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The radiolytic behaviors of aqueous ammonia solutions under γ-ray irradiation were investigated, focusing on several factors, including initial ammonia concentration, absorbed dose, and H3BO3 concentration. The main species including ammonia, H2O2, nitrogen oxides, and H2, were quantitatively analyzed. The results revealed the significant influence of the initial ammonia concentration on the radiolytic behavior of the aqueous ammonia solution. The existence of ammonia in the solution exhibited suppression of the concentrations of H2O2 and O2. Furthermore, the radiolysis of aerated aqueous ammonia solution led to the formation of nitrogen oxides (NO2− and NO3−). This process was driven by multiple oxidation reactions, in which O2 and ·OH played crucial roles. Interestingly, the addition of H3BO3 provided protection to ammonia during γ irradiation, while the concentration of H2O2 was increased. [ABSTRACT FROM AUTHOR]

In this work, the effects of the tungsten (W) converter and molybdenum target thickness on the 99Mo yield in the production of 99Mo via 100Mo(γ, n)99Mo photonuclear reaction were studied. The FLUKA program was applied to simulate the optimal size of the targets for the production of 99Mo under 50 MeV electron conditions, where the thicknesses of the W and Mo targets were 0.3 and 1.4 cm, respectively. The relative error between the calculation and the experimental results was less than 8%. The process of irradiating natural (natMo) and enriched (100Mo) molybdenum targets using electrons with a 1 mA average beam current was further simulated. The specific activity of enriched 100Mo is nearly ten times higher than that of natMo. The use of 100Mo targets also produces fewer radioactive impurities. This study provides a guidance on the size of W conversion and molybdenum targets, as well as the selection of molybdenum species, when producing 99Mo via photonuclear reaction. [ABSTRACT FROM AUTHOR]

Reduced graphene oxide (rGO) composite aerogels were synthesized by the radiation reduction of graphene oxide (GO) with the assistance of Eu3+, which demonstrated excellent adsorption performance for diverse organic pollutants. Eu3+ promoted the formation of the gel by inducing the pre-assembly of GO so that the required pH range for synthesizing the rGO aerogel by radiation reduction was broadened and the minimum absorbed dose was also reduced. At pH 2, the Eu3+-induced pre-assembly fabricated more mesopores and enlarged the specific surface area of the obtained hierarchically porous rGO-Eu composite aerogel, which enabled the high-capacity (81–395 g g−1) and ultrafast removal of organic solvents. The different effects of organic solvents on the unique fluorescence emission of Eu(III) also allowed the in situ detection of certain organic solvents such as pyridine. At pH 6, Eu3+ enhanced the reduction of GO by capturing more hydrated electrons, the most reductive species produced by water radiolysis, and synergistically reduced GO. The obtained rGO-Eu composite aerogel with a high reduction degree, demonstrated outstanding adsorption capacities for various anionic organic dyes (40.5–1572.5 mg g−1) owing to the strong π–π interaction and electrostatic attraction. Benefitting from high reduction, it demonstrated adsorption capacity for cationic dyes (97.3–1367.6 mg g−1) comparable to other reported graphene-based aerogels. The rGO-Eu aerogel prepared by radiation reduction might be suitable as a broad-spectrum adsorbent for organic pollutants. [ABSTRACT FROM AUTHOR]

A mathematical model of co-decontamination process (1A) containing U(VI), Pu(IV), Zr(IV), and Ru(III) was developed with a high-performance Iteration of Extraction Equilibrium (ITEE) algorithm. ITEE algorithm not only guarantees the positive solution set but also possesses better computational efficiency than L-BFGS-B and fsolve algorithms. This model was used to study the effects of the HNO3 concentration and the location of the feed stage on the extraction and decontamination efficiencies. The results show HNO3 is beneficial to the extraction of U, Pu, and Zr. More extraction stages boost the extraction of U and Pu into the organic phase. [ABSTRACT FROM AUTHOR]

The efficient exfoliation of hexagonal boron nitride (h-BN) to fabricate boron nitride nanosheets (BNNS) is a challenging task in the popular field of two-dimensional material preparation. In this paper, a new radiation-induced reduction-exfoliation method is introduced to achieve the one-step exfoliation of h-BN to form Ni-nanoparticle-(NiNP)-bound BNNS (Ni/BNNS) in a binary isopropanol/water medium using gamma-ray radiation at ambient temperature and pressure. The process involves the effective intercalation of Ni2+ ions into h-BN interlayers dispersed in the isopropanol/water medium, followed by the in situ growth of NiNPs under gamma-ray irradiation. Taking advantage of the volume expansion effect generated by the growth of the NiNPs and with help from a cationic surfactant, such as hexadecyltrimethylammonium chloride (CTAC), sheet-like Ni/BNNS in 200 nm squares and with an average BNNS thickness of less than 5 nm can be peeled from h-BN and stably dispersed in water. The prepared magnetic Ni/BNNS exhibits good catalytic performance, excellent structural stability, and reusability toward the reduction of 2-nitroaniline (2-NA). After 5 cycles, the conversion of 2-NA still reaches 95.9% within 500 s. More interestingly, when Ni/BNNS was dispersed in water/methanol solution at a content of 0.17 mg mL−1 followed by exposure to simulated sunlight irradiation, H2 evolution of 8404.3 μmol gNi−1 within 2 h can be detected. This work not only provides a new idea for realizing the exfoliation of layers of nanoscale sheets from h-BN, but it also opens a new route to the one-step preparation of two-dimensional-material-supported nanometal catalysts by taking advantage of gamma-ray radiation. [ABSTRACT FROM AUTHOR]

