水溶性锰卟啉模拟酶体系快速混合停流谱研究

采用快速混合停流技术,考察了不同pH值条件下水溶性锰卟啉MnⅢ(TMPyP)与四种单氧给体m CPBA、KHSO5、NaOCl及H2O2构建的细胞色素P 450模拟酶体系催化氧化活性物种的生成及催化烯烃环氧化过程.低pH值时,主要生成四价锰氧中间体2;而在高pH值时,首先生成五价锰氧中间体1,该中间体再向四价中间体2转化.     

新型不对称卟啉配体及其锌配合物的合成与荧光性能

以3,5-二羟基苯甲酸丙酯和5-(4-硝基)苯基-10,15,20-三苯基卟啉为起始原料,合成了新型的不对称卟啉配体——5-[4-(3,5-二-十六烷氧基苯甲酰亚胺基)苯基]-10,15,20-三苯基卟啉(1)及其锌配合物(2),其结构经UV-Vis,1H NMR,IR和元素分析表征。用荧光激发光谱研究了1和2的荧光性能,结果表明:在激发波长为420 nm时,1和2的荧光发射峰分别在650 nm,709 nm和600 nm,644 nm。     

Adsorption Behavior of a Water-soluble Porphyrin at the Glass-water Interface as Studied by Synchronous Total Internal Reflection Fluorescence Spectroscopy

Total imernal reflection fluorescence spectroscopy (TIRF) and synchronous scanning technique were combined to study the adsorption behavior of the meso-tetrakis (4-sulfonatophenyl)porphyrin (TPPS) at the glass-water interface without any surfactant. The pH dependence of synchronous fluorescence signal at the interface was analyzed. Both unprotonated (TPPS^4-) and diprotonated (H2TPPS^2-) forms of TPPS were observed at the interface. But the interface favored the adsorption of. The apparent estimated pKa2 value shifted from 5.00 in the bulk solution to 2.7 at the interface. STIRF provides a good technique to study multi-component systems at the interface.     

基于荧光寿命机理的光纤温度传感器研究

为了实现恶劣环境下温度的测量,设计了一种基于荧光寿命机理的光纤温度传感系统.温度传感系统选用415 nm LED作为光源,以稀土荧光材料Y2O2S:Eu作为温度敏感材料,通过探测放大器和信号采集模块测量了敏感材料的荧光寿命,并由荧光寿命与温度的单调关系最终实现了温度的测量.采用油浴加热的方法进行温度实验,实验结果表明,温度传感系统在25~80℃实现了温度的测量,分辨率为0.5℃.     

基于卟啉衍生物红光材料的合成及物性研究

利用Schiff base反应合成了两个卟啉衍生物TPP-AQ, TPP-PD. 通过循环伏安、紫外可见吸收光谱、荧光光谱及理论计算等对其物性进行了研究. 结果显示: TPP-AQ, TPP-PD氧化电位分别为E_1/2＝1.07, 1.30 V和1.21, 1.36 V, 与TPP-PD相比, TPP-AQ的两个氧化还原电位都发生了负移|TPP-AQ与TPP-PD的最大紫外可见吸收峰分别在441和431 nm, TPP-AQ的吸收波长较TPP-PD有一定程度的红移, 通过理论计算可知这是由于TPP-AQ共轭程度优于TPP-PD导致的. TPP-AQ和TPP-PD的荧光主发射峰分别在657和656 nm, 半峰宽分别为30和27 nm, 有较好的红光色纯度.     

