Reversible pH-Gated MXene Membranes with Ultrahigh Mono-/Divalent-Ion Selectivity.

Artificial ion channel membranes hold high promise in water treatment, nanofluidics, and energy conversion, but it remains a great challenge to construct such smart membranes with both reversible ion-gating capability and desirable ion selectivity. Herein, we constructed a smart MXene-based membrane via p-phenylenediamine functionalization (MLM-PPD) with highly stable and aligned two-dimensional subnanochannels, which exhibits reversible ion-gating capability and ultrahigh metal ion selectivity similar to biological ion channels. The pH-sensitive groups within the MLM-PPD channel confers excellent reversible Mg2+-gating capability with a pH-switching ratio of up to 100. The mono/divalent metal-ion selectivity up to 1243.8 and 400.9 for K+/Mg2+ and Li+/Mg2+, respectively, outperforms other reported membranes. Theoretical calculations combined with experimental results reveal that the steric hindrance and stronger PPD-ion interactions substantially enhance the energy barrier for divalent metal ions passing through the MLM-PPD, and thus leading to ultrahigh mono/divalent metal-ion selectivity. This work provides a new strategy for developing artificial-ion channel membranes with both reversible ion-gating functionality and high-ion selectivity for various applications.

Sorption enhancement of lead ions from water by surface charged polystyrene-supported nano-zirconium oxide composites.

A novel hybrid nanomaterial was fabricated by encapsulating ZrO2 nanoparticles into spherical polystyrene beads (MPS) covalently bound with charged sulfonate groups (-SO3(-)). The resultant adsorbent, Zr-MPS, exhibited more preferential sorption toward Pb(II) than the simple equivalent mixture of MPS and ZrO2. Such observation might be ascribed to the presence of sulfonate groups of the polymeric host, which could enhance nano-ZrO2 dispersion and Pb(II) diffusion kinetics. To further elucidate the role of surface functional groups, we encapsulated nano-ZrO2 onto another two macroporous polystyrene with different surface groups (i.e., -N(CH3)3(+)/-CH2Cl, respectively) and a conventional activated carbon. The three obtained nanocomposites were denoted as Zr-MPN, Zr-MPC, and Zr-GAC. The presence of -SO3(-) and -N(CH3)3(+) was more favorable for nano-ZrO2 dispersion than the neutral -CH2Cl, resulting in the sequence of sorption capacities as Zr-MPS > Zr-MPN > Zr-GAC > Zr-MPC. Column Pb(II) sorption by the four nanocomposites further demonstrated the excellent Pb(II) retention by Zr-MPS. Comparatively, Zr-MPN of well-dispersed nano-ZrO2 and high sorption capacities showed much faster breakthrough for Pb(II) sequestration than Zr-MPS, because the electrostatic repulsion of surface quaternary ammonium group of MPN and Pb(II) ion would result in a poor sorption kinetics. This study suggests that charged groups in the host resins improve the dispersion of embedded nanoparticles and enhance the reactivity and capacity for sorption of metal ions. Suitably charged functional groups in the hosts are crucial in the fabrication of efficient nanocomposites for the decontamination of water from toxic metals and other charged pollutants.

Enhanced fluoride removal from water by nanosized cerium oxides impregnated porous polystyrene anion exchanger.

Efficient elimination of fluoride from wastewater is an urgent need for ensuring water safety. In the present study, a stable and reusable nanocomposite (NCO@PAE) was synthesized by impregnating nanosized cerium oxides (NCO) inside a porous polystyrene anion exchanger (PAE) host for efficient fluoride removal from wastewater. The newly fabricated NCO@PAE exhibited excellent resistance to acid and alkali environment, allowing it to be utilized in a wide pH range (2-12). Fluoride uptake onto NCO@PAE was a pH-dependent process, which could reach the maximum capacity at pH 3.0. Compared with its host PAE, NCO@PAE showed conspicuous adsorption affinity towards fluoride in the coexistence of other competing anions at high concentrations. Adsorption kinetics confirmed its high efficiency for achieving equilibrium within 120 min. Fixed-bed adsorption runs demonstrated that the effective processing capacity of NCO@PAE for synthetic fluoride-containing wastewater (initial fluoride 2.5 mg/L) was about ~330 BV (bed volume), while only 22 BV for the host PAE. The exhausted NCO@PAE could be effectively revived by a simple in-situ desorption method for long-term cycle operation without conspicuous capacity loss. All the results indicated that NCO@PAE is a reliable and promising adsorbent for water defluoridation.

