侧链键合锰卟啉的线型聚甲基丙烯酸缩水甘油酯的制备及其谱学性质

采用Adler法合成了Meso-四(对羟基苯基)卟啉(THPP), 在均相体系中使聚甲基丙烯酸缩水甘油酯(PGMA)与THPP发生开环反应, 得到侧链键合有羟基苯基卟啉的线型PGMA(HPP-PGMA); 进一步使HPP-PGMA与锰离子发生配合作用, 得到侧链键合有锰卟啉(MnP)的线型PGMA(MnP-PGMA), 测定了HPP-PGMA的1H NMR谱, 表征了其化学结构; 测定了HPP-PGMA与MnP-PGMA的UV-Vis光谱及荧光发射光谱, 考察了其光物理行为. 实验结果表明, 通过THPP外环上羟基与PGMA侧基环氧键的开环成醚反应, 可以顺利地将羟基苯基卟啉及其锰配合物键合在PGMA的侧链上. HPP-PGMA具有THPP的特征电子吸收光谱与荧光发射光谱, 且随着THPP键合度的增加, 光谱的强度增强. MnP-PGMA具有小分子锰卟啉的特征电子吸收光谱与荧光特征, 其Soret吸收带发生显著红移(红移58 nm), Q吸收带的数量减为3个吸收峰; 实验发现, MnP-PGMA与小分子锰卟啉类似, 在Q发射带没有荧光发射.     

系列双亲卟啉在水溶液及盐溶液中的不同聚集行为

分析了中性条件下在水溶液及盐溶液中系列双亲卟啉随其浓度连续变化的紫外-可见吸收光谱。结果表明,在中性条件下不同侧链取代基对双亲卟啉的聚集行为有很大影响,盐的加入导致卟啉的聚集形态发生改变,初步解释了影响卟啉聚集的原因。     

Templated synthesis of a large and flexible covalent porphyrinic cage bearing orthogonal recognition sites

A large covalent cage incorporating two porphyrins attached by four long and flexible polyether chains each bearing two 3-pyridyl ligands was synthesized from a DABCO-templated olefin metathesis reaction. The X-ray structure of the cage with the DABCO coordinated inside the cavity to the two zinc(II) porphyrins reveals a highly symmetric structure.     

Side-chain-controlled H- and J-aggregation of amphiphilic porphyrins in CTAB micelles

The aggregation behavior of a series of amphiphilic 4-hydroxyphenyl porphyrins with one (P1), two (P2) and three (P3) hexadecyl side chains in cetyltrimethylammonium bromide (CTAB) micelles has been studied by means of UV-vis and fluorescence spectra. It was found that the number of hexadecyl side chains not only controls the H- and J-aggregation of the porphyrins in CTAB micelles, but also influences the aggregation concentration and tendency. With increasing porphyrin concentration, P1 and P2 form H-aggregates in CTAB micelles, while P3 forms J-aggregates. Porphyrins with more hexadecyl side chains tend to form aggregates more easily and at lower concentrations in CTAB micellar solutions.     

Synthesis and cellular studies of PEG-functionalized meso-tetraphenylporphyrins

The total syntheses of four PEG-functionalized porphyrins, containing one to four low molecular weight PEG chains linked via amide bonds to the para-phenyl positions of meso-tetraphenylporphyrin, are reported. The hydrophobic character of the PEG-porphyrins decreases with the number of PEG chains linked to the porphyrin ring, while their tendency for aggregation in buffered aqueous solution increases. The porphyrins containing one or two PEG chains accumulated within human HEp2 cells to a much higher extent than those having three or four PEGs at the macrocycle periphery. All PEG-porphyrins were found to be non-toxic in the dark, and only those containing one or two PEG chains were phototoxic (IC(50)=2 microM at 1J/cm(2) light dose). The preferential sites of subcellular localization of the porphyrins containing one or two PEG chains were found to be the mitochondria and endoplasmic reticulum (ER), while those containing three or four PEG chains localize preferentially in the lysosomes.     

