ZIF-62 glass foam self-supported membranes to address CH4/N2 separations.

Membranes with ultrahigh permeance and practical selectivity could greatly decrease the cost of difficult industrial gas separations, such as CH4/N2 separation. Advanced membranes made from porous materials, such as metal-organic frameworks, can achieve a good gas separation performance, although they are typically formed on support layers or mixed with polymeric matrices, placing limitations on gas permeance. Here an amorphous glass foam, agfZIF-62, wherein a, g and f denote amorphous, glass and foam, respectively, was synthesized by a polymer-thermal-decomposition-assisted melting strategy, starting from a crystalline zeolitic imidazolate framework, ZIF-62. The thermal decomposition of incorporated low-molecular-weight polyethyleneimine evolves CO2, NH3 and H2O gases, creating a large number and variety of pores. This greatly increases pore interconnectivity but maintains the crystalline ZIF-62 ultramicropores, allowing ultrahigh gas permeance and good selectivity. A self-supported circular agfZIF-62 with a thickness of 200-330 µm and area of 8.55 cm2 was used for membrane separation. The membranes perform well, showing a CH4 permeance of 30,000-50,000 gas permeance units, approximately two orders of magnitude higher than that of other reported membranes, with good CH4/N2 selectivity (4-6).

Fluorinated MOF-Based Hexafluoropropylene Nanotrap for Highly Efficient Purification of Octafluoropropane Electronic Specialty Gas.

High-purity octafluoropropane (C3F8) electronic specialty gas is a key chemical raw material in semiconductor and integrated circuit manufacturing industry, while selective removal of hexafluoropropylene (C3F6) impurity for C3F8 purification is essential but a challenging task. Here we report a fluorinated cage-like MOF Zn-bzc-CF3 (bzc=5-(trifluoromethyl)-1H-pyrazole-4-carboxylic acid) for C3F6/C3F8 separation. The incorporation of -CF3 groups not only provides suitable pore aperture size for highly efficient size-exclusive C3F6/C3F8 separation, but also creates hydrophobic microenvironments, endowing Zn-bz-CF3 high chemical stability. Remarkably, Zn-bzc-CF3 exhibits high C3F6 adsorption capacity while excluding C3F8, achieving ideal molecular-sieving C3F6/C3F8 separation. Breakthrough experiments show that Zn-bzc-CF3 can efficiently separate C3F6/C3F8 mixture and high-purity C3F8 (99.9 %) can be obtained.

Engineering Single-Atom Sites with the Irving-Williams Series for the Simultaneous Co-photocatalytic CO2 Reduction and CH3CHO Oxidation.

The bonding effects between 3d transition-metal single sites and supports originate from crystal field stabilization energy (CFSE). The 3d transition-metal atoms of the spontaneous geometrical distortions, that is the Jahn-Teller effect, can alter CFSE, thereby leading to the Irving-Williams series. However, engineering single-atom sites (SASs) using the Irving-Williams series as an ideal guideline has not been reported to date. Herein, alkynyl-linked covalent phenanthroline frameworks (CPFs) with phenanthroline units are developed to anchor the desired 3d single metal ions from d5 to d10 (Mn2+, Fe3+, Co2+, Ni2+, Cu2+, and Zn2+). The Irving-Williams series was employed to accurately predict the bonding effects between 3d transition-metal atoms and phenanthroline units. To verify this, theoretical calculations and experimental results reveal that Cu-SASs/CPFs exhibits higher stability and faster charge-transfer efficiency, far surpassing other metal-SASs/CPFs. As expected, Cu-SASs/CPFs demonstrates a high photoreduction of CO2-to-CO activity (~30.3 µmol ⋅ g-1 ⋅ h-1) and an exceptional photooxidation of CH3CHO-to-CH3COOH activity (~24.7 µmol ⋅ g-1 ⋅ h-1). Interestingly, the generated *O2 - is derived from the process of CO2 reduction, thereby triggering a CH3CHO oxidation reaction. This work provides a novel design concept for designing SASs by the Irving-Williams to regulate the catalytic performances.

