motion where two adjacent atomic layers shift relative to one another. The swap motion results in twin nucleation, and it also serves as a basic unit of movement for twin propagation. Our calculations reveal that the swap motion is a phonon eigenmode of the face-centered cubic crystal structure of Pb, and it is enhanced by the quantum size effect of nanocrystals.

Heterogeneous Hollow Multi-Shelled Structures with Amorphous-Crystalline Outer-Shells for Sequential Photoreduction of CO2.

Constructing delicate nano-/microreactors with tandem active sites in hierarchical architectures is a promising strategy for designing photocatalysts to realize the challenging but attractive CO2 reduction. Herein, hollow multi-shelled structure (HoMS) based microreactors with spatial ordered hetero-shells are fabricated, which achieve two-step CO2 -to-CH4 photoreduction. The multiple inner CeO2 shells increase the number of active catalytic sites to ensure efficient first-step reaction for generating CO, along with enriching the local CO concentration. The second-step CO-to-CH4 reaction is consequently induced by amorphous TiO2 (A-TiO2 ) composites on the adjacent outer-most shell, thus realizing the CO2 -to-CH4 conversion capability using one CeO2 @CeO2 /A-TiO2 HoMS. In-depth explorations in the microreactors provide compositional, structural, and interfacial guidance for engineering HoMS-based microreactors with temporally-spatially ordered shells toward efficient tandem catalysis.

Effect of Enrichment Items on the Physiology and Behavior of Sows in the Third Trimester of Pregnancy.

Modern intensive pig breeding harms animal welfare, which is especially noticeable for pregnant sows kept in confinement stalls. This study aimed to evaluate the effects of enrichment items on the movement and physiological parameters of sows in the third trimester of pregnancy. A total of 30 large white pregnant sows were randomly divided into three equal treatment groups (n = 10): control, pine wood, and scented wood groups. Interestingly, compared with the control group, the sows in the pine wood or scented wood groups showed less ventral lying and more lateral lying behavior (p < 0.01), coupled with significant reduction in the frequency of scratching and sham-chewing (p < 0.01), but with no significant difference in the degree of preference for these enrichment items (p > 0.05). Additionally, the sows in the pine wood or scented wood groups also decreased significantly in the concentration of immunoglobulin A (IgA) (p < 0.01) and the concentration of tumor necrosis factor-α (TNF-α) (p < 0.05) throughout the late pregnancy period. Overall, adding enrichment items to confinement stalls can alleviate the chronic stress and the stereotypic behavior of sows, suggesting their potential to reduce welfare compromise.

Hollow Multishell-Structured TiO2/MAPbI3 Composite Improves Charge Utilization for Visible-Light Photocatalytic Hydrogen Evolution.

Interfacial photogenerated charge separation and transport have demonstrated great influence on photocatalytic performance. Herein, the composite photocatalysts of methylammonium lead iodide perovskite (MAPbI3) in TiO2 with a hollow multishell structure (HoMS) are designed and synthesized. The results indicate that the heterogeneous interface within the MAPbI3/Pt/TiO2-HoMS can help enhance the separation of photogenerated charges. HoMSs assembled with multiple shells can not only support large surfaces available for building a heterogeneous interface and photocatalytic reactions but also improve the light absorption capability of photocatalysts. Besides, the thin shell structure can also reduce the transmission distance of carriers so as to hinder charge recombination and improve charge utilization. As a result, samples of MAPbI3/Pt/triple-shelled TiO2 hollow structure displayed a H2 yield of 6856.2 µmol h-1 g-1 under visible light, which is greatly better than that of bare MAPbI3 (268.6 µmol h-1 g-1).

Accurately Localizing Multiple Nanoparticles in a Multishelled Matrix Through Shell-to-Core Evolution for Maximizing Energy-Storage Capability.

Robust and fast lithium energy storage with a high energy density is highly desired to accelerate the market adoption of electric vehicles. To realize such a goal requires the development of electrode materials with a high capacity, however, such electrode materials suffer from huge volume expansion and induced short cycling life. Here, using tin (Sn) as an example, an ideal structure is designed to effectively solve these problems by separately localizing multiple Sn nanoparticles in a nitrogen-doped carbon hollow multishelled structure with duplicated layers for carbon shell (Sn NPs@Nx C HoMS-DL). The fabricated composite can promote ion and electron diffusion owing to the conductive network formed by connected multiple shells and cores, effectively buffer the volume expansion, and maintain a stable electrode-electrolyte interface. Despite the challenging fabrication, such a structure is realized through an innovative and facile synthesis strategy of "in situ evolution of shell to core", which is applicable for diverse low-melting-point materials. As expected, such a structure enables the high-capacity electrode material to realize nearly its theoretical lithium-storage capability: the developed Sn NPs@Nx C HoMS-DL electrode maintains 96% of its theoretical capacity after 2000 cycles at 2C.

Highly Efficient Photothermal Conversion and Water Transport during Solar Evaporation Enabled by Amorphous Hollow Multishelled Nanocomposites.

Solar evaporation, which enables water purification without consuming fossil fuels, has been considered the most promising strategy to address global scarcity of drinkable water. However, the suboptimal structure and composition designs still result in a trade-off between photothermal conversion, water transport, and tolerance to harsh environments. Here, an ultrastable amorphous Ta2 O5 /C nanocomposite is designed with a hollow multishelled structure (HoMS) for solar evaporation. This HoMS results in highly efficient photoabsorption and photothermal conversion, as well as a decrease of the actual water evaporation enthalpy. A superfast evaporation speed of 4.02 kg m-2 h-1 is achieved. More importantly, a World Health Organization standard drinkable water can be achieved from seawater, heavy-metal- and bacteria-containing water, and even from extremely acidic/alkaline or radioactive water sources. Notably, the concentration of pseudovirus SC2-P can be decreased by 6 orders of magnitude after evaporation.