四-(邻氯苯基)卟吩及其金属络合物的核磁共振谱

在四-(邻氯苯基)卟吩及其金属络合物中,苯环上一个邻位质子被氯原子取代,导致其余苯环质子和全部苯环碳原子成为磁不等性核,从而出现比未取代的四苯基卟吩及其金属络合物为多的化学位移。对于In(OClTPP)Cl,NMR时标上缓慢的轴向配位体交换和苯环相对于卟啉平面的缓慢旋转,导致苯环两侧的不等性;因此,苯环邻位和间位的质子和碳原子各呈现两个不同的化学位移值。本工作测量和归属了H_2(OClTPP)及其诈、镉、镍、铟络合物的质子谱和~(13)C谱,使用偏共振实验以辅助谱的归属。     

四-(邻氯苯基)卟吩及其金属络合物的制备和光谱研究

卟啉化合物与很多学科有着十分密切的关系。四-(邻氯苯基)卟吩(OCITPP)化合物与实验室常用模拟物四苯基卟吩(TPP)及苯环间、对位取代的四苯基卟吩比较,化学和光谱性质上较为独特,应用上较为优越,且前人做过的工作极少。     

乙酰葡萄糖氧代金属卟啉的合成及其对环己烷羟基化反应的催化作用

由吡咯和葡萄糖取代苯甲醛直接缩合制备了两种葡萄糖取代卟吩:四(邻位乙酰葡萄糖氧代苯基)卟吩和四(间位乙酰葡萄糖氧代苯基)卟吩,进一步金属化合成了4种葡萄糖金属卟啉:氯化四(邻位乙酰葡萄糖氧代苯基)卟吩合铁、氯化四(间位乙酰葡萄糖氧代苯基)卟吩合铁、氯化四(邻位四乙酰葡萄糖氧代苯基)卟吩合锰和氯化四(间位乙酰葡萄糖氧代苯基)卟吩合锰.它们的结构由紫外-可见光谱、核磁共振和元素分析证实.研究了这些葡萄糖取代金属卟啉对亚碘酰苯常温常压下氧化环己烷反应的催化作用.研究结果表明,4种糖基金属卟啉催化下的环己烷反应产率和反应速率都比一般金属卟啉高.反应动力学分析表明,在常温常压下,糖基金属卟啉催化下的环己烷氧化反应具有酶催化反应的动力学关系.     

乙酰糖基金属卟啉的合成及其对烷烃温和氧化的选择性催化作用

由吡咯和葡萄糖取代苯甲醛直接缩合制备了两种葡萄糖取代卟吩,四(邻位乙酰葡萄糖氧代苯基)卟吩和四(间位乙酰葡萄糖氧代苯基)卟吩,它们进一步金属化合成了四种葡萄糖金属卟啉,氯化四(邻位乙酰葡萄糖氧代苯基)卟吩合铁、氯化四(间位乙酰葡萄糖氧代苯基)卟吩合铁、氯化四(邻位四乙酰葡萄糖氧代苯基)卟吩合锰和氯化四(间位乙酰葡萄糖氧代苯基)卟吩合锰。它们的结构由紫外-可见光谱、元素分析和核磁共振证实。研究了这些葡萄糖取代金属卟啉对亚碘酰苯常温常压下氧化异戊烷反应的选择性催化作用。研究表明,糖基金属卟啉催化异戊烷端基碳氢键的氧化,对一级碳氢键表现出专一性催化作用。非糖基金属卟啉催化异戊烷二级和三级碳氢键的氧化。与非糖基金属卟啉比较,糖基金属卟啉对烷烃羟基化反应的催化行为更接近细胞色素P-450单充氧酶。     