Large-Area Ultrathin Metal-Organic Framework Membranes Fabricated on Flexible Polymer Supports for Gas Separations.

Ultrathin continuous metal-organic framework (MOF) membranes have the potential to achieve high gas permeance and selectivity simultaneously for otherwise difficult gas separations, but with few exceptions for zeolitic-imidazolate frameworks (ZIF) membranes, current methods cannot conveniently realize practical large-area fabrication. Here, we propose a ligand back diffusion-assisted bipolymer-directed metal ion distribution strategy for preparing large-area ultrathin MOF membranes on flexible polymeric support layers. The bipolymer directs metal ions to form a cross-linked two-dimensional (2D) network with a uniform distribution of metal ions on support layers. Ligand back diffusion controls the feed of ligand molecules available for nuclei formation, resulting in the continuous growth of large-area ultrathin MOF membranes. We report the practical fabrication of three representative defect-free MOF membranes with areas larger than 2,400 cm2 and ultrathin selective layers (50-130 nm), including ZIFs and carboxylate-linker MOFs. Among these, the ZIF-8 membrane displays high gas permeance of 3,979 GPU for C3H6, with good mixed gas selectivity (43.88 for C3H6/C3H8). To illustrate its scale-up practicality, MOF membranes were prepared and incorporated into spiral-wound membrane modules with an active area of 4,800 cm2. The ZIF-8 membrane module presents high gas permeance (3,930 GPU for C3H6) with acceptable ideal gas selectivity (37.45 for C3H6/C3H8).

Effective C4 Separation by Zeolite Metal-Organic Framework Composite Membranes.

Inorganic zeolites have excellent molecular sieving properties, but they are difficult to process into macroscopic structures. In this work, we use metal-organic framework (MOF) glass as substrates to engineer the interface with inorganic zeolites, and then assemble the discrete crystalline zeolite powders into monolithic structures. The zeolites are well dispersed and stabilized within the MOF glass matrix, and the monolith has satisfactory mechanical stabilities for membrane applications. We demonstrate the effective separation performance of the membrane for 1,3-butadiene (C4H6) from other C4 hydrocarbons, which is a crucial and challenging separation in the chemical industry. The membrane achieves a high permeance of C4H6 (693.00±21.83 GPU) and a high selectivity over n-butene, n-butane, isobutene, and isobutane (9.72, 9.94, 10.31, and 11.94, respectively). This strategy opens up new possibilities for developing advanced membrane materials for difficult hydrocarbon separations.

Portrait stylized rendering for 3D light-field display based on radiation field and example guide.

With the development of three-dimensional (3D) light-field display technology, 3D scenes with correct location information and depth information can be perceived without wearing any external device. Only 2D stylized portrait images can be generated with traditional portrait stylization methods and it is difficult to produce high-quality stylized portrait content for 3D light-field displays. 3D light-field displays require the generation of content with accurate depth and spatial information, which is not achievable with 2D images alone. New and innovative portrait stylization techniques methods should be presented to meet the requirements of 3D light-field displays. A portrait stylization method for 3D light-field displays is proposed, which maintain the consistency of dense views in light-field display when the 3D stylized portrait is generated. Example-based portrait stylization method is used to migrate the designated style image to the portrait image, which can prevent the loss of contour information in 3D light-field portraits. To minimize the diversity in color information and further constrain the contour details of portraits, the Laplacian loss function is introduced in the pre-trained deep learning model. The three-dimensional representation of the stylized portrait scene is reconstructed, and the stylized 3D light field image of the portrait is generated the mask guide based light-field coding method. Experimental results demonstrate the effectiveness of the proposed method, which can use the real portrait photos to generate high quality 3D light-field portrait content.

Angiogenesis modulated by CD93 and its natural ligands IGFBP7 and MMRN2: a new target to facilitate solid tumor therapy by vasculature normalization.

