基于甲基三苯乙炔基硅烷的新型聚三唑树脂的制备与性能

首先采用格氏试剂法合成了甲基三苯乙炔基硅烷(MTPES),通过傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1 H-NMR)对其结构进行了表征。然后以MTPES和4,4’-二叠氮甲基联苯(BAMBP)为原料制备了新型聚三唑树脂(MPTA)。利用FT-IR和差示扫描量热(DSC)研究了MPTA树脂的固化行为,通过动态力学热分析(DMA)和热重分析(TG)研究了炔基与叠氮基配比对树脂热性能的影响,并通过测试凝胶时间随贮存时间的变化研究了树脂及其四氢呋喃(THF)溶液的贮存稳定性。结果表明,固化后的树脂玻璃化转变温度(Tg)达到236℃,在氮气中的5%热失重温度(T_(d5))在320℃左右。MPTA树脂在35℃和25℃下分别贮存7d和20d后,100℃下树脂的凝胶时间分别为40min和25min,MPTA树脂的THF溶液在同样条件下贮存28d后,凝胶时间分别为54min和61min,具有比现有聚三唑树脂更好的贮存稳定性。单向T700碳纤维-MPTA复合材料常温下的弯曲强度为1 660 MPa,弯曲模量为129 GPa,150℃下的弯曲强度保留率为70%。     

血管紧张素转换酶与抑制肽结合模式的分子动力学研究

应用分子模拟方法研究了血管紧张素转换酶(Angiotensin-converting enzyme,ACE)C端结构域(C-domain)与两种抑制肽(RIGLF/AHEPVK)的结合机制,预测了两个体系的结合模式,提出在C-domain-RIGLF中His353,Asp377,Asp453,Phe457,His513,Tyr523和Phe527为RIGLF主要结合残基,而在C-domainAHEPVK中Gln281,His353,Ser355,Glu384,Lys511,His513和Tyr523等残基起关键作用.应用结合自由能计算比较了两个体系的结合能力,结果表明,RIGLF和AHEPVK均与C-domain活性位点残基存在较强作用,且AHEPVK对C-domain的结合能力较强,与实验结果一致.     

N_2-DART-Orbitrap中的特征气相离子反应及在西药快速检测中的应用

采用实时直接分析(DART)离子源串联高分辨质谱Orbitrap技术(DART-Orbitrap MS),对8种市售常见西药进行有效成分分析,建立了一种快速、简便、准确测定西药中有效成分的方法.对DART离子源的离子化温度、扫描模式、操作气体种类、辅助溶剂种类及其酸碱性等实验条件进行了优化,得到最佳实验条件.实验结果表明,正谱条件下,采用N_2气作为操作气体时,待测组分准分子离子峰[M+H]+同样具有较高的灵敏度和谱图辨识度.因此,N2气可以替代昂贵的He气作为DART离子源的操作气体用于8种药物有效成分的现场实时检测.该方法具备成本低、快速和操作简便的特点.通过分析待测组分的特征碎片离子,发现了N2-DART离子源中的特征离子反应,包括氧化反应和重排反应.根据获得的特征碎片离子对N_2-DART-MS中发生的反应机理进行推导,并结合理论计算对其进行验证.N_2-DART-MS技术有望应用于复杂基质混合物的现场快速检测中.     

膨胀石墨/聚苯胺/Fe_3O_4复合材料的制备及吸波性能

采用原位聚合方法制备了膨胀石墨/聚苯胺(EG/PANI)复合材料,将Fe_3O_4负载于EG/PANI表面,得到具有电磁吸收性能的EG/PANI/Fe_3O_4复合材料.通过扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)及矢量网络分析仪(VNA)等对复合材料的形貌、成分和吸波性能进行了研究.吸波性能分析结果表明,当掺杂浓度为0.05 mol/L,匹配厚度d=2 mm时,样品的最小反射损耗(RLmin)在8.64 GHz处达到-37 dB.随着掺杂浓度的增加,最小反射损耗峰向低频移动,对应的匹配厚度逐渐变厚.材料的介电弛豫极化、涡流损耗及λ/4模型的干涉相消现象出现的双峰,使EG/PANI/Fe_3O_4复合材料在电磁波吸收领域有一定的应用前景.     

N-脒基脲二硝酰胺盐晶体形貌的分子动力学研究

采用分子动力学方法,在正侧(NVT)系综下研究了N-脒基脲二硝酰胺盐(FOX-12)在溶剂中的晶体形貌.通过构建溶剂分子层-晶面的界面吸附模型模拟其动力学平衡构型,计算溶剂与晶体表面间的结合能,进而对真空附着能进行修正并获得溶剂条件下的晶貌.使用自然冷却法在水和水/甲醇中培养FOX-12晶体并利用扫描电子显微镜进行了表征.结果表明,在真空条件下决定FOX-12晶貌的6个重要晶面为(110),(200),(201),(011),(002)和(111);FOX-12在水溶液条件下的主要晶面为(110)和(011),在水/甲醇溶液条件下的主要晶面为(200)和(011),预测的晶体形貌与实验结果相吻合.对水分子和FOX-12的(110)面间的径向分布函数进行了计算,分析了水分子和晶面间的分子间作用力.     

