Enzymatic Reaction Generates Biomimic Nanominerals with Superior Bioactivity.

In vivo mineralization is a multistep process involving mineral-protein complexes and various metastable compounds in vertebrates. In this complex process, the minerals produced in the mitochondrial matrix play a critical role in initiating extracellular mineralization. However, the functional mechanisms of the mitochondrial minerals are still a mystery. Herein, an in vitro enzymatic reaction strategy is reported for the generation of biomimic amorphous calcium phosphate (EACP) nanominerals by an alkaline phosphatase (ALP)-catalyzed hydrolysis of adenosine triphosphate (ATP) in a weakly alkalescent aqueous condition (pH 8.0-8.5), which is partially similar to the mitochondrial environment. Significantly, the EACP nanomineral obviously promotes autophagy and osteogenic differentiation of human bone marrow-derived mesenchymal stem cells by activating an AMPK related pathway, and displays a high performance in promoting bone regeneration. These results provide in vitro evidence for the effect of ATP on the formation and stabilization of the mineral in the mineralization process, demonstrating a potential strategy for the preparation of the biomimic mineral for treating bone related diseases.

[Health Risk Assessment of Heavy Metals in Soil and Wheat Grain in the Typical Sewage Irrigated Area of Shandong Province].

Sewage irrigation is a common alternative to make up for the shortage of agricultural irrigation in intensive agricultural areas. Abundant organic matter and nutrients in sewage can improve soil fertility and crop yield, but hazardous materials, such as heavy metals, will damage the soil environmental quality and threaten human health. To better understand the characteristics of heavy metal enrichment and potential health risk in a sewage irrigated soil-wheat system, a total of sixty-three pairs of topsoil and wheat grain samples were collected from the sewage irrigated area of Longkou City in Shandong Province. The contents of Cr, Cu, Ni, Pb, Zn, As, Cd, and Hg were determined to analyze heavy metal contamination and calculate bio-accumulation factor (BAF), estimated daily absorption (EDA), as well as hazard quotient (HQ). The results showed that the average contents of the eight heavy metals were 61.647, 30.439, 29.769, 36.538, 63.716, 8.058, 0.328, and 0.028 mg·kg-1, respectively, which all exceeded the background values of corresponding heavy metals in the eastern Shandong Province. Especially, the average content of Cd was higher than the current standard value of soil environmental quality of agricultural land soil pollution risk control, indicating the apparent soil contamination. However, the correlations between the heavy metal contents in soil and wheat grains were not significant, suggesting that it is difficult to conclude the enrichment degree of heavy metals in wheat grains merely by the heavy metal contents in soil. The results of BAF showed that the high enrichment capacity of wheat grain was primarily obtained with Zn, Hg, Cd, and Cu. According to the national food safety limit standard, the over-limit ratios of Ni (100%) and Pb (96.8%) in wheat grains were the most serious. As a result, under the current consumption of local wheat flour, the EDAs of Ni and Pb were high, accounting for 28.278% and 1.955% of the acceptable daily intakes (ADI) for adults and 131.980% and 9.124% of the ADIs for children. The results of the health risk assessment exhibited that As and Pb were the main sources causing health risks, accounting for approximately 80% of the total risk. Although the sums of the HQ of the eight heavy metals for adults and children were below 10, the total HQ of children was 1.245 times higher than that of adults. The food safety of children should receive more attention. When considering spatial characteristics, the health risk in the southern study area was higher than that in the northern part of the study area. The prevention and control of heavy metal contamination in the southern area should be strengthened in the future.

A Single Electronic Tattoo for Multisensory Integration.

Wearable electronics are garnering growing interest in various emerging fields including intelligent sensors, artificial limbs, and human-machine interfaces. A remaining challenge is to develop multisensory devices that can conformally adhere to the skin even during dynamic-moving environments. Here, a single electronic tattoo (E-tattoo) based on a mixed-dimensional matrix network, which integrates two-dimensional  MXene nanosheets and one-dimensional cellulose nanofibers/Ag nanowires, is presented for multisensory integration. The multidimensional configurations endow the E-tattoo with excellent multifunctional sensing capabilities including temperature, humidity, in-plane strain, proximity, and material identification. In addition, benefiting from the satisfactory rheology of hybrid inks, the E-tattoos are able to be fabricated through multiple facile strategies including direct writing, stamping, screen printing, and three-dimensional printing on various hard/soft substrates. Especially, the E-tattoo with excellent triboelectric properties also can serve as a power source for activating small electronic devices. It is believed that these skin-conformal E-tattoo systems can provide a promising platform for next-generation wearable and epidermal electronics.

Ti3C2Tx MXene-Coated Electrospun PCL Conduits for Enhancing Neurite Regeneration and Angiogenesis.

