"Ion-imprinting" strategy towards metal sulfide scavenger enables the highly selective capture of radiocesium.

Highly selective capture of radiocesium is an urgent need for environmental radioactive contamination remediation and spent fuel disposal. Herein, a strategy is proposed for construction of "inorganic ion-imprinted adsorbents" with ion recognition-separation capabilities, and a metal sulfide Cs2.33Ga2.33Sn1.67S8·H2O (FJSM-CGTS) with "imprinting effect" on Cs+ is prepared. We show that the K+ activation product of FJSM-CGTS, Cs0.51K1.82Ga2.33Sn1.67S8·H2O (FJMS-KCGTS), can reach adsorption equilibrium for Cs+ within 5 min, with a maximum adsorption capacity of 246.65 mg·g-1. FJMS-KCGTS overcomes the hindrance of Cs+ adsorption by competing ions and realizes highly selective capture of Cs+ in complex environments. It shows successful cleanup for actual 137Cs-liquid-wastes generated during industrial production with removal rates of over 99%. Ion-exchange column filled with FJMS-KCGTS can efficiently treat 540 mL Cs+-containing solutions (31.995 mg·L-1) and generates only 0.12 mL of solid waste, which enables waste solution volume reduction. Single-crystal structural analysis and density functional theory calculations are used to visualize the "ion-imprinting" process and confirm that the "imprinting effect" originates from the spatially confined effect of the framework. This work clearly reveals radiocesium capture mechanism and structure-function relationships that could inspire the development of efficient inorganic adsorbents for selective recognition and separation of key radionuclides.

All-in-one treatment: Capture and immobilization of 137Cs by ultra-stable inorganic solid acid materials HMMoO6·nH2O (M = Ta, Nb).

Capture and immobilization of 137Cs is urgent for radioactive contamination remediation and spent fuel treatment. Herein, an effective all-in-one treatment method to simultaneously adsorb and immobilize Cs+ without high-temperature treatment is proposed. According to the strategy of incorporating high-valency metal ions into molybdates to increase the material stability and affinity towards radionuclides, layered HMMoO6·nH2O (M = Ta (1), Nb (2)) are prepared. Both materials exhibit excellent acid resistance (even 15 mol/L HNO3). They maintain remarkable adsorption capacity for Cs+ in 1 mol/L HNO3 solutions and can selectively capture Cs+ under excessive competitive ions. Furthermore, they show successful cleanup for actual 137Cs-liquid-wastes generated during industrial production. In particular, adsorbed Cs+ can be firmly immobilized in interlayer spaces of materials due to the highly stable anionic framework. The removal mechanism is attributed to ion exchange between Cs+ and interlayer H+ by multiple characterizations. Study of the structure-function relationship shows that the occurrence of Cs+ ion exchange is closely related to plate-like layered structure. This work develops an efficient all-in-one treatment method for capturing and immobilizing radiocesium by ultra-stable inorganic solid acid materials with low energy consumption and high safety for radionuclide remediation.

High-capacity recovery of Cs+ ions by facilely synthesized layered vanadyl oxalatophosphates with the clear insight into remediation mechanism.

Radiocesium remediation is of great significance for the sustainable development of nuclear energy and ecological protection. It is very challenging for the effective recovery of 137Cs from aqueous solutions due to its strong radioactivity, solubility and mobility. Herein, the efficient recovery of Cs+ ions has been achieved by three layered vanadyl oxalatophosphates, namely (NH4)2[(VO)2(HPO4)2C2O4]·5 H2O (NVPC), Na2[(VO)2(HPO4)2C2O4]·2 H2O (SVPC), and K2.5[(VO)2(HPO4)1.5(PO4)0.5(C2O4)]·4.5 H2O (KVPC). NVPC exhibits the ultra-fast kinetics (within 5 min) and high adsorption capacity for Cs+ (qmCs = 471.58 mg/g). It also holds broad pH durability and excellent radiation stability. Impressively, the entry of Cs+ can be directly visualized by the single-crystal structural analysis, and thus the underlying mechanism of Cs+ capture by NVPC from aqueous solutions has been illuminated at the molecular level. This is a pioneering work in the removal of radioactive ions by metal oxalatophosphate materials which highlights the great potential of metal oxalatophosphates for radionuclide remediation.

Highly Efficient Uptake of Cs+ by Robust Layered Metal-Organic Frameworks with a Distinctive Ion Exchange Mechanism.

137Cs with strong radioactivity and a long half-life is highly hazardous to human health and the environment. The efficient removal of 137Cs from complex solutions is still challenging because of its high solubility and easy mobility and the influence of interfering ions. It is highly desirable to develop effective scavengers for radiocesium remediation. Here, the highly efficient uptake of Cs+ has been realized by two robust layered metal-organic frameworks (MOFs), namely [(CH3)2NH2]In(L)2·DMF·H2O (DMF = N,N'-dimethylformamide, H2L= H2aip (5-aminoisophthalic acid) for 1 and H2hip (5-hydroxyisophthalic acid) for 2). Remarkably, 1 and 2 hold excellent acid and alkali resistance and radiation stabilities. They exhibit fast kinetics, high capacities (q m Cs = 270.86 and 297.67 mg/g for 1 and 2, respectively), excellent selectivity for Cs+ uptake, and facile elution for the regeneration of materials. Particularly, 1 and 2 can achieve efficient Cs+/Sr2+ separation in a wide range of Sr/Cs molar ratios. For example, the separation factor (SF Cs/Sr) is up to ∼320 for 1. Moreover, the Cs+ uptake and elution mechanisms have been directly elucidated at the molecular level by an unprecedented single-crystal to single-crystal (SC-SC) structural transformation, which is attributed to the strong interactions between COO- functional groups and Cs+ ions, easily exchangeable [(CH3)2NH2]+, and flexible and robust anionic layer frameworks with open windows as "pockets". This work highlights layered MOFs for the highly efficient uptake of Cs+ ions in the field of radionuclide remediation.

