Equilibrium and crystallographic measurements of the binary tetrahydrofuran and helium clathrate hydrates

Clathrate compounds are crystalline materials formed by a physical interaction between host and relatively light guest molecules. Various types of nano-sized cages surrounded by host frameworks exist in the highly unique crystalline structures and free guest molecules are entrapped in an open host-guest network. Recently, we reported two peculiar phenomena, swapping and tuning, naturally occurring in the hydrate cages. Helium, one of the smallest light guest molecules, must be the challengeable material in the sense of physics and moreover possesses versatile applications in the field of superconductivity technology and thermonuclear industry. In this regard, we attempted for the first time to synthesize helium hydrates at moderate temperature and pressure conditions. According to inclusion phenomena, helium itself normally cannot form clathrate hydrates due to being too small molecularly without the help of hydrate former molecules (sI, sII, and sH formers). In this study, the hydrate equilibria of the binary clathrate hydrate containing tetrahydrofuran, helium, and water were determined at 2, 3, 5.56 THF mol%. Direct volumetric measurements were also carried out to confirm the exact amount of helium captured in the hydrate cages. Finally, the crystalline structure of the formed mixed hydrates was identified by powder X-ray diffraction, resulting in structure II.     

Electrochemical determination of estradiol using a poly(l-serine) film-modified electrode

A thin film of poly(l-serine) was prepared via electropolymerization for the determination of trace levels of estradiol. In pH 5.0 phosphate buffer, l-serine was oxidized during the cyclic potential sweeps between −0.60 and 2.0 V, forming a thin film at the electrode surface. The electrochemical behavior of estradiol was investigated. The oxidation peak potential of estradiol shifts negatively at the poly(l-serine) film-coated glassy carbon electrode (GCE) compared with that at the bare GCE. Otherwise, the oxidation peak current greatly increases at the poly(l-serine) film-modified GCE. These phenomena suggest that the poly(l-serine) film exhibits catalytic activity towards the electrochemical oxidation of estradiol. Based on this, a sensitive, rapid and simple electrochemical method was proposed for the determination of estradiol. The limit of detection is evaluated to be 2.0 × 10⁻⁸ mol L⁻¹. Finally, this method was successfully used to determine estradiol in blood serum.     

Influence of polymer modulus on the percolation threshold of latex-based composites

Monodispersed copolymer emulsions with different glass transition temperatures were synthesized to investigate the effect of room temperature polymer matrix modulus on the electrical properties of carbon black (CB) filled segregated network composites. The emulsion with the highest modulus at room temperature produced composites with the lowest percolation threshold. The threshold for a composite made from a copolymer latex containing an equal ratio of butyl acrylate and methyl methacrylate (BA5) is 1.5 vol%, while the percolation threshold for the much lower modulus BA7 (7:3 BA/MMA ratio) is 4.93 vol%. The microstructure of each composite shows significant differences in the level of CB dispersion within the polymer matrix. Higher modulus polymer particles push the CB more efficiently into the interstitial space between them, resulting in a lower percolation threshold. This modulus effect was confirmed by increasing the drying temperature, where the moduli of latexes (BA5, BA5.5, and BA6) were more similar and the percolation thresholds for three composites also become closer to one another.     

陆相碎屑岩储层隔夹层成因、特征及其识别

陆相储层隔夹层是形成储层流体流动非均质的主要因素之一，也是储层精细表征的重要内容，油田勘探开发实践表明，陆相储层隔夹层主要可分为泥质隔夹层、钙质隔夹层和物性隔夹层三大类。根据这种分类，深入分析和总结了这三类隔夹层成因、岩性特征、分布特征和测井识别特征，并比较其区别，这对以后新老区块隔夹层研究有参考和适用价值。     

真空蒸发沉积VOPc薄膜及磁场对薄膜结构与性能的影响

用真空蒸发制备了酞菁氧钒 (VOPc)薄膜 ,并在磁场中进行了热处理。用X光电子能谱、X射线衍射、紫外 可见吸收光谱、原子力显微镜等手段对制备的薄膜进行了表征。结果表明沉积的酞菁氧钒薄膜为α 型 ,成分接近酞菁氧钒的分子式。制备的薄膜在磁场中进行了热处理 ,发现磁场使酞菁氧钒薄膜性质发生改变 :UV VIS吸收谱Q带发生红移 ;XRD谱图衍射峰强度明显增强 ,峰位略有变化 ;原子力显微镜 (AFM)分析发现晶粒大小无明显变化。以上结果说明磁场的存在使得VOPc分子在热处理过程中发生了定向的排列     

Diamino telechelic polybutadienes for solventless styrene-butadiene-styrene (SBS) triblock copolymer formation

High molecular weight, high functionality diamino telechelic polybutadienes (TPBs) were synthesized by ring-opening metathesis polymerization (ROMP) of 1,5-cyclooctadiene (COD) in the presence of a chain transfer agent, 1,8-dicyano-4-octene, followed by lithium aluminum hydride reduction. Melt coupling of diamino TPB with anhydride-terminated polystyrene (PS-anh) resulted in the formation of styrene-butadiene-styrene (SBS) triblock copolymers; ca. 80% maximum conversion of PS-anh was achieved within 30 s. The results from SAXS, TEM, and rheological measurements of the coupling products confirmed the formation of SBS triblock copolymers having lamellar morphology. A fluorescent-labeled PS-anh was used to study the coupling kinetics by diluting the reactants by the addition of non-functional PS.     

