胡椒醛缩合卟啉化合物的合成及其光谱性能

以胡椒醛及羟基芳香醛为原料与吡咯在丙酸中回流,合成了6种卟啉化合物,其结构用1HNMR,IR,UV-V is和ESI-MS确定。与四苯基卟啉(TPP)相比,胡椒醛的引入增大了卟啉环的共轭性,使几种化合物的光学吸收波长均发生不同程度的红移,其中,Soret带最大红移11 nm;同时,胡椒醛的引入缩小了基态与激发态之间的能极差,化合物荧光发射波长发生1~5 nm的红移。     

β-硝基和β-氨基取代卟啉的合成及光谱分析

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。     

萘基卟啉的合成与性能研究

以萘基醛类化合物为原料与吡咯在丙酸中回流合成了3种含萘基的新型卟啉化合物,其中2种化合物尚未见文献报道,其结构通过1H NMR,IR和UV-V is确定。与四苯基卟啉相比,萘基的引入增大了卟啉环的共轭性,使得光学吸收波长与荧光发射波长均发生不同程度的红移,Q带吸收峰形改变且激发波长增长。结合卟啉光谱四轨道理论对该变化进行了讨论。     

系列尾式卟啉化合物的合成及光电性质研究

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。     

四苯基卟吩的合成及其在光电化电池中的应用

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     

有机化学中的邻基参与和超共轭效应之辨析

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。     

卟啉与金属卟啉的光电导性能研究

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。     

有机化合物酸性的教学探讨

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...     

“芘”核化合物合成与单/双光子性能

本文合成了四个"芘"核化合物并进行了结构验证,同时本文还研究了不同"枝"及"枝"数的不同对"芘"核化合物的单、双光子荧光性质的影响。实验结果表明,随着"枝"数增加,共轭度的增加,所得化合物的单、双光子荧光强度明显增强。而在共轭度相同的条件下(共轭度:P-T1=P-B1,P-T3=P-B3),三苯胺结构的扭曲运动消耗了能量,以热的形式释放,使得三苯胺枝化合物的单光子荧光强度明显减弱。     

Meso-四(对十六烷氧基萘基)卟啉的合成及光谱性能

本文以4-羟基1-萘甲醛为原料合成了新型萘基卟啉化合物meso-四(对十六烷氧基萘基)卟啉,该化合物未见文献报道,其结构通过1HNMR,IR和UV-Vis确定。同时,测定了其光谱性能,并与四苯基卟啉进行对比研究。研究表明长碳链萘基的引入增大了卟啉环的共轭程度,使其光学吸收波长与荧光发射波长发生红移。另外,本文对原料4-羟基1-萘甲醛及其醚化产物的合成进行了工艺条件优化。     

Phosphonate coating of SiO<Subscript>2</Subscript> nanoparticles abrogates inflammatory effects and local changes of the lipid composition in the rat lung: a complementary bioimaging study

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.

     

四苯基卟啉锶配合物的合成及发光性能

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。     

A NIR luminescent copolymer based on platinum porphyrin as high permeable dissolved oxygen sensor for microbioreactors

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     

Synthesis and properties of tetrathiafulvalene-porphyrin assemblies

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.     

双光子聚合3D打印

3D打印是一种快速成型的增材制造技术。光固化立体印刷(SLA)是技术较成熟和应用较广的一种3D打印技术。SLA是采用紫外激光的单光子聚合过程,其加工分辨率受经典光学衍射极限的限制,难以满足分辨率高的微纳结构的加工。不同于SLA,利用近红外波长飞秒激光的双光子聚合3D打印技术可以突破经典光学衍射的限制,制造分辨率高的纳米尺度任意形状三维结构。本文将介绍双光子吸收和双光子聚合的原理、双光子聚合的发展和双光子聚合3D打印技术的应用,最后对该技术的发展进行展望。     

β-取代卟啉及卟啉锰对氧化破坏的稳定性

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。     

含不对称碳原子的苯并吡喃-2-酮骨架化合物的液晶性和凝胶性能

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。     

Increased optical nonlinearities of graphene nanohybrids covalently functionalized by axially-coordinated porphyrins

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.     

Ca1-nBanS:Cu+,Eu2+的合成及其光谱特征

研究了Ｃｕ＋,Ｅｕ２＋共激活的Ｃａ１－ｎＢａｎＳ的发光性质、余辉特性、基质组份Ｃａ／Ｂａ摩尔比与发光性质的关系．随着基质中Ｂａ含量的增加,Ｃｕ＋的蓝区发射带（４１６ｎｍ附近）及Ｅｕ２＋的红区发射带（６３０ｎｍ附近）均逐渐向绿区移动,且蓝光与红光的相对发射强度发生变化．实验证明,Ｃａ１－ｎＢａｎＳ：０．００５Ｃｕ＋,０．００１Ｅｕ２＋是一种红、蓝发射强度可调的单基双能光转换材料．