Background: Precise diagnosis of the tissue origin for metastatic cancer of unknown primary (CUP) is essential for deciding the treatment scheme to improve patients' prognoses, since the treatment for the metastases is the same as their primary counterparts. The purpose of this study is to identify a robust gene signature that can predict the origin for CUPs.Methods: The within-sample relative gene expression orderings (REOs) of gene pairs within individual samples, which are insensitive to experimental batch effects and data normalizations, were exploited for identifying the prediction signature.Results: Using gene expression profiles of the lung-limited metastatic colorectal cancer (LmCRC), we firstly showed that the within-sample REOs in lung metastases of colorectal cancer (CRC) samples were concordant with the REOs in primary CRC samples rather than with the REOs in primary lung cancer. Based on this phenomenon, we selected five gene pairs with consistent REOs in 498 primary CRC and reversely consistent REOs in 509 lung cancer samples, which were used as a signature for predicting primary sites of metastatic CRC based on the majority voting rule. Applying the signature to 654 primary CRC and 204 primary lung cancer samples collected from multiple datasets, the prediction accuracy reached 99.36%. This signature was also applied to 24 LmCRC samples collected from three datasets produced by different laboratories and the accuracy reached 100%, suggesting that the within-sample REOs in the primary site could reveal the original tissue of metastatic cancers.Conclusions: The result demonstrated that the signature based on within-sample REOs of five gene pairs could exactly and robustly identify the primary sites of CUPs. [ABSTRACT FROM AUTHOR]

Predicting the electrical corrosion potential (ECP) of type 304 stainless steel, the structural material of recirculation pipes in fusion power plants, is important because the growth rate of intergranular stress corrosion crack (IGSCC) of 304 stainless steel is closely related to ECP. In this work, a new model has been developed, by modifying existing models, to calculate the ECP of recirculation pipes in future fusion power plant. The calculation results indicate that merely injecting hydrogen cannot reduce ECP below EIGSCC if the dose rate exceeds a threshold, other assisted water chemistry controlling method is necessary. [ABSTRACT FROM AUTHOR]

The separation and recovery of U(VI) and Th(IV) from rare earths are very important to avoid environmental pollution. A functional fibrous hierarchically bimodal mesoporous silica (F-SiO-DP) as an high efficient adsorbent for selective adsorption of uranium and thorium, which had hierarchically bimodal mesoporous structure and specific surface area of ca. 474.1 m g, was prepared by post-modification method using 2,9-diamide-1,10-phenanthroline. The synthesized adsorbent was characterized by HR-TEM, SEM, FT-IR, N adsorption-desorption, TGA techniques, XRD and NMR spectroscopy. The effects of pH, contact time, initial U(VI) and Th(IV) concentration, temperature and the presence of competitive metal ions on U(VI) and Th(IV) adsorption behavior were studied in detail. The hierarchically bimodal mesoporous structure endows F-SiO-DP with faster adsorption rate, which can reach equilibrium within 10 min, as well as higher adsorption capacities for U(VI) and Th(IV) compared with unimodal mesoporous silica like MCM-41 functionalized with 2,9-diamide-1,10-phenanthroline. The maximum adsorption capacities reach 416 mg g for U(VI) at pH 5.0 and 277 mg g for Th(IV) at pH 3.8, which are much higher than most of previously reported mesoporous silica-based adsorbents. The selectivity coefficient of U(VI) and Th(IV) over Ce(III), Nd(III), Sm(III), Eu(III), Gd(III), Y(III) and Yb(III) is all larger than 9 at pH 3.8, indicating that F-SiO-DP possesses a good simultaneously selective adsorption performance for U(VI) and Th(IV). This work demonstrates that F-SiO-DP with hierarchically bimodal mesoporous structure has promising application in adsorption and separation of actinides from lanthanides, which is crucial to the environmental protection. [ABSTRACT FROM AUTHOR]

