Constructing 2D Polyphenols-Based Crosslinked Networks for Ultrafast and Selective Uranium Extraction from Seawater.

The role of tannins (TA), a well-known abundant and ecologically friendly chelating ligand, in metal capture has long been studied. Different kinds of TA-containing adsorbents are synthesized for uranium capture, while most adsorbents suffer from unfavorable adsorption kinetics. Herein, the design and preparation of a TA-containing 2D crosslinked network adsorbent (TANP) is reported. The ≈1.8-nanometer-thick TANP films curl up into micrometer-scale pores, which contribute to fast mass transfer and full exposure of active sites. The coordination environment of uranyl (UO2 2+) ions is explored by integrated analysis of U L3-edge XANES and EXAFS. Density functional theory calculations indicate the energetically favorable UO2 2+ binding. Consequently, TANP with excellent adsorption kinetics presents a high uranium capture capacity (14.62 mg-U g-Ads-1) and a high adsorption rate (0.97 mg g-1 day-1) together with excellent selectivity and biofouling resistance. Life cycle assessment and cost analysis demonstrate that TANP has tremendous potential for application in industrial-scale uranium extraction from seawater.

Yeast-Raised Polyamidoxime Hydrogel Prepared by Ice Crystal Dispersion for Efficient Uranium Extraction from Seawater.

Uranium extraction from seawater has attracted worldwide attention due to the massive reserves of uranium. Due to the straightforward synthesis and strong affinity toward uranyl ions (UO2 2+), the amidoxime group shows promise for use in highly efficient uranium capture.  However, the low mass transfer efficiency within traditional amidoxime-based adsorbents severely limits the adsorption rate and the utilization of adsorption sites. In this work, a macroporous polyamidoxime (PAO) hydrogel is prepared by yeast-based biological foaming combined with ice crystal dispersion that effectively maintained the yeast activity. The yeast-raised PAO (Y-PAO) adsorbent has numerous bubble-like holes with an average pore diameter >100 µm. These macropores connected with the intrinsic micropores of PAO to construct efficient diffusion channels for UO2 2+ provided fast mass transporting channels, leading to the sufficient exposure of hidden binding sites. The maximum adsorption capacity of Y-PAO membrane reached 10.07 mg-U/g-ads, ≈1.54 times higher than that of the control sample. It took only eight days for Y-PAO to reach the saturation adsorption capacity of the control PAO (6.47 mg-U/g-ads, 28 days). Meanwhile, Y-PAO possessed excellent ion selectivity, good reusability, and low cost. Overall, the Y-PAO membrane is a highly promising adsorbent for use in industrial-scale uranium extraction from seawater.

Decorating Channel Walls in Metal-Organic Frameworks with Crown Ethers for Efficient and Selective Separation of Radioactive Strontium(II).

Nuclear accidents and the improper disposal of nuclear wastes have led to serious environmental radioactive pollutions. The rational design of adsorbents for the highly efficient separation of strontium(II) is essential in treating nuclear waste and recovering radioactive strontium resources. Metal-organic frameworks (MOFs) are potential materials for the separation of aqueous metal ions owing to their designable structure and tunable functionality. Herein, a novel 3D MOF material MOF-18Cr6, in which 1D channels are formed using 18-crown-6-ether-containing ligands as channel walls, is fabricated for strontium(II) separation. In contrast to traditional MOFs designed by grafting functional groups in the framework pores, MOF-18Cr6 possesses regular 18-crown-6-ether cavities on the channel walls, which not only can transport and intake strontium(II) via the channels, but also prevent blockage of the channels after the binding of strontium(II). Consequently, the functional sites are fully utilized to achieve a high strontium(II) removal rate of 99.73 % in simulated nuclear wastewater. This study fabricates a highly promising adsorbent for the separation of aqueous radioactive strontium(II), and more importantly, can provide a new strategy for the rational design of high-performance MOF adsorbents for separating target substances from complex aqueous environments.

Characterization of bacteriophage vB_KleM_KB2 possessing high control ability to pathogenic Klebsiella pneumoniae.

