A carbothermic hybrid synthesized using waste halogenated plastic in sub/supercritical CO2 and its application for lithium recovery.

Facile fabrication of porous carbon materials from waste halogenated plastic is highly attractive but frequently hampered due to potential release of halogenated organic pollutants. In this study, a novel type of carbon hybrid was tentatively synthesized from a real-world halogenated plastic as an inexpensive carbon source by sub/supercritical carbon dioxide carbonization technique. It was found that halogen-free carbon carrier was advantageously synthesized through carbonization of halogenated plastic without using catalysts due to zip depolymerization, random chain cracking and free radical reactions induced by sub/supercritical carbon dioxide technique. Exhibiting with more abundant functional groups including C-O, CO groups than pyrolytic carbon carrier, the derived carbon carrier demonstrated excellent performance in selective recovery of lithium from cathode powder with highest recovery efficiency of 93.6%. Mechanism study indicated that cathode powder was transformed into low-valence states of transition metals/metal oxides and released lithium as lithium carbonate due to collapse of oxygen framework via carbothermic reduction. This work provides an applicable and green process for synthesis of alternative carbon carrier from waste halogenated plastic and its application as carbothermic reductant in lithium recovery.

Rapid fabrication of precise high-throughput filters from membrane protein nanosheets.

Biological membranes are ideal for separations as they provide high permeability while maintaining high solute selectivity due to the presence of specialized membrane protein (MP) channels. However, successful integration of MPs into manufactured membranes has remained a significant challenge. Here, we demonstrate a two-hour organic solvent method to develop 2D crystals and nanosheets of highly packed pore-forming MPs in block copolymers (BCPs). We then integrate these hybrid materials into scalable MP-BCP biomimetic membranes. These MP-BCP nanosheet membranes maintain the molecular selectivity of the three types of ß-barrel MP channels used, with pore sizes of 0.8 nm, 1.3 nm, and 1.5 nm. These biomimetic membranes demonstrate water permeability that is 20-1,000 times greater than that of commercial membranes and 1.5-45 times greater than that of the latest research membranes with comparable molecular exclusion ratings. This approach could provide high performance alternatives in the challenging sub-nanometre to few-nanometre size range.

Creating cross-linked lamellar block copolymer supporting layers for biomimetic membranes.

The long-standing goal in membrane development is creating materials with superior transport properties, including both high flux and high selectivity. These properties are common in biological membranes, and thus mimicking nature is a promising strategy towards improved membrane design. In previous studies, we have shown that artificial water channels can have excellent water transport abilities that are comparable to biological water channel proteins, aquaporins. In this study, we propose a strategy for incorporation of artificial channels that mimic biological channels into stable polymeric membranes. Specifically, we synthesized an amphiphilic triblock copolymer, poly(isoprene)-block-poly(ethylene oxide)-block-poly(isoprene), which is a high molecular weight synthetic analog of naturally occurring lipids in terms of its self-assembled structure. This polymer was used to build stacked membranes composed of self-assembled lamellae. The resulting membranes resemble layers of natural lipid bilayers in living systems, but with superior mechanical properties suitable for real-world applications. The procedures used to synthesize the triblock copolymer resulted in membranes with increased stability due to the crosslinkability of the hydrophobic domains. Furthermore, the introduction of bridging hydrophilic domains leads to the preservation of the stacked membrane structure when the membrane is in contact with water, something that is challenging for diblock lamellae that tend to swell, and delaminate in aqueous solutions. This new method of membrane fabrication offers a practical model for making channel-based biomimetic membranes, which may lead to technological applications in reverse osmosis, nanofiltration, and ultrafiltration membranes.

Highly permeable artificial water channels that can self-assemble into two-dimensional arrays.