meso-四(烷氧基苯基)卟啉及其金属络合物的波谱研究

采用^1H NMR、MS、IR、UV、元素分析等分析测试表征手段确证了所合成的10个系列卟啉及其金属络合物的结构,研究了不同位置、不同链长烷氧基四苯基卟啉和不同金属离子卟啉络合物的结构与^1HNMR、IR和UV等波谱之间的关系,总结了卟啉配体及其金属络合物的^1H NMR、IR和UV判据,报道和解释了meso-四(烷氧基苯基)卟啉铜、锰络合物和meso-四(邻烷氧基苯基)卟啉钴络合物的^1H NMR研究结果,通过MS、^1H NMR、IR、UV、元素分析确证了我们所合成的铁卟啉为μ-氧桥联夹心二聚体结构,且存在两种典型构象,导致同系列络合物有四种类型^1H NMR谱图。     

2-(2-氨基苯基)苯并噻唑与四苯基卟啉及四苯基锌卟啉的荧光共振能量转移

采用紫外光谱和荧光光谱法研究了四氢呋喃溶液中2-(2-氨基苯基)苯并噻唑(APBT)与四苯基卟啉(TPP)、四苯基锌卟啉(ZnTPP)之间的相互作用.结果表明,APBT可作为能量供体分子分别与能量受体分子TPP或ZnTPP构成荧光共振能量转移(FRET)体系,APBT的作用将使TPP和ZnTPP的荧光增强.在此FRET...     

模拟细胞色素P-450的仿生氧化反应的研究 T.氯合5,10,15,20-四苯基卟吩合铁(III)催化下不同亚碘酰芳烃及其衍生物的结构对环己烷充氧化反应的影响

在氯合5,10,15,20-四苯基卟吩合铁(Ⅲ)[TPPFe(Ⅲ)Cl]催化下,带有不同取代基的亚碘酰苯和亚碘酰苯的衍生物作充氧化剂对环己烷进行了仿生单充氧化反应的研究.取代亚碘酰苯中对位取代基的电子效应和间位取代基的电子及立体效应对氧化产物环己醇的产率有良好线性相关性.亚碘酰苯的衍生物苯亚碘酸二醋酐与苯亚碘酸单对甲苯磺酸酐对环己烷的充氧化能力和邻、间、对亚碘酰苯甲酸与邻亚碘酰苯甲酸酯相似,环己醇产率接近零.从而提出亚碘酰苯甲酸及邻亚碘酰苯甲酸酯存在分子内或分子间I(OH)OCO成键结构的论点.     

模拟细胞色素P-450的仿生氧化反应的研究 I:氯合5,10,15,20-四苯基卟吩合铁(III)催化下不同亚碘酰芳烃及其衍生物的结构对环己烷充氧化反应的影响

在氯合5,10,15,20-四苯基卟吩合铁(III)[TPPFe(III)Cl]催化下, 带有不同取代基的亚碘酰苯和亚碘酰苯的衍生物作充氧化剂对环己烷进行了仿生单充氧化反应的研究.取代亚碘酰苯中对位取代基的电子效应和间位取代基的电子及立体效应对氧化产物环己醇的产率有良好线性相关性. 亚碘酰苯的衍生物苯亚碘酸二醋酐与苯亚碘酸单对甲苯磺酸酐对环己烷的充氧化能力和邻、间、对亚碘酰苯甲酸与邻亚碘酰苯甲酸酯相似, 环己醇产率接近零. 从而提出亚碘酰苯甲酸及邻亚碘酰苯甲酸酯存在分子内或分子间I(oh)oco成键结构的论点.     