New approach to enhance adhesions between carbon nanotube emitters and substrate by the combination of electrophoresis and successive electroplating

Complementary electroplating combined with electrophoresis enhanced the field emission characteristics of emitters by improving the adhesions between CNT emitters and substrate. The emitting current of the CNT emitters prepared by our combined method increased nine times higher than that of CNT emitters prepared by electrophoresis only, since electroplating improved the adhesion of CNT emitters. During the life-time measurement for 10 h, the emitting current of CNT emitters fabricated by electrophoresis only was drastically decreased to 13% of the initial current, while that prepared by the combination of electrophoresis and successive electroplating decreased to 64% of the initial current. We suggest that our method is a promising approach for the efficient fabrication of reliable CNT emitters.     

Effects of tube rupture modeling and the parameters on the analysis of multiple steam generator tube rupture event progression in APR1400

A multiple steam generator tube rupture (MSGTR) event in APR1400 has been investigated using the best estimate thermal hydraulic system code, MARS1.4. The effects of the parameters such as the number of ruptured tubes, rupture location, affected steam generator on the analysis of the MSGTR event in APR1400 are examined. In particular, tube rupture modeling methods, single tube modeling (STM) and double tube modeling (DTM), are compared. The APR1400 is found to have the capability of allowing more than 30 min to operators for the MSGTR event of five tubes. The effects of rupture location on the MSSV lift time is not significant in the case of STM, but the MSSV lift time for tube-top rupture is found to be 25.3% larger than that for rupture at the hot-leg side tube sheet in the case of DTM. The MSSV lift time for the cases that both steam generators are affected (4C5x, 4C23x) are found to be larger than that of the single steam generator cases (4A5x, 4B5x) due to a bifurcation of the primary leak flow. The discharge coefficient of Cd is found to affect the MSSV lift time only for a smaller value of 0.5. It is found that the most dominant parameter governing the MSSV lift time is the leak flow rate. Whether any modeling method is used, it gives the similar MSSV lift time if the leak flow rate is close, except in the case where both steam generators are affected. Therefore, the system performance and the MSSV lift time of the APR1400 are strongly dependent on the break flow model used in the best estimate system code.     

Epitaxial growth of GaN on (0001) Al<Subscript>2</Subscript>O<Subscript>3</Subscript> via solution-cast seed layer formation process using Ga(mDTC)<Subscript>3</Subscript>

This paper reports an alternative method for the growth of GaN epitaxial layer on (0001) Al₂O₃ substrate by hot-wall vapor phase epitaxy technique. Tris (N,N-dimethyldithiocarbamato)-gallium (III), Ga(mDTC)₃ was introduced as a precursor material for the seed layer formation in the growth of GaN. Optimal growth conditions with seed layers formed by the Ga(mDTC)₃ concentration of 0.047 mol/L were identified: Growth temperature was found to be 850 °C, and optimal distance between the reactant outlet and substrate was determined to be 12.5 cm. Characterization results showed that this growth method produce high-crystallinity GaN epitaxial layers at a relatively lower growth temperature compared to the existing growth techniques and simplify the growth process.     

High affinity hormone binding to the extracellular N-terminal exodomain of the follicle-stimulating hormone receptor is critically modulated by exoloop 3

The human follicle-stimulating hormone receptor (FSH-R) consists of two distinct domains of >330 amino acids, the N-terminal extracellular exodomain and membrane-associated endodomain. The exodomain alone binds hormone with high affinity, whereas the endodomain is the site of receptor activation. Coordination of these two domains is essential for successful hormone action but little is known about their functional and structural relationship. In this communication, we report that exoloop 3 of FSH-R constrains follicle-stimulating hormone binding to the exodomain. When the FSH-R exodomain was prepared by truncating its endodomain, the hormone binding affinity of the exodomain was slightly improved, compared with the wild type receptor. The binding affinity was further improved by >3-fold when the exodomain was attached to the membrane-associated domain of CD8. These results suggest that the FSH-R endodomain attenuates hormone binding at the exodomain. As a first step to test this hypothesis, the 11 amino acids except Ala589 of exoloop 3 were individually substituted with Ala. Ala substitution for Leu583 or Ile584 improved the hormone binding affinity by 4-6-fold while totally abolishing cAMP induction, indicating an inverse relationship. The Ala substitution for Lys580 or Pro582 had a similar trend but to a lesser extent. This significant improvement in the binding affinity suggests that the four residues at the N-terminal region of exoloop 3 interact with the exodomain and constrain the hormone binding in the wild type receptor. This effect is specific since substitutions for other than the 4 residues did not improve the hormone binding affinity. Computer modeling shows that the 4 residues can be positioned on one side of exoloop 3. This result and the apparent inverse relationship of hormone binding and cAMP induction suggest that these two essential functions may work against each other. Therefore, hormone binding might be compromised to preserve cAMP inducibility while maintaining a reasonably high, but below maximum, binding affinity.