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991.
利用正电子湮没技术对侧链型热致高分子液晶丙烯酸酯共聚物进行了变温相变研究.除实验标识出样品的相变温度点外,根据试样中自由体积随温度的变化关系,对高分子液晶材料内部立链、侧链以及介晶基元的相变行为特点进行了探讨,并就与小分子液晶变化特点的一些不同做了解释.  相似文献   
992.
从溶胀平衡研究玻璃态高聚物的凝聚缠结网络   总被引:1,自引:0,他引:1  
在13~15℃室温条件下对聚苯乙烯(PS)颗粒在二氧六环/水混合溶剂中的溶胀情况进行目视观察,可以看到,当减小混合溶剂二氧六环/水中的水含量时,PS颗粒从玻璃态到溶胀的玻璃态、溶胀的高弹态、流体态的转变,与PS颗粒升温时从玻璃态到高弹态、流体态的转变相对应.选定混合溶剂二氧六环/水(水6·8wt%)对一个单分散PS试样(Mw=1·68×105)在30℃进行分相平衡和溶胀平衡的测定.分相平衡是先将PS/二氧六环/水(混合溶剂水含量6·8wt%)体系加热到130℃使PS溶解成一均相溶液,然后在冷却过程中分相,在30℃达分相平衡(30天)时,浓相高分子体积浓度p″=0·304,稀相几乎为纯溶剂.从Flory-Huggins相平衡理论得出此体系的高分子-溶剂相互作用参数χ=0·63.本工作使用的单分散PS试样在选定的混合溶剂,即二氧六环/水(水6·8wt%)中,30℃时不能溶解只能溶胀,单分散PS颗粒淬冷试样(密度ρp=1·0451g/mL)到达溶胀平衡(80天)时浓相高分子体积浓度p″=0·308.而此淬冷试样经在80℃热处理100h后的老化试样(ρp=1·0470g/mL)达溶胀平衡(70天)时p″=0·312.从溶胀过程中浓相体积变化曲线可知试样经在80℃热处理过程中凝聚网络趋向于更均一,更接近热处理温度下的平衡态,试样密度增大,网络产生了新的链间凝聚,物理交联密度增大(凝聚点间分子量减小).从溶胀平衡理论并取χ=0·63(分相平衡)可得到淬冷试样的物理交联点间分子量Mc=11·6×104,老化试样的物理交联点间分子量Mc=6·9×104.实验结果说明溶胀过程及溶胀平衡的测定可以反映玻璃态高聚物中的凝聚网络结构的细节,而且非常敏感.  相似文献   
993.
A sample preparation method that combines a modified target plate with a nanoscale reversed-phase column (nanocolumn) was developed for detection of neuropeptides by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). A gold-coated MALDI plate was modified with an octadecanethiol (ODT) self-assembled monolayer to create a hydrophobic surface that could concentrate peptide samples into a approximately 200-500-microm diameter spot. The spot sizes generated were comparable to those obtained for a substrate patterned with 200-microm hydrophilic spots on a hydrophobic substrate. The sample spots on the ODT-coated plate were 100-fold smaller than those formed on an unmodified gold plate with a 1-microl sample and generated 10 to 50 times higher mass sensitivity for peptide standards by MALDI-TOF MS. When the sample was deposited on an ODT-modified plate from a nanocolumn, the detection limit for peptides was as low as 20 pM for 5-microl samples corresponding to 80 amol deposited. This technique was used to analyze extracts of microwave-fixed tissue from rat brain striatum. Ninety-eight putative peptides were detected including several that had masses matching neuropeptides expected in this brain region such as substance P, rimorphin, and neurotensin. Twenty-three peptides had masses that matched peaks detected by capillary liquid chromatography with electrospray ionization MS.  相似文献   
994.
A series of new 2‐aryl‐7‐cyano/ethoxycarbonyl‐6‐methylthio‐1H‐imidazo[1,2‐b]pyrazoles ( 5 ) have been synthesized in moderate to good yields, via a two‐step cyclocondensation procedure of 5‐amino‐4‐cyano/ethoxycarbonyl‐3‐methylthio‐1H‐pyrazole ( 1 ) and α‐bromoacetophenones ( 3 ) or α‐tosyloxyacetophenones ( 2 ), which were prepared by the reactions of acetophenones with [hydroxy(tosyloxy)iodo]benzene (HTIB). The intermediates, 5‐amino‐1‐(aroylmethyl)‐4‐ cyano/ethoxycarbonyl‐3‐methylthio‐1H‐pyrazoles ( 4 ), have been isolated, serving as evidence for the regioselectivity. When utilizing α‐tosyloxy‐acetophenones, the reactions were more eco‐friendly, the reaction time was significantly reduced and the synthetic procedure was more convenient and easier to manipulate. Surprisingly, using potassium carbonate to displace sodium carbonate in the synthesis of 4 , in the case of 1 (R? CN), two novel cyclocondensation products have been isolated and fully characterized, followed by the proposal of a plausible mechanism.  相似文献   
995.
