DGA-grafting pyridine for ultra-selective and prior extraction of 99TcO4- from simulated spent nuclear fuel.

Selective and prior extraction of 99TcO4- ahead of uranium and plutonium separation is a beneficial strategy for the modern nuclear fuel cycle. Herein, a novel DGA-grafting pyridine ligand BisDODGA-DAPy (L1) was tailored for the efficient separation of TcO4- from simulated spent nuclear fuel based on the selectivity of pyridine and synergistic effect of diglycolamide (DGA) group. Compared to the ligands BisDOSCA-DAPy (L2) and BisDODGA-MPDA (L3) with similar structure, BisDODGA-DAPy (L1) demonstrated the better separation performance including good extraction efficiency, reusability, and high loading capacity for TcO4- under high acidic medium. The interactions of the ligands with Tc(VII)/Re(VII) have been investigated in detail using FT-IR, 1H NMR titration, UV-Vis spectrophotometric titration, ESI-HRMS and DFT simulations. The extraction mechanism affected by the protonation of ligand was elucidated under different acidity. BisDODGA-DAPy (L1) demonstrated the ultra-selective extraction ability for TcO4- from simulated spent nuclear fuel. The maximum SFTc/U and SFTc/Pu values were up to 1.29 × 104 and 5.08 × 103, respectively. In the presence of 9 × 104-fold excess of NO3-, the extraction of TcO4- was almost unaffected. Moreover, the good radiolytic stability further highlights the promising potential of this ligand for 99Tc separation. DFT calculation revealed the dominant role of DAPy and DODGA in TcO4- extraction, providing the theoretical evidence for BisDODGA-DAPy (L1) to selectively bind TcO4- over NO3-.

Effectiveness and mechanisms of combined use of antioxidant nutrients in protecting against oxidative stress-induced neuronal loss and related neurological deficits.

BACKGROUND: Oxidative stress is a well-known pathological factor driving neuronal loss and age-related neurodegenerative diseases. Melatonin, coenzyme Q10 and lecithin are three common nutrients with an antioxidative capacity. Here, we examined the effectiveness of them administrated individually and in combination in protecting against oxidative stress-induced neuronal death in vitro, and neurodegenerative conditions such as Alzheimer's disease and associated deficits in vivo. METHODS: Mouse neuroblastoma Neuro-2a (N2a) cells were exposed with H2O2 for 6 h, and subsequently treated with melatonin, coenzyme Q10, and lecithin alone or in combination for further 24 h. Cell viability was assessed using the CCK-8 assay. Eight-week-old male mice were intraperitoneally injected with D-(+)-galactose for 10 weeks and administrated with melatonin, coenzyme Q10, lecithin, or in combination for 5 weeks starting from the sixth week, followed by behavioral tests to assess the effectiveness in mitigating neurological deficits, and biochemical assays to explore the underlying mechanisms. RESULTS: Exposure to H2O2 significantly reduced the viability of N2a cells and increased oxidative stress and tau phosphorylation, all of which were alleviated by treatment with melatonin, coenzyme Q10, lecithin alone, and, most noticeably, by combined treatment. Administration of mice with D-(+)-galactose-induced oxidative stress and tau phosphorylation, brain aging, impairments in learning and memory, anxiety- and depression-like behaviors, and such detrimental effects were mitigated by melatonin, coenzyme Q10, lecithin alone, and, most consistently, by combined treatment. CONCLUSIONS: These results suggest that targeting oxidative stress via supplementation of antioxidant nutrients, particularly in combination, is a better strategy to alleviate oxidative stress-mediated neuronal loss and brain dysfunction due to age-related neurodegenerative conditions.

Ultrafast and selective separation of 99mTc from molybdenum matrix using DBDGA deliberately tailored macrocyclic crown-ethers.

Technetium-99m (99mTc) is an important medical radionuclide. Due to the crisis in supply of molybdenum-99 (99Mo), production of 99mTc directly via the 100Mo (p, 2 n) reaction by cyclotron was proposed. In this process, the most critical challenge is to rapidly and efficiently separate 99mTc from high concentration of molybdenum. In this work, a novel ligand, bis(N,N-dibutyldiglycolamide)dibenzo-18-crown-6 (BisDBDGA-DB18C6) was successfully synthesized and used for extraction of TcO4- /ReO4- from molybdenum. The results demonstrated that BisDBDGA-DB18C6 expressed excellent selectivity for TcO4- with a high separation factor of 1.6 × 105 against Mo, a fast extraction kinetic (within 45 s), and a high extraction capacity of 211 mmol ReO4- (99TcO4-)/per mole of extractant. The extraction mechanism was proposed as a co-interaction of macrocyclic crown ether and N,N-dibutyldiglycolamide group through slope analysis, FT-IR, ESI-MS, 1H NMR titration and theory calculations. Importantly, 99Tc in the organic phase can be quantitatively (> 99%) and easily back-extracted using deionized water, which can be directly used for medical applications.

Enhanced removal of radioactive iodine anions from wastewater using modified bentonite: Experimental and theoretical study.

Efficient and cost-effective removal of radioactive iodine anions from contaminated water has become a crucial task and a great challenge for waste treatment and environmental remediation. Herein, we present hexadecylpyridinium chloride monohydrate modified bentonite (HDPy-bent) for the efficient and selective removal of iodine anions (I- and IO3-) from contaminated water. Batch experiments showed that HDPy-bent could remove more than 95% of I- and IO3- within 10 min, and had maximum I- and IO3- adsorption capacities of 80.0 and 50.2 mg/g, respectively. Competitive experiments indicated that HDPy-bent exhibited excellent I- and IO3- selectivity in the excessive presence of common concomitant anions including PO43-, SO42-, HCO3-, NO3-, Cl- (maximum mole ratio of anions vs iodine anions was ∼50,000). An anion exchange mechanism was proposed for the selective adsorption of iodine anions. Optimal adsorption structure of HDPy+/I- (IO3-) at atomic level and driving forces of the I- (IO3-) adsorption were calculated by density functional theory (DFT) simulations. Moreover, the good durability and reusability of the HDPy-bent has been demonstrated with 5 adsorption-desorption cycles. Dynamic column experiment also demonstrated that HDPy-bent exhibited excellent removal and fractional recovery capabilities towards I- and IO3- from simulated groundwater and environmental water samples. In conclusion, this work presents a promising adsorbent material for the decontamination of radioactive iodine anions from wastewater on a large scale.