The tumor vasculature was different from the normal vasculature in both function and morphology, which caused hypoxia in the tumor microenvironment (TME). Previous anti-angiogenesis therapy had led to a modest improvement in cancer immunotherapy. However, antiangiogenic therapy only benefitted a few patients and caused many side effects. Therefore, there was still a need to develop a new approach to affect tumor vasculature formation. The CD93 receptor expressed on the surface of vascular endothelial cells (ECs) and its natural ligands, MMRN2 and IGFBP7, were now considered potential targets in the antiangiogenic treatment because recent studies had reported that anti-CD93 could normalize the tumor vasculature without impacting normal blood vessels. Here, we reviewed recent studies on the role of CD93, IGFBP7, and MMRN2 in angiogenesis. We focused on revealing the interaction between IGFBP7-CD93 and MMRN2-CD93 and the signaling cascaded impacted by CD93, IGFBP7, and MMRN2 during the angiogenesis process. We also reviewed retrospective studies on CD93, IGFBP7, and MMRN2 expression and their relationship with clinical factors. In conclusion, CD93 was a promising target for normalizing the tumor vasculature.

Metal-Organic Framework Membrane Constructor: A Tool for High-Throughput Construction of Metal-Organic Framework Membrane Models.

With the rapid development of metal-organic framework (MOF) membranes for separation applications, computational screening of their separation performance has attracted increasing interest in the design and fabrication of such materials. Although bulk crystal models in MOF databases are often used to represent MOF membrane structures, membrane models in slab geometries are still essential for researchers to simulate the separation performance, particularly to understand the effects of the surface/interface structure, pore sieving, and exposed lattice plane on guest permeability. However, to date, no database or method has been established to provide researchers with numerous membrane models, restricting the further development of related theoretical studies. Herein, we propose an algorithm and develop a tool called the "MOF-membrane constructor" to realize the high-throughput construction of membrane models based on the MOF crystal structures. Using this tool, membrane models can be generated with desired sizes, reasonable surface terminations, and assigned exposed crystal planes. The tool can also deduce the most prominent surface in the Bravais-Friedel-Donnay-Harker morphology or identify the pores in MOF crystals and automatically determine an exposed plane for each membrane model. Thus, an MOF-membrane database can be established rapidly according to user simulation requirements. This study can considerably improve the efficiency of building MOF membrane models and may be beneficial for the future development of simulation studies on MOF membranes.

Stepwise Engineering the Pore Aperture of a Cage-like MOF for the Efficient Separation of Isomeric C4 Paraffins under Humid Conditions.

The separation of isomeric C4 paraffins is an important task in the petrochemical industry, while current adsorbents undergo a trade-off relationship between selectivity and adsorption capacity. In this work, the pore aperture of a cage-like Zn-bzc (bzc=pyrazole-4-carboxylic acid) is tuned by the stepwise installation methyl groups on its narrow aperture to achieve both molecular-sieving separation and high n-C4 H10 uptake. Notably, the resulting Zn-bzc-2CH3 (bzc-2CH3 =3,5-dimethylpyrazole-4-carboxylic acid) can sensitively capture n-C4 H10 and exclude iso-C4 H10 , affording molecular-sieving for n-C4 H10 /iso-C4 H10 separation and high n-C4 H10 adsorption capacity (54.3 cm3 g-1 ). Breakthrough tests prove n-C4 H10 /iso-C4 H10 can be efficiently separated and high-purity iso-C4 H10 (99.99 %) can be collected. Importantly, the hydrophobic microenvironment created by the introduced methyl groups greatly improves the stability of Zn-bzc and significantly eliminates the negative effect of water vapor on gas separation under humid conditions, indicating Zn-bzc-2CH3 is a new benchmark adsorbent for n-C4 H10 /iso-C4 H10 separation.

Metal-Organic Framework Crystal-Glass Composite Membranes with Preferential Permeation of Ethane.