全内反射荧光光谱法研究水溶性卟啉在正己烷/水界面的吸附行为

在自行组装的全内反射荧光测定装置上实现了液／液界面全内反射荧光光谱的测绘,比较了水溶性的meso-四（对磺酸基苯基）卟啉（TPPS）在正己彬水界面上与在水相中荧光性质的差异,研究了全内反射荧光强度随表面活性剂种类、浓度及溶液pH值的变化情况,探索了TPPS的界面吸附行为,着重考察了阳离子表面活性剂CTMAB对TPPS界面荧光性质的影响。结果表明,在阳离子表面活性剂存在的条件下,未质子化的TPPS能够选择性地吸附在正己烷／水界面上,静电力在TPPS界面吸附过程中应起重要作用。     

Study on the Interaction between Lanthanide Cationic Porphyrin Complex and Bovine Serum Albumin

The interaction between lanthanide cationic porphyri

n and bovine serum albumin （BSA） was studied by fluorescence and UV-Vis spectrum. The static quenching of BSA was observed in the presence of YbTMPyP. According to the thermodynamic parameters, this binding was regarded as ＂enthalpy-driven＂ reaction. Furthermore, YbTMPyP is so close to the residues of BSA that molecular resonance energy transfer occurs between them. Besides, the red drift and hypochromicity of absorption spectrum of YbTMPyP were accompanied with the binding reaction.     

基于Eu~(3+)配合物纳米颗粒温敏薄膜的制备及荧光性能研究

Eu3+配合物的发光具有针状发射峰、大的斯托克斯位移、长荧光寿命以及对温度高度敏感性等特点,这使得它们成为温度探针材料的最佳候选之一。合成了新型可以被可见光激发的Eu3+配合物(Eu-DT),在此基础上分别制备了基于Eu-DT分子和Eu-DT纳米颗粒的温敏薄膜,并对它们的荧光寿命的温度敏感性进行了测试。这两类薄膜的荧光寿命均表现出良好的温度敏感性,特别是基于纳米颗粒的温敏薄膜,由于纳米颗粒基质的保护作用,表现出更高的荧光稳定和温度敏感性。     

含有酚羟基的吖嗪类荧光探针的阴离子识别与传感研究

设计合成了含有酚羟基的萘吖嗪类荧光探针分子,利用紫外-可见吸收光谱和荧光发射光谱研究了探针分子的阴离子识别和光化学传感性能。研究结果表明,该探针分子可以通过比色（紫外-可见吸收光谱）和荧光发射光谱双通道识别检测氟离子。该探针分子是一类比率型阴离子荧光探针,作用方式为探针分子酚羟基的去质子化作用,这种激发态质子转移（ESIPT）是探针分子呈现比率荧光特性的原因。通过本实验不但可以让学生掌握紫外-可见吸收光谱和荧光发射光谱仪的使用方法,还能培养学生在分子识别与光化学传感领域的科研兴趣。     

刚果红功能化水溶性碳纳米管膜电极的制备及在电化学传感器中的应用

基于刚果红(CR)表面修饰多壁碳纳米管(MWNTs)在干燥时所具有的良好成膜性能,在玻碳电极表面制备了一种水溶性MWNTs(MWNTs-CR)膜,用扫描电镜(SEM)、傅立叶红外光谱(FTIR)和交流阻抗谱(ElS)对其进行了表征.结果表明,MWNTs-CR能在电极表面形成一层致密、均匀含有大量纳米级微孔的纳米结构薄膜.和裸玻碳电极相比,MWNTs-CR膜修饰电极能极大的增强雌酮和羟甲香豆素的电化学响应.在体系中加入表面活性剂后,其电化学响应能得到进一步的提高.羟甲香豆素的浓度在8.0×10-8～4.0×10-6 mol/L范围内,其氧化峰电流与浓度呈现出良好的线性关系.在开路条件下富300 s后,HMC的检出限为2.0×10-8 mol/L.实验证明水溶性MWNTs膜是构建碳纳米管电化学传感器的理想材料.     

