克量级铀中微量铕和铽的放化分离方法研究

为提高中子诱发铀裂变时低产额裂变产物¹⁵⁶Eu和¹⁶¹Tb产额测量的精度，需获得放化纯的¹⁵⁶Eu和¹⁶¹Tb样品。本工作建立了氢氧化物共沉淀法除铝、氟化钙共沉淀法除铀、TRPO萃取法提取稀土元素、阳离子交换色谱法从混合稀土元素中分离Eu和Tb的流程，可用于大量铀、铝和裂变产物中微量Eu和Tb的分离。在待分离样品中含2 g铀、0.65 g铝和裂变产物的条件下，该流程对Eu、Tb的化学回收率均大于80%，对U、²³⁹Np、⁹⁵Zr、¹⁰³Ru、¹³¹I、¹³²Te、¹⁴⁰Ba、¹⁴⁰La、¹⁴¹Ce、¹⁴⁷Nd等主要干扰物质的去污因子达到106。该方法可满足中子诱发铀裂变时¹⁵⁶Eu和¹⁶¹Tb产额精确测量的要求。     

First principles computational studies of spontaneous reduction reaction of Eu(III) in eutectic LiCl‐KCl molten salt

Using first principles calculations, we study fundamental mechanism of spontaneous reduction reaction of Eu³⁺ to Eu²⁺ in eutectic LiCl‐KCl molten salt. We decouple the reaction Gibbs free energy into enthalpy and entropy contributions by using rigorous thermodynamic formalism. Key structural features of the solvation shell are characterized by the radial distribution function and the coordination number. Compared with Eu²⁺, the Eu³⁺ ion has a more rigid framework of the solvation shells, corroborating its stronger electrostatic interaction with neighboring ligands of Cl^? ions and a more favorable state on the aspect of enthalpy. Computations on vibrational frequency, however, pose significant contribution of vibrational entropy to the reaction Gibbs free energy for the reduction. Vibration frequency of Eu²⁺ is smaller than that of Eu³⁺, driving a more positive change of the entropy in the reduction reaction. Furthermore, an Eu²⁺ diffuses more quickly than an Eu³⁺ in the LiCl‐KCl molten salt with switching mechanism of ligand Cl^? ions in the solvation shell. Our results propose that the spontaneity of the reduction reaction is driven by the entropic contribution by overcoming the penalty of the reaction enthalpy.     

萃取色层分离测定钐铕钆富集物中的钐铕钆铽

研究了在P_(507)-HCl-(NH_4)_2SO_4体系中用萃取色层法定量分离钕、钐、铕、钆、铽和镝的条件,实验表明当用0.42mol/L HCl-0.5mol/L(NH_4)_2SO_4作淋洗剂时,上述元素都能定量分离。方法能用于钐、铕、钆富集物中钐、铕、钆和铽的测定。     

两种高效低成本咪唑啉类缓蚀剂的研制

为了缓解油田设备因腐蚀引起的问题,实验通过有机合成方法,用苯甲酸(油酸)和三乙烯四胺及氯化苄合成得到咪唑啉季铵盐缓蚀剂,经过油酸咪唑啉季铵盐缓蚀剂与苯甲酸咪唑啉季铵盐缓蚀剂的复配后,通过静态失重法进行评价。结果表明这类缓蚀剂的最佳加药浓度为30 mg·L-1,此时两种酸类咪唑啉季铵盐含量比为2∶3时的缓蚀效率可以达到97.4%;主剂(苯甲酸∶油酸=2∶3)与硫脲、乌洛托品、乙酰苯胺按比例10∶5∶2∶1复配缓蚀效率可以达到98.4%,符合油田生产需求。     

金属铕配合物的合成及其晶体结构

合成了席夫碱N-亚水杨基-2-氨基吡啶,并以此为有机配体与过渡金属铕反应,得到了相应的配合物,且在一定的条件下培养得到配合物的单晶,解析出其晶体结构,并对其进行了荧光性质研究。     

PTFE中空纤维膜萃取苯甲酸工艺研究

以氢氧化钠溶液为萃取剂,采用PTFE中空纤维膜萃取料液中的苯甲酸,考察了料液相苯甲酸的初始浓度、料液相初始pH、料液相与萃取相流量比、萃取剂的初始浓度对苯甲酸萃取率(η)的影响。结果表明,随着料液初始浓度增大,η增大,当苯甲酸浓度1 g/L时,η减小,但膜通量基本不变,即存在一个最大膜通量,此时苯甲酸浓度变化对传质无影响;料液的pH值下降,η增大;萃取相氢氧化钠浓度增大,η增大;存在一个最佳相流量比(Q料/Q萃)为1.8。另外,温度升高有利于膜萃取。     