An electrical signal is the key basis of normal physiological function of the nerve, and the stimulation of the electric signal also plays a very special role in the repair process of nerve injury. Electric stimulation is shown to be effective in promoting axonal regeneration and myelination, thereby promoting nerve injury repair. At present, it is considered that electric conduction recovery is a key aspect of regeneration and repair of long nerve defects. Conductive neural scaffolds have attracted more and more attention due to their similar electrical properties and good biocompatibility with normal nerves. Herein, PCL and MXene-PCL nerve guidance conduits (NGCs) were prepared; their effect on nerve regeneration was evaluated in vitro and in vivo. The results show that the NGCs have good biocompatibility in vitro. Furthermore, a sciatic nerve defect model (15 mm) of SD rats was made, and then the fabricated NGCs were implanted. MXene-PCL NGCs show similar results with the autograft in the sciatic function index, electrophysiological examination, angiogenesis, and morphological nerve regeneration. It is possible that the conductive MXene-PCL NGC could transmit physiological neural electric signals, induce angiogenesis, and stimulate nerve regeneration. This paper presents a novel design of MXene-PCL NGC that could transmit self-originated electric stimulation. In the future, it can be combined with other features to promote nerve regeneration.

Lightweight and flexible MXene/CNF/silver composite membranes with a brick-like structure and high-performance electromagnetic-interference shielding.

With the increasing global electromagnetic pollution, it is more and more important to develop lightweight, flexible, and high electromagnetic shielding materials. Two-dimensional (2D) transition metal material MXenes have good conductivity and excellent electromagnetic shielding performance. Herein, a facile and effective method is reported to synthesize lightweight and flexible MXene/CNF/silver (MCS) composite membranes with a brick-like structure and high-performance electromagnetic interference shielding. MCS composite membranes have an electromagnetic shielding performance of ≈50.7 dB due to MXene self-reduction of silver nanoparticles and the brick-like structure, compared with that of MXene/CNF (MC) membranes (≈14.98 dB). In addition, the MCS composite membranes exhibit super-thin thickness (46 µm) and good tensile strength (up to 32.1 MPa), and their good mechanical properties are attributed to the addition of CNFs. Moreover, the MCS composite membranes show good electrical conductivity (588.2 S m-1). Therefore, MCS composite membranes that are lightweight and flexible and have high electromagnetic shielding performance can replace other electromagnetic shielding materials and be used in aerospace, weapon equipment, and wearable smart materials.

Sonochemical synthesis of cellulose/hydroxyapatite nanocomposites and their application in protein adsorption.

Hydroxyapatite (HA) is the main mineral constituent in the hard tissue of vertebrate, which is recognized as an important biomedical material owing to its excellent bioactivity and biocompatibility. Herein, we report a facile and green sonochemical route for the rapid synthesis of cellulose/HA nanocomposites in NaOH/urea aqueous solution. The in vitro behavior of the cellulose/HA nanocomposites was studied to evaluate the biological response of the nanocomposites following immersion in simulated body fluid for various periods (maximum of 28 days). The HA crystals formed on the surface of the nanocomposites were carbonate-containing apatite, which is similar to the naturally occurring calcium phosphate materials. The HA nanosheets (assembly of nanorods) were mineralized on the surface of the nanocomposites, and maximum mass of the nanocomposites was reached 1.82 times of initial mass after 28 days of soaking. Moreover, the as-prepared cellulose/HA nanocomposites have good cytocompatibility, and show a relatively high protein adsorption ability using hemoglobin as a model protein. These results indicate that the as-prepared cellulose/HA nanocomposites are promising for applications in various biomedical fields such as tissue engineering and protein/drug delivery.

Binary Strengthening and Toughening of MXene/Cellulose Nanofiber Composite Paper with Nacre-Inspired Structure and Superior Electromagnetic Interference Shielding Properties.

With the growing popularity of electrical communication equipment, high-performance electromagnetic interference (EMI) shielding materials are widely used to deal with radiation pollution. However, the large thickness and poor mechanical properties of many EMI shielding materials usually limit their applications. In this study, ultrathin and highly flexible Ti3C2T x (d-Ti3C2T x, MXene)/cellulose nanofiber (CNF) composite paper with a nacre-like lamellar structure is fabricated via a vacuum-filtration-induced self-assembly process. By the interaction between one-dimensional (1D) CNFs and two-dimensional (2D) d-Ti3C2T x MXene, the binary strengthening and toughening of the nacre-like d-Ti3C2T x/CNF composite paper has been successfully achieved, leading to high tensile strength (up to 135.4 MPa) and fracture strain (up to 16.7%), as well as excellent folding endurance (up to 14 260 times). Moreover, the d-Ti3C2T x/CNF composite paper exhibits high electrical conductivity (up to 739.4 S m-1) and excellent specific EMI shielding efficiency (up to 2647 dB cm2 g-1) at an ultrathin thickness (minimum thickness 47 µm). The nacre-inspired strategy in this study offers a promising approach for the design and preparation of the strong integrated and flexible MXene/CNF composite paper, which may be applied in various fields such as flexible wearable devices, weapon equipment, and robot joints.

Ultrasensitive Wearable Soft Strain Sensors of Conductive, Self-healing, and Elastic Hydrogels with Synergistic "Soft and Hard" Hybrid Networks.

