改性纳米炭黑/聚氨酯复合物的制备及表征

利用有机硅偶联剂改性的纳米炭黑和聚氨酯制备了纳米炭黑/聚氨酯复合物. 采用红外光谱、透射电镜、流变学及力学性能等测试方法对纳米粒子及其聚氨酯复合物进行了表征. 红外光谱表明, 纳米粒子的存在使聚氨酯的氢键结构发生了改变. 适量改性纳米炭黑粒子明显提高了聚氨酯的拉伸强度和断裂伸长率等力学性能. 流变学测试结果表明, 溶液中改性纳米炭黑粒子与聚氨酯分子间存在明显的相互作用.     

聚乙二醇基质中纳米乙酰丙酮铽的荧光特性研究

在高分子聚乙二醇基质中制得了纳米乙酰丙酮铽的络合物并对其荧光特性进行了研究。结果表明,纳米乙酰丙酮铽的荧光光谱在峰位、峰形、峰强和主峰的半高宽等方面都与普通乙酰丙酮铽有明显差别。     

铽-乙酰丙酮螯合物的荧光——铽的荧光光度测定

乙酰丙酮(AA)早已用作稀土的萃取剂,以及Tb-AA-EDTA异配络合物的荧光研究。但关于Tb-AA螯合物荧光性质的研究仍未见报导。我们发现于pH8-8.5,Tb-AA螯合物在301nm波长光的激发下,于540nm发射出很强的铽的特征荧光。因此,我们对Tb-AA螯合物的荧光性质进行了系统地研究,拟订了稀土氧化物中微量氧化铽的荧光光度测定法。试剂及仪器:乙酰丙酮溶液,0.025M;pH8.5的HAc-NH_4OH缓冲溶液;铽标准溶液用光谱纯Tb_4O_7配制。     

有机金属催化剂对脂肪族聚氨酯树脂储存稳定性的影响

以聚己二酸乙二醇丁二醇酯(PBGA)为软段,异佛尔酮二异氰酸酯(IPDI)、1,4-丁二醇(BDO)和异佛尔酮二胺(IPDA)为硬段,分别采用辛酸亚锡、二月桂酸二丁基锡、MB 20、BiCAT Zn、乙酰丙酮锆、乙酰丙酮镍、新癸酸钕和新癸酸铈8种有机金属催化剂,合成弱溶剂体系的脂肪族聚氨酯树脂.采用FTIR和GPC研究了聚氨酯树脂的合成;采用机械性能测试仪对聚氨酯弹性体膜进行了机械性能测试;通过高温储存实验,考察了有机金属催化剂对聚氨酯树脂储存稳定性的影响;采用FTIR、GPC和1H-NMR等技术研究了聚氨酯树脂的降解机理.结果表明,不同金属离子催化剂对聚氨酯的合成及其储存稳定性有显著影响;树脂在高温储存过程中的黏度降低是聚氨酯分子链结构中的酯基发生醇解,进而导致分子量降低,弹性体机械性能下降.     

铕(Ⅲ)、铽(Ⅲ) β-二酮配合物的制备及表征

醋酸铕、醋酸铽分别与乙酰丙酮在60°C水浴下加热回流,生成两种稀土β-二酮配合物,即乙酰丙酮铕(Eu(acac)3?3H2O)和乙酰丙酮铽(Tb(acac)3?3H2O),在紫外灯下观察配合物发光现象,乙酰丙酮铕在紫外灯下显暗红色,乙酰丙酮铽在紫外灯下显亮绿色。红外分析结果与理论相吻合,荧光分析表明它们是较好的荧光材料,热分析结果说明它们的热稳定性相对较高。     

X射线不透性体温固化聚氨酯髓核假体材料的研究

为了制备X光可显影且可以体温固化的聚氨酯,合成了N,N'-双(1,3-二羟基丙基)-2,3,5,6-四碘对苯二甲酰胺(BDTIP)含碘四元醇,将其作为聚氨酯固化的交联剂和X光显影剂,与聚氨酯预聚物混合反应得到一种新的可用于人工髓核假体的材料.利用红外光谱监测BDTIP的反应程度;利用X射线对不同BDTIP含量的聚氨酯材料的显影效果进行评定;利用噻唑蓝(MTT)比色法测试材料细胞毒性,并对具有不同碘含量聚氨酯材料的力学性能进行了对比研究.结果表明,碘的加入对聚氨酯的显影效果有很好的促进作用,较低碘含量(0.2 wt%)的聚氨酯材料即有较好的X光显影效果,而且此时聚氨酯依然保持较好的力学性能;MTT法测试表明含BDTIP的聚氨酯材料不具有细胞毒性.     

