尼龙6/液晶聚合物共混体系中化学反应对体系热行为及形貌的影响

采用漫反射红外光谱法(DRIFT)和示差扫描量热法(DSC)研究了2种不同特性黏数的尼龙6与3种液晶聚合物(Vectra A950、Vectra B950和Rodrun LC5000)之间的酯-酰胺交换反应.DRIFT测试证实了尼龙6与LC5000之间存在化学反应.DSC分析表明,酯-酰胺交换反应使体系中尼龙6的熔点下降、结晶度降低.增加反应时间和增大共混体系中液晶聚合物的含量有利于酯-酰胺交换反应的发生.与Vectra A950和Vectra B950相比,分子链柔性较强的Rodrun LC5000与尼龙6之间的化学反应更容易进行.扫描电子显微镜(SEM)观察表明,随着共混时间的延长,分散相形貌由球状粒子发展为短棒状纤维,乃至最终形成直径更细的微纤结构.     

二环己基18-冠-6异构体D与十五个稀土硝酸盐配合物的合成及其性质的研究

合成了二环己基18-冠-6-的异构体D与十五个稀土硝酸盐的配合物,系统研究了它们的FOURIER变换红外光谱的变化规律;测定了部分配合物的核磁共振氢谱和碳谱。结果均表明,在稀土系列内离子直径与冠醚穴大小的比例是否合适是影响配合稳定性的主要因素。文中还讨论了配合物中NO3[-]与稀土离子形成接触离子对对红外光谱及核磁共振谱的影响。在NO3[-]v6(B1)中观察到镧系"斜W"规律。基于红外光谱及核磁共振谱的结果,初步讨论了配合物的结构。     

稀土胆酸络合物在凝胶中的周期沉淀现象

在稀土胆酸凝胶扩散体系中观察到了周期沉淀现象，并用红外光谱（ＦＴＩＲ）和扩展Ｘ射线原子精细结构光谱（ＥＸＡＦＳ）对图形沉淀进行了表征。结果表明：稀土离子与胆酸反应容易产生周期沉淀，沉淀的成分与相应的络合物相近。     

生物滤池中生物膜和出水悬浮物的元素分析和红外光谱比较

对生物滤池中不同高度的生物膜和出水悬浮物的碳氢氮三元素和红外光谱进行了分析比较.元素分析结果表明,悬浮物的无机成份比生物膜高.悬浮物和生物膜的红外吸收光谱图主要由蛋白质的吸收带、碳水化合物的吸收带组成.1655 cm-1处的吸收峰为酰胺Ⅰ带,是C=O的伸缩振动,1542 cm-1的吸收峰是酰胺Ⅱ带,是N-H的弯曲振动和C-N的伸缩振动,1240 cm-1是酰胺Ⅲ带,是C-N的伸缩振动和N-H的弯曲振动引起的.1460 cm-1处的吸收峰为CH3和CH2的弯曲振动峰.悬浮物的蛋白质特征峰强度比生物膜低,而1050cm-1处的吸收峰强度比生物膜大.     

尖吻蝮蛇毒抗凝血因子Ⅰ的稀土离子荧光探针研究

稀土离子(Nd3+, Sm3+, Eu3+, Gd3+, Tb3+)对抗凝血因子(ACF Ⅰ)的内源荧光有不同程度的淬灭作用.稀土离子与ACF Ⅰ荧光滴定的结果表明, ACF Ⅰ分子中有两个稀土离子结合位点,稀土离子和钙离子在ACF Ⅰ分子中两个结合位点是共同的竞争结合位点.每个稀土离子与ACF Ⅰ的结合常数K1和K2相接近,说明两个结合位点的结构可能基本一致.不同的稀土离子与ACF Ⅰ之间有相近的结合常数K1或K2,表明ACF Ⅰ分子中的两个结合位点在结构上都有较大的柔性,这种结构柔性为钙离子在ACF Ⅰ与活化凝血因子X的结合反应中所起的激活作用提供了结构基础.     

CL—5709萃淋树脂吸附及分离稀土元素性能的研究(Ⅰ)

CL—5709萃淋树脂是异烷基膦酸(1—甲基庚基)酯萃淋树脂,含5709 50％6。本文报导了该树脂在盐酸体系中对稀土元素的静态分配系数,并与偶氮胂Ⅰ螯合树脂作了比较。讨论了温度、树脂用量、振摇时间对吸附稀土百分率的影响。测定了树脂吸附稀土的饱和容量及树脂的含磷量,并由此确定树脂所含功能基对稀土的配位比。用红外光谱探讨了该萃淋树脂吸附稀土离子的机理。     

尼龙6升温过程的二维红外相关分析研究

通过二维红外相关分析来研究尼龙6在25～200℃范围内酰胺氢键和碳氢链段的结构变化．结果证明,尼龙6中酰胺氢键的吸收峰和主链上亚甲基的伸缩振动对于温度变化所导致的结构变化是十分敏感的,因此可以通过对二维红外相关谱图的分析,确定尼龙6在升温过程中酰胺氢键的解离和碳氢链段结构变化的先后顺序．     