A Dual Read-out Molecularly Imprinted Composite Membrane Sensor Based on Zinc Porphyrin for the Detection of Dimethyl Methylphosphonate

Molecularly imprinted membrane-zinc porphyrin-mathacrylate(MIM-Zn-MAA), a dual read-out sensor based on a molecularly imprinted membrane, was developed to recognize and detect dimethyl methylphosphonate (DMMP) as an intermediate molecule of organophosphorus pesticides. The membranes were prepared via thermal polymerization of two functional monomers(zinc porphyrin and mathacrylate) on the surface of a glass slide functionalized with ethylene glycol dimethacrylate and azobisisobutyronitrile. The morphology of the as-synthesized MIM-Zn-MAA was determined with scanning electronic microscopy. The composite membranes exhibited macrovoid morphologies, which were affected by the functional monomers. These membranes were selectively adsorbed onto the template molecule and displayed higher adsorbing capacity toward DMMP compared with their structural analogs. Changes in the fluorescent spectra were qualitatively and quantitatively monitored via fluorescence photometry. Difference maps were also obtained using colorimetry before and after the reaction between MIM-Zn-MAA and DMMP at various concentrations. The maps showed a wide linear range varying from 0.1 μmol/L to 10 mmol/L with a low detection limit of 0.1 μmol/L. These preliminary results demonstrate that the as-fabricated dual read-out sensor displays good sensitivity and selectivity toward DMMP, indicating its considerable potential in DMMP detection in practical applications.     

Novel Mixed LB Films of Porphyrin and Phthalocyanine Based on Molecular Recognition

Phthalocyaninesaresyntheticsubstancesrelatedtothenaturallyoccurringporphyrins.Itsthermalandchemicalstabilitymakesitveryusefulinmolecularelectronicsl.TheLBfilmsofphthalocyaninehavebeenwidelystudiedinthepastdecade.ButfewreportsonthemixedLBfilmsofphthalocyanineandporphyrinhavebeenpublished"'HerewereportanovelmixedLBfilmfabricatedbydepositingporphyrinandphthalocyaineinonelayerbasedonmolecularrecognition.Figure1.ThestructureofcompoundAandBAsymmetricallysubstitutedphthalocyanineAandporphyrinBa…     

DFT Study on Structural Distortion and Vibronic Coupling of Vanadyl Porphyrin Anion and Cation

The geometries of one-electron reduced/oxidized species （[TOP]-/[VOP] ＋） of vanadyl por- phyrin （VOP） have been calculated with PBE1PBE method. The results show that for both [VOP]- and [VOP]＋ the ground states are triplet, in which one of the two unpaired electron occupies the dxy orbital of the V atom while the other occupies the n-orbital of porphyrin ring. Thus both [VOP]- and [VOP]＋ can be considered as n-radicals. The ground state of neutral VOP molecule is doublet with the unpaired electron occupying dxy orbital of V atom. In contract to the C4v symmetry of neutral VOP molecule, [VOP]- anion has a ＂rectangular＂ distorted C2v structure due to Jahn-Teller effect. The linear vibronic coupling constants for the Jahn-Teller active modes of [TOP]- were evaluated and the node patterns of frontier KS orbitals are used to explain the reason why the distortion occurs along specific modes. The ground state [VOP]＋ has a porphyrin ring with pronounced bond length alternation due to pseudo-Jahn-Teller effect, causing its symmetry declined from C4v to Ca. The bond length alternation is well explained with the node patterns of re-constructed frontier KS orbitals.     

A Highly Efficient Fluorescent Sensor Based on AIEgen for Detection of Nitrophenolic Explosives

The detection of nitrophenolic explosives is important in counterterrorism and environmental protection, but it is still a challenge to identify the nitroaromatic compounds among those with a similar structure. Herein, a simple tetraphenylethene (TPE) derivative with aggregation-induced emission (AIE) characteristics was synthesized and used as a fluorescent sensor for the detection of nitrophenolic explosives (2, 4, 6-trinitrophenol, TNP and 2, 4-dinitrophenol, DNP) in water solution and in a solid state with a high selectivity. Meanwhile, it was found that only hydroxyl containing nitrophenolic explosives caused obvious fluorescence quenching. The sensing mechanism was investigated by using fluorescence titration and ¹H NMR spectra. This simple AIE-active probe can potentially be applied to the construction of portable detection devices for explosives.     