Mechanical force-promoted osteoclastic differentiation via periodontal ligament stem cell exosomal protein ANXA3.

Exosomes play a critical role in intracellular communication. The biogenesis and function of exosomes are regulated by multiple biochemical factors. In the present study, we find that mechanical force promotes the biogenesis of exosomes derived from periodontal ligament stem cells (PDLSCs) and alters the exosomal proteome profile to induce osteoclastic differentiation. Mechanistically, mechanical force increases the level of exosomal proteins, especially annexin A3 (ANXA3), which facilitates exosome internalization to activate extracellular signal-regulated kinase (ERK), thus inducing osteoclast differentiation. Moreover, the infusion of exosomes derived from PDLSCs into mice promotes mechanical force-induced tooth movement and increases osteoclasts in the periodontal ligament. Collectively, this study demonstrates that mechanical force treatment promotes the biogenesis of exosomes from PDLSCs and increases exosomal protein ANXA3 to facilitate exosome internalization, which activates ERK phosphorylation, thus inducing osteoclast differentiation. Our findings shed light on new mechanisms for how mechanical force regulates the biology of exosomes and bone metabolism.

A novel water-stable two-dimensional zeolitic imidazolate frameworks thin-film composite membrane for enhancements in water permeability and nanofiltration performance.

Polymer membranes for water treatment are constrained by the permeability-separation trade-off. Herein, two-dimensional (2D) zeolitic imidazolate frameworks (ZIFs) made of benzimidazole interconnected with Zn ions are used to create 2D Zn2(Bim)4 molecular sieve nanosheets, which is explored as an asymmetric, thin-film composite (TFC) nanofiltration (NF) membrane for removing organic dyes and salts from water with a high water permeability under a low operating pressure (1 bar). The 2D Zn2(Bim)4 TFC NF membrane is synthesized via ionic bonds between polycations and the peripheral hydroxy groups of 2D Zn2(Bim)4 nanosheets, regulating the assembly of 2D Zn2(Bim)4 to create a novel crack-free functional layer on top of a polyvinylidene fluoride (PVDF) ultrafiltration membrane. FESEM and XPS confirmed the presence of a polycations-regulated ultrathin functional layer with a thickness of ∼37 nm on the PVDF support. Benefiting from its structural feature, our 2D Zn2(Bim)4 TFC NF membrane could achieve an ultra-high flux of ∼290 L/(m2·h·bar) (5-10-fold higher than that of graphene-based membranes), good anti-fouling properties and high rejection rates (above 98%) for organic dyes. Moreover, the desalinization rate is 50-75%. That is, our membrane is endowed with NF capability, and its intrinsic ultrafiltration features (high water permeance, ultrafast, and energy-saving) are also well maintained.

Stem cells from human exfoliated deciduous teeth ameliorate concanavalin A-induced autoimmune hepatitis by protecting hepatocytes from apoptosis.

BACKGROUND: Autoimmune hepatitis is a serious autoimmune liver disease that threatens human health worldwide, which emphasizes the urgent need to identify novel treatments. Stem cells from human exfoliated deciduous teeth (SHED), which are easy to obtain in a non-invasive manner, show pronounced proliferative and immunomodulatory capacities. AIM: To investigate the protective effects of SHED on concanavalin A (ConA)-induced hepatitis in mice, and to elucidate the associated regulatory mechanisms. METHODS: We used a ConA-induced acute hepatitis mouse model and an in vitro co-culture system to study the protective effects of SHED on ConA-induced autoimmune hepatitis, as well as the associated underlying mechanisms. RESULTS: SHED infusion could prevent aberrant histopathological liver architecture caused by ConA-induced infiltration of CD3+, CD4+, tumor necrosis-alpha+, and interferon-gamma+ inflammatory cells. Alanine aminotransferase and aspartate aminotransferase were significantly elevated in hepatitis mice. SHED infusion could therefore block ConA-induced alanine aminotransferase and aspartate aminotransferase elevations. Mechanistically, ConA upregulated tumor necrosis-alpha and interferon-gamma expression, which was activated by the nuclear factor-kappa B pathway to induce hepatocyte apoptosis, resulting in acute liver injury. SHED administration protected hepatocytes from ConA-induced apoptosis. CONCLUSION: SHED alleviates ConA-induced acute liver injury via inhibition of hepatocyte apoptosis mediated by the nuclear factor-kappa B pathway. Our findings could provide a potential treatment strategy for hepatitis.