乙酰葡萄糖氧代金属卟啉的合成及其对环己烷羟基化反应 …

由吡咯和葡萄糖取代苯甲醛直接缩合制备了两种葡萄糖取代卟吩：四（邻位乙酰葡萄糖氧代苯基）卟吩和四（间位乙酰葡萄糖氧代苯基）卟吩,进一步金属化合成了４种葡萄糖金属卟啉：氯化四（邻位乙酰葡萄糖氧代苯基）卟吩合铁、氯化四（间位乙酰葡萄糖氧代苯基）卟吩合锰。它们的结构由紫外－可见光谱、核磁共振和元素分明,４种糖基金属卟啉催化下的环己烷反应的催化作用。研究结果表明,４种糖基金属卟啉催化下的环己烷反应产率和反应     

4,5-二溴邻硝基苯基荧光酮与镧(Ⅲ)显色反应研究与应用

研究了在表面活性剂吐温-80存在下,镧(Ⅲ)与4,5-二溴邻硝基苯基荧光酮(DBONPF)的高灵敏显色反应,并建立了测定镧(Ⅲ)的新方法。实验发现,在pH=10.3 NH4Cl-NH3缓冲溶液中,镧(Ⅲ)与4,5-二溴邻硝基苯基荧光酮形成紫色络合物,络合物的最大吸收波长为594.0 nm,表观摩尔吸光系数ε=2.31×105L.mol-1.cm-1。镧(Ⅲ)的浓度在0~35μg/25mL的范围内符合比耳定律。本法用于铜合金试样中微量镧的测定,结果令人满意。     

稀土金属卟吩的红外光谱

测得了Ln(OCITPP)_acac和Ln(TPP)_acac两个系列稀土金属卟吩的4000—100cm^-1波长范围的红外光谱,并作了归属。找出了苯环邻位氯取代的稀土金属卟吩与未取代对应物相比较在光谱上所出现的差异,并给予解释。     

Effect of zeolite properties on ground-state and triplet-triplet absorption, prompt and oxygen induced delayed fluorescence of tetraphenylporphyrin at gas/solid interface

The ground-state and transient absorption, prompt and delayed fluorescence of tetraphenylporphyrin (TPP) adsorbed onto the external surface of different zeolites was monitored using diffuse-reflectance steady-state and laser flash photolysis. The delayed fluorescence (DF) of TPP detected in the presence of O2 is attributed to the energy transfer from 3TPP to 3O2 to form 1O2 and subsequent energy transfer from 1O2 to some other 3TPP within the organised molecular ensembles on the zeolite surface. The spectroscopic and kinetic parameters, namely the yield of DF (2-20% relative to prompt fluorescence), depend on the zeolite properties: the observed differences were correlated with the acid-base properties of the two zeolite series studied in this work (KA, NaA, CaA) and (NaA, NaX, NaY).     

A fluorescent sensing membrane for iodine based on intramolecular excitation energy transfer of anthryl appended porphyrin

A single anthryl appended meso-tetraphenylporphyrin (TPP) dyad has been synthesized and applied in fluorescence sensing of iodine based on the intramolecular excitation energy transfer. The molecular recognition of the sensor is based on the interaction of iodine with inner anthracene moiety of the dyad, while the signal reporter for the recognition process is the TPP fluorescence quenching. Because the emission spectrum of anthracene is largely overlapped with the Soret band absorption of TPP, intramolecular excitation energy transfer interaction occurs between the donor, anthracene and acceptor, TPP. This energy transfer leads to TPP fluorescence emission by excitation of anthracene. The sensor was constructed by immobilizing the dyad in a plasticized poly(vinyl chloride) (PVC) membrane. The sensing membrane shows higher sensitivity compared to the sensors by using anthracene, TPP, or a mixture of anthracene and TPP as sensing materials. Under the optimum conditions, iodine in a sample solution can be determined from 2.04 to 23.6 mmol·L⁻¹ with a detection limit of 33 nmol·L⁻¹. The sensing membrane shows satisfactory response characteristics including good reproducibility, reversibility and stability, as well as the short response time of less than 60 s. Except for Cr₂O₇²⁻ and MnO₄⁻, other common metal ions and anions in foodstuff do not interfere with iodine determination. The proposed method was applied in the determination of iodine in table salt samples. The results agree well with those obtained by other methods. Supported by the National Outstanding Youth Science Foundation of China (Grant No. 20525518), the National Natural Science Foundation of China (Grant No. 20775005), and the National Natural Science Foundation of Hunan province (Grant No. JJ076021)     

Effective enhancement of the emission efficiency of tetraphenylporphyrin in solid state by tetraphenylethene modification

Evidently enhanced red emission efficiency from the solid state of tetraphenylporphyrin derivative was achieved by modification with tetraphenylethene units.     

