共查询到19条相似文献,搜索用时 140 毫秒
1.
2.
《精细化工》2017,(5)
以5,10,15,20-四苯基卟啉(TPP)为原料,用硝酸铜硝化法合成了β-NO_2-TPP及其铜配合物(β-NO_2-CuTPP),经还原反应制备了β-NH_2-TPP及其铜配合物(β-NH_2-CuTPP)。当n(Cu-TPP)∶n[Cu(NO3)2]=1∶1时,40℃下,β-NO_2-CuTPP的产率为83.2%;当n(SnCl_2)∶n(β-NO_2-TPP)=1∶1时,65℃下,β-NH_2-TPP的产率为68.0%。通过MS、1HNMR、UV-Vis和IR对所合成化合物进行了表征,考察了其紫外和荧光光谱性质。结果表明:与TPP相比,UV-Vis光谱中,β-NO_2-TPP、β-NH_2-TPP、β-NO_2-CuTPP和β-NH_2-CuTPP的Q带吸收峰有4~19nm的红移;荧光光谱中,相对于TPP,β-NH_2-TPP的最大发射峰红移了4 nm,β-NO_2-TPP的两个发射峰则分别红移1 nm和蓝移27 nm,β-NO_2-CuTPP和β-NH_2-CuTPP发生了荧光淬灭;当溶剂从甲苯变为二氯甲烷、氯仿和乙腈时,β-NH_2-TPP的荧光发射波长从656 nm变为655、656和654 nm,相对于溶剂极性的增大,未显示出明显的变化。但β-NH_2-TPP的荧光量子产率则从0.359 7增加到了0.668 1,0.719 0和1.084 7。卟啉化合物产生单线态氧降解1,3-二苯基异苯并呋喃(DPBF)实验结果表明:在25 min时,β-NH_2-TPP和TPP使DPBF的降解率分别达到了27%和23%,说明β-NH_2-TPP产生单线态氧的能力明显优于TPP。 相似文献
3.
4.
卟啉化合物是一类具有共面的18π电子共轭大环体系化合物,其卟啉环上可引入各类取代基,并能与多种金属配位。设计合成了3种带有不同取代基的甲基丙烯酰氧基修饰的尾式卟啉配体,并以有机金属盐法、苯甲腈法合成了与其对应的金属锌、铂配合物。通过红外光谱、核磁共振氢谱和UV-Vis光谱等对卟啉化合物的结构进行表征,证实了所合成的化合物为目标产物,并系统研究了卟啉化合物在二氯甲烷溶剂中的荧光性质与电化学性质。实验结果表明,通过改变卟啉苯环上取代基的种类及中心金属配位,可以对卟啉化合物的光学性质和电化学性质产生明显的影响。 相似文献
5.
四苯基卟吩的合成及其在光电化电池中的应用 总被引:2,自引:1,他引:2
四苯基卟吩(meso-tetraphenylporphin,TPP)是结构很对称的大共轭分子,在卟啉类中是比较稳定的,耐酸碱和日晒,光牢度达八级。它是高度着色的,主要吸收带有很高的消光系数(ε>10~5),靠近400毫微米的强Soret吸收带是大环共轭(18~22个π电子)的特征吸收谱带。用TPP作原料还 相似文献
6.
文章对基础有机化学中的邻基参与和超共轭效应进行了辨析,厘清了邻基参与和超共轭效应的关系。在有机化学反应过程中,邻基通过未共用电子对或带负电荷的原子或原子团,或含有π键的双键和苯基等参与反应,形成过渡态或中间体促进反应的发生。而超共轭效应实质上是邻基参与的一种类型,它是通过σ,?共轭效应来体现。 相似文献
7.
卟啉与金属卟啉的光电导性能研究 总被引:5,自引:1,他引:4
以苯甲醛和吡咯为原料,丙酸和硝基苯为溶剂,合成了四苯基卟啉(TPP),收率达29.8%。TPP与金属ZnCo、Mn盐合成相应的金属卟啉配合物,收率>90%。用核磁和质谱对化合物结构进行了表征。紫外-可见吸收光谱分析结果表明,TPP有强的Soret吸收带和四个Q带,形成金属卟啉后,Q带减少至两个,且Soret带红移。X射线衍射光谱分析显示,TPP和四苯基金属卟啉粉末均有较高的结晶度。分别以这些卟啉化合物为电荷产生材料,制备了功能分离型双层光电导体,并对它们的光电导性能进行了研究。结果表明,四苯基锌、钴卟啉配合物的光敏性明显优于TPP,其光敏度(E2/3)分别为11和10lx·s。 相似文献
8.