Highly selective cesium(I) capture under acidic conditions by a layered sulfide.

Radiocesium remediation is desirable for ecological protection, human health and sustainable development of nuclear energy. Effective capture of Cs+ from acidic solutions is still challenging, mainly due to the low stability of the adsorbing materials and the competitive adsorption of protons. Herein, the rapid and highly selective capture of Cs+ from strongly acidic solutions is achieved by a robust K+-directed layered metal sulfide KInSnS4 (InSnS-1) that exhibits excellent acid and radiation resistance. InSnS-1 possesses high adsorption capacity for Cs+ and can serve as the stationary phase in ion exchange columns to effectively remove Cs+ from neutral and acidic solutions. The adsorption of Cs+ and H3O+ is monitored by single-crystal structure analysis, and thus the underlying mechanism of selective Cs+ capture from acidic solutions is elucidated at the molecular level.

An Efficient Uranium Adsorption Magnetic Platform Based on Amidoxime-Functionalized Flower-like Fe3O4@TiO2 Core-Shell Microspheres.

Efficient removal of uranium (U) from aqueous solutions is crucial for ecological safety. Functionalized magnetic nanoparticles provide a promising strategy for radionuclide recovery and separation. However, designing and synthesizing magnetic adsorbents with high sorption capacity and selectivity, accompanied by excellent stability and reusability, remain a challenge. In this work, novel amidoxime-functionalized flower-like magnetic Fe3O4@TiO2 core-shell microspheres are designed and synthesized to efficiently remove U(VI) from aqueous solutions and actual seawater. The magnetic Fe3O4 core facilitates easy separation by an external magnetic field, and flower-like TiO2 nanosheets provide abundant specific surface areas and functionalization sites. The grafted amidoxime (AO) groups could function as a claw for catching uranium. The maximum adsorption capacity on U(VI) of the designed nanospheres reaches 313.6 mg·g-1 at pH 6.0, and the adsorption efficiency is maintained at 97% after 10 cycles. In addition, the excellent selectivity of the magnetic recyclable AO-functioning Fe3O4@TiO2 microspheres endows the potential of uranium extraction from seawater. The designed material provides an effective and applicable diagram for radioactive element elimination and enrichment.

[Immune responses of silicotic rats to the antigen of sheep red blood cells].

OBJECTIVE: To explore the immune response of silicotic rats to sheep red blood cells(SRBC). METHODS: Silicotic rats were immunized with SRBC by tracheal instillation(Group 1) or intraperitoneal injection (Group 2), and non-silicotic rats were immunized by tracheal instillation as normal control(Group 3). The levels of serum hemolytic index(HC50) were measured on 7, 12, 20, 25, and 32 days after primary immunization and 5, 12, 15 days after the second immunization. Special anti-SRBC IgG was measured with ELISA(A490 nm) on 12, 20, 25, 32 days and 5, 12, 15, 27 days respectively. Delayed-type hypersensitivity(DTH) to SRBC was measured 20 days after second immunization and DTH reaction was determined at 24, 48, 72, and 96 h after administration. Total cell count and cell populations in the bronchoalveolar lavage fluid(BALF), lung associated lymph node(LALN) and spleen weight, special IgG secreted from spleen cells were measured at the end of the experiment. RESULTS: The HC50 of Group 1(47.4 +/- 1.0, 52.2 +/- 4.6, 31.1 +/- 11.9, 43.8 +/- 3.5, 33.6 +/- 16.8, 49.0 +/- 2.3, 92.9 +/- 20.2, 87.7 +/- 5.2) were statistically higher than those of Group 3(40.4 +/- 10.6, 2.8 +/- 2.5, 0.8 +/- 0.6, 6.6 +/- 5.8, 1.4 +/- 0.1, 36.5 +/- 16.5, 53.0 +/- 33.2, 2.6 +/- 2.2). The special anti-SRBC IgG response in Group 1(1.67 +/- 0.19, 1.98 +/- 0.36, 1.12 +/- 0.50, 1.38 +/- 0.30, 2.75 +/- 0.15, 2.60 +/- 0.28, 2.86 +/- 0.10, 2.50 +/- 0.20) were much stronger than those in Group 3 (0.59 +/- 0.30, 0.56 +/- 0.21, 0.21 +/- 0.16, 0.22 +/- 0.01, 0.81 +/- 0.25, 0.74 +/- 0.25, 0.69 +/- 0.26, 1.38 +/- 0.41). Furthermore, the results of DTH showed positive response and the ratios for diameter of skin rash > 5 mm at 24, 48, 72, 96 h were 16/16, 16/16, 16/16, 15/16 respectively in Group 1, while those in Group 3 were 8/15, 1/15, 1/15, 1/15 respectively. Total cell count in the BALF, LALN and spleen weight, and special IgG secreted from spleen cells in Group 1 were higher too. Group 2 expressed almost of the same but with mild immunologic responses as Group 1. CONCLUSION: Silicosis-induced extremely strong DTH and over-response of humoral immunity to some antigens may contribute to the likelihood of silicosis complicated with tuberculosis.