Bioinspired artificial water channels aim to combine the high permeability and selectivity of biological aquaporin (AQP) water channels with chemical stability. Here, we carefully characterized a class of artificial water channels, peptide-appended pillar[5]arenes (PAPs). The average single-channel osmotic water permeability for PAPs is 1.0(± 0.3) × 10(-14) cm(3)/s or 3.5(± 1.0) × 10(8) water molecules per s, which is in the range of AQPs (3.4 ∼ 40.3 × 10(8) water molecules per s) and their current synthetic analogs, carbon nanotubes (CNTs, 9.0 × 10(8) water molecules per s). This permeability is an order of magnitude higher than first-generation artificial water channels (20 to ∼ 10(7) water molecules per s). Furthermore, within lipid bilayers, PAP channels can self-assemble into 2D arrays. Relevant to permeable membrane design, the pore density of PAP channel arrays (∼ 2.6 × 10(5) pores per µm(2)) is two orders of magnitude higher than that of CNT membranes (0.1 ∼ 2.5 × 10(3) pores per µm(2)). PAP channels thus combine the advantages of biological channels and CNTs and improve upon them through their relatively simple synthesis, chemical stability, and propensity to form arrays.

Realveolarization with inhalable mucus-penetrating lipid nanoparticles for the treatment of pulmonary fibrosis in mice.

The stemness loss-associated dysregeneration of impaired alveolar type 2 epithelial (AT2) cells abolishes the reversible therapy of idiopathic pulmonary fibrosis (IPF). We here report an inhalable mucus-penetrating lipid nanoparticle (LNP) for codelivering dual mRNAs, promoting realveolarization via restoring AT2 stemness for IPF treatment. Inhalable LNPs were first formulated with dipalmitoylphosphatidylcholine and our in-house-made ionizable lipids for high-efficiency pulmonary mucus penetration and codelivery of dual messenger RNAs (mRNAs), encoding cytochrome b5 reductase 3 and bone morphogenetic protein 4, respectively. After being inhaled in a bleomycin model, LNPs reverses the mitochondrial dysfunction through ameliorating nicotinamide adenine dinucleotide biosynthesis, which inhibits the accelerated senescence of AT2 cells. Concurrently, pathological epithelial remodeling and fibroblast activation induced by impaired AT2 cells are terminated, ultimately prompting alveolar regeneration. Our data demonstrated that the mRNA-LNP system exhibited high protein expression in lung epithelial cells, which markedly extricated the alveolar collapse and prolonged the survival of fibrosis mice, providing a clinically viable strategy against IPF.

High-density reconstitution of functional water channels into vesicular and planar block copolymer membranes.

The exquisite selectivity and unique transport properties of membrane proteins can be harnessed for a variety of engineering and biomedical applications if suitable membranes can be produced. Amphiphilic block copolymers (BCPs), developed as stable lipid analogs, form membranes that functionally incorporate membrane proteins and are ideal for such applications. While high protein density and planar membrane morphology are most desirable, BCP-membrane protein aggregates have so far been limited to low protein densities in either vesicular or bilayer morphologies. Here, we used dialysis to reproducibly form planar and vesicular BCP membranes with a high density of reconstituted aquaporin-0 (AQP0) water channels. We show that AQP0 retains its biological activity when incorporated at high density in BCP membranes, and that the morphology of the BCP-protein aggregates can be controlled by adjusting the amount of incorporated AQP0. We also show that BCPs can be used to form two-dimensional crystals of AQP0.

Conversion of cellulose into levulinic acid under the catalysis of Brønsted acidic ionic liquid and erbium chloride in water.

We propose a new approach for the synergistically catalytic conversion of cellulose to levulinic acid (LA) in water by SO3H-functionalized ionic liquid (SFIL) and lanthanide chloride (LnCl3). Compared with using 1-methyl-3-(3-sulfopropyl)imidazolium chloride ([MIMPS]Cl) only, the LA yield using [MIMPS]Cl and ErCl3 increased by 14.4% and 13.6% at 50 mol% of IL and 30 mol% of IL, respectively. Moreover, the combined [MIMPS]Cl and ErCl3 system can tolerate high concentrations of substrates and maintain high activity at eleven runs. We also investigated the effects of the cation structure of ionic liquids (alkyl chain length, hydroxyl groups on the side chains, and aromatic properties) on LA production. The observations can provide useful information for designing efficient ionic liquid catalysts for biomass utilization.

