气相色谱法分析1,3-丁二烯产品中的二聚物及痕量抽提剂含量

利用GC-MS确定了1,3-丁二烯中二聚物的3种存在形态,通过对色谱柱的筛选、分析条件的优化,使用高压液体进样阀与Rtx-200毛细管色谱柱,建立了测定1,3-丁二烯中3种二聚物,3种痕量抽提剂乙腈、N,N-二甲基甲酰胺、N-甲基吡咯烷酮及甲苯等组分的色谱分析方法。实验结果表明,各组分的回收率在86.9%~108.2%之间,6次重复测定的相对标准偏差均小于8.4%,3种抽提剂的检出限均小于1.0 mg/kg,所建立的方法定量结果准确可靠,数据重复性良好,满足工业上对1,3-丁二烯中二聚物和痕量抽提剂杂质的分析需求。     

Oligomerization and Nitration of the Grass Pollen Allergen Phl p 5 by Ozone,Nitrogen Dioxide,and Peroxynitrite: Reaction Products,Kinetics, and Health Effects

The allergenic and inflammatory potential of proteins can be enhanced by chemical modification upon exposure to atmospheric or physiological oxidants. The molecular mechanisms and kinetics of such modifications, however, have not yet been fully resolved. We investigated the oligomerization and nitration of the grass pollen allergen Phl p 5 by ozone (O₃), nitrogen dioxide (NO₂), and peroxynitrite (ONOO^–). Within several hours of exposure to atmospherically relevant concentration levels of O₃ and NO₂, up to 50% of Phl p 5 were converted into protein oligomers, likely by formation of dityrosine cross-links. Assuming that tyrosine residues are the preferential site of nitration, up to 10% of the 12 tyrosine residues per protein monomer were nitrated. For the reaction with peroxynitrite, the largest oligomer mass fractions (up to 50%) were found for equimolar concentrations of peroxynitrite over tyrosine residues. With excess peroxynitrite, the nitration degrees increased up to 40% whereas the oligomer mass fractions decreased to 20%. Our results suggest that protein oligomerization and nitration are competing processes, which is consistent with a two-step mechanism involving a reactive oxygen intermediate (ROI), as observed for other proteins. The modified proteins can promote pro-inflammatory cellular signaling that may contribute to chronic inflammation and allergies in response to air pollution.     

叠氮甲烷二聚体分子间相互作用的abinitio研究

运用ab initio方法,在HF水平6-311G**基组下求得叠氮甲烷二聚体势能面上六种优化构型和电子结构.经MP2电子相关和基组叠加误差(BSSE)以及零点能(ZPE)校正,求得分子间相互作用能;结合能(9.49 kJ*mol-1)最大的二聚体为存在两个CHN氢键的六元环构型,属于D2h群.探讨了甲基内旋转对相互作用能的影响.由自然键轨道(NBO)分析揭示了相互作用的本质.对单体和六种二聚体优化构型进行简谐振动分析,研究了IR光谱变化规律.此外还基于统计热力学求得273.15～800.00 K温度范围从单体形成二聚体的热力学性质变化.     

提高水基聚氨酯树脂凃膜耐水性的研究

对丙酮法合成的水基聚氨酯树脂凃膜耐水性的提高进行了报导。作者选用了硬脂酸单甘脂(GMS)、聚硅氧烷二醇作为小分子扩链剂并以二聚酸聚酯二醇作为软段合成了含有侧链的水基聚氨酯树脂系列、探讨了DMPA用量、聚氨酯侧链结构种类等因素对水基聚氨酯树脂分散体涂膜耐水性的影响。合成出了耐水性更好的水基聚氨酯树脂皮革涂饰剂。     

AKD施胶新工艺应用

以浙江某纸厂生产定量140g／m2的挂面箱纸板为试验研究对象,详细探讨了AKD施胶应用的新工艺配比。试验表明：15％含量的AKD乳液配合阴离子垃圾捕捉剂0．jkg／t纸、助留剂0．4kg／t纸时,其用量仅为6kg／t纸,相比单独用AKD复配中性胶综合成本降低。     