Metal-organic framework (MOF) glass is an easy to process and self-supported amorphous material that is suitable for fabricating gas separation membranes. However, MOF glasses, such as ZIF-62 and ZIF-4 have low porosity, which makes it difficult to obtain membranes with high permeance. Here, a self-supported MOF crystal-glass composite (CGC) membrane was prepared by melt quenching a mixture of ZIF-62 as the membrane matrix and ZIF-8 as the filler. The conversion of ZIF-62 from crystal to glass and the simultaneous partial melting of ZIF-8 facilitated by the melt state of ZIF-62 make the CGC membrane monolithic, eliminating non-selective grain boundaries and improving selectivity. The thickness of CGC membrane can be adjusted to fabricate a membrane without the need of a support substrate. CGC membranes exhibit a C2 H6 permeance of 41 569 gas permeation units (GPU) and a C2 H6 /C2 H4 selectivity of 7.16. The CGC membrane has abundant pores from the glassy state of ZIF-62 and the crystalline ZIF-8, which enables high gas permeance. ZIF-8 has preferential adsorption for C2 H6 and promotes C2 H6 transport in the membrane, and thus the GCG membrane exhibits ultrahigh C2 H6 permeance and good C2 H6 /C2 H4 selectivity.

Real-time realistic computer-generated hologram with accurate depth precision and a large depth range.

Holographic display is an ideal technology for near-eye display to realize virtual and augmented reality applications, because it can provide all depth perception cues. However, depth performance is sacrificed by exiting computer-generated hologram (CGH) methods for real-time calculation. In this paper, volume representation and improved ray tracing algorithm are proposed for real-time CGH generation with enhanced depth performance. Using the single fast Fourier transform (S-FFT) method, the volume representation enables a low calculation burden and is efficient for Graphics Processing Unit (GPU) to implement diffraction calculation. The improved ray tracing algorithm accounts for accurate depth cues in complex 3D scenes with reflection and refraction, which is represented by adding extra shapes in the volume. Numerical evaluation is used to verify the depth precision. And experiments show that the proposed method can provide a real-time interactive holographic display with accurate depth precision and a large depth range. CGH of a 3D scene with 256 depth values is calculated at 30fps, and the depth range can be hundreds of millimeters. Depth cues of reflection and refraction images can also be reconstructed correctly. The proposed method significantly outperforms existing fast methods by achieving a more realistic 3D holographic display with ideal depth performance and real-time calculation at the same time.

Fast virtual view synthesis for an 8K 3D light-field display based on cutoff-NeRF and 3D voxel rendering.

Three-dimensional (3D) light-field displays can provide an immersive visual experience, which has attracted significant attention. However, the generating of high-quality 3D light-field content in the real world is still a challenge because it is difficult to capture dense high-resolution viewpoints of the real world with the camera array. Novel view synthesis based on CNN can generate dense high-resolution viewpoints from sparse inputs but suffer from high-computational resource consumption, low rendering speed, and limited camera baseline. Here, a two-stage virtual view synthesis method based on cutoff-NeRF and 3D voxel rendering is presented, which can fast synthesize dense novel views with smooth parallax and 3D images with a resolution of 7680 × 4320 for the 3D light-field display. In the first stage, an image-based cutoff-NeRF is proposed to implicitly represent the distribution of scene content and improve the quality of the virtual view. In the second stage, a 3D voxel-based image rendering and coding algorithm is presented, which quantify the scene content distribution learned by cutoff-NeRF to render high-resolution virtual views fast and output high-resolution 3D images. Among them, a coarse-to-fine 3D voxel rendering method is proposed to improve the accuracy of voxel representation effectively. Furthermore, a 3D voxel-based off-axis pixel encoding method is proposed to speed up 3D image generation. Finally, a sparse views dataset is built by ourselves to analyze the effectiveness of the proposed method. Experimental results demonstrate the method's effectiveness, which can fast synthesize novel views and 3D images with high resolution in real 3D scenes and physical simulation environments. PSNR of the virtual view is about 29.75 dB, SSIM is about 0.88, and the synthetic 8K 3D image time is about 14.41s. We believe that our fast high-resolution virtual viewpoint synthesis method can effectively improve the application of 3D light field display.

Binocular holographic display based on the holographic optical element.