Highly Soluble Porphyrin (TPP)-Perylene Diimide (PDI) Dyad and Triad:Synthesis and Spectroscopic Studies

Novel porphyrin‐perylene diimide dyad (TPP‐PDI) and porphyrin‐perylene diimide‐porphyrin triad (TPP‐PDI‐TPP) were synthesized and characterized. Their structure and properties were studied by UV, FL, ¹H NMR, MS, elemental analysis, etc. The variation of fluorescence feature and UV spectra of TPP‐PDI‐TPP triad were investigated at different concentration of CF₃COOH in THF. The incorporation of CF₃COOH leads to the closure of the efficient charge transfer decay. After protonation of porphyrin units, the fluorescence intensity of TPP‐PDI‐TPP triad increased greatly. The fluorescence intensity of TPP‐PDI‐TPP triad restored after addition of triethylamine into the solution. Thus, TPP‐PDI‐TPP triad was a proton‐type fluorescence switch based on acid‐base control. Moreover, different from porphyrin‐perylene type molecular switches reported before, this TPP‐PDI‐TPP triad has wonderful solubility in organic solvents.     

Covalently linked bisporphyrins bearing tetraphenylporphyrin and perbromoporphyrin units: Synthesis and their properties

A series of covalently linked bisporphyrins bearingmeso-tetraphenylporphyrin (TPP) and octabromotetraphenylporphyrin (OBTPP) units have been synthesised and characterised. Electrochemical studies on these bisporphyrins showed an anodic shift (∼ 30–60 mV) of the TPP unit and a cathodic shift (∼40-80 mV) of OBTPP in redox potentials. Further, steady-state fluorescence studies on bisporphyrins indicated dramatic decrease in fluorescence quantum yields of the TPP moiety. Electrochemical redox and fluorescence data seem to suggest the possible existence of intramolecular interactions in these bisporphyrins     

Photophysical properties of a rhodium tetraphenylporphyrin-tin corrole dyad. The first example of a through metal-metal bond energy transfer

The luminescence spectroscopy study and the determination of the photophysical parameters for the M-M'-bonded rhodium meso-tetraphenylporphyrin-tin(2,3,7,13,17,18-hexamethyl-8,12-diethylcorrole) complex, (TPP)Rh-Sn(Me6Et2Cor) 1, was investigated. The emission bands as well as the lifetimes (tau(e)) and the quantum yields (Phi(e); at 77 K using 2MeTHF as solvent) were compared with those of (TPP)RhI 2 (TPP = tetraphenylporphyrin) and (Me6Et2Cor)SnCl 3 (Me6Et2Cor = 2,3,7,13,17,18-hexamethyl-8,12-diethylcorrole) which are the two chemical precursors of 1. The energy diagram has been established from the absorption, fluorescence and phosphorescence spectra. The Rh(TPP) and Sn(Me6Et2Cor) chromophores are the energy donor (D) and acceptor (A), respectively. The total absence of fluorescence in 1 (while fluorescence is observed in the tin derivative 3) indicates efficient excited state deactivation, presumably due to heavy atom effect and intramolecular energy transfer (ET). The large decreases in tau(P) and Phi(P) of the Rh(TPP) chromophore going from 2 to 1 indicate a significant intramolecular ET in the triplet states of 1 with an estimated rate ranging between 10(6) and 10(8) s(-1). Based on the comparison of transfer rates with other related dyads that exhibit similar D-A separations and no M-M' bond, and for which slower through space ET processes (10(2)-10(3) s(-1)) operate, a through M-M' bond ET has been unambiguously assigned to 1.     