合成反应的加料方式对多嵌段聚醚聚氨酯动态力学性能的影响

本文研究了在溶液聚合两步法制备多嵌段聚醚聚氨酯(SPEU)过程中,两种不同的加料方式对SPEU动态力学性能的影响。实验结果表明:在反应物组成、配比相同条件下,采用先将聚醚溶液滴加入到4,4′-二苯基于烷二异氰酸酯(MDI)的溶液中,俟反应完成后再滴加入扩链剂的加料方式制得的SPEU,比采用由MDI溶液先向聚醚溶液中滴加,再加入扩链剂所制得的SPEU有较高的微相分离程度。     

一种X-射线不透性聚氨酯显影材料的制备及性能研究

利用对碘苯胺对含有过量异氰酸根的聚氨酯分子进行封端,合成了一种新型的X-射线不透性聚氨酯显影材料.利用X-射线映射对不同封端量聚氨酯的显影效果进行评定;利用DSC和TGA对其热性能进行表征,并评估封端反应对聚氨酯热稳定性的影响;利用噻唑蓝(MTT)比色法测试了材料的细胞毒性;并对具有不同碘含量聚氨酯材料的显影效果、相对分子量及其分布、力学性能进行了对比研究.研究结果表明,当碘含量达到3.5wt%左右时聚氨酯材料即可达到同等厚度铝板相同的显影效果,而且在此条件下,聚氨酯材料依然保持较好的力学性能和热稳定性.MTT法测试表明对碘苯胺封端的聚氨酯材料不具有细胞毒性.     

新型网状超分子聚氨酯的制备与表征

以端基为并氰酸酯基团的聚氨酯预聚物为基体与端基为氨基的2-脲-4[H]-嘧啶酮(UPy)反应合成了线性超分子聚氨酯(HP1400-UPy),同时将端氨基聚醚T5000与端基为异氰酸酯基团的UPy反应获得T5000-UPy,然后将HP1400-UPy和T5000-UPy以不同配比共混制得一系列超分子网状结构聚氨酯.利用FT-IR、1H-NMR、TGA、DMA和力学性能测试等手段对该聚氨酯的结构和性能进行了表征.结果表明:T5000-UPy的加入对聚合物的热稳定性影响不大,却能使其断裂强度与断裂伸长率有较大的提高,且T5000-UPy量少时提高更为显著.随着T5000-UPy的加入量增加,生成的超分子网状结构聚氨酯交联密度增大,链段运动难度增加,内耗减少,储能模量增大,从玻璃态向高弹态转变的温度向高温方向移动.     

有机硅改性聚氨酯/纳米SiO2复合超疏水涂层的制备

以4,4'-二苯基甲烷二异氰酸酯(MDI)、聚四氢呋喃醚二醇(PTMEG)、羟基封端的聚二甲基硅氧烷(HO-PDMS)、1,4-丁二醇(BDO)为原料,合成了有机硅改性的聚氨酯溶液,通过核磁共振、红外光谱技术对其结构进行表征,并研究了羟基硅油加入量对聚氨酯热稳定性、疏水性的影响.以有机硅改性的聚氨酯溶液为基体、含氟硅烷偶联剂改性的纳米二氧化硅颗粒为填料,喷涂制备超疏水涂层,研究了填料添加量对复合涂层疏水性的影响.结果表明:当硅油加入量为9 wt%,填料加入量为60 wt%时,复合涂层性能最优,水接触角为153.3°,滞后角为6.3°.经过200℃加热1 h后,仍然具有大于150°的水接触角.对复合涂层进行磨损实验与防冰测试,结果表明:该复合涂层在磨损过程中,在基底暴露之前,整个涂层基体都具有超疏水性;并且该涂层能有效降低结冰温度,延长结冰时间,具有良好的防冰性能.     

环丙沙星铽荧光配合物与DNA的相互作用及染色新方法

合成了环丙沙星铽荧光配合物,并研究其与DNA分子的相互作用.对比DNA分子吸附配合物分子前后的显微红外及荧光光谱发现,以环丙沙星分子为配体的稀土配合物同DNA间存在相互作用,这种作用诱导了DNA二级结构的构象变化.基于这种相互作用,研究了环丙沙星铽配合物对口腔粘膜组织切片的荧光染色,得到了同经典的苏木精-伊红染色法类似的反差效果.     

Spectroscopic study and thermal behavior of trivalent lanthanides and yttrium(III) chelates of EDTA using TG-DSC, FTIR, and TG-DSC coupled to FTIR

Solid-state compounds of yttrium and lanthanide chelates of ethylenediaminetetraacetic acid have been synthesized. Simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC), theoretical and experimental infrared spectroscopy (FTIR), elemental analysis, complexometry and TG-DSC coupled to FTIR were used to characterize and to study the thermal decomposition of these compounds. The results provided information about the composition, dehydration, thermal stability, thermal decomposition and identification of gaseous products evolved during the thermal decomposition of these compounds. The theoretical and experimental spectroscopic data suggest the possible modes of coordination of the ligand with the lanthanum and terbium metal ions.     

Lanthanide-sensitized lanthanide luminescence: terbium-sensitized ytterbium luminescence in a trinuclear complex

A heterotrinuclear lanthanide complex has been prepared which contains two terbium ions in DO3A-derived binding sites and a single ytterbium ion in a DTPA-like site. The luminescence properties of the system have been investigated, showing that the terbium remains in a seven-coordinate binding site throughout the synthesis, while the ytterbium occupies the eight-coordinate site. Pumping the 488 nm absorption band of the terbium ion results in energy transfer to ytterbium with emission at 980 nm.     

