4KG-M制冷机做冷源的自循环氦液化装置研制；Development of helium liquefaction self-circulation system with 4 K G-M cryocoolers

采用5台1.5W/4.2KG-M制冷机(日本住友RDK415D)并联研制出了1台方便实验室使用的小型氦液化装置,并为其建立了性能测量实验台。实验结果表明:液氦温度为4.17K(饱和压力为96kPa)时,氦液化率为74L/d;液氦温度为4.42K(饱和压力为121kPa)时,液化率为116L/d,经拟合,在4.2K(饱和压力为100kPa)时液化率为83L/d,并且通过100小时以上的连续运行,说明该氦液化装置自循环性能良好。通过实验发现:实测氦液化率远大于制冷机冷头制冷量对应的计算氦液化率。分析认为:G-M制冷机气缸壁对氦气预冷是提高实际氦液化率的主要因素。

文冠果壳苷对侧脑室注射Aβ_(1-42)致小鼠学习记忆障碍的改善作用

目的研究文冠果壳苷对侧脑室注射β肽淀粉样蛋白1-4(2Aβ1-42)小鼠学习记忆障碍的改善作用,并初步探讨了其作用机制。方法通过避暗和水迷宫实验检测了小鼠的学习记忆能力;使用分光光度计检测小鼠大脑组织中乙酰胆碱酯酶(AchE)和胆碱乙酰转移酶(ChAT)活性的变化。结果小鼠侧脑室注射凝聚态Aβ1-42显著降低了小鼠被动回避学习记忆能力及空间学习记忆能力(P<0.01),并且小鼠大脑AchE和ChAT活性显著降低(P均<0.05);而文冠果壳苷能够显著减少避暗错误次数,延长潜伏期(分别P<0.05、P<0.01);剂量依赖性地缩短水迷宫实验中小鼠到达安全台的游泳时间(分别P<0.05、P<0.01),不同程度地抑制Aβ1-42模型小鼠的AchE和ChAT活性的降低(P<0.05和<0.01)。结论文冠果壳苷对侧脑室注射Aβ1-42小鼠学习记忆障碍具有显著的改善作用,其作用机制可能与保护中枢胆碱能神经细胞,改善中枢胆碱能神经系统功能等有关。

Synthesis of isomeric bis(amine anhydride)s for novel poly(amine imide)s by Pd-catalyzed amination of 4-chlorophthalic anhydride

Two novel bis(amine anhydride) monomers, N,N'-bis(3,4-dicarboxyphenyl)-1,4-phenylenediamine dianhydride I and N,/N'-bis(3,4-dicarboxyphenyl)-1,3-phenylenediamine dianhydride 11, were prepared via palladium-catalyzed amination reaction of 4-chloro-N-methylphthaliniide with 1,4-phenylenediamine or 1,3-phenylenediamine, followed by alkaline hydrolysis of the intermediate bis(amine imide)s and subsequent dehydration of the resulting tetraacids. A series of new poly(amine imide)s were prepared from the synthesized dianhydride monomers with various diamines in NMP via conventional two-step method.

Crystallization behavior of a thermoplastic polyimide derived from 3,3 ',4,4 '-oxydiphthalic dianhydride and 4,4 '-oxydianiline

Nonisothermal and isothermal crystallization kinetics of an aromatic thermoplastic polyimide derived from 3,3',4,4'-oxydiphthalic dianhydride and 4,4'-oxydianiline have been investigated by means of differential scanning calorimetry (DSC) and wide-angle X-ray diffraction. The results for nonisothermal crystallization study showed that a weak melting peak appeared during the first heating process, whereas no crystallization peak appeared in the DSC curve during the subsequent cooling process. On the other hand, the study for the isothermal crystallization in the temperature range of 260-330 degrees C showed that a new exothermic peak appeared at lower temperature for the samples crystallized for 100 min at 300 degrees C.

Highly 3,4-Selective Polymerization of Isoprene with NPN Ligand Stabilized Rare-Earth Metal Bis(alkyl)s. Structures and Performances

Deprotonation of (ArNHPPh2NAr2)-N-1 (H[NPN](n), n = 1 - 10) by Ln(CH2SiMe3)(3)(THF)(2) (Ln = Lu, Y, Sc, Er) generated a series of rare-earth metal bis(alkyl) complexes [NPN](n)Ln(CH2SiMe3)(2)(THF)(2) (1-10), which under activation with [Ph3C][B(C6F5)(4)] and AliBu(3) were tested for isoprene polymerization. The correlation between catalytic performances and molecular structures of the complexes has been investigated. Complexes 1-5 and 8, where Ar-1 is nonsubstituted or ortho-alkyl-substituted phenyl, adopt trigonal-bipyramidal geometry. The Ar-1 and Ar-2 rings are perpendicular in 1-4 and 8 but parallel in 5. When Ar-1 is pyridyl, the resultant lutetium and yttrium complexes 9a and 9b adopt tetragonal geometry with the ligand coordinating to the metal ions in a N,N,N-tridentate mode, whereas in the scandium analogue 9c, the ligand coordinates to the Sc3+ ion in a N,N-bidentate mode. These structural characteristics endow the complexes with versatile catalytic performances, With increase of the steric bulkiness of the ortho-substituents Ar-1 and Ar-2, the 3,4-selectivity increased stepwise from 81.6% for lutetium complex 1 to 96.8% for lutetium complex 6 and to 97.8% for lutetium complex 7a. However, further increase of the steric bulk of the ligand led to a slight drop of 3,4-selectivity for the attached complex 5 (95.1%).