Modulation of Cyclins,p53 and Mitogen-Activated Protein Kinases Signaling in Breast Cancer Cell Lines by 4-(3,4,5-Trimethoxyphenoxy)benzoic Acid

Despite the advances in cancer therapy and early detection, breast cancer remains a leading cause of cancer-related deaths among females worldwide. The aim of the current study was to investigate the antitumor activity of a novel compound, 4-(3,4,5-trimethoxyphenoxy)benzoic acid (TMPBA) and its mechanism of action, in breast cancer. Results indicated the relatively high sensitivity of human breast cancer cell-7 and MDA-468 cells towards TMPBA with IC₅₀ values of 5.9 and 7.9 μM, respectively compared to hepatocarcinoma cell line Huh-7, hepatocarcinoma cell line HepG2, and cervical cancer cell line Hela cells. Mechanistically, TMPBA induced apoptotic cell death in MCF-7 cells as indicated by 4′,6-diamidino-2-phenylindole (DAPI) nuclear staining, cell cycle analysis and the activation of caspase-3. Western blot analysis revealed the ability of TMPBA to target pathways mediated by mitogen-activated protein (MAP) kinases, 5′ adenosine monophosphate-activated protein kinase (AMPK), and p53, of which the concerted action underlined its antitumor efficacy. In addition, TMPBA induced alteration of cyclin proteins’ expression and consequently modulated the cell cycle. Taken together, the current study underscores evidence that TMPBA induces apoptosis in breast cancer cells via the modulation of cyclins and p53 expression as well as the modulation of AMPK and mitogen-activated protein kinases (MAPK) signaling. These findings support TMPBA’s clinical promise as a potential candidate for breast cancer therapy.     

Removal of Liquid and Solid Impurities from Uranyl Nitrate Hexahydrate Crystalline Particles in Crystal Purification Process

The purification behavior of uranyl nitrate hexahydrate (UNH) was investigated to evaluate the decontamination performance of liquid and solid impurities using a dissolver solution of mixed oxide (MOX) fuel in batch experiments. The UNH crystal recovered from the MOX fuel dissolver solution containing simulated fission products (FPs) was purified by a sweating and melt filtration process. Although the decontamination factors (DFs) of Pu, Cs, and Ba did not change in the sweating process, that of Eu increased with increases in temperature and time. These results indicate that liquid impurities such as Eu were effectively removed by the sweating method, but solid impurities such as Pu, Cs, and Ba were minimally affected in the batch experiments. On the other hand, the DF of Ba increased with 0.45 and 5.0 μ filters in the melt filtration process. Since Pu and Cs formed as Cs₂Pu(NO₃)₆ in the course of U crystallization and was accompanied with the UNH crystal, these behaviors were similar to each other. Although the DFs of Pu and Cs did not change with the 5.0 μ filter, it increased approximately twofold with the 0.45 μ filter. The particle size of Cs₂Pu(NO₃)₆ is relatively small and might pass through the 5.0 μ filter in the melt filtration process. The liquid impurities as Eu remained in the molten UNH crystal with some filters.     

苯甲酸型低共熔溶剂吸收一氧化氮的性能研究

低共熔溶剂（DESs）已被广泛研究并应用于酸性气体的吸收，本研究发现苯甲酸类DESs能够可逆高效地吸收一氧化氮（NO）。以苯甲酸（BA）、硫脲、尿素和咪唑为氢键供体（HBD），以离子液体为氢键受体（HBA）制备了一系列的DESs。吸收NO的实验结果表明，以氯化四丁基膦（P₄₄₄₄Cl）为HBA和以BA为HBD的DESs表现出较高的NO吸收速率和饱和吸收量。BA/P₄₄₄₄Cl (1∶2) DES在101.3 kPa、303.15 K下，NO吸收量为2.75 mol/mol。热重测试和再生实验的结果表明，BA/P₄₄₄₄Cl (1∶2) DES具有理想的热稳定性和重复使用性。通过FTIR、¹H NMR和高斯模拟计算，探讨了BA/P₄₄₄₄Cl (1∶2) DES对NO的吸收机理，发现NO与BA的含氢氧原子之间存在化学相互作用，且BA的易去质子化性质有利于NO的吸收。