ZSM-5分子筛催化甲醇制汽油反应中的晶粒粒径效应研究

通过调控水热合成ZSM-5凝胶液中H_2O/Si物质的量比,实现了粒径为70、200、400和650 nm四种单分散ZSM-5的可控合成。采用XRD、TEM、BET和NH_3-TPD等多种表征对其微观结构进行分析,结合催化性能评价,考察了晶粒粒径对其催化甲醇制汽油反应性能的影响机制。结果表明,整体上随着ZSM-5晶粒粒径的增加,其外比表面积减小,结晶度提高,酸量呈现出先增加后基本不变的趋势。但外表面附着小晶粒的粒径为650 nm的分子筛体现出了大的外表面积和强的酸性。ZSM-5晶粒粒径的增加整体上降低了其催化MTG反应的寿命和最高收率。晶粒粒径为70 nm时,ZSM-5体现出了96 h的催化寿命和30.8%的最高收率。晶粒粒径为650 nm样品由于其大的外比表面积和较强的表面酸性,也体现出91 h的寿命。在大晶粒ZSM-5外表面附着生长小晶粒ZSM-5,是一种制备高性能催化剂的新方法。     

超高效液相色谱-串联质谱法鉴定猪肉的特异性肽生物标志物

以亲缘关系较近的猪、牛和羊3个物种的肌肉组织为研究对象,采用超高效液相色谱-串联质谱(UPLC-MS),筛选并确认了猪物种肉特异性肽生物标志物.3种纯肉样品经蛋白质提取、胰蛋白酶消化和UPLC-TripleTOF-MS分离鉴定,得到的总离子流图谱(TIC)与Uniprot蛋白质数据库对比分析,筛选出3个物种肉的3种高丰度同源蛋白和8种潜在的肽生物标志物;潜在的肽生物标志物经QTRAP-MS质谱的多反应模式(MRM)分析,最终确认了猪物种肉的5种肽生物标志物,其中3种肽生物标志物未见文献报道.     

Exploring Si/Mg composite supported Ziegler-Natta Ti-based catalysts for propylene polymerization

A series of(Si_O2/MgO/ID/MgCl_2)·TiClx Ziegler-Natta catalysts for propylene polymerization has been prepared with a new method. These catalysts were synthesized using soluble Mg-compounds as the Mg-source and the preparation progress was relatively simple. The catalyst could copy the spherical shape of the carrier very well. The propylene polymerization results showed that the catalyst revealed the best activity with 9,9-di(methoxymethyl)fluorene(BMMF) as internal donor at 50 °C with the optimal molar ratio Al/Ti = 5, which was much lower than what the industrial polypropylene catalyst used(at least molar ratio Al/Ti = 100), resulting in great cost saving. Additionally, the polymerization kinetics of the catalyst exhibited very stable property after achieving a relatively high value. These catalysts possessed rather high activity and good hydrogen response. The isotactic index(Ⅱ.) value of the PP products could be higher than 98% in the presence of both internal and external electron donors. Moreover, temperature rising elution fractionation method was used to understand the influence of donors and H2 on the properties of the PP products.     

Low Temperature Catalytic Hydrolysis of Carbon Disulfide on Activated Carbon Fibers Modified by Non-thermal Plasma

In order to improve the carbon disulfide (CS₂) catalytic hydrolysis efficiency of activated carbon fibers (ACFs), ACFs surface was modified by non-thermal plasma (NTP). In particular, the effects of modification conditions on the catalyst properties were studied, including the reactor structure, modification atmosphere, modification time, output voltage and discharge gap. The catalytic activity study showed that ACFs with NTP modification enhanced CS₂ catalytic hydrolysis. The optimal reactor structure, modification atmosphere, modification time, output voltage and discharge gap was a coaxial cylinder, an N₂ atmosphere, 5 min, 7 kV and 7.5 mm, respectively. The effect of the NTP modification on the micro-structural properties of the ACFs was characterized using scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) and X-ray photoelectron spectroscopy (XPS) methods. The results showed that NTP modification improved the dispersion of functional groups and increased the number of oxygen-containing and nitrogen-containing functional groups, thus the catalytic activity could be enhanced. The present results indicated that NTP modification was an effective way to manipulate ACFs surface properties for the CS₂ catalytic hydrolysis reaction.     

Effects of precipitants and surfactants on catalytic activity of Pd/CeO<Subscript>2</Subscript> for CO oxidation

A series of precipitants and commercial surfactants (soft templates) were employed to synthesize mesoporous/nano CeO₂ by a hydrothermal method. As-prepared CeO₂ was impregnated with palladium and employed for low-temperature catalytic oxidation of CO. It was found that both soft templates and precipitants had significant effects on the morphology, particle size, crystallinity, and porous structure of the CeO₂, having a significant effect on the surface palladium abundance, molar ratios of surface species, and catalytic activity of the final impregnated Pd/CeO₂. Using ammonia as precipitant could facilitate increased surface palladium abundance and surface molar ratios of PdO/Pd _SMSI , Ce³⁺/(Ce³⁺ + Ce⁴⁺), and O_surface/O_lattice. The catalytic activity of the final Pd/CeO₂ catalysts could be enhanced as well. The optimal P123-assisted ammonia-precipitated Pd/CeO₂ catalyst exhibited over 99% catalytic conversion of CO at 50 °C.