介绍了一种判断有机化合物酸性强弱的教学方法,将化合物共轭碱的稳定性作为化合物酸性强弱的判断标准,共轭碱越稳定,对应化合物酸性越强.共轭碱的稳定性则结合诱导效应、共轭效应、空间效应、场效应、氢键作用、芳香性等理论来判断.以习题的形式展示了这些理论在判断共轭碱稳定性中的应用,论文内容能为该知识点的教学及有机化学初学者提供参... 相似文献
9.
10.
11.
Mandy Großgarten Matthias Holzlechner Antje Vennemann Anna Balbekova Karin Wieland Michael Sperling Bernhard Lendl Martina Marchetti-Deschmann Uwe Karst Martin Wiemann 《Particle and fibre toxicology》2018,15(1):31
Background
The well-known inflammatory and fibrogenic changes of the lung upon crystalline silica are accompanied by early changes of the phospholipid composition (PLC) as detected in broncho-alveolar lavage fluid (BALF). Amorphous silica nanoparticles (NPs) evoke transient lung inflammation, but their effect on PLC is unknown. Here, we compared effects of unmodified and phosphonated amorphous silica NP and describe, for the first time, local changes of the PLC with innovative bioimaging tools.Methods
Unmodified (SiO2-n), 3-(trihydroxysilyl) propyl methylphosphonate coated SiO2-n (SiO2-p) as well as a fluorescent surrogate of SiO2-n (SiO2-FITC) nanoparticles were used in this study. In vitro toxicity was tested with NR8383 alveolar macrophages. Rats were intratracheally instilled with SiO2-n, SiO2-p, or SiO2-FITC, and effects on lungs were analyzed after 3 days. BALF from the right lung was analyzed for inflammatory markers. Cryo-sections of the left lung were subjected to fluorescence microscopy and PLC analyses by matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MS), Fourier transform infrared microspectroscopy (FT-IR), and tandem mass spectrometry (MS/MS) experiments.Results
Compared to SiO2-p, SiO2-n NPs were more cytotoxic to macrophages in vitro and more inflammatory in the rat lung, as reflected by increased concentration of neutrophils and protein in BALF. Fluorescence microscopy revealed a typical patchy distribution of SiO2-FITC located within the lung parenchyma and alveolar macrophages. Superimposable to this particle distribution, SiO2-FITC elicited local increases of phosphatidylglycerol (PG) and phosphatidylinositol (PI), whereas phoshatidylserine (PS) and signals from triacylgyceride (TAG) were decreased in the same areas. No such changes were found in lungs treated with SiO2-p or particle-free instillation fluid.Conclusions
Phosphonate coating mitigates effects of silica NP in the lung and abolishes their locally induced changes in PLC pattern. Bioimaging methods based on MALDI-MS may become a useful tool to investigate the mode of action of NPs in tissues.12.
利用醋酸锶与四苯基卟啉反应,合成了四苯基卟啉锶配合物。利用元素分析、红外、核磁共振等对该配合物进行了结构表征。采用紫外-可见吸收光谱、荧光光谱和循环伏安法研究了该配合物的光电性能。四苯基卟啉锶配合物紫外-可见吸收光谱有一个强的吸收峰和一个次强的吸收峰,分别为428、457 nm。荧光光谱有一个强的发射峰和一个弱的发射峰,分别为610、676 nm。循环伏安法测得其氧化峰电位为1.558 V和1.051 V。与四苯基卟啉相比,四苯基卟啉锶紫外吸收发生红移,而荧光发射发生蓝移。 相似文献
13.
Pengwei Jin Ju Chu Yu Miao Jun Tan Siliang Zhang Weihong Zhu 《American Institute of Chemical Engineers》2013,59(8):2743-2752
Microbioreactors with multioptical sensors have become increasingly important because of their small working volumes, high degree of parallelization and the available robotics. A novel hydrophobic luminescent copolymer P(Pt‐TPP‐TFEMA) along with reference P(Pt‐TPP‐EMA) containing the pendant group of 5,10,15,20‐tetraphenylporphyrin (TPP) moiety as low‐cost dissolved oxygen (DO) chemosensor film for high‐throughput microbioreactors is designed. Its sensor film exhibits fast response to DO with good stability and fatigue resistance, being capable of applying as a low‐cost DO indicator for high‐throughput bioprocess measurement. Results show that the quenching response of DO increases with the enhancement in the copolymeric hydrophobicity using the presented hybrid fluorinated ethyl methacrylate. Furthermore, the long emission band at 650 nm of chromophore TPP with large Stoke's shift about 250 nm brings several advantages, such as low scattering, deep penetration, and minimal interferences of absorption and fluorescence from the fermentation system, which shows high‐promising application in bioprocess monitoring. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2743–2752, 2013 相似文献
14.