Upcycling of blending waste plastics as zwitterionic hydrogel for simultaneous removal of cationic and anionic heavy metals from aqueous system.

Upcycling of waste plastics as functional materials is a new approach for synthesizing low-cost and durable adsorbents with zwitterionic property. Herein, a facile process for recycling blending waste plastics to fabricate zwitterionic plastic-g-hydrogel (ZPH) for simultaneous adsorbing cationic and anionic heavy metals was developed. ZPH possessed high affinities for cations and anions in both acid and alkaline conditions owing to its zwitterionic property, and the maximum adsorption capacities of Pb2+, Cd2+, Ba2+, and Cr(VI) (Cr2O72-) were 132.13, 85.58, 69.92 and 85.15 mg/g, respectively. Mechanism study indicated the incompatibility of blending plastics was skillfully overcome through the crosslinking between sodium alginate (SA)/chitosan (CTS) and plastics. Cations were adsorbed onto ZPH via electrostatic interaction, cation exchange and coordination interactions with Cl/N/O-containing groups. Furthermore, the reduction of Cr(VI) to Cr(III) was another important path for ZPH to capture anionic Cr2O72-, and subsequently Cr(III) was adsorbed via coordination interaction and cation exchange. Moreover, the regeneration experiment showed ZPH possessed excellent reusability and stable structure. Accordingly, this research provides a profitable approach for recycling blending plastics, and ZPH has potentials for industrial application in wastewater treatment or contaminated site remediation with complex heavy metals pollution.

Interaction between humic acid and silica in reverse osmosis membrane fouling process: A spectroscopic and molecular dynamics insight.

Combined organic and inorganic fouling is a primary barrier constraining the performance of reverse osmosis (RO) membrane. In this work, we conducted a systematic study focusing on the synergetic fouling effects of silica and humic acid (HA) in RO process, and found the critical silica concentration where the fouling pattern changed qualitatively. When the silica concentration was lower than 6 mM at a typical HA concentration of 50 mg·L-1, no severe fouling was observed, while silica reaching this critical point could cause severe synergetic fouling with HA. Concentrated silica above the critical point acted as the prior foulant with marginal fouling effect caused by HA. A variety of solutions and surface-based characterizations were performed to elucidate the synergistic fouling responsibility for silica and HA. Our study suggests that the carboxylic groups from HA formed hydrogen bonds with silica hydrate, inducing silica adsorption onto HA aggregates at low silica particle concentrations. The HA network was bridged together to form large foulants due to the silica-silica interaction above the silica critical concentration. These mechanisms were further confirmed by molecular dynamics simulations. This study provides an in-depth insight into the combined organic-inorganic fouling and can serve as a guideline to optimize feed conditions in order to mitigate fouling of RO in wastewater reusing industry.

Are contralateral submental artery perforator flaps feasible for the reconstruction of postoperative defects of oral cancer?

BACKGROUND: We evaluated the clinical applications of the reconstruction of postoperative defects of the oral cavity using contralateral submental artery flaps. METHODS: A retrospective study of 18 patients with postoperative intraoral cancer defects reconstructed with contralateral submental artery perforator flaps between October 2018 and October 2019 in our department was conducted. The defect area, flap size, and complications were evaluated. RESULTS: All patients were diagnosed based on pathological examinations: 2 with adenoid cystic carcinoma and 16 with squamous cell carcinoma. The submental artery perforator flap used for simultaneous repair was 8 to 15 cm in length and 4 to 6.5 cm in width. The survival rate of flap reconstruction was 100% with no donor site complications. CONCLUSIONS: Contralateral submental artery flap reconstruction is a suitable alternative for moderate to large intraoral defects, postoperative mouth floor defects, and oral cavity composite defects of oral malignant tumors without contralateral lymph node metastases.