In the crystal structure of the title complex, [Ni2(C10H20N4O2)(C12H12N2)2](ClO4)2 or [Ni(dmaeoxd)Ni(dmbp)2](ClO4)2 {H2dmaeoxd is N,N′‐bis­[2‐(dimethyl­amino)ethyl]oxamide and dmbp is 4,4′‐dimethyl‐2,2′‐bipyridine}, the deprotonated dmaeoxd2− ligand is in a cis conformation and bridges two NiII atoms, one of which is located in a slightly distorted square‐planar environment, while the other is in an irregular octa­hedral environment. The cation is located on a twofold symmetry axis running through both Ni atoms. The dmaeoxd2− ligands inter­act with each other via C—H⋯O hydrogen bonds and π–π inter­actions, which results in an extended chain along the c axis.  相似文献   
996.
During the past decades, there has been a renewed interest in the application of solvent extraction to the recovery of Au (I) from cyanide solutions1,2. Among those various extractants, the amine extractants with the addition of organic phosphorus oxide as cosolvent have been widely investigated3,4. Various diluents and modifiers have been selected to optimize the extraction system so as to increase the loading capacity, improve the selectivity and/or reduce emulsification5. Quaternary amm…  相似文献   
997.
The CCSD(T)/11e-RECP//MP2/11e-RECP method was used to explore the potential energy surfaces (PESs) of the formation of Agn (n = 2–6) clusters. Two kinds of reaction mechanisms were revealed in the formation of Agn clusters, the association mechanism for the formation of Ag2, Ag5, and Ag6 clusters and the association–isomerization mechanism for the formation of Ag3 and Ag4 clusters. Based on the canonical transition state theory, the calculated rate constants of the formation of Agn clusters displayed an odd–even effect: the rate constants of formation of Agn clusters with odd number were larger than those with even number. The rate constant of formation of Ag4 was the lowest, whereas that of Ag5 was the highest among Agn (n = 2–6) clusters. The formation of Ag4 was the most difficult step in the aggregation process of the silver clusters. The formation of Ag4 may be related with the critical point in the silver aggregation process.  相似文献   
998.
本文研究了二(2,4,4-三甲基戊基)膦酸(Cyanex272)-上胺205-正庚烷乳状液膜分离Sc(Ⅲ)、Fe(Ⅲ)和Lu(Ⅲ)。考察了外相酸度、表面活性剂浓度、流动载体浓度及内相盐酸浓度对Sc(Ⅲ)迁移的影响。并探讨了该液膜体系分离Sc(Ⅲ)、Fe(Ⅲ)和Lu(Ⅲ)的可能性,结果表明,该体系对于稀土矿中Sc(Ⅲ)的分离与分析有良好的应用前景。  相似文献   
999.
A copper(Ⅱ) complex [Cu2(m-MBA)4(2,2′-bipy)2(H2O)]·H2O with m-methylbenzoic acid (m-MBA), 2,2′-bipyridine (2,2′-bipy) and water molecule has been synthesized by means of hydrothermal way and characterized. Crystal data for this complex: monoclinic, space group C2/c, a=2.591 8(5) nm, b=1.414 2(3) nm, c=1.790 8(4) nm, β=131.80(3)°, V=4.893 3(17) nm3, Dc=1.379 g·cm-3, Z=4, F(000)=2 104 , Final GooF=1.034, R1=0.065 6, wR2=0.197 6. The crystal structure shows that two neighboring copper(Ⅱ) ions are linked together by two bridging-chelating m-methylbenzoic acid groups, one bridging water molecule, forming a cage structure and the Cu(Ⅱ)-Cu(Ⅱ) bond distance is 0.366 7 nm. Each copper(Ⅱ) ion is coordinated with two nitrogen atoms of one 2,2′-bipyridine molecule and four oxygen atoms from three m-methylbenzoic acid molecules and one water molecule, repectiveley, forming a distorted octahedral coordination geometry. The cyclic voltammetric behavior of the Complex was also investigated. CCDC: 648619.  相似文献   
1000.
Pt微粒修饰纳米纤维聚苯胺电极对甲醇氧化电催化   总被引:9,自引:0,他引:9  
以脉冲电流法制备的纳米纤维状聚苯胺(PANI)为Pt催化剂载体,用它制备了甲醇阳极氧化的催化电极Pt/(nano-fibular PANI).研究结果表明, Pt/(nano-fibular PANI)电极对甲醇氧化具有很好的电催化活性,并有协同催化作用.在相同的Pt载量条件下, Pt/(nano-fibular PANI)电极比Pt微粒修饰的颗粒状聚苯胺电极Pt/(granular PANI)具有更好的电催化活性.此外, Pt的电沉积修饰方法同样影响Pt/(nano-fibular PANI)电极对甲醇氧化的催化活性.脉冲电流法沉积Pt形成的复合电极较循环伏安法电沉积得到的Pt复合电极具有更优异的催化活性.  相似文献   
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