Dipicolinic acid (DPA) assay revisited and appraised for spore detection

Delayed gate fluorescence detection of dipicolinic acid (DPA), a universal and specific component of bacterial spores, has been appraised for use in a rapid analytical method for the detection of low concentrations of bacterial spores. DPA was assayed by fluorimetric detection of its chelates with lanthanide metals. The influence of the choice and concentration of lanthanide and buffer ions on the fluorescence assay was studied as well as the effects of pH and temperature. The optimal system quantified the fluorescence of terbium monodipicolinate in a solution of 10 microM terbium chloride buffered with 1 M sodium acetate, pH 5.6 and had a detection limit of 2 nM DPA. This assay allowed the first real-time monitoring of the germination of bacterial spores by continuously quantifying exuded DPA. A detection limit of 10(4) Bacillus subtilis spores ml-1 was reached, representing a substantial improvement over previous rapid tests.     

Luminescent lanthanide-binding peptides: sensitising the excited states of Eu(III) and Tb(III) with a 1,8-naphthalimide-based antenna

The investigation into the luminescence properties of a lanthanide-binding peptide, derived from the Ca-binding loop of the parvalbumin, and modified by incorporating a 1,8-naphthalimide (Naph) chromophore at the N-terminus is described. Here, the Naph is used as a sensitising antenna, which can be excited at lower energy than classical aromatic amino acids, such as tryptophan (the dodecapeptide of which was also synthesised and studied herein). The syntheses of the Naph antenna, its solid phase incorporation into the dodecapeptide, and the NMR investigation into the formation of the corresponding lanthanide complexes in solution is presented. We also show that this Naph antenna can be successfully employed to sensitize the excited states of both europium and terbium ions, the results of which was used to determined the stability constants of their formation complexes, and we demonstrated that our peptide 'loop' can selectively bind these lanthanide ions over Ca(II).     

Lanthanide complexes of DOTA monoamide derivatives bearing an isophthalate pendent arm

An isophthalate-bearing DOTA monoamide derivative has been synthesised and used to prepare a family of lanthanide complexes. Luminescence and NMR studies in solution show that the predominant form of the complexes in solution is a mono-capped square antiprism about the lanthanide centre, in which a solvent molecule occupies the ninth coordination site. The crystal structure of the terbium complex is presented and is in close agreement with the solution state data.     

稀土等离子与铁生物调控

本文在简介转铁蛋白、转铁蛋白受体的铁（Ⅲ）调控作用研究进展的基础上,综述了稀土离子、镓与转铁蛋白的作用及稀土离子、镓代谢与铁（Ⅲ）调控系统的关系。     

Photochromic Terbium Phosphonates with Photomodulated Luminescence and Metal Ion Sensitive Detection

Rational selection and modification of rare earth metal centers and photoactive organic linkers enables designable multiphotofunctionality to come to fruition in new hybrid coordination polymer materials. By using a viologen‐functionalized diphosphonate linker, two terbium phosphonate compounds ( Tb‐1 and Tb‐2 ) have been constructed, which display reversible photochromic reactions in response to UV light and soft X‐ray irradiation. In addition, the photo‐induced electron‐transfer reaction can modulate the luminescent emission to thus realize photoluminescence switching behavior. Furthermore, both terbium phosphonates can serve as highly sensitive sensors to probe Cu²⁺ in solution through their luminescence. Thus, they represent the first photochromic examples of lanthanide phosphonate‐based materials with photomodulated luminescence and sensitive detection of metal ions.     

原位复合法制备含铽(Ⅲ)配合物光学树脂及其荧光性质的研究

稀土元素因其独特的电子结构而具有光、电、磁、激光等特性,被誉为新材料的宝库,尤其是稀土配合物具有的Antenna效应,使发光强度明显增强.含稀土的高分子材料既具有稀土离子的发光性能,又具有高分子材料质量轻、抗冲击力强和易加工成型等优点,从而引起广泛的关注.我们曾用直接掺杂法制备含稀土配合物的光学树脂,但因稀土配合物与树脂的亲和性较小,难以均匀地.     

Synthesis,crystal structures and luminescence properties of europium and terbium picolinamide complexes

The novel coordination structures of europium and terbium chloride-picolinamide complexes （EuCl3-（C6H6N2O）2.5H2O, Eu-pa and TbCl3.（C6H6N2O）2.5H2O, Tb-pa） are reported. The crystal structures in the solid state are characterized by X-ray single crystal diffraction, FTIR, Raman, FIR, THz and luminescence spectroscopy. In the crystal structures, the pyridyl nitrogen and carbonyl oxygen atoms in picolinamide are coordinated to the metal ions to form a five-membered ring structure. The experimental results indicate the similar coordination structures of Eu and Tb-pa complexes and the changes of hydrogen bonds and conformation provide models for the coordination structures of the ligands induced by complexation. The results of lanthanide ions with ligands having amide groups.