Ionic polymer-coated laccase with high activity and enhanced stability: application in the decolourisation of water containing AO7.

Eliminating dyes in environmental water purification remains a formidable challenge. Laccase is a unique, environmentally friendly and efficient biocatalyst that can degrade pollutants. However, the use of laccase for the degradation of pollutants is considerably limited by its susceptibility to environmental changes and its poor reusability. We fabricated a novel biocatalyst (LacPG) by coating polyethylenimine onto the native laccase (Lac) followed by crosslinking with glutaraldehyde. The stability of the resulting LacPG was highly enhanced against pH variations, thermal treatments and provided better long-term storage with a negligible loss in enzymatic activity. Compared to Lac, LacPG exhibited significantly higher decolourisation efficiency in the degradation of a representative azo dye, acid orange 7 (AO7), which resulted from the electrostatic attraction between the coating and AO7. LacPG was separated from the AO7 solution using an ultrafiltration unit. The increased size and modified surface chemistry of LacPG facilitated ultrafiltration and reduced membrane fouling. LacPG exhibited enhanced stability, high catalytic activity and favourable properties for membrane separation; therefore, LacPG could be continuously reused in an enzymatic membrane reactor with a high efficiency for decolourising water containing AO7. The developed strategy appears to be promising for enhancing the applicability of laccase in practical water treatment.

Enhanced removal of arsenic from a highly laden industrial effluent using a combined coprecipitation/nano-adsorption process.

Effective arsenic removal from highly laden industrial wastewater is an important but challenging task. Here, a combined coprecipitation/nano-adsorption process, with ferric chloride and calcium chloride as coprecipitation agents and polymer-based nanocomposite as selective adsorbent, has been validated for arsenic removal from tungsten-smelting wastewater. On the basis of operating optimization, a binary FeCl3 (520 mg/L)-CaCl2 (300 mg/L) coprecipitation agent could remove more than 93% arsenic from the wastewater. The resulting precipitate has proved environmental safety based on leaching toxicity test. Fixed-bed column packed with zirconium or ferric-oxide-loaded nanocomposite was employed for further elimination of arsenic in coprecipitated effluent, resulting in a significant decrease of arsenic (from 0.96 to less than 0.5 mg/L). The working capacity of zirconium-loaded nanocomposite was 220 bed volumes per run, much higher than that of ferric-loaded nanocomposite (40 bed volumes per run). The exhausted zirconium-loaded nanocomposite could be efficiently in situ regenerated with a binary NaOH-NaCl solution for reuse without any significant capacity loss. The results validated the combinational coprecipitation/nano-adsorption process to be a potential alternative for effective arsenic removal from highly laden industrial effluent.

Bioregeneration of hyper-cross-linked polymeric resin preloaded with phenol.

In this study, the preliminary feasibility of bio-regeneration of a hyper-cross-linked polymeric resin NDA-802 preloaded with phenol was investigated. As compared to the abiotic experiments, phenol preloaded with NDA-802 could be effectively desorbed and biodegraded, and the bioregenerated NDA-802 could be employed for multiple use. The concentration gradient hypothesis could interpret such bioregeneration process reasonably. A slight drop in adsorption capacity of NDA-802 after bioregeneration possibly resulted from the mesopore blockage by microbial metabolic by-products. In general, bioregeneration could serve as a potential choice for the exhausted hyper-cross-linked polymeric resin in wastewater treatment.

Preparation methods for monodispersed garlic oil microspheres in water using the microemulsion technique and their potential as antimicrobials.

