Introduction of multiple γ-ray detection to charged particle activation analysis

Charged particle activation analysis (CPAA) is a rapid method with high accuracy which can analyze multi-elements simultaneously. Since multiple γ-ray detection method is expected to improve the detection efficiency and the signal-to-noise ratio, we study what design of the γ-ray detector array is the most suitable for CPAA. We take up four design candidates and investigated the responses by the radiation simulation code Geant 4. From the results, we have deduced the best design with 5 germanium detectors in close geometry. By inspecting the sensitivity in CPAA, the method is proved to be useful and applicable to 116 nuclides.

     

On Partitional Labelings of Graphs

The notion of partitional graphs, a subclass of sequential graphs, is introduced, and the cartesian product of a partitional graph and K ₂ is shown to be partitional. Every sequential graph is harmonious and felicitous. The partitional property of some bipartite graphs including the n-dimensional cube Q _n is studied, and thus this paper extends what was known about the sequentialness, harmoniousness and felicitousness of such graphs.     

Chalcogen Chiral Ylides for the Catalytic Asymmetric Epoxidation of Aldehydes: From Sulfur to Selenium and Tellurium

Abstract

The reaction of novel chiral selenonium and telluronium ylides was investigated with aldehydes and compared to the sulfur analogues. (2R,5R)-2,5-Dimethylselenolane was prepared and reacted as a catalyst for the benzylidenation of aldehydes. Disubstituted epoxides were readily prepared with a (surprising) absence of diastereoselectivity, and with enantiomeric excesses higher than 90%. The reaction of a tellurium analogue, (2S,5S)-2,5-diethyltellurolane, afforded the oxirane in very moderate yield and e.e.'s in the range of 62–82%. Though this was less productive, it is the first report of a chiral telluronium ylide leading to an asymmetric epoxidation of aldehydes.     

Radiation-Induced Polymerization of Tetrafluoroethylene

Polymerization of tetrafluoroethylene was carried out in bulk at low temperatures by initiation with γ-rays from a ⁶⁰ Co source. It was found that a remarkable postpolymerization takes place even in the liquid phase. Kinetical analysis has been made of the in-source and postpolymerizations. An activation energy of 2.7 kcal/mole was obtained for the in-source polymerization and 10.3 kcal/mole for the postpolymerization. The long lifetime of polymer radicals in the liquid phase at -78°C seems to be due to the slow recombination rate of the polymer radicals, based on the rodlike shape of the polymer radicals.     

The effect of phenoxy oxygen atoms on extremely high extraction ability and less separation efficiency of trivalent rare earth elements with tetraphosphonic acid derivative of calix[4]arene

A cone confomational p-t-octylcalix[4]arene with four methylenephosphonic acids at the lower rim as well as its monomeric analog have been synthesized as a new extraction reagent to investigate the extraction behavior of the nine trivalent rare earth elements: Y, La, Pr, Nd, Sm, Eu, Gd, Ho and Er. The new calix[4]arene exhibited significantly higher extraction capacity than not only the monomeric derivative and the commercial extraction reagent, 2-ethylhexyl hydrogen 2-ethylhexylphosphonate, but also the cone conformational calix[4]arene extractants employed in our previous work, composed of a tetrapropylenephosphonic acid with a longer spacer, a tetraphosphonic acid at the upper rim, and tetraacetic acid at the lower rim. A dependence on the pH was observed for the new extractant in the highly acidic region, and the extraction took place via a simple ion-exchange mechanism. Using slope analysis, the stoichiometries of tetrameric and monomeric extractants to rare earth metal ions were determined to be 2:1 and 3:1, respectively. Using the proposed extraction equations, extraction equilibrium constants and separation factors were estimated. The extremely high extraction ability and moderate separation efficiency were attributed to the chelating effect of the phosphonic acid and the phenoxy oxygen atom. The effect of the phenoxy oxygen atom on extraction ability and separation efficiency of calix[4]arene derivatives was found to be significant.     