Artificial water channels enable fast and selective water permeation through water-wire networks.

Artificial water channels are synthetic molecules that aim to mimic the structural and functional features of biological water channels (aquaporins). Here we report on a cluster-forming organic nanoarchitecture, peptide-appended hybrid[4]arene (PAH[4]), as a new class of artificial water channels. Fluorescence experiments and simulations demonstrated that PAH[4]s can form, through lateral diffusion, clusters in lipid membranes that provide synergistic membrane-spanning paths for a rapid and selective water permeation through water-wire networks. Quantitative transport studies revealed that PAH[4]s can transport >109 water molecules per second per molecule, which is comparable to aquaporin water channels. The performance of these channels exceeds the upper bound limit of current desalination membranes by a factor of ~104, as illustrated by the water/NaCl permeability-selectivity trade-off curve. PAH[4]'s unique properties of a high water/solute permselectivity via cooperative water-wire formation could usher in an alternative design paradigm for permeable membrane materials in separations, energy production and barrier applications.

Achieving high permeability and enhanced selectivity for Angstrom-scale separations using artificial water channel membranes.

Synthetic polymer membranes, critical to diverse energy-efficient separations, are subject to permeability-selectivity trade-offs that decrease their overall efficacy. These trade-offs are due to structural variations (e.g., broad pore size distributions) in both nonporous membranes used for Angstrom-scale separations and porous membranes used for nano to micron-scale separations. Biological membranes utilize well-defined Angstrom-scale pores to provide exceptional transport properties and can be used as inspiration to overcome this trade-off. Here, we present a comprehensive demonstration of such a bioinspired approach based on pillar[5]arene artificial water channels, resulting in artificial water channel-based block copolymer membranes. These membranes have a sharp selectivity profile with a molecular weight cutoff of ~ 500 Da, a size range challenging to achieve with current membranes, while achieving a large improvement in permeability (~65 L m-2 h-1 bar-1 compared with 4-7 L m-2 h-1 bar-1) over similarly rated commercial membranes.

Dental prostheses mimic the natural enamel behavior under functional loading: A review article.

Alumina- and zirconia-based ceramic dental restorations are designed to repair functionality as well as esthetics of the failed teeth. However, these materials exhibited several performance deficiencies such as fracture, poor esthetic properties of ceramic cores (particularly zirconia cores), and difficulty in accomplishing a strong ceramic-resin-based cement bond. Therefore, improving the mechanical properties of these ceramic materials is of great interest in a wide range of disciplines. Consequently, spatial gradients in surface composition and structure can improve the mechanical integrity of ceramic dental restorations. Thus, this article reviews the current status of the functionally graded dental prostheses inspired by the dentino-enamel junction (DEJ) structures and the linear gradation in Young's modulus of the DEJ, as a new material design approach, to improve the performance compared to traditional dental prostheses. This is a remarkable example of nature's ability to engineer functionally graded dental prostheses. The current article opens a new avenue for recent researches aimed at the further development of new ceramic dental restorations for improving their clinical durability.

Multiple antibiotic resistance genes distribution in ten large-scale membrane bioreactors for municipal wastewater treatment.

Wastewater treatment plants are thought to be potential reservoirs of antibiotic resistance genes. In this study, GeoChip was used for analyzing multiple antibiotic resistance genes, including four multidrug efflux system gene groups and three ß-lactamase genes in ten large-scale membrane bioreactors (MBRs) for municipal wastewater treatment. Results revealed that the diversity of antibiotic genes varied a lot among MBRs, but about 40% common antibiotic resistance genes were existent. The average signal intensity of each antibiotic resistance group was similar among MBRs, nevertheless the total abundance of each group varied remarkably and the dominant resistance gene groups were different in individual MBR. The antibiotic resistance genes majorly derived from Proteobacteria and Actinobacteria. Further study indicated that TN, TP and COD of influent, temperature and conductivity of mixed liquor were significant (P<0.05) correlated to the multiple antibiotic resistance genes distribution in MBRs.