Electrosynthesis and characterization of 1,2-dibenzyl C-60: A revisit

A reinvestigation of the reaction between C-60(2-) and benzyl bromide in benzonitrile containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) has shown that there are more reaction products than previously reported. Use of a silica rather than a "Buckyclutcher I" column for HPLC purification led to isolation of two previously unattained products in the reaction mixture, one of which was identified as 1,2-(PhCH2)(2)C-60 by UV-vis and NMR. The earlier incorrectly assigned 1,2-(PhCH2)(2)C-60 was identified as the methanofullerene C61HPh by X-ray single-crystal diffraction. The electrochemistry of genuine 1,2-(PhCH2)(2)C-60 shows that its first reduction potential in PhCN containing 0.1 M TBAP is cathodically shifted by 100 mV with respect to E-1/2 for reduction of 1,4-(PhCH2)(2)C-60, indicating that the addition pattern significantly affects the electrochemistry of derivatized C-60. Visible and near-IR spectra of the monoanion and dianion of 1,2-(PhCH2)(2)C-60 are also reported.

聚对苯二甲酸1,3-丙二醇酯溶液浇铸薄膜形态结构

聚对苯二甲酸 1 ,3-丙二醇酯 ( PTT)是典型的半结晶聚合物 ,从熔体结晶形成球晶 ,在某一结晶温度范围内 ,在球晶中可观察到环带结构[1～ 4 ] .一般认为 ,环带球晶的形成归因于片晶沿球晶径向的周期性扭曲[1,2 ] .本文研究了 PTT溶液浇铸薄膜在溶剂挥发过程中等温结晶的形态结构 .1　实验部分　　 PTT样品为美国壳牌化学公司产品 ,熔点为 2 2 8℃ .将 PTT粒料于 1 1 0℃溶解在苯酚和1 ,1 ,2 ,2 -四氯乙烷 (质量比为 60∶ 40 )的混合溶剂中 ,配成质量分数为 0 .2 %～ 2 %的溶液 ,滴少许溶液在加热的云母片上 ,在预先设定的结晶温度 ( 90～ 2 0 0℃ )下等温结晶 ,然后将 PTT薄膜快速冷却至室温 .用 Leica DMLP偏光显微镜 ( PL M)和 SPA- HV30 0原子力显微镜 ( AFM)进行形态表征 .2　结果与讨论　　图 1为 PTT溶液浇铸薄膜在不同温度下等温结晶后的 PLM图 ,可以清楚地看到 Maltese十字消光现象 .PTT溶液浇铸薄膜在 90～ 1 30℃的结晶温度范围内 ,形成环带球晶 ;当结晶温度为 1 40℃...

Syntheses and properties of novel polyimides derived from 2-(4-aminophenyl)-5-aminopyrimidine

2-(4-Aminophenyl)-5-aminopyrimidine (4) is synthesized via a condensation reaction of vinamidium salts and amidine chloride salts, followed by hydrazine palladium catalyzed reduction. A series of novel homo- and copolyimides containing pyrimidine unit are prepared from the diamine and 1,4-phenylenediamine (PDA) with pyromellitic dianhydride (PMDA) or 3,3',4,4'-biphenyl tertracarboxylic dianhydride (BPDA) via a conventional two-step thermal imidization method. The poly(amic acid) precursors had inherent viscosities of 0.97-4.38 dL/g (c = 0.5 g/dL, in DMAc, 30 degrees C) and all of them could be cast and thermally converted into flexible and tough polyimide films. All of the polyimides showed excellent thermal stability and mechanical properties. The glass transition temperatures of the resulting polyimides are in the range of 307-434 degrees C and the 10% weight loss temperature is in the range of 556-609 degrees C under air. The polyimide films possess strength at break in the range of 185-271 MPa, elongations at break in the range of 6.8-51%, and tensile modulus in the range of 3.5-6.46 GPa. The polymer films are insoluble in common organic solvents, exhibiting high chemical resistance.

Electrochemical study of 4-ferrocene thiophenol monolayers assembled on gold nanoparticles

In this paper, 4-ferrocene thiophenol was employed as a novel capping agent to synthesize electroactive gold nanoparticles. Transmission electron microscopy showed an average core diameter of 2.5 nm. The optical and electrochemical properties of the 4-ferrocene thiophenol capped gold nanoparticles were characterized by UV-Vis spectroscopy and cyclic voltammograms. Surface plasmon absorbance was detected at 522 nm. Cyclic voltammograms revealed the adsorbed layer reaction controlled electrode process, and the formal potential of electroactive ferrocene centers shifted anodically compared with ferrocene in solution, which could be attributed to the electron-withdrawing phenyl moiety linked to ferrocene.