Regulation of Hard Segment Cluster Structures for High-performance Poly(urethane-urea) Elastomers.

Elastomers are widely used in daily life; however, the preparation of degradable and recyclable elastomers with high strength, high toughness, and excellent crack resistance remains a challenging task. In this report, a polycaprolactone-based poly(urethane-urea) elastomer is presented with excellent mechanical properties by optimizing the arrangement of hard segment clusters. It is found that long alkyl chains of the chain extenders lead to small and evenly distributed hard segment clusters, which is beneficial for improving mechanical properties. Together with the multiple hydrogen bond structure and stress-induced crystallization, the obtained elastomer exhibits a high strength of 63.3 MPa, an excellent toughness of 431 MJ m-3 and an outstanding fracture energy of 489 kJ m-2, while maintaining good recyclability and degradability. It is believed that the obtained elastomer holds great promise in various application fields and it contributes to the development of a sustainable society.

Confined liquid crystallization governed by electric field for API crystal polymorphism screening and massive preparation.

Active pharmaceutical ingredients (APIs) crystal preparation is a significant issue for the pharmaceutical development attributed to the effect on anti-inflammatory, anti-bacteria, and anti-viral, etc. While, the massive preparation of API crystal with high polymorphism selectivity is still a pendent challenge. Here, we firstly proposed a criterion according to the molecular aggregation, molecular orientation, and hydrogen bond energy between INA molecules from molecular dynamics (MD) simulations, which predicted the hydrogen bond architecture in crystal under different electric fields, hinting the recognition of crystal polymorphism. Then, an electric field governing confined liquid crystallization was constructed to achieve the INA crystal polymorphism screening relying on the criterion. Further, magnifying confined liquid volume by 5000 times from 1.0 µL to 5.0 mL realized the massive preparation of INA crystal with high polymorphic purity (>98.4%), giving a unique pathway for crystal engineering and pharmaceutical industry on the development of innovative and generic API based drugs.

Exposure to volatile organic compounds induces cardiovascular toxicity that may involve DNA methylation.

Volatile organic compounds (VOCs) are common air pollutants and water contaminants. We previously found maternal exposure to VOCs was associated with offspring congenital heart disease (CHD). However, little information is available about the effects of VOCs on cardiovascular development at embryonic stage and the underlying mechanism remains unclear. In this study, we aimed to investigate the effects of a mixture of six VOCs on cardiovascular development in zebrafish embryos. Embryos were exposed to different concentrations of VOCs mixture (32 mg/L, 64 mg/L and 128 mg/L) for 96 h, cardiovascular abnormalities including elongated heart shape, increased distance between sinus venosus and bulbus arteriosus, slowed circulation and altered heart rate were observed in a dose- and time-dependent manner. Meanwhile, VOCs exposure increased global DNA methylation levels in embryos. Analysis identified hundreds of differentially methylated sites and the enrichment of differentially methylated sites on cardiovascular development. Two differentially methylated-associated genes involved in MAPK pathway, hgfa and ntrk1, were identified to be the potential genes mediating the effects of VOCs. By enzyme-linked immunosorbent assay, altered human serum hgf and ntrk1 levels were detected in abnormal pregnancies exposed to higher VOCs levels with fetal CHD. For the first time, our study revealed exposure to VOCs induced severe cardiovascular abnormalities in zebrafish embryos. The toxicity might result from alterations in DNA methylation and corresponding expression levels of genes involved in MAPK pathway. Our study provides important information for the risk of VOCs exposure on embryonic cardiovascular development.

Constructing Gas Transmission Pathways in Two-Dimensional Composite Material ZIF-8@BNNS Mixed-Matrix Membranes to Enhance CO2/N2 Separation Performance.

Two-dimensional (2D) nanomaterials, due to their high aspect ratio and high specific surface area, which provide a more tortuous pathway for larger gas molecules, are frequently used in membrane separation. However, in mixed-matrix membranes (MMMs), the high aspect ratio and high specific surface area of 2D fillers can increase transport resistance, thereby reducing the permeability of gas molecules. In this work, we combine boron nitride nanosheets (BNNS) with ZIF-8 nanoparticles to develop a novel material, ZIF-8@BNNS, to improve both CO2 permeability and CO2/N2 selectivity. Growth of ZIF-8 nanoparticles on the BNNS surface is achieved using an in-situ growth method where the amino groups of BNNS are complexed with Zn2+, creating gas transmission pathways that accelerate CO2 transmission. The 2D-BNNS material acts as a barrier in MMMs to improve CO2/N2 selectivity. The MMMs with a 20 wt.% ZIF-8@BNNS loading achieved a CO2 permeability of 106.5 Barrer and CO2/N2 selectivity of 83.2, surpassing the Robeson upper bound (2008) and demonstrating that MOF layers can efficiently reduce mass transfer resistance and enhance gas separation performance.

Porous MgO-modified biochar adsorbents fabricated by the activation of Mg(NO3)2 for phosphate removal: Synergistic enhancement of porosity and active sites.