Physical chemistry of porphyrins and their interactions with membranes: the importance of pH

The physicochemical properties of dicarboxylic porphyrins are examined with particular emphasis on acid-base equilibria. Interactions with membranes appear to be dominated by the charge of the propionic acid chains and the hydrophobic character of other peripheral substituents. A physicochemical basis for the effect of pH on the incorporation of porphyrins within membranes is given. The effect of lowered tumour pH on the incorporation of porphyrins within membranes and on porphyrin retention is discussed.     

EVALUATION OF PORPHYRIN CHARACTERISTICS REQUIRED FOR PHOTODYNAMIC THERAPY

The cytotoxicity (in the dark), phototoxicity (red light) and subcellular localization (using confocal laser scanning microscopy) were determined for 15 porphyrins (1-15) in C6 glioma cells. The partition coefficient in 2-octanol was also determined for each porphyrin at pH 7.4. The cytotoxicity increased with pi (log of partition coefficient) up to pi values of +2. The 7 porphyrins with cationic side chains exhibited a classical parabolic correlation between phototoxicity and pi, with maximal activity at a pi value of approximately 1.0. There was also a significant correlation between subcellular localization and degree of phototoxicity, with the three most photosensitive porphyrins all possessing cationic side chains, and all three localizing in mitochondria.     

具有不同取代链长的卟啉衍生物LB膜的结构研究

本文研究了三种羧酸取代的四苯基卟啉衍生物在空气/Cd^2^+水溶液界面上所形成的单层膜及LB膜。这三种卟啉衍生物中, 一种没有脂链, 另外两种具有不同长度的脂链。由π-A等温线得到的平均表观分子面积相差很大。紫外-可见光谱表明, LB膜中卟啉的Soret吸收带相对于溶液的吸收均红移, 但红移程度不同。LB膜的偏振紫外-可见光谱表明, LB膜中三种卟啉衍生物的卟啉环具有基本一致的取向。运用亚相降低法得到了三种卟啉衍生物单层LB膜, 其紫外-可见光谱与用垂直提拉法得到的LB膜的紫外-可见光谱具有一致的特征。这些结果表明: 卟啉衍生物有无取代链及取代链长的不同对平均表观分子面积的大小和膜中环间的距离有影响, 但对环的取向没有影响。环的取向由环本身及环上的亲水取代基来确定。气/液界面上三种卟啉衍生物的单层膜中环也具有一致的取向, 且与LB膜中环的取向相差不大。提拉不会对膜中环的取向及膜的结构造成大的改变。     

Dynamic Molecular Invasion into a Multiply Interlocked Catenane

A multiply interlocked catenane with a novel molecular topology was synthesized; a phthalocyanine bearing four peripheral crown ethers was quadruply interlocked with a cofacial porphyrin dimer bridged with four alkylammonium chains. The supramolecular conjugate has two nanospaces surrounded by a porphyrin, a phthalocyanine, and four alkyl chains to accommodate guest molecules. Because the phthalocyanine can move along the alkyl chains, it acts as an adjustable wall, thus permitting the invasion of large molecules into the nanospaces without spoiling the affinity of the association. The dynamic molecular invasion allowed the intercalation of dianionic porphyrins into both nanospaces with high affinity. A photometric titration experiment revealed the two‐step inclusion phenomenon. The multiply interlocked catenane complexed with three Cu²⁺ ions, and the spin–spin interaction was switched off by the intercalation of dianionic porphyrins.     