Klebsiella pneumoniae is a widespread pathogen of several human diseases. The emergence of multidrug-resistant K. pneumoniae makes the treatment of these diseases a significant challenge. The application of bacteriophages is a potential approach for dealing with the emergence of multidrug-resistant pathogenic bacteria. This study isolates a novel bacteriophage vB_KleM_KB2 that infects the multidrug-resistant clinical isolates of K. pneumoniae. The bacteriophage exhibits a short latent period of 10 min, and can effectively lyse the bacterium within 60 min. Notably, the bacteriophage can completely inhibit the growth of the host bacterium at the initial concentration of 107 CFU/mL with a low multiplicity of infection of 0.001, which proves its high lytic activity. Furthermore, the bacteriophage shows high environmental tolerances, which can facilitate the practical application of the bacteriophage. Analysis of the bacteriophage genome shows that the bacteriophage possesses a novel genome sequence and can represent a new bacteriophage genus. Considering the high lytic activity, short latent period, high stability, and novel genetic background, bacteriophage vB_KleM_KB2 enriches the bacteriophage library and provides a new alternative for controlling the diseases caused by multidrug-resistant pathogenic K. pneumoniae.

High-efficiency uranium extraction from seawater by low-cost natural protein hydrogel.

Utilization of uranium resource in seawater are highly possible to meet the growth demands for the sustainable development of nuclear energy industry. Bio-adsorbents exhibit high performance in terms of adsorption selectivity, equilibrium speed, and environmental friendliness, while the high fabrication cost hinders their practical application. In this study, a low-cost soy protein isolate (SPI) is used to fabricate adsorbent named SPI hydrogel for uranium extraction. This is the first report on applying bio-adsorbents derived from low-cost natural proteins for uranium extraction. The SPI hydrogel showed high uranium adsorption capacity of 53.94 mg g-1 in simulated nuclear wastewater and 5.29 mg g-1 is achieved in natural seawater, which is higher than all currently available adsorbents based on non-modified natural biomolecules. The amino and oxygen-containing groups are identified as the functional groups for uranyl binding by providing four oxygen and two nitrogen atoms to form equatorial coordination with uranyl, which guarantees the high binding selectivity and affinity to uranyl ions. The low cost for accessing the raw material together with the environmental friendliness, high salt tolerance, high uranium adsorption ability, and high selectivity to uranium, make SPI hydrogel a promising adsorbent for uranium extraction from seawater and nuclear wastewater.

Ultrafast extraction of uranium from seawater using photosensitized biohybrid system with bioinspired cascaded strategy.

The highly effective utilization of uranium resources in global seawater is a viable method to satisfy the rising demands for fueling nuclear energy industry. Herein, inspired by the multi-mechanisms of the marine bacteria for uranium immobilization, CdS nanoparticles are deposited on the cell of marine bacterial strain Bacillus velezensis UUS-1 to create a photosensitized biohybrid system UUS-1/CdS. This system achieves high uranium extraction efficiency using a cascaded strategy, where the bacterial cells guarantee high extraction selectivity and the photosensitive CdS nanoparticles realize cascading photoreduction of high soluble U(VI) to low soluble U(IV) to enhance extraction capacity. As one of the fastest-acting adsorbents in natural seawater, a high extraction capacity for uranium of 7.03 mg g-1 is achieved with an ultrafast extraction speed of 4.69 mg g-1 d-1. The cascaded strategy promisingly improves uranium extraction performance and pioneers a new direction for the design of adsorbents to extract uranium from seawater.

Photothermal-enabled single-atom catalysts for high-efficiency hydrogen peroxide photosynthesis from natural seawater.

Hydrogen peroxide (H2O2) is a powerful industrial oxidant and potential carbon-neutral liquid energy carrier. Sunlight-driven synthesis of H2O2 from the most earth-abundant O2 and seawater is highly desirable. However, the solar-to-chemical efficiency of H2O2 synthesis in particulate photocatalysis systems is low. Here, we present a cooperative sunlight-driven photothermal-photocatalytic system based on cobalt single-atom supported on sulfur doped graphitic carbon nitride/reduced graphene oxide heterostructure (Co-CN@G) to boost H2O2 photosynthesis from natural seawater. By virtue of the photothermal effect and synergy between Co single atoms and the heterostructure, Co-CN@G enables a solar-to-chemical efficiency of more than 0.7% under simulated sunlight irradiation. Theoretical calculations verify that the single atoms combined with heterostructure significantly promote the charge separation, facilitate O2 absorption and reduce the energy barriers for O2 reduction and water oxidation, eventually boosting H2O2 photoproduction. The single-atom photothermal-photocatalytic materials may provide possibility of large-scale H2O2 production from inexhaustible seawater in a sustainable way.

Protocol for optical detection of iodide ions in aqueous environments using a zirconium(IV)-enhanced strategy.