蒽醌与稀土离子间的能量转移研究

分子间或分子内的电子激发态能量转移是重要的初级光化学过程，很多体系电子激发态能量转移过程已经报导[1-3]，对稀土离子和谈基化合物的研究发现，用光激发配体时，激发了的配体可将能量转移给稀土离子，使稀土离子激发到发光能级，可观察到稀土的特征荧光，若稀土离子和谈基     

土壤中腐殖酸与稀土离子作用的傅里叶变换红外光谱

采用NaOH碱提法提取和纯化了黑土中胡敏酸（humic acid,HA)用傅里叶变换红外光谱（FTIR）研究了HA与La^3 、Ce^3 、Cd^3 和Y^3 4种稀土离子作用前后的光谱特征。结果表明,HA与稀土离子作用后的红外光谱中归属于COO^-1600cm^-1、1400cm^-1处的振动吸收峰增强,表明腐殖酸与稀土离子之间发生了配合作用。     

稀土HEH[EHP]固体配合物的红外光谱

本文制备了La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Y等十五种稀土与2-乙基己基膦酸单(2-乙基己基)酯的固体配合物,测定了4000-100cm~(-1)的FT-IR光谱,对其主要红外光谱吸收带进行了归属。指认150cm~(-1)为Ln-O键的伸缩振动带,250cm~(-1)附近的谱带为COPO,CCPO骨架扭曲振动与Ln-O键的耦合振动带。结果表明配合物为多聚体系,PO_2与稀土离子可能为桥式配位形式。Ln-O键基本上为离子键。     

Potential of two-dimensional near-infrared correlation spectroscopy in studies of pre-melting behavior of nylon 12

This review paper discusses the potential of generalized two-dimensional (2D) near-infrared (NIR) correlation spectroscopy in studies of pre-melting behavior and hydrogen bonds of nylon 12. A 2D NIR study on dissociation and hydrogen bonds of N-methylacetamide (NMA) is also reviewed here as a model compound study of nylon 12. Fourier transform (FT)-NIR spectra in the region of 9000–5000 cm⁻¹ of nylon 12 were measured over a temperature range of 30–150°C where gradual weakening of inter- or intramolecular associative interactions and decrease of local order leading to the eventual fusion of nylon 12 crystals are observed. The 2D correlation analysis provided the following conclusions for the pre-melting behavior of nylon 12. (i) There are at least eight bands in the 6800–6100 cm⁻¹ region assignable to free- and hydrogen-bonded NH groups of nylon 12 in various environments. The asynchronous 2D correlation spectrum in the above region indicates that the amide groups with free carbonyl oxygen appear first and then the unassociated free amide and amide groups with free NH follow as the temperature is increased. (ii) The asynchronous spectrum in the 6000–5500 cm⁻¹ region, where the first overtones of the CH₂ stretching modes are expected to appear, indicates that substantial amount of disordered or dissociated components start appearing before the disappearance of more ordered components. It seems that they appear as the pre-melting precursors (or even possibly as the indirect cause) to the precipitous decrease of the ordered components associated with melting of nylon 12 occurring at a much higher temperature.     

Cannizzaro-type disproportionation of aromatic aldehydes to amides and alcohols by using either a stoichiometric amount or a catalytic amount of lanthanide compounds

Aromatic aldehydes can be directly converted to the corresponding amides and alcohols in good to excellent yields by the treatment of aromatic aldehydes with lithium amide LiN(SiMe3)2 in the presence of catalytic lanthanide chlorides LnCl3 or by the treatment of aromatic aldehydes with a stoichiometric amount of lanthanide amides [(Me3Si)2N]3Ln(mu-Cl)Li(THF)3 at ambient temperature. The effects of solvents, substitutents on the phenyl ring, and lanthanide metals on the reaction have been examined. The mechanism of the disproportionation reaction was proposed based on the experimental results.     

油/水界面表面活性剂的复配协同机制

采用耗散颗粒动力学(DPD)方法模拟了椰油酸二乙醇酰胺(6501)分别与十二烷基-α-烯烃磺酸钠(DAOS)、椰油酰胺丙基二甲基甜菜碱(CAB)和十二烷基苯磺酸钠(SDBS)复配体系中表面活性剂在油/水界面的排布行为, 探讨了盐度及分子结构对单一和复配表面活性剂界面活性的影响, 从界面效率、界面密度和分子排布等角度讨论了油水界面表面活性剂混合体系的复配协同增效机制.     