席夫碱类高选择性氟离子化学传感器的研究

以邻羟基萘甲醛和水合肼合成了席夫碱类化合物荧光黄101(DHNA),在F-存在的情况下,其紫外可见光谱和荧光光谱都发生明显的变化,同时溶液颜色和荧光的变化可以通过肉眼直接观测到.在Cl-、Br-、1-、HSO4-、H2PO4-;等干扰离子存在的情况下,DHNA对F-具有良好的选择性.因此,荧光黄101可用于制备检测F-的高灵敏度颜色.荧光传感器.     

离子受体对自由卟啉探针荧光识别性能的影响

通过对2个N,N-二吡啶胺基受体修饰的自由卟啉化合物（Porphyrin-2-DPA）光学识别性能的系统研究,可以得知：该卟啉化合物中心刚性共轭的四吡咯环状结构不仅作为灵敏的光学信号基团、更是作为第一离子配位受体,在非共轭的N,N-二吡啶胺基受体辅助下,对Pb²⁺/Cu²⁺离子表现出灵敏的多重信号分析识别功能。     

Imine Gels Based on Ferrocene and Porphyrin and Their Electrocatalytic Property

A series of porphyrin‐based imine gels have been synthesized via dynamic covalent gelation between 5,10,15,20‐tetra(4‐aminophenyl)‐21H,23H‐porphyrin (H₂TAPP) derivatives and various aldehyde compounds. The porphyrin‐ferrocene imine gels based on MTAPP (M=H₂, Ni²⁺, Co²⁺, Pd²⁺ and Zn²⁺) and ferrocene‐1,1′‐dicarbaldehyde (NA) display efficient HER, OER and ORR activities in alkaline media. Among the gels, CoTAPP‐NA shows an HER current density of 10 mA cm^?2 at low overpotential of 470 mV and small Tafel slope of 110 mV decade^?1 in alkaline media. CoTAPP‐NA also exhibits OER catalytic activity with low overpotential (416 mV for 10 mA cm^?2). CoTAPP‐NA shows ability in overall water splitting in alkaline media. In addition, CoTAPP‐NA exhibits onset potential (E_p) of 0.95 V and half‐wave potential (E_1/2) of 0.84 V in 1.0 mol L^?1 KOH solution for oxygen reduction. Moreover, the gel catalyst shows good stability.     

A Triazatruxene‐Based Glycocluster as a Fluorescent Sensor for Concanavalin A

A new triazatruxene‐based fluorescent glycocluster has been designed, synthesized, and fully characterized by NMR spectroscopy and mass spectrometry. Furthermore, its specific and selective binding properties with concanavalin A (Con A) have been investigated by fluorescence spectroscopy, circular dichroism (CD) spectroscopy, and turbidity assay. The obtained results showed that the multivalent mannose‐modified triazatruxene exhibited specific binding with Con A, but no binding to peanut agglutinin (PNA) lectin or bovine serum albumin (BSA), corresponding to a two‐orders‐of‐magnitude higher affinity than that of monovalent mannose ligands. Most interestingly, a fluorescence enhancement of the triazatruxene‐based glycocluster was observed upon binding with Con A because of hydrophobic interactions involving sites close to the triazatruxene moiety. Furthermore, the inhibitory ability of the triazatruxene‐based glycocluster against ORN178‐ induced haemagglutination has been investigated by haemagglutination inhibition assay. The results indicated selective binding with ORN178.     

卟啉及其衍生物对生物分子的识别研究进展

卟啉及其衍生物作为主体分子对生物分子的识别具有独特的优点：分子结构多样、形状选择、稳定性好和敏感性高等。 本文着重介绍了国内外关于卟啉对DNA、氨基酸、醌和胺等的分子识别研究进展。