Synthesis of thermo‐responsive 4‐arm star‐shaped porphyrin‐centered poly(N,N‐diethylacrylamide) via reversible addition‐fragmentation chain transfer radical polymerization

Tetrafunctional porphyrins‐containing trithiocarbonate groups were synthesized by an ordinary esterification method. This tetrafunctional porphyrin (TPP‐CTA) could be used as a chain transfer agent in a controlled reversible addition‐fragmentation chain transfer (RAFT) radical polymerization to prepare well‐defined 4‐arm star‐shaped polymers. N,N‐Diethylacrylamide was polymerized using TPP‐CTA in 1,4‐dioxane. Poly(N,N‐diethylacrylamide) (PDEA) is known to be a thermo‐responsive polymer, and exhibits a lower critical solution temperature (LCST) in water. The star‐shaped PDEA polymer (TPP‐PDEA) was therefore also thermo‐responsive, as expected. The LCST of this polymer depended on its concentration in water, as confirmed by turbidity, dynamic light scattering (DLS), static light scattering (SLS), and ¹H NMR measurements. The porphyrin cores were compartmentalized in PDEA shells in aqueous media. Below the LCST, the fluorescence intensity of TPP‐PDEA was about six times larger than that of a water‐soluble low molecular weight porphyrin compound (TSPP), whose fluorescence intensity was independent of temperature. Above the LCST, the fluorescence intensity of TPP‐PDEA decreased, while the intensity was about three times higher than that of TSPP. These observations suggested that interpolymer aggregation occurred due to the hydrophobic interactions of the dehydrated PDEA arm chains above the LCST, with self‐quenching of the porphyrin moieties arising from these interactions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

基于分子内荧光能量转移的碘聚合膜荧光传感器

合成了基于分子内荧光能量转移的蒽（An）-四苯基卟啉（TPP）双发色团碘荧光探针1．由于An的荧光光谱与TPP的S吸收带具有较好的重叠,供体An与受体TPP之间可以发生有效的分子内荧光能量转移,以An的最大吸收波长作为激发波长时,由于分子内荧光能量转移,受体TPP发出荧光．当碘与探针分子中的识别基团An作用时,导致探针分子的荧光转导基团TPP荧光淬灭．与An、TPP和An＋TPP混合物作敏感材料相比,将探针1固定在PVC膜中制备的敏感膜对碘选择性高、灵敏度好．另外,敏感膜具有很好的重现性、可逆性和稳定性,响应时间小于60S．除Cr2O7^2-和MnO4^-外,食品中常见的无机离子和可能存在的干扰物质不影响碘的测定．在最优条件下,传感器的线性范围为2．04×10^-6-2．36×10^-2mol／L,检出限为3．30×10^-8mol／L．本方法应用于加碘食盐中碘含量的测定,结果满意．     

含四-苯基卟啉基团聚酰亚胺膜的光电导性能研究

分剐以均苯四酸二酐(PMDA)与四(4-氨基苯基)卟啉(TAPP)／4，4′-二苯醚(ODA)、TAPP／3，6-二氨基-N-甲基咔唑(DACz)聚合得到两个系列含四-苯基卟啉基团(TPP)聚酰亚胺(PI)共聚膜，并时其作为载流子发生层(CGL)制成的感光体的光电导性能进行了测试。结果表明：PI共聚膜的光电导性能随分子链中TPP基团含量的提高而增强；当TPP基团含量相同时，PMDA／TAPP／ODA系列的光电导性能较PMDA／TAPP／DACz系列好；含TPP基团PI共聚膜的光电导性能明显优于四-苯基卟啉分子掺杂体系；在CGL与导电铝基间引入聚甲基丙烯酸甲酯(PMMA)阻挡层(CBL)不能提高感光体的光电导性能。从光电导机理分析了TPP基团、四-苯基卟啉分子的聚集结构与PI膜光电导性能的关系。