Robust, stretchable, and strain-sensitive hydrogels have recently attracted immense research interest because of their potential application in wearable strain sensors. The integration of the synergistic characteristics of decent mechanical properties, reliable self-healing capability, and high sensing sensitivity for fabricating conductive, elastic, self-healing, and strain-sensitive hydrogels is still a great challenge. Inspired by the mechanically excellent and self-healing biological soft tissues with hierarchical network structures, herein, functional network hydrogels are fabricated by the interconnection between a "soft" homogeneous polymer network and a "hard" dynamic ferric (Fe3+) cross-linked cellulose nanocrystals (CNCs-Fe3+) network. Under stress, the dynamic CNCs-Fe3+ coordination bonds act as sacrificial bonds to efficiently dissipate energy, while the homogeneous polymer network leads to a smooth stress-transfer, which enables the hydrogels to achieve unusual mechanical properties, such as excellent mechanical strength, robust toughness, and stretchability, as well as good self-recovery property. The hydrogels demonstrate autonomously self-healing capability in only 5 min without the need of any stimuli or healing agents, ascribing to the reorganization of CNCs and Fe3+ via ionic coordination. Furthermore, the resulted hydrogels display tunable electromechanical behavior with sensitive, stable, and repeatable variations in resistance upon mechanical deformations. Based on the tunable electromechanical behavior, the hydrogels can act as a wearable strain sensor to monitor finger joint motions, breathing, and even the slight blood pulse. This strategy of building synergistic "soft and hard" structures is successful to integrate the decent mechanical properties, reliable self-healing capability, and high sensing sensitivity together for assembling a high-performance, flexible, and wearable strain sensor.

[Source Analysis, Spatial Distribution and Pollution Assessment of Heavy Metals in Sewage Irrigation Area Farmland Soils of Longkou City].

Farmland soils in sewage irrigation area at Longkou City were collected, soil pH together with the heavy metal content were tested. Taking 70 soil points as the study object, this paper investigated the source of heavy metals in this area based on the correlation analysis and PCA of multivariate statistical analysis theory. We studied the spatial variation and distribution characteristics about heavy metals using both the theory of geostatistics and GIS spatial interpolation method. At last, the heavy metal pollution was evaluated in the way of Nemerow Index and improved fuzzy evaluation method. It turned out that, 9 kinds of heavy metal elements in the soil of research area had a certain degree of enrichment, among them the average of Cd was 3.06 times as high as the background value, and its enrichment was most severe. The result of Nemerow Index showed that, the values of comprehensive pollution index of Cu, Cd and Pb respectively were 7.06, 6.10 and 5.54, and they all belonged to high levels of pollution. According to the results of correlation analysis and principal component analysis, Cu, Zn together with Pb, Cd were mainly affected by human factors, sewage irrigation was their common pollution factor, the pollution sources for the first two heavy metals included excessive use of chemical fertilizers and pesticides in agricultural production and the accumulation of long time, whereas pollution from northern coal mining and coal gangue piled up as well as plating, machinery manufacturing and other industrial pollution were the pollution sources of the latter two elements. Other elements (Co, Cr, Mn, Ni and As) were mainly influenced by natural factors such as parent material. Comprehensive evaluation results showed that, among the 70 points, 13 points had moderate pollution,23 points belonged to light pollution, 28 points were at alert level, 6 points were in the safe range. From the perspective of spatial distribution,high value areas of heavy metal contents were mainly concentrated in towns of Zhuyouguan and Xufu. This showed that, sewage irrigation caused a certain degree of heavy metal pollution to local soil.

[Spatial Characteristics and Environmental Risk of Heavy Metals in Typical Gold Mining Area of Shandong Province].

In order to reveal the influence of anthropogenic factors on soil environment quality, a total of seventy-seven samples in topsoils were collected from Jiaojia gold mining area in Shandong province and were determined for Cu, Pb, Zn, Cr contents. Spatial structure, spatial distributions of concentrations and risk probability of heavy metals were analyzed using spatial statistic analysis. The average concentrations of Cu, Pb, Zn and Cr were 19.41 mg·kg-1, 27.32 mg·kg-1, 49.81 mg·kg-1 and 39.27 mg·kg-1, respectively. Pb, Zn and Cr were distributed normally and Cu was distributed normally after logarithm transformation. Semivariance analysis demostrated that Pb could be fitted to exponential model, and Cu, Zn and Cr were fit for spherical model. Nugget coefficents of Cu and Pb were between 0.25 and 0.75, which illustrated middle spatial autocorrelation; Zn and Cr showed the structural variation with nugget values below 0.25. Cu and Pb in the topsoils were distributed dispersedly due to effects of some human factors, whereas contents of Zn and Cr indicated relatively regular distributions and were mainly affected by natural factors. Spatial distributions of the 4 heavy metals were approximately consisitent and the high value areas appeared in the gold mines band. The result of hot spot analysis and indicator kriging interpolation revealed that the relatively high risk areas were located in Jincheng town, the boundary zone of Xinzhuang town and Canzhuang town, while the safe zone was situated in south part of the study area. Pb had higher probability exceeding the threshold and the middle or high environmental risk areas of Pb were distributed widely, which should be paid more attentions.