Detection of radioactive iodide ions (I-) is important for protecting human beings from the hazards of radioactive pollution. Herein, we present a protocol for detecting I- using a zirconium(IV)-enhanced strategy. We describe steps for optimizing the I- detection approach, establishing standard curves, and finally applying the approach. The use of zirconium(IV) greatly improves the detection performance and endows this approach with an ultralow detection limit of 0.176 nM together with wide applicability in various aqueous environments. For complete details on the use and execution of this protocol, please refer to Feng et al. (2022).1.

Ligand-Assistant Iced Photocatalytic Reduction to Synthesize Atomically Dispersed Cu Implanted Metal-Organic Frameworks for Photo-Enhanced Uranium Extraction from Seawater.

Uranium extraction from natural seawater is one of the most promising routes to address the shortage of uranium resources. By combination of ligand complexation and photocatalytic reduction, porous framework-based photocatalysts have been widely applied to uranium enrichment. However, their practical applicability is limited by poor photocatalytic activity and low adsorption capacity. Herein, atomically dispersed Cu implanted UiO-66-NH2 (Cu SA@UiO-66-NH2 ) photocatalysts are prepared via ligand-assistant iced photocatalytic reduction route. N-Cu-N moiety acts as an effective electron acceptor to potentially facilitate charge transfer kinetics. By contrast, there exist Cu sub-nanometer clusters by the typical liquid phase photoreduction, resulting in a relatively low photocatalytic activity. Cu SA@UiO-66-NH2 adsorbents exhibit superior antibacterial ability and improved photoreduction conversion of the adsorbed U(VI) to insoluble U(IV), leading to a high uranium sorption capacity of 9.16 mg-U/g-Ads from natural seawater. This study provides new insight for enhancing uranium uptake by designing SA-mediated MOF photocatalysts.

4-Trifluorophenylammonium Iodide-Based Dual Interfacial Modification Engineering toward Improved Efficiency and Stability of SnO2-Based Perovskite Solar Cells.

Passivation engineering has been identified as an effective strategy to eliminate the targeted interfacial defects for improving the efficiency and stability of perovskite solar cells (PSCs). Herein, 4-trifluorophenylammonium iodide (CF3PhAI) is presented as a multifunctional passivation agent to modify buried SnO2/perovskite and perovskite/hole transport layer (HTL) interfaces. Upon incorporation of CF3PhAI between SnO2 and perovskite, CF3PhAI can chemically link to SnO2 via Lewis coordination and electrostatic coupling, thereby effectively passivating under-coordinated Sn and filling the oxygen vacancy. Meanwhile, CF3PhAI helps anchor PbI2 and organic cations (MA+/FA+) to control the crystallization of the perovskite. Consequently, reduced interfacial defects, homogeneous perovskite crystallites, and better energetic alignment can be simultaneously achieved. When CF3PhAI was further used to modify the perovskite/HTL interface, the fabricated PSCs yielded an impressive power conversion efficiency of 23.06% together with negligible J-V hysteresis. The unencapsulated devices exhibited long-term stability in wet conditions (91.8% efficiency retention after 1000 h) due to the water-resistant CF3PhAI. We also achieved good light soaking stability, maintaining 86.1% of its initial efficiency after aging for 720 h. Overall, our finding provides a promising strategy for modifying the dual contact interfaces of PSCs toward improved efficiency and stability.

Cuttlefish ink loaded polyamidoxime adsorbent with excellent photothermal conversion and antibacterial activity for highly efficient uranium capture from natural seawater.

Owing to the abundant uranium reserves in the oceans, the collection of uranium from seawater has aroused the widespread interest. Compared to the uranium extraction from ore, uranium collection from seawater is a more environmentally friendly strategy. The amidoxime (AO) functional group has been considered as one of the most efficient chelating groups for uranium capture. In this work, by drawing upon the photothermal character and antibacterial activity of cuttlefish ink, a cuttlefish ink loaded polyamidoxime (CI-PAO) membrane adsorbent is developed. Under one-sun illumination, the CI-PAO membrane shows a high extraction capacity of 488.76 mg-U/g-Ads in 500 mL 8 ppm uranium spiked simulated seawater, which is 1.24 times higher than PAO membrane. The adsorption rate of CI-PAO membrane is increased by 32.04%. Furthermore, exhibiting roughly 75% bacteriostatic rate in composite marine bacteria, the CI-PAO shows a dramatically antibacterial activity, which effectively prevents the functional sites on the adsorbent surface from being occupied by the biofouling blocks. After immersing in natural seawater for 4 weeks, light-irradiated CI-PAO gave high uranium uptake capacity of 6.17 mg-U/g-Ads. Hence, the CI-PAO membrane adsorbent can be considered as a potential candidate for the practical application for uranium extraction from seawater.