BiI3-nylon11纳米复合材料的XPS及ATR-IR分析

用X射线光电子能谱法（XPS）测定了BiI₃与nylon11作用生成纳米复合材料后聚合物中酰胺基团的N、O内层能级电子结合能变化,同时用衰减全反射红外光谱法（ATR-IR）研究了BiI₃-nylon11复合材料中BiI₃对尼龙酰胺基团之间氢键作用的影响.结果表明,与纯nylon11聚合物相比,BiI₃-nylon11纳米复合材料中N1s、O1s的结合能要稍高一些;N-H伸缩振动、酰胺I谱带、酰胺II谱带振动频率在X射线照射前均发生显著位移,而X射线照射后没有明显的变化,只是谱带变宽.另一方面,无论X射线照射与否,CH₂伸缩振动基本不变.实验所得结果对于理解聚合物中氢键相互作用及其对复合材料的结构和性能的影响有一定意义.     

Facile amidation of esters with aromatic amines promoted by lanthanide tris (amide) complexes

The development of catalysts capable of catalyzing amidation of esters with amines to construct amides under mild conditions is of great importance. Compared to aliphatic amines, the direct catalytic amidation of esters with less nucleophilic aromatic amines is rather difficult. Employing simple lanthanide tris (amide) complexes Ln[N (SiMe₃)₂]₃(μ-Cl)Li (THF)₃ as the catalysts, it was found a broad range of aromatic amines and esters were efficiently converted into various amides in good yields under mild conditions. A plausible mechanism for this transformation was experimentally supported as starting from an amide exchange reaction between the lanthanide tris (amide) complex and the substrate amine.     

Mechanistic insight into the lanthanide(III) salt catalysed monoacylation of symmetrical diols from structural models

Model studies are presented that suggest the mechanism of the lanthanide(III) salt catalysed mono acylation of symmetrical diols proceeds via chelation of the diol and the anhydride to the lanthanide salt, followed by an 'intramolecular' acyl transfer.     

近红外光谱法研究升温导致的尼龙1010结晶区域的变化

采用近红外光谱技术和二维相关分析法研究尼龙1010膜在升温过程中的结构变化. 为了排除非晶区域酰胺基团的影响, 事先对尼龙1010的样品膜进行了氘代, 并测量了其最终氘代率. 结果证明, 尼龙1010的结晶区域在升温过程中被逐渐破坏, 首先是其主链碳氢结构发生调整, 进一步影响到结合酰胺, 导致氢键作用减弱并最后生成自由胺基.     

P?N ligands in lanthanide chemistry

The coordination chemistry of inorganic amides in Group 3 and lanthanide chemistry is discussed. Three different ligand systems (phosphino‐amides, bis(phosphino)amides, and bis(phosphinimino)methanides) that consist of one or more P N units were used. In this series the steric demand of the ligands is increased in a stepwise fashion and the negative charge is delocalized over more atoms. These properties were used in the design of new lanthanide complexes. For all three compounds the synthesis of the alkali metal derivatives is reported first, followed by the reaction of the alkali metal salts with various lanthanide trichlorides. Further reactions of the obtained lanthanide complexes as well as their application as catalysts are discussed. Most of the reported complexes show a dynamic behavior in solution. In phosphinoamide and bis(phosphino)amide complexes, in which the phosphorus atom is in oxidation state +3, there is always a weak coordination of the phosphorus atom to the lanthanide atom observed. In bis(phosphinimino)methanide complexes, in which the phosphorus atom is in oxidation state +5, no such interaction is noticeable. Instead a weak coordination of the methine atom to the center metal can be seen in the solid state. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:514–520, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10096     

Unprecedented 4(2)6(4) topological 2-D rare-earth coordination polymers from a flexible tripodal acid with additional amide groups

Novel lanthanide(III) coordination polymers based on a flexible tripodal ligand with additional amide groups were obtained with interestingly unprecedented four-connected 4(2)6(4) topology from the pyramidal nodes and reversible crystal-to-amorphous transformation properties.     

Green Chemistry and Glycochemistry

With the increasing environmental concerns and the regulatory constraints faced in the chemical and pharmaceutical industries, development of environmentally benign organic reactions (also called Green Chemistry) has become a crucial and demanding research area in modem organic chemical research. Our contribution to this rapidly growing field involves use of certain lanthanide salts such as lanthanide(Ⅲ) trifluoromethanesulfonates as stable Lewis acids in protic solvent such as water or alcohols to catalyze a variety of organic transformations under nearly neutral conditions. This benign approach has the potential to replace many traditional reaction systems which are either conducted in strong acidic conditions or in environmentally less-friendly solvents. For example, aza Diels-Alder (DA) reaction in aqueous solution conveniently combines three reactant components (an aldehyde, an amine salt and a diene) in aqueous solution and generates nitrogen-containing heterocyclic products. However, this reaction is limited to either the smallest aldehyde or activated aldehydes such as glyoxylates. We have found that lanthanide(Ⅲ) triflates catalyze the aza DA reactions of a larger,inactivated aldehyde and an amine hydrochloride with a diene in aqueous solution[1]. Other examples of application of lanthanide triflates in protic solvents include Chicliibabin pyridine synthesis[2],condensation of indoles with aldehydes or ketones[3], and use of ion-exchange resin supported lanthanide catalysts[4].