Meijiang LI Rui HUANG Changzhi WU Hujin ZUO Guoqiao LAI Yongjia SHEN 《Frontiers of Chemical Science and Engineering》2011,5(4):422-428
Two donor-σ-acceptor molecular systems incorporating tetrathiafulvalene (TTF) and tetraphenylporphyrin (TPP) units, TTF-TPP (dyad 1 ) and TTF-TPP-TTF (triad 2 ), were synthesized. Both dyad 1 and triad 2 and their synthetic intermediates have been characterized by 1H nuclear magnetic resonance (1H NMR) and mass spectrography (MS). Their ultraviolet and visible spectroscopy (UV-Vis) and cyclic voltammetry (CV) showed negligible intramolecular charge transfer interaction in their ground states. Their fluorescence intensity was strongly quenched compared with TPP, which implied the photoinduced electron transfer occurred from the TTF unit to the TPP unit in the excited state. On the other hand, their fluorescence intensity could be modulated by sequential oxidation of the TTF unit using chemical methods, which exhibited their potential application in fluorescence molecular switch. 相似文献
15.
16.
在假一级条件下,以亚碘酰苯为氧化剂,通过测定β-未取代的四苯基卟啉(TPP),以及不同β-取代的β-Cl8TPP、β-Br8TPP、β-Br4TPP、β-NO2TPP、β-(CH3)8TPP及其金属锰配合物的氧化破坏反应的表观动力学常数,获得了卟啉配体的稳定性顺序为TPP>β-(CH3)8TPP>β-Br8TPP>β-Cl8TPP>β-Br4TPP>β-NO2TPP,β位位阻越大相应的卟啉配体越稳定,并由此推导PhIO由β位进攻卟啉配体。β-取代锰卟啉的稳定性顺序为:Mn(β-Cl8TPP)Cl>Mn(β-Br8TPP)Cl>Mn(β-Br4TPP)Cl>Mn(β-NO2TPP)Cl>Mn(TPP)Cl>Mn[β-(CH3)8TPP]Cl,并与在催化氧化环己烷反应中的稳定性一致,β位吸电子作用越大相应的锰卟啉越稳定,并推导由氧化能力更强的高价金属-氧中间体以位阻较小的面对面方式进攻β-取代锰卟啉。 相似文献
17.
对苯并吡喃-2-酮-6-基-4-烷氧基苯甲酸酯(1-n)的烷基链进行化学修饰,引入了不对称碳原子,合成了苯并吡喃-2-酮-6-基-4(S)-烷氧基苯甲酸酯(2 H-chromen-2-on-6-yl 4-(S)-alkoxy-benzo-ates,1-n*)化合物。研究了化合物1-n*的液晶性和凝胶性能。与化合物1-n相比,长碳链的化合物1-n*显示近晶A相。化合物1-n*能够同多种有机溶剂形成凝胶,测试了在各种溶剂中的临界凝胶浓度。扫描电子显微镜观察结果表明,干凝胶呈纤维状三维网络结构,化合物1-7*的凝胶纤维呈右旋结构,化合物1-8*的凝胶纤维则呈左旋结构与已报道的凝胶剂相比,凝胶剂1-n*具有化学结构简单、相对分子质量小、内酯骨架形状宽度大和偶极矩大的特点,偶极作用在增强凝胶性能方面起到重要的作用。 相似文献
18.
《Carbon》2013
Two graphene oxide (GO)-based nanohybrid materials possessing covalent linkages to axially-coordinated tetraphenylporphyrin (TPP), GO–TPP, were prepared and were characterized by Fourier transform infrared (FT-IR), Ultraviolet–visible (UV–Vis) absorption, steady state fluorescence, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), thermogravimetric analysis (TGA), elemental analysis and Raman spectroscopic techniques. The nonlinear optical properties and optical limiting performance of GO, GO–TPP nanohybrids and the free porphyrins dihydroxotin(IV) tetraphenylporphyrin (SnTPP) and the phosphorus-cored porphyrin (PTPP) were investigated using nanosecond and picosecond Z-scan measurements at 532 nm. At the identical mass concentration of 0.2 mg mL−1, GO–TPP nanohybrids exhibited enhanced nonlinear optical properties and optical limiting performance, ascribed to a combination of nonlinear scattering and/or two-photon absorption with reverse saturable absorption, and the photo-induced electron or energy transfer from the electron-donor porphyrin moiety to the acceptor graphene. 相似文献