Halogen hydrogen-bonded organic framework (XHOF) constructed by singlet open-shell diradical for efficient photoreduction of U(VI).

Synthesis of framework materials possessing specific spatial structures or containing functional ligands has attracted tremendous attention. Herein, a halogen hydrogen-bonded organic framework (XHOF) is fabricated by using Cl- ions as central connection nodes to connect organic ligands, 7,7,8,8-tetraaminoquinodimethane (TAQ), by forming a Cl-···H3 hydrogen bond structure. Unlike metallic node-linked MOFs, covalent bond-linked COFs, and intermolecular hydrogen bond-linked HOFs, XHOFs represent a different kind of crystalline framework. The electron-withdrawing effect of Cl- combined with the electron-rich property of the organic ligand TAQ strengthens the hydrogen bonds and endows XHOF-TAQ with high stability. Due to the production of excited electrons by TAQ under light irradiation, XHOF-TAQ can efficiently catalyze the reduction of soluble U(VI) to insoluble U(IV) with a capacity of 1708 mg-U g-1-material. This study fabricates a material for uranium immobilization for the sustainability of the environment and opens up a new direction for synthesizing crystalline framework materials.

Amidoxime Group-Anchored Single Cobalt Atoms for Anti-Biofouling during Uranium Extraction from Seawater.

Marine biofouling is one of the most significant challenges hindering practical uranium extraction from seawater. Single atoms have been widely used in catalytic applications because of their remarkable redox property, implying that the single atom is highly capable of catalyzing the generation of reactive oxygen species (ROS) and acts as an anti-biofouling substance for controlling biofouling. In this study, the Co single atom loaded polyacrylamidoxime (PAO) material, PAO-Co, is fabricated based on the binding ability of the amidoxime group to uranyl and cobalt ions. Nitrogen and oxygen atoms from the amidoxime group stabilize the Co single atom. The fabricated PAO-Co exhibits a broad range of antimicrobial activity against diverse marine microorganisms by producing ROS, with an inhibition rate up to 93.4%. The present study is the first to apply the single atom for controlling biofouling. The adsorbent achieves an ultrahigh uranium adsorption capacity of 9.7 mg g-1 in biofouling-containing natural seawater, which decreased only by 11% compared with that in biofouling-removed natural seawater. These findings indicate that applying single atoms would be a promising strategy for designing biofouling-resistant adsorbents for uranium extraction from seawater.

Ultrasensitive Detection of Aqueous Uranyl Based on Uranyl-Triggered Protein Photocleavage.

The detection of environmental uranyl is attracting increasing attention. However, the available detection strategies mainly depend on the selective recognition of uranyl, which is subject to severe interference by coexisting metal ions. Herein, based on the unique uranyl-triggered photocleavage property, the protein BSA is labelled with fluorescent molecules that exhibit an aggregation-induced emission effect for uranyl detection. Uranyl-triggered photocleavage causes the separation of the fluorescent-molecule-labelled protein fragments, leading to attenuation of the emission fluorescence, which is used as a signal for uranyl detection. This detection strategy shows high selectivity for uranyl and an ultralow detection limit of 24 pM with a broad detection range covering five orders of magnitude. The detection method also shows high reliability and stability, making it a promising technique for practical applications in diverse environments.

In Situ Synthesis of Uranyl-Imprinted Nanocage for Selective Uranium Recovery from Seawater.

An adaptive coordination structure is vital for selective uranium extraction from seawater. By strategy of molecular imprinting, uranyl is introduced into a multivariate metal-organic framework (MOF) during the synthesis process to guide the in situ construction of proper nanocage structure for targeting uranyl binding. Except for the coordination between uranium with four oxygen from the materials, the axial oxygen of uranyl also forms hydrogen bonds with hydrogen from the phenolic hydroxyl group, which enhances the binding affinity of the material to uranyl. Attributing to the high binding affinity, the adsorbent shows high uranium binding selectivity to uranyl against not only the interfering metal ions, but also the carbonate group that coordinates with uranyl to form [UO2 (CO)3 ]4- in seawater. In natural seawater, the adsorbent realizes a high uranium adsorption capacity of 7.35 mg g-1 , together with an 18.38 times higher selectivity to vanadium.

Highly efficient immobilization of environmental uranium contamination with Pseudomonas stutzeri by biosorption, biomineralization, and bioreduction.