Scanning tunneling microscopy observation of self-assembled monolayers of strapped porphyrins

In this paper, we reveal that the free-base and zinc strapped porphyrins possessing long alkyl chains, C 24OPP-HQ and Zn(C 24OPP-HQ), respectively, can be arranged on surfaces. We used scanning tunneling microscopy (STM) to observe alkyl-chain-assisted self-assembled monolayers (SAMs) of these strapped porphyrins at the solid-liquid interface. STM images revealed that the strapped benzene moiety was detectable on the porphyrin core: that is, the strapped porphyrins could be differentiated from nonstrapped analogues. We compared the population of the nonstrapped porphyrin (C 24OPP) and either of the strapped porphyrins C 24OPP-HQ or Zn(C 24OPP-HQ) in the mixed SAMs. We then confirmed that Zn(C 24OPP-HQ) is more favorably incorporated in the mixed SAMs than C 24OPP-HQ. From (1)H NMR spectroscopic and X-ray crystallographic analyses, we concluded that the factors increasing the population of Zn(C 24OPP-HQ) in the mixed SAMs are the enhanced rigidity of the porphyrin core by the zinc coordination and the flat structure of the porphyrin moiety in the saddle conformation. This study demonstrates that strapped porphyrins possessing long alkyl chains are available to arrange the functional modules on the surface via chemical modification on the strapped moiety.     

Surface-tuned assembly of porphyrin coordination oligomers

Two self-complementary phenanthroline-strapped porphyrins bearing imidazole arms and C 12 or C 18 alkyl chains were synthesized, and their surface self-assembly was investigated by atomic force microscopy (AFM) on mica and highly ordered pyrrolitic graphite (HOPG). Upon zinc(II) complexation, stable porphyrin dimers formed, as confirmed by DOSY (1)H NMR and UV-visible spectroscopy. In solution, the dimers formed J-aggregates. AFM studies of the solutions dip-coated onto mica or drop-casted onto HOPG revealed that the morphologies of the assemblies formed were surface-tuned. On mica, fiber-like assemblies of short stacks of J-aggregates were observed. The strong influence of the mica's epitaxy on the orientation of the fibers suggested a surface-assisted assembly process. On HOPG, interactions between the alkyl chains and the graphite surface resulted in the stabilization and trapping of monomer species followed by their subsequent association into coordination polymers on the surface. Interdigitation of the alkyl chains of separate polymer strands induced lateral association of wires to form islands that grew preferentially upon drop-casting and slow evaporation. Clusters of laterally assembled wires were observed for the more mobile functionalized porphyrins bearing C 12 chains.     

Coordination-induced branched self-assembly of porphyrins bearing two redox-active phenylenediamine chains

The porphyrins bearing two three-dimensionally regulated oligoaniline chains with terminal pyridyl groups were synthesized. The self-assembled branched polymer complex by introducing Zn(II) to the porphyrin was achieved in solution, which underwent dropcasting on the surface of mica to result in dome-like nanostructures.     

Meso‐Substituted Liquid Porphyrins

Meso‐substituted A₄‐porphyrins bearing 3,4,5‐trialkoxyphenyl substituents are efficiently synthesized and characterized. Porphyrins bearing twelve C10 and C11 alkyl chains turned out to be liquid at room temperature. The remaining porphyrins, bearing C8, C9, C12, and C18 alkyl chains, have low melting points and high solubility in nonpolar solvents. Their differential scanning calorimetry distinctly shows, in most cases, only one phase transition.     

Properties of polyethylene glycol supported tetraarylporphyrin in aqueous solution and its interaction with liposomal membranes

5,10,15,20-Tetrakis(4-hydroxyphenyl)porphyrin was functionalized by covalent attachment of poly(ethylene glycol) (PEG) chains of various molecular weights, 350, 2000, and 5000 Da. The properties of PEG-functionalized tetraarylporphyrins in aqueous solution and their interactions with liposomes have been studied. Electronic absorption spectroscopy, dynamic light scattering, atomic force microscopy, and fluorescence quenching were used to monitor aggregation of porphyrin chromophores and behavior of the attached PEG chains in the aqueous solution. The tendency for aggregation of porphyrin chromophores in aqueous solution and the efficiency of fluorescence quenching by KI decrease with increasing length of PEG chain linked to the porphyrin ring. The experimental results indicate that polymer clusters are present in aqueous solution of all pegylated porphyrins. The interactions between the pegylated porphyrins and phosphatidylcholine liposomes in the aqueous solution were studied using the fluorescence methods. The apparent binding constants of porphyrin chromophores to liposomes were determined. The degree of binding was found to be dependent on the molecular weight of the attached polymer.     