In situ deposition of a personalized nanofibrous dressing via a handy electrospinning device for skin wound care.

Current strategies for wound care provide limited relief to millions of patients who suffer from burns, chronic skin ulcers or surgical-related wounds. The goal of this work is to develop an in situ deposition of a personalized nanofibrous dressing via a handy electrospinning (e-spinning) device and evaluate its properties related to skin wound care. MCM-41 type mesoporous silica nanoparticles decorated with silver nanoparticles (Ag-MSNs) were prepared by a facile and environmentally friendly approach, which possessed long-term antibacterial activity and low cytotoxicity. Poly-ε-caprolactone (PCL) incorporated with Ag-MSNs was successfully electrospun (e-spun) into nanofibrous membranes. These in situ e-spun nanofibrous membranes allowed the continuous release of Ag ions and showed broad-spectrum antimicrobial activity against two common types of pathogens, Staphylococcus aureus and Escherichia coli. In addition, the in vivo studies revealed that these antibacterial nanofibrous membranes could reduce the inflammatory response and accelerate wound healing in Wistar rats. The above results strongly demonstrate that such patient-specific dressings could be broadly applied in emergency medical transport, hospitals, clinics and at the patients' home in the near future.

3D FEA of cemented glass fiber and cast posts with various dental cements in a maxillary central incisor.

This study aimed to analyse and compare the stability of two dental posts cemented with four different luting agents by examining their shear stress transfer through the FEM. Eight three-dimensional finite element models of a maxillary central incisor restored with glass fiber and Ni-Cr alloy cast dental posts. Each dental post was luted with zinc phosphate, Panavia resin, super bond C&B resin and glass ionomer materials. Finite element models were constructed and oblique loading of 100 N was applied. The distribution of shear stress was investigated at posts and cement/dentine interfaces using ABAQUS/CAE software. The peak shear stress for glass fiber post models minimized approximately three to four times of those for Ni-Cr alloy cast post models. There was negligible difference in peak of shear stress when various cements were compared, irrespective of post materials. The shear stress had same trend for all cement materials. This study found that the glass fiber dental post reduced the shear stress concentration at interfacial of post and cement/dentine compared to Ni-Cr alloy cast dental post.

Linkages between microbial functional potential and wastewater constituents in large-scale membrane bioreactors for municipal wastewater treatment.

Large-scale membrane bioreactors (MBRs) have been widely used for the municipal wastewater treatment, whose performance relies on microbial communities of activated sludge. Nevertheless, microbial functional structures in MBRs remain little understood. To gain insight into functional genes and their steering environmental factors, we adopted GeoChip, a high-throughput microarray-based tool, to examine microbial genes in four large-scale, in-operation MBRs located in Beijing, China. The results revealed substantial microbial gene heterogeneity (43.7-85.1% overlaps) among different MBRs. Mantel tests indicated that microbial nutrient cycling genes were significantly (P < 0.05) correlated to influent COD, [Formula: see text] -N, TP or sulfate, which signified the importance of microbial mediation of wastewater constituent removal. In addition, functional genes shared by all four MBRs contained a large number of genes involved in antibiotics resistance, metal resistance and organic remediation, suggesting that they were required for degradation or resistance to toxic compounds in wastewater. The linkages between microbial functional structures and environmental variables were also unveiled by the finding of hydraulic retention time, influent COD, [Formula: see text] -N, mixed liquid temperature and humic substances as major factors shaping microbial communities. Together, the results presented demonstrate the utility of GeoChip-based microarray approach in examining microbial communities of wastewater treatment plants and provide insights into the forces driving important processes of element cycling.