电感耦合等离子体原子发射光谱法测定辛酸铑催化剂中铂钯铅铁铜铝镍

准确测定辛酸铑催化剂中杂质元素含量,是判定产品是否合格的重要指标之一。以往常采用直流电弧发射光谱法(摄谱法)进行检测,但测定周期长,且重复性较差。用电感耦合等离子体原子发射光谱法(ICP-AES)测定辛酸铑催化剂中微量杂质元素时,辛酸铑催化剂样品中含有的大量有机组分和铑基体会对测定有严重干扰。实验采用反复滴加硝酸消解样品中有机组分,再用王水溶解盐类,选用合适背景点扣除的方式消除铑基体的干扰,建立了使用ICP-AES测定辛酸铑催化剂中0.001%~0.1%(质量分数)Pt、Pd、Pb、Fe、Cu、Al、Ni等7种微量杂质元素的方法。各元素在0.10~10.00μg/mL范围内与其发射强度呈线性关系,相关系数均大于0.9999;方法检出限(μg/mL)为0.075(Pt)、0.0033(Pd)、0.015(Pb)、0.0036(Fe)、0.010(Cu)、0.001(Al)、0.012(Ni)。实验方法用于测定辛酸铑催化剂样品中Pt、Pd、Pb、Fe、Cu、Al、Ni,结果的相对标准偏差为(RSD,n=7)为1.4%~9.6%。按照实验方法测定辛酸铑催化剂中Pt、Pd、Pb、Fe、Cu、Al、Ni,并与直流电弧发射光谱法的测定结果进行比对,结果相一致。     

On the Catalytic Activity of Sn Monomers and Dimers at Graphene Edges and the Synchronized Edge Dependence of Diffusing Atoms in Sn Dimers

In this study, in situ transmission electron microscopy is performed to study the interaction between single (monomer) and paired (dimer) Sn atoms at graphene edges. The results reveal that a single Sn atom can catalyze both the growth and etching of graphene by the addition and removal of C atoms respectively. Additionally, the frequencies of the energetically favorable configurations of an Sn atom at a graphene edge, calculated using density functional theory calculations, are compared with experimental observations and are found to be in good agreement. The remarkable dynamic processes of binary atoms (dimers) are also investigated and is the first such study to the best of the knowledge. Dimer diffusion along the graphene edges depends on the graphene edge termination. Atom pairs (dimers) involving an armchair configuration tend to diffuse with a synchronized shuffling (step-wise shift) action, while dimer diffusion at zigzag edge terminations show a strong propensity to collapse the dimer with each atom diffusing in opposite directions (monomer formation). Moreover, the data reveals the role of C feedstock availability on the choice a single Sn atom makes in terms of graphene growth or etching. This study advances the understanding single atom catalytic activity at graphene edges.     

司班-80/二聚酸作为润滑油添加剂的摩擦聚合机制研究

采用盘-销式摩擦试验机,以司班-80/二聚酸体系作润滑油添加剂,在陶瓷-陶瓷(A l2O3-A l2O3)表面进行摩擦磨损实验。采用差示扫描量热法(DSC)探讨了单体在陶瓷表面的吸附类型;采用扫描电子显微镜(SEM)、X射线光电子能谱仪(XPS)、傅立叶红外光谱仪(IR)对盘上磨痕进行表面分析。结果表明添加剂在磨痕处生成了保护性体型聚酯膜。其摩擦聚合机制为:在摩擦过程中,二聚酸以物理吸附的方式吸附在陶瓷表面;由于二聚酸的羧基与司班-80的羟基发生摩擦聚合反应,在陶瓷表面生成体型聚酯膜,从而降低陶瓷表面的磨损。     

基于全电介质复合纳米天线荧光传感器的研究

为了增强量子点的定向发光强度,提出了一种由硅柱二聚体和二氧化钛圆盘组成的复合纳米天线结构。利用时域有限差分方法系统研究了硅柱二聚体的轴参数、截面类型以及复合纳米天线结构对量子点定向发光增强的影响。结果表明,对于中心波长为600nm的量子点,硅柱二聚体的轴参数对量子点的发光影响不大,椭圆形截面的硅柱二聚体可以实现较大的量子点发光增强。此外,在复合纳米天线的作用下,不仅可以获得较大的量子效率增强,还可以实现量子点高度定向的发射效果,量子效率增强约6倍,定向收集效率可以达到50%。