Garlic oil is considered as a natural broad-spectrum antibiotic because of its well-known antimicrobial activity. However, the characteristics of easy volatility and poor aqueous solubility limit the application of garlic oil in industry. The purpose of the present work is to develop and evaluate an oil-free microemulsion by loading garlic oil in microemulsion system. Microemulsions were prepared with ethoxylated hydrogenated castor (Cremophor RH40) as surfactant, n-butanol (or ethanol) as cosurfactant, oleic acid-containing garlic oil as oil phase, and ultrapure water as water phase. The effects of the ratio of surfactant to cosurfactant and different oil concentration on the area of oil-in-water (O/W) microemulsion region in pseudoternary phase diagrams were investigated. The particle size and garlic oil encapsulation efficiency of the formed microemulsions with different formulations were also investigated. In addition, the antimicrobial activity in vitro against Escherichia coli and Staphylococcus aureus was assessed. The experimental results show that a stable microemulsion region can be obtained when the mass ratio of surfactant to cosurfactant is, respectively, 1:1, 2:1, and 3:1. Especially, when the mixture surfactants of RH40/n-butanol 2/1 (w/w) is used in the microemulsion formulation, the area of O/W microemulsion region is 0.089 with the particle size 13.29 to 13.85 nm and garlic oil encapsulation efficiency 99.5%. The prepared microemulsion solution exhibits remarkable antibacterial activity against S. aureus.

Simple fabrication of polymer-based Trametes versicolor laccase for decolorization of malachite green.

A highly efficient and stable biocatalyst (denoted D201_Lac) was fabricated by encapsulating Trametes versicolor laccase within a macroporous and strongly basic exchange resin D201 through a simple adsorption process. Transmission electron micrographs and Fourier transform infrared spectra of the resultant D201_Lac proved that nanosized laccase clusters were embedded into the inner nano-pores/channels of D201. As compared to the free laccase, D201_Lac showed enhanced resistance in the pH range of 3-7 or at temperature of 30-60°C. Besides, negligible laccase was leached out from the host polymer D201 in solution of pH 3-7 and NaCl concentration up to 0.5M, which might be attributed to the electrostatic attraction and the possible twining between long-chain laccase and the cross-linking host resin. Continuous seven-cycle batch decoloration of malachite green demonstrates that decoloration efficiency of D201_Lac kept constant for more than 320-h operation.

Profiling of amine metabolites in human biofluids by micellar electrokinetic chromatography with laser-induced fluorescence detection.

A rapid and sensitive capillary electrophoresis (CE) method has been developed for profiling organic metabolites containing amine functional groups in mammalian biofluids. Metabolites containing an amine group were derivatized with 4-fluoro-7-nitrobenzo-2,1,3-oxadiazol (NBD-F), separated by micellar electrokinetic chromatography (MEKC), and detected by argon-ion (488 nm) laser-induced fluorescence detection. The optimized MEKC background electrolyte conditions were: 50 mmol L-1 sodium cholate, 5 mmol L-1 beta-cyclodextrin, and 20 mmol L-1 Brij 35 in 20 mmol L-1 aqueous borate buffer, pH 9.3, containing 7% methanol. Under these conditions all the amine compounds in mammalian biofluids, for example plasma, saliva, and urine, were derivatized directly, without extraction, in a minimum volume of 100 nL and the derivatives could be separated within 16 min. Up to 90% of the amine-containing metabolites in plasma and saliva could be identified by reference to standard compounds. For twenty amine standards linearity of calibration was better than R2=0.99. Migration-time and peak-area reproducibility were better than RSD 1.5% and 15% respectively. In replicate analysis of human plasma bioanalytical precision ranged between 0.7 and 3.8 RSD% for a 5.0-microL volume and between 1.7 and 5.5 RSD% for 100-nL volume. The concentrations measured were found to be in agreement with literature values.

[The effect of dog bilateral distraction osteogensis in temporomandibular joint].

OBJECTIVE: To investigate the effect of bilateral mandibular distraction osteogenesis in the condyles. METHODS: 16 adult hybrid dogs were randomly divided into normal control group and experiment group. Experimental dogs underwent bilateral mandibular osteodistraction at a rate of 1 min/day. 4 dogs were killed respectively in distraction period, 2 and 8 weeks after completion of 10 days distraction. The bilateral condyles specimens were harvested and examined with histological and immunohistochemical methods. RESULTS: Compared with normal control group, various degrees of irregularities and erosion were found in fibrocartilage of condyle in experiment group, including damage in fibrous layer, hyperplasia layer and proliferative layer and osteogenic activity in cartilage layer. A significant increase of TGF-beta1 expression was also found in experiment groups. TGF-beta1 positive staining was noted in hypertrophic cell, matrix and chondroblast, osteoblast and matrix in osteogenic activity areas. These changes were the most obvious in 2 weeks after completion of distraction. CONCLUSION: Gradual bilateral mandibular distraction at a rate of 1 mm/day brought degenerative changes of condyle, but the changes are reversible.