Molecular cloning, overexpression and characterization of a novel water channel protein from Rhodobacter sphaeroides.

Aquaporins are highly selective water channel proteins integrated into plasma membranes of single cell organisms; plant roots and stromae; eye lenses, renal and red blood cells in vertebrates. To date, only a few microbial aquaporins have been characterized and their physiological importance is not well understood. Here we report on the cloning, expression and characterization of a novel aquaporin, RsAqpZ, from a purple photosynthetic bacterium, Rhodobacter sphaeroides ATCC 17023. The protein was expressed homologously at a high yield (∼20 mg/L culture) under anaerobic photoheterotrophic growth conditions. Stopped-flow light scattering experiments demonstrated its high water permeability (0.17±0.05 cm/s) and low energy of activation for water transport (2.93±0.60 kcal/mol) in reconstituted proteoliposomes at a protein to lipid ratio (w/w) of 0.04. We developed a fluorescence correlation spectroscopy based technique and utilized a fluorescent protein fusion of RsAqpZ, to estimate the single channel water permeability of RsAqpZ as 1.24 (±0.41) x 10(-12) cm(3)/s or 4.17 (±1.38)×10(10) H2O molecules/s, which is among the highest single channel permeability reported for aquaporins. Towards application to water purification technologies, we also demonstrated functional incorporation of RsAqpZ in amphiphilic block copolymer membranes.

Tensile stress distribution in maxillary central incisors restored with cast-made and prefabricated dental posts

AIM: To analyze and compare the tensile stress distribution in endodontically treated teeth restored with cast-made (Ni-Cr and gold) and prefabricated (titanium and glass fibre) dental posts. METHODOLOGY: Four threedimensional finite element (FE) models of a maxillary central incisor restored with Ni-Cr cast-made (Model Ni-Cr), gold cast-made (Model GO), prefabricated titanium (Model TI) and prefabricated glass fibre (Model FP) posts were constructed. An oblique loading of 100N was applied to each three-dimensional model. Tensile stress distribution within the root dentine and at the post and surrounding structure interfaces were analysed. RESULTS: In all the FE models studied, a higher magnitude of tensile stresses was observed on the palatal aspect of the cervical dentin as compared to the labial aspect and progressively decreases from the outer to the inner part of the root. The gold cast-made and glass fibre post models showed significantly less tensile stress concentration in the post-core component than the other experimental models. The maximum tensile stress was seen on the palatal aspect of the Ni-Cr compared to other posts. The higher magnitude interfacial tensile stress concentration was observed in a pulpless tooth restored with a Ni-Cr cast-made post, followed by titanium and gold castmade posts, respectively. However, the minimum interfacial tensile stress was noticed in a pulpless tooth restored with a glass fibre post. CONCLUSION: Glass fibre posts tend to transfer tensile stress more homogenously within the tooth and at interfaces than the other types of investigated posts.

Fouling characteristics in a membrane bioreactor coupled with anaerobic-anoxic-oxic process for coke wastewater treatment.

Experiments were conducted to investigate the fouling characteristics of a membrane bioreactor combined with anaerobic-anoxic-oxic process for coke wastewater treatment. Supernatant from the oxic tank was characterized as different hydrophilic/hydrophobic fractions by DAX-8 resin, with joint size partition also undertaken. Polysaccharides and proteins, mainly the fraction with molecular weight above 100kDa, were liable to accumulate in the supernatant. Hydrophilic fraction, mainly contributing to the subclass of molecular weight above 100kDa, was found most likely responsible for the flux deterioration by means of dead-end filtration tests. Analyses of particle and membrane pore size distribution revealed that major foulants had size comparable to the pore diameter. It can be inferred that steric factor (i.e. size exclusion) behaved primarily in the initial stage of fouling, while the role of hydrophobic interaction was of less significance.