Due to the limited pixel pitch of the spatial light modulator (SLM), the field of view (FOV) is insufficient to meet binocular observation needs. Here, an optimized controlling light method of a binocular holographic three-dimensional (3D) display system based on the holographic optical element (HOE) is proposed. The synthetic phase-only hologram uploaded onto the SLM is generated with the layer-based angular spectrum diffraction theory, and two different reference waves are introduced to separate the left view and the right view of the 3D scene. The HOE with directional controlling light parameters is employed to guide binocular information into the left-eye and the right-eye viewing zones simultaneously. Optical experiments verify that the proposed system can achieve binocular holographic augmented reality 3D effect successfully with real physical depth, which can eliminate the accommodation-vergence conflict and visual fatigue problem. For each perspective, the FOV is 8.7° when the focal length of the HOE is 10 cm. The width of the viewing zone is 2.3 cm when the viewing distance is 25 cm.

Pressure-Responsive Two-Dimensional Metal-Organic Framework Composite Membranes for CO2 Separation.

The regulation of permeance and selectivity in membrane systems may allow effective relief of conventional energy-intensive separations. Here, pressure-responsive ultrathin membranes (≈100 nm) fabricated by compositing flexible two-dimensional metal-organic framework nanosheets (MONs) with graphene oxide nanosheets for CO2 separation are reported. By controlling the gas permeation direction to leverage the pressure-responsive phase transition of the MONs, CO2 -induced gate opening and closing behaviors are observed in the resultant membranes, which are accompanied with the sharp increase of CO2 permeance (from 173.8 to 1144 gas permeation units) as well as CO2 /N2 and CO2 /CH4 selectivities (from 4.1 to 22.8 and from 4 to 19.6, respectively). The flexible behaviors and separation mechanism are further elucidated by molecular dynamics simulations. This work establishes the relevance of structural transformation-based framework dynamics chemistry in smart membrane systems.

Metal-induced ordered microporous polymers for fabricating large-area gas separation membranes.

Metal-induced ordered microporous polymers (MMPs), a class of porous polymer, are synthesized from amine-bearing polymers, small organic linkers and divalent metal ions using a polymer-directed chemical synthesis process. Specifically, small organic linkers first coordinate to metal ions, with the resulting unit cells then self-assembling along the extension of polymer chains to construct three-dimensional frameworks. The MMPs demonstrate good controllability of crystal and framework size, as well as hydrolytic stability. MMP dispersions were coated on a modified polysulfone substrate to fabricate MMP/mPSf membranes with an ultrathin selective layer (below 50 nm) and surface areas of >100 cm2. The MMPs are readily fabricated into defect-free thin selective-layered membranes with high CO2 permeance (3,000 GPU) and stable CO2/N2 selectivity (78) under both humid and dry gas feed conditions, demonstrating promising CO2 membrane separation performance. This synthetic methodology could be extended to other polymers, potentially enabling facile synthesis of membrane materials.

Highly Chemically Stable MOFs with Trifluoromethyl Groups: Effect of Position of Trifluoromethyl Groups on Chemical Stability.

Metal-organic frameworks (MOFs) are a class of advanced porous crystalline materials. However, numerous MOFs have poor chemical stability, significantly restricting their industrial application. The introduction of trifluoromethyl groups around clusters of MOFs results in a shielding effect caused by their hydrophobicity and bulkiness, thus preventing guest molecules from attacking the coordination bonds. To prove such a shielding effect, the position of the trifluoromethyl groups is rationally adjusted, with trifluoromethyl groups at the ortho positions of carboxyl groups significantly improving the chemical stability of UiO-67. The prepared UiO-67- o-2CF3 remains intact after treatment with boiling water, 8 M HCl, 10 mM NaOH, and 50 ppm of NaF aqueous solutions. As the control experiment, trifluoromethyl groups at the meta positions of carboxyl groups have no shielding effect; hence, UiO-67- m-2CF3 has a stability that is lower than that of UiO-67- o-2CF3. In addition, the shielding effect is also applied to other MOFs, including DUT-5- o-2CF3 and Al-TPDC- o-2CF3, confirming the universality of this strategy.

Electrochemical sensors based on molecularly imprinted polymers on Fe3O4/graphene modified by gold nanoparticles for highly selective and sensitive detection of trace ractopamine in water.