FER分子筛中铝原子的受限落位

分子筛是一类具有规则孔道或笼状结构的多孔材料,因其独特的结构和可调的酸性而广泛用于石油化工、精细化学品合成、现代煤化工等诸多行业.2006年Iglesia等在具有8元环孔道结构/侧口袋的FER和MOR分子筛上实现了无卤素添加、无贵金属存在条件下,由二甲醚羰基化合成乙酸甲酯的反应.乙酸甲酯通过进一步加氢可实现煤基乙醇的绿色生产.MOR分子筛通常具有较高的催化活性,但失活迅速;FER分子筛表现出良好的催化稳定性,但活性较低.如何在保证FER分子筛稳定性的前提下,进一步提升其羰基化活性是目前研究的热点.前期理论和实验研究发现,二甲醚羰基化反应活性与分子筛8元环孔道中的Br?nsted酸位密度存在正相关.因此,通过优化合成条件,选择性调控铝原子分布在"ferrierite"笼中,可以提高FER分子筛的羰基化反应活性.尽管研究者已在调节FER分子筛铝分布方面进行了大量研究,但对于不同T位上Al原子的精准识别以及对应Br?nsted酸位的可接触性还缺少系统和深入的认识.本文选取了几种代表性模板剂,分别在碱性和含氟体系下制备了系列FER分子筛样品,利用Rietveld精修和模拟退火算法,在原子水平揭示了模板剂种类以及合成介质变化对Al原子在不同T位分布的影响,并结合二甲醚羰基化反应进行了结构和性能的关联.首先选取不同尺寸大小的环状胺(环己胺、哌啶、吡啶、吡咯烷)和链状胺(乙二胺)合成了具有相似形貌、孔结构、酸密度的系列FER分子筛样品.以CHA-Na-FER为例,PXRD精修结果显示,Na+(平衡35％的骨架负电荷)分布在10元环孔道中与O1形成氢键,质子化的环己胺分布在"ferrierite"笼中,并且环己胺上的N与O3形成氢键.这说明与O1相连的T3位以及与O3相连的T1位都有可能是Al富集的位置.为了进一步验证该结论,本文还精修了吸附探针分子吡啶的样品CHA-Na-FER-Py-60h.原粉以及吸附吡啶样品的精修结果表明,T1位和T3位是样品中铝富集的位置.随后,运用相同方法研究了Py-Na-FER,PI-Na-FER,En-Na-FER和Pyrr-HF-FER样品中的Al落位,发现T1/T3位均是样品中Al富集的位置.此外,理论计算结果表明T1/T3位上Al原子的取代能较低,说明Al优先取代T1/T3位上的Si,这与精修结果相一致.前期理论模拟结果表明,FER分子筛中T2-O5和T4-O7位点的CO插入反应能垒较低,是二甲醚羰基化反应的活性位.本文吡啶吸附实验、热重分析以及PXRD精修结果表明,FER分子筛中大部分Al富集在T1/T3位,与T2/T4位相关的Br?nsted酸约占18％～30％.最后,对各样品进行了二甲醚羰基化反应评价,结果显示PI-Na-FER,Py-Na-FER,En-Na-FER和CHA-Na-FER催化剂的乙酸甲酯生成速率相近,约为0.10 mol/(mol H+?h).Pyrr-HF-FER催化剂的乙酸甲酯生成速率最高,可达到0.16 mol/(mol H+?h),这可能是由于Pyrr-HF-FER催化剂具有更多T2/T4位相关的Br?nsted酸.虽然Pyrr-HF-FER催化剂的乙酸甲酯生成速率较其他四个催化剂有一定提升,但其仍远低于MOR分子筛上乙酸甲酯生成速率(0.40 mol/(mol H+·h)).综上,有机模板剂的选择与合成介质的改变对FER分子筛中Al分布的调控作用是有限的,即Al原子总是优先分布于T1/T3位.而与T1和T3位相关的Br?nsted酸位不是二甲醚羰基化反应的活性位点.因此与MOR相比,FER分子筛在二甲醚羰基化反应中表现出较低的催化活性.     

Effect of Particle Size on Electro-Optic Properties of Liquid Crystal Devices Doped with γ-Cyclodextrin Stabilized Barium Titanate Nanoparticles

Barium titanate stabilized by γ-cyclodextrin nanoparticles were prepared by using a microwave reactor equipped with ultrasonic nozzle mixing at 240°C in a tetraethylene glycol solution of barium ethoxide and titanium ethoxide in the presence of γ-cyclodextrin. Particles in γ-cyclodextrin-stabilized BaTiO₃ nanoparticles had an average diameter of 2.1 nm and mainly distributed within the range of about 1 to 4 nm. The γ-cyclodextrin-stabilized BaTiO₃ nanoparticles were mixed with 4-cyano-4′-pentylbiphenyl at room temperature resulting in a liquid crystal sol of 4-cyano-4′-pentylbiphenyl. The response time of liquid crystal devices in the presence of γ-cyclodextrin-stabilized BaTiO₃ nanoparticles was faster than that in the absence.     

Effects of Roxadustat on Erythropoietin Production in the Rat Body

Anemia is a major complication of chronic renal failure. To treat this anemia, prolylhydroxylase domain enzyme (PHD) inhibitors as well as erythropoiesis-stimulating agents (ESAs) have been used. Although PHD inhibitors rapidly stimulate erythropoietin (Epo) production, the precise sites of Epo production following the administration of these drugs have not been identified. We developed a novel method for the detection of the Epo protein that employs deglycosylation-coupled Western blotting. With protein deglycosylation, tissue Epo contents can be quantified over an extremely wide range. Using this method, we examined the effects of the PHD inhibitor, Roxadustat (ROX), and severe hypoxia on Epo production in various tissues in rats. We observed that ROX increased Epo mRNA expression in both the kidneys and liver. However, Epo protein was detected in the kidneys but not in the liver. Epo protein was also detected in the salivary glands, spleen, epididymis and ovaries. However, both PHD inhibitors (ROX) and severe hypoxia increased the Epo protein abundance only in the kidneys. These data show that, while Epo is produced in many tissues, PHD inhibitors as well as severe hypoxia regulate Epo production only in the kidneys.