Designing functionalized porphyrins capable of pseudo-2D self-assembly on surfaces

A crystallography-instructed strategy to highly ordered layering of porphyrins with different topologies on HOPG is developed based on meso-tetraarylporphyrins bearing 2-ethoxyethanol side chains as "sticky ends". These sticky ends are capable of displaying directive hydrogen bonding motifs with the inherent D4h symmetry of the porphyrins. Solvent effects are shown to have an important role in fabricating the adsorption. Metalation and subsequent axial ligation was a key controlling factor in the topology of the layer, leading to pseudo-2D structures on HOPG.     

Aggregation of deuteroporphyrin IX diesters in aqueous-organic binary solution

The aggregation properties of a series of deuteroporphyrin IX diesters in the THF-Buffer (0.1 mol L-1 Tris-HCl) aquiorgano solvent have been studied by means of UV-Vis and fluorescence spectrometers.Experimental data show that the dimerization of porphyrins is mainly determined by π-πinteraction in pure organic solution while further aggregation of porphyrins with long hydrocarbon chains is more likely driven by hydrophobic-lipophilic interaction in aqueous-organic binary solution.The appearance of the aggregates induces a red shift in absorption spectra and fluorescence quenching in fluorescence spectra.The chain-length effect and chain-foldability effect have also been observed.     

对微环境敏感的系列双亲卟啉的光谱研究

研究了系列双亲卟啉(四苯酚基卟啉P₀及其烷氧基衍生物P₁,P₂,P₃)在不同微环境下的电子吸收光谱和荧光发射及荧光激发光谱.研究发现,卟啉在THF溶液中以单体形式存在,并且其侧链取代基对卟啉电子态的影响很小;然而卟啉在CTAB胶束溶液中的光谱特性却表现出很大差异,由此分析了不同侧链取代基对卟啉分子聚集行为和定位性质的影响,初步解释了卟啉在CTAB胶束溶液中随体系pH值改变而发生的荧光猝灭现象.     

Interactions of cationic porphyrins with double-stranded oligodeoxynucleotides: a study by electrospray ionisation mass spectrometry

Electrospray ionisation mass spectrometry (ESI-MS), electrospray ionisation tandem mass spectrometry (ESI-MS/MS) and Ultraviolet-visible (UV-vis) spectroscopy were used to investigate the non-covalent interactions between small oligonucleotide duplexes with the GC motif and a group of cationic meso(N-methylpyridynium-4-yl)porphyrins (four free bases with one to four positive charges, and the zinc complex of the tetracationic free base).The results obtained point to outside binding of the porphyrins, with the binding strength increasing with the number of positive charges. Fragmentations involving losses from both chains were observed for the porphyrins with N-methylpyridinium-4-yl groups in opposite meso positions.     

Synthesis of Highly Functionalized Fluorinated Porphyrins

Highly functionalized fluorinated porphyrins were synthesized by a convergent strategy. Nucleophilic substitution using fluorinated branched unit and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin afforded highly functionalized fluorinated porphyrin 8 containing 24 fluorinated chains in the peripheral region.     

SUBCELLULAR LOCALIZATION OF PORPHYRINS USING CONFOCAL LASER SCANNING MICROSCOPY

The in vitro subcellular distribution patterns of 10 porphyrins, varying in hydrophobicity and charge, were studied using confocal laser scanning microscopy on two cell lines (V79 and C6 glioma cells) for incubation times up to 24 h. All of the porphyrins were taken up rapidly by both cell lines and distinct classes of subcellular distribution patterns were observed: general cytoplasmic staining; localization in lysosomes (usually associated with general cytoplasmic staining); localization in mitochondria (and general cytoplasmic staining); localization in mitochondria with subsequent uptake into lysosomes. Structure-localization relationships which have emerged are that porphyrins with dominantly cationic side chains localize in mitochondria, whereas those with a more anionic character tend to localize in lysosomes.