A novel molecular imprinting polymer (MIP)-based electrochemical senor, consisting of Fe3O4 nanobeads and gold nanoparticles on a reduced graphene oxide (RGO) substrate, was fabricated to detect ractopamine (RAC) in water using the reversible addition fragmentation chain transfer (RAFT) polymerization technique. The Au nanoparticles widely dispersed on RGO can significantly increase the response current for RAC detection in water, which is confirmed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and theoretical calculations. By means of the differential pulse voltammetry technique, the as-prepared MIP-based electrode shows a dynamic linear range of 0.002 to 0.1 µM with a correlation coefficient of 0.992 and a remarkably low detection limit of 0.02 nM (S/N = 3). Additionally, the sensor exhibits high binding affinity and selectivity towards RAC with excellent reproducibility. Our study demonstrates the potential for the proposed electrochemical sensors in monitoring organic pollutants in water.

Pulling force and surface tension drive membrane fusion.

Despite catalyzed by fusion proteins of quite different molecular architectures, intracellular, viral, and cell-to-cell fusions are found to have the essential common features and the nearly same nature of transition states. The similarity inspires us to find a more general catalysis mechanism for membrane fusion that minimally depends on the specific structures of fusion proteins. In this work, we built a minimal model for membrane fusion, and by using dissipative particle dynamics simulations, we propose a mechanism that the pulling force generated by fusion proteins initiates the fusion process and the membrane tension regulates the subsequent fusion stages. The model shows different features compared to previous computer simulation studies: the pulling force catalyzes membrane fusion through lipid head overcrowding in the contacting region, leading to an increase in the head-head repulsion and/or the unfavorable head-tail contacts from opposing membranes, both of which destabilize the contacting leaflets and thus promote membrane fusion or vesicle rupture. Our simulations produce a variety of shapes and intermediates, closely resembling cases seen experimentally. Our work strongly supports the view that the tight pulling mechanism is a conserved feature of fusion protein-mediated fusion and that the membrane tension plays an essential role in fusion.

Exploring the shape deformation of biomembrane tubes with theoretical analysis and computer simulation.

The shape deformation of membrane nanotubes is studied by a combination of theoretical analysis and molecular simulation. First we perform free energy analysis to demonstrate the effects of various factors on two ideal states for the pearling transition, and then we carry out dissipative particle dynamics simulations, through which various types of membrane tube deformation are found, including membrane pearling, buckling, and bulging. Different models for inducing tube deformation, including the osmotic pressure, area difference and spontaneous curvature models, are considered to investigate tubular instabilities. Combined with free energy analysis, our simulations show that the origin of the deformation of membrane tubes in different models can be classified into two categories: effective spontaneous curvature and membrane tension. We further demonstrate that for different models, a positive membrane tension is required for the pearling transition. Finally we show that different models can be coupled to effectively deform the membrane tube.

Covalent Triazine-Based Frameworks with Ultramicropores and High Nitrogen Contents for Highly Selective CO2 Capture.

Porous organic frameworks (POFs) are a class of porous materials composed of organic precursors linked by covalent bonds. The objective of this work is to develop POFs with both ultramicropores and high nitrogen contents for CO2 capture. Specifically, two covalent triazine-based frameworks (CTFs) with ultramicropores (pores of width <7 Å) based on short (fumaronitrile, FUM) and wide monomers (1,4-dicyanonaphthalene, DCN) were synthesized. The obtained CTF-FUM and CTF-DCN possess excellent chemical and thermal stability with ultramicropores of 5.2 and 5.4 Å, respectively. In addition, they exhibit excellent ability to selectively capture CO2 due to ultramicroporous nature. Especially, CTF-FUM-350 has the highest nitrogen content (27.64%) and thus the highest CO2 adsorption capacity (57.2 cc/g at 298 K) and selectivities for CO2 over N2 and CH4 (102.4 and 20.5 at 298 K, respectively) among all CTF-FUM and CTF-DCN. More impressively, as far as we know, the CO2/CH4 selectivity is larger than that of all reported CTFs and ranks in top 10 among all reported POFs. Dynamic breakthrough curves indicate that both CTFs could indeed separate gas mixtures of CO2/N2 and CO2/CH4 completely.