Uranium is a heavy metal with both chemotoxicity and radiotoxicity. Due to the increasing consumption of uranium, the remediation of uranium contamination and recovery of uranium from non-conventional approach is highly needed. Microorganism exhibits high potential for immobilization of uranium. This study for the first time isolated a marine Pseudomonas stutzeri strain MRU-UE1 with high uranium immobilization capacity of 308.72 mg/g, which is attributed to the synergetic mechanisms of biosorption, biomineralization, and bioreduction. The uranium is found to be immobilized in forms of tetragonal chernikovite (H2(UO2)2(PO4)2·8H2O) by biomineralization and CaU(PO4)2 by bioreduction under aerobic environment, which is rarely observed and would broaden the application of this strain in aerobic condition. The protein, phosphate group, and carboxyl group are found to be essential for the biosorption of uranium. In response to the stress of uranium, the strain produces inorganic phosphate group, which transformed soluble uranyl ion to insoluble uranium-containing precipitates, and poly-ß-hydroxybutyrate (PHB), which is observed for the first time during the interaction between microorganism and uranium. In summary, P. stutzeri strain MRU-UE1 would be a promising alternative for environmental uranium contamination remediation and uranium extraction from seawater.

Correction: Microenvironment-responsive multifunctional hydrogels with spatiotemporal sequential release of tailored recombinant human collagen type III for the rapid repair of infected chronic diabetic wounds.

Correction for 'Microenvironment-responsive multifunctional hydrogels with spatiotemporal sequential release of tailored recombinant human collagen type III for the rapid repair of infected chronic diabetic wounds' by Cheng Hu et al., J. Mater. Chem. B, 2021, 9, 9684-9699, DOI: 10.1039/D1TB02170B.

Microenvironment-responsive multifunctional hydrogels with spatiotemporal sequential release of tailored recombinant human collagen type III for the rapid repair of infected chronic diabetic wounds.

Recently, the incidence of chronic diabetic wounds increases continuously, and the existing clinical treatment is less effective. Thus, it is an urgent need to solve these problems for better clinical treatment effects. Herein, we prepared a brand-new tailored recombinant human collagen type III (rhCol III) and constructed a multifunctional microenvironment-responsive hydrogel carrier based on multifunctional antibacterial nanoparticles (PDA@Ag NPs) and our tailored rhCol III. The multifunctional smart hydrogel disintegrated quickly at the chronic diabetic wound sites and achieved the programed on-demand release of different therapeutic substances. The first released PDA@Ag NPs showed great antibacterial properties against S. aureus and E. coli. They could kill bacteria rapidly, and also showed antioxidant and anti-inflammatory effects at the wound site. The subsequent release of our tailored rhCol III could promote the proliferation and migration of mouse fibroblasts and endothelial cells during the proliferation and remodeling process of wound healing. Relevant results showed that the multifunctional smart hydrogel could promote the expression levels of basic fibroblast growth factor (bFGF) and vascular endothelial growth factor (VEGF), decrease the inflammatory response, accelerate the deposition of collagen and increase cell proliferation and angiogenesis, thereby speeding up the healing of infected chronic wounds. In a word, the hydrogel, which took into consideration the complex microenvironment at the wound site and multi-stage healing process, could achieve programmed and responsive release of different therapeutic substances to meet the treatment needs in different wound healing stages. More importantly, our work illustrated the great application potential of our brand-new rhCol III in promoting chronic wound repair and regeneration.

Accelerated Chemical Thermodynamics of Uranium Extraction from Seawater by Plant-Mimetic Transpiration.

The extraction of uranium from seawater, which is an abundant resource, has attracted considerable attention as a viable form of energy-resource acquisition. The two critical factors for boosting the chemical thermodynamics of uranium extraction from seawater are the availability of sufficient amounts of uranyl ions for supply to adsorbents and increased interaction temperatures. However, current approaches only rely on the free diffusion of uranyl ions from seawater to the functional groups within adsorbents, which largely limits the uranium extraction capacity. Herein, inspired by the mechanism of plant transpiration, a plant-mimetic directional-channel poly(amidoxime) (DC-PAO) hydrogel is designed to enhance the uranium extraction efficiency via the active pumping of uranyl ions into the adsorbent. Compared with the original PAO hydrogel without plant-mimetic transpiration, the uranium extraction capacity of the DC-PAO hydrogel increases by 79.33% in natural seawater and affords the fastest reported uranium extraction average rate of 0.917 mg g-1 d-1 among the most state-of-the-art amidoxime group-based adsorbents, along with a high adsorption capacity of 6.42 mg g-1 within 7 d. The results indicate that the proposed method can enhance the efficiency of solar-transpiration-based uranium extraction from seawater, particularly in terms of reducing costs and saving processing time.