Engineering magnesium oxide (MgO)-modified biochar (MgO-biochar) with high porosity and active MgO load is a feasible pathway to enhance phosphate adsorption capacity. However, the blockage to pores caused by MgO particles is ubiquitous during the preparation, which seriously impaired the enhancement in adsorption performance. In this research, with the intent to enhance phosphate adsorption, an in-situ activation method based on Mg(NO3)2-activated pyrolysis technology was developed to fabricate MgO-biochar adsorbents with abundant fine pores and active sites simultaneously. The SEM image revealed that the tailor-made adsorbent has well-developed porous structure and abundant fluffy MgO active sites. Its maximum phosphate adsorption capacity was coming up to 1809 mg/g. The phosphate adsorption isotherms are in accordance well with the Langmuir model. The kinetic data, which agreed with the pseudo-second-order model, indicated that chemical interaction is existing between phosphate and MgO active sites. This work verified that the phosphate adsorption mechanism on MgO-biochar was composed of protonation, electrostatic attraction, monodentate complexation and bidentate complexation. In general, the facile in-situ activation method using Mg(NO3)2 pyrolysis illuminated biochar activation with fine pores and highly efficient adsorption sites for efficient wastewater treatment.

Shaping droplet by semiflexible micro crystallizer for high quality crystal harvest.

Droplet crystallization behavior held great potential in crystal preparation, micromaterial engineering, and molecular assembly. However, restricted by natural surface tension, the intrinsic crystallization regulation and efficient harvest of high quality crystal in diverse droplet features were still a great challenge. Herein, we developed a 3D printed semiflexible micro crystallizer with two aspectant sessile platforms that could simultaneously construct a series of heteromorphic droplets (HDs) and controllable HD shape. By shaping HD on the interface of the platform, central-converging micro-flows were generated by coordinating the gas-liquid interface and flow intensity (i.e., Ra/Ma) during HD crystallization from 'barrel', 'can', to 'sand clock' shape, which was validated via simulative and experimental research. Therefore, HDs, constructed in semiflexible micro crystallizer, exhibited efficient screening (>70 %) of single cubic crystal just at the center zone of platform, even under wide ranges of concentration and volume, manifesting excellent repeatability on high quality crystal harvest and relevant interfacial science research.

A Covalent Organic Framework Membrane with Homo Hierarchical Pores for Confined Reactive Crystallization.

Gas-liquid (G-L) reactive crystallization is a major technology for advanced materials construction, which requires a short diffusion path on the interface to ensure the reactant supply and stable crystal nucleation under ultrahigh supersaturation. Herein, a covalent organic framework (COF) membrane with homo hierarchical pore structures was proposed as an effective interfacial material for the regulation of confined reactive crystallization. By combining the ordered nanopores of COFs and micropores of anodic aluminum oxide (AAO), the COF membrane simultaneously provided an excellent nanoscale diffusion-reaction regulation network as the molecular-level confined G-L reactive interface and adjustable submicrometer gas mass transfer channels. The highly selective construction of CaCO3 superstructures was then achieved. When the submicrometer primary pore size rp of the constructed COF membrane ranged from 120 to 1.6 nm, the diffusion mechanism of CO2 varied from viscous flow diffusion to Knudsen diffusion. The growth orientation of CaCO3 crystals was well confined to obtain spindle-shaped crystals with high selectivity. Meanwhile, the crystal selectivity factor (cube/sphere) increased from 0 to 3.53 under the low interfacial nuclear barrier. Thus, the COF membrane with coupled micro-nanostructures successfully screened the directional preparation conditions for diverse CaCO3 superstructures, which also paved a meaningful path for the functional application of COFs in accurate mass transfer control and confined chemical reactions.

Bioinspired Hybrid Micro/Nanostructure Composited Membrane with Intensified Mass Transfer and Antifouling for High Saline Water Membrane Distillation.

Membrane distillation (MD) holds great promise for high-saline solution treatment, but it is typically impeded by the trade-off between the high mass transfer and antifouling properties of the membrane. Herein, a new MD utilized membrane with bioinspired micro/nanostructure (lotus leaf and fish gill) was constructed on commercial PP membrane, which can simultaneously enhance the permeation flux and antifouling in the hypersaline MD operation. On the basis of the classic nucleation theory and hydrodynamics simulation, the nanoscale structure can intensify the interfacial nanoscale turbulent flow and hinder the crystal deposition, which works like the fish gill. In addition, the optimized nanoscale feature size renders the membrane with the heterogeneous nucleation barrier very similar to the homogeneous system, which works like the lotus leaf and hinders the induced nucleation effectively. The microscale structure as the supporting platform of nanostructure can additionally enlarge the effective evaporative surface with superior hydrophobicity and then promote the permeation transfer through the membrane. The hybrid micro/nanostructures render the fabricated membrane with excellent high-permeation flux and significantly prolonged fouling induction time, which sheds light on a new approach for the development of ideal MD utilized membrane.

Novel Triple Tertiary Amine Polymer-Based Hydrogen Bond Network Inducing Highly Efficient Proton-Conducting Channels of Amphoteric Membranes for High-Performance Vanadium Redox Flow Battery.