The radiation-induced reactions of a water-soluble coumarin derivative, coumarin-3-carboxyl acid (C3CA), have been investigated in aqueous solutions by pulse radiolysis with a 35 MeV electron beam, final product analysis following 60Co γ-irradiations and deterministic model simulations. Pulse radiolysis revealed that C3CA reacted with both hydroxyl radicals (•OH) and hydrated electrons (e− aq) with near diffusion-controlled rate constants of 6.8 × 109 and 2.1 × 1010 M−1 s−1, respectively. The reactivity of C3CA towards O2• − was not confirmed by pulse radiolysis. Production of the fluorescent molecule, 7-hydroxy-coumarin-3-carboxylic acid (7OH-C3CA), was confirmed by final product analysis with a fluorescence spectrometer coupled to a high performance liquid chromatography (HPLC) system. Production yields of 7OH-C3CA following 60Co γ-irradiations depended on the irradiation conditions and ranged from 0.025 to 0.18 (100 eV) −1. Yield varied with saturating gas, additive and C3CA concentration, implying the presence of at least two pathways capable of providing 7OH-C3CA as a stable product following the scavenging reaction of C3CA with •OH, including a peroxidation/elimination sequence and a disproportionation pathway. A reaction mechanism for the two pathways was proposed and incorporated into a deterministic simulation, showing that the mechanism can explain experimentally measured 7OH-C3CA yields with a constant conversion factor of 4.7% from •OH scavenging to 7OH-C3CA production, unless t-BuOH was added. [ABSTRACT FROM AUTHOR]

The oxidation processes of the radiation-generated, three-electron-bonded intermediates AcMet 2 [S∴S] + and AcMet [S∴Br] were investigated by pulse radiolysis via their reactions with tryptophan (TrpH). These intermediates were derived from N-acetyl-methionine amide ( N-AcMetNH 2) and N-acetyl-methionine methyl ester ( N-AcMetOMe). The bimolecular rate constant k of the reaction between each intermediate and l-tryptophan (TrpH) was measured. For N-AcMetNH 2, k for the reaction of AcMet 2 [S∴S] + with TrpH were 3.4 × 10 8 and 2.2 × 10 8 dm 3 mol −1 s −1 at pH = 1 and 4.5, respectively. For N-AcMetOMe, k for the reaction of AcMet 2 [S∴S] + with TrpH were 4.0 × 10 8 and 2.8 × 10 8 dm 3 mol −1 s −1 at pH 1 and 4.5, respectively. The rate constants for the intermolecular transformation of Met [S∴Br] into TrpH + or Trp were also estimated. For N-AcMetNH 2, k for the reaction of AcMet 2 [S∴Br] with TrpH were 2.6 × 10 8 and 3.3 × 10 8 dm 3 mol −1 s −1 at pH 1 and 4.5, respectively. Related mechanisms were discussed. [ABSTRACT FROM AUTHOR]

The flavonolignans (silybin and analogues) are important natural compounds with multiple biological activities operating at various cell levels. Many of these effects are connected with their radical scavenging activities. In the present study, free-radical scavenging and antioxidant activities of four natural flavonoids, namely silybin, naringenin, naringin, and hesperetin, have been studied using nanosecond pulse radiolysis techniques. The kinetics and mechanisms of the reactions of silybin and analogues with various oxidizing radicals (such as •OH,N3•, CCl3OO•, SO4•−) have been investigated. Furthermore, the transient species has been assigned and radical scavenging rate constants have also been measured. Moreover, the structure-activity relationships between chemical structures of the flavonoids and their radical scavenging activities are further analayzed by theoretical calculation. Combined our previous observation of the fast reparation of DNA damage and efficient DNA protection against radiation damage in vitro, it can be confirmed that test flavonoids are promising molecules to be used for their potential antioxidant properties. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 590-597, 2011 [ABSTRACT FROM AUTHOR]

Silybin (extracted from Silybum marianum) is the major active constituent of silymarin which possesses a wide range of medicinal properties. These properties may be, in part, due to the potent scavenging capacity of oxidizing free radicals. In this context, scavenging radicals (hydroxyl, azide, dibromide anion radicals, nitrite, carbonate, etc.) of silybin have been studied to understand the mechanistic aspects of its action against free radicals. The transients produced in these reactions have been assigned and the rate constants have been measured by pulse radiolysis techniques. Reduction potential determined both by cyclic voltammetry gave a value 0.62±0.02 V vs NHE at pH 9. Quantum chemical calculations have been performed to further confirm the different activities of individual hydroxyl groups with the difference of heat of formation. Moreover, silybin also protected plasmid pUC18 DNA from soft X-ray radiation which induced strand breaks. These results are expected to be helpful for a better understanding of the anti-oxidative properties of silybin. [ABSTRACT FROM AUTHOR]

Transient radicals (hydrated electron, (SCN)[sub 2][sup .-] and CO[sub 3][sup .-]) formed in supercritical water have been observed by the pulse radiolysis technique. The change of spectra of these radicals with temperature has been measured. It was found that the spectra and absorption coefficients of the radicals, e[sup -][sub aq] and (SCN)[sub 2][sup .-], are strongly dependent on the temperature of the water. Since it was found that the absorption spectrum and molar absorption coefficient of CO[sub 3][sup .-] radical seem to be almost independent of temperature, G-values of OH and e[sup -][sub aq] could be derived. Then, the absolute values of the absorption coefficients for the radicals could be calculated. The G-values of the radical products in water radiolysis tend to increase with increasing temperature up to 400°C. Based on the above observation, radiolysis of supercritical water is discussed. [ABSTRACT FROM AUTHOR]