A novel amphoteric membrane was designed by blending triple tertiary amine-grafted poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TTA) with sulfonated poly(ether ether ketone) (SPEEK) for vanadium redox flow batteries. An "acid-base pair" effect is formed by the combination of the tertiary amine group and sulfonic group, and extra nonbonding amine groups could be protonated. Both of them constitute a hydrogen bond network, which facilitates proton conduction and also hinders vanadium permeability because of the lowered swelling ratio and Donnan effect. All these contribute to improve the ion selectivity of the membrane while maintaining ionic conductivity. Compared with other amphoteric and SPEEK-based membranes, the membrane exhibits an excellent performance. The amphoteric membrane containing 15% PPO-TTA exhibits an ultralow vanadium permeability of 3.4 × 10-9 cm2 s-1 and a low area resistance of 0.39 Ω cm-2. Consequently, the cell assembled with this membrane shows excellent performances far superior to SPEEK and Nafion 212. The Coulombic efficiency and energy efficiency of the cell are 94.3-98.3 and 90.3-77.1% at 40-200 mA cm-2, respectively, and have no significant reductions after 200 cycles. This performance is at a high level among the amphoteric and SPEEK-based membranes reported in recent years. The cell's open circuit voltage is maintained for up to 165 h. In addition, the membrane's chemical stability is improved by the effective barrier to the vanadium ion.

Tailored Robust Hydrogel Composite Membranes for Continuous Protein Crystallization with Ultrahigh Morphology Selectivity.

The tailored and robust hydrogel composite membranes (HCMs) with diverse ion adsorption and interfacial nucleation property are prepared and successfully used in the continuous lysozyme crystallization. Beyond the heterogeneous supporter, the HCMs functioning as an interface ion concentration controller and nucleation generator are demonstrated. By constructing accurately controlled nucleation and growth circumstances in the HCM-equipped membrane crystallizer, the target desired morphology (hexagon cube) and brand-new morphology (multiple flower shape) that differ from the ones created in the conventional crystallizer are continuously and repetitively generated with ultrahigh morphology selectivity. These tailored robust HCMs show great potential for improving current approaches to continuous protein crystallization with specific crystal targets from laboratorial research to actual engineering applications.

Effect of Hydrogen-Bonding Interaction on the Arrangement and Dynamics of Water Confined in a Polyamide Membrane: A Molecular Dynamics Simulation.

An increasing demand for freshwater inspires further understanding of the mechanism of water diffusion in reverse-osmosis membranes for the development of high-performance membranes for desalination. Water diffusion has a close relationship with the structural and dynamical characteristics of hydrogen bonds, which is not well-understood for the confining environment inside the polyamide membrane at the molecular level. In this work, an atomistic model of a highly cross-linked polyamide membrane was built with an equilibrated mixture of m-phenylenediamine and trimesoyl chloride monomers. The structure and dynamics of water in the regions from the bulk phase to the membrane interior were investigated by molecular dynamics simulations. Explicit hydrogen bond criteria were determined for hydrogen-bonding analysis. The local distribution and orientation of water reveal that the hydrogen-bonding affinity of the hydrophilic functional groups of polymers inhibits water diffusion inside the membrane. The affinity helps to produce percolated water channels across the membrane. The hydrogen-bonding structures of water in different regions indicate dehydration is required for the entry of water into the polyamide membrane, which dominates water flux across the membrane. This paper not only deepens the understanding of the structure and dynamics of water confined in the polyamide membrane but also stimulates the future work on high-performance reverse-osmosis membranes.

Structural characteristics of hydrated protons in the conductive channels: effects of confinement and fluorination studied by molecular dynamics simulation.

The relationship between the proton conductive channel and the hydrated proton structure is of significant importance for understanding the deformed hydrogen bonding network of the confined protons which matches the nanochannel. In general, the structure of hydrated protons in the nanochannel of the proton exchange membrane is affected by several factors. To investigate the independent effect of each factor, it is necessary to eliminate the interference of other factors. In this paper, a one-dimensional carbon nanotube decorated with fluorine was built to investigate the independent effects of nanoscale confinement and fluorination on the structural properties of hydrated protons in the nanochannel using classical molecular dynamics simulation. In order to characterize the structure of hydrated protons confined in the channel, the hydrogen bonding interaction between water and the hydrated protons has been studied according to suitable hydrogen bond criteria. The hydrogen bond criteria were proposed based on the radial distribution function, angle distribution and pair-potential energy distribution. It was found that fluorination leads to an ordered hydrogen bonding structure of the hydrated protons near the channel surface, and confinement weakens the formation of the bifurcated hydrogen bonds in the radial direction. Besides, fluorination lowers the free energy barrier of hydronium along the nanochannel, but slightly increases the barrier for water. This leads to disintegration of the sequential hydrogen bond network in the fluorinated CNTs with small size. In the fluorinated CNTs with large diameter, the lower degree of confinement produces a spiral-like sequential hydrogen bond network with few bifurcated hydrogen bonds in the central region. This structure might promote unidirectional proton transfer along the channel without random movement. This study provides the cooperative effect of confinement dimension and fluorination on the structure and hydrogen bonding of the slightly acidic water in the nanoscale channel.