Oligomeric cholates: amphiphilic foldamers with nanometer-sized hydrophilic cavities

The hydroxyl at the C-3 of cholic acid was converted to an amino group, and the resulting amino-functionalized cholic acid was used as a monomer to prepare amide-linked oligomeric cholates. These cholate oligomers fold into helical structures with nanometer-sized hydrophilic internal cavities in solvent mixtures consisting of mostly nonpolar solvents such as carbon tetrachloride or ethyl acetate/hexane and 2-5% of a polar solvent such as methanol or DMSO. The conformations of the foldamers were studied by UV, fluorescence, fluorescence quenching, and fluorescence resonance energy transfer. The nature of the polar/nonpolar solvents and their miscibility strongly influenced the folding reaction. Folding was cooperative, as evidenced by the sigmoidal curves in solvent denaturation experiments. The folded conformers became more stable with an increase in the chain length. The folding/unfolding equilibrium was highly sensitive toward the amount of polar solvent. One percent variation in the solvent composition could change the folding free energies by 0.5-1.4 kcal/mol.     

CLEARANCE TIMES OF PORPHYRIN DERIVATIVES FROM MICE AS MEASURED BY in vivo FLUORESCENCE SPECTROSCOPY

Abstract
The clearance times of 17 different porphyrin derivatives from SKH:HR-1 mice have been measured using the technique of in vivo fluorescence spectroscopy. This technique monitors the in vivo porphyrin fluorescence observed from the external skin surface. Most hydrophilic porphyrin derivatives show relatively short clearance times, in the order of 2.5–6 h. The dicarboxylic acid porphyrins, proto-, hydroxyethylvinyldeutero-and hematoporphyrin IX have clearance times of 7.8, 12.2 and 14.7 h respectively. The mixture hematoporphyrin derivative has an intermediate clearance time of 12.6 h. N -methylated porphyrins show clearance times in the vicinity of 15–22 h. Monoaspartyl chlorin e₆ shows the longest clearance time of all porphyrin derivatives measured (30.3 h).     

CLEARANCE TIMES OF PORPHYRIN DERIVATIVES FROM MICE AS MEASURED BY in vivo FLUORESCENCE SPECTROSCOPY

The clearance times of 17 different porphyrin derivatives from SKH:HR-1 mice have been measured using the technique of in vivo fluorescence spectroscopy. This technique monitors the in vivo porphyrin fluorescence observed from the external skin surface. Most hydrophilic porphyrin derivatives show relatively short clearance times, in the order of 2.5-6 h. The dicarboxylic acid porphyrins, proto-, hydroxyethylvinyldeutero- and hematoporphyrin IX have clearance times of 7.8, 12.2 and 14.7 h respectively. The mixture hematoporphyrin derivative has an intermediate clearance time of 12.6 h. N-methylated porphyrins show clearance times in the vicinity of 15-22 h. Monoaspartyl chlorin e6 shows the longest clearance time of all porphyrin derivatives measured (30.3 h).     

Time-resolved fluorescence spectroscopy of hematoporphyrin, mesoporphyrin, pheophorbide a and chlorin e6 in ethanol and aqueous solution

The fluorescence decay I(t) and time-resolved spectra I(lambda, t) of some porphyrins and chlorins in ethanol and phosphate-buffered aqueous solution were investigated with a time-correlated single-photon-counting apparatus with a mode-locked Ar+ laser (514.5 nm) as the excitation source. The fluorescence of hematoporphyrin, mesoporphyrin and pheophorbide aa is considerably influenced by the conditions of aggregation (these compounds undergo aggregation in phosphate-buffered solution but not in ethanolic solution). The fluorescence decay of chlorin e6 which remains monomeric in both solvents is single exponential in all cases. The fluorescence spectra of hematoporphyrin, mesoporphyrin and pheophorbide a in phosphate-buffered solution are shifted with respect to the spectra obtained in ethanol; moreover, a new emission band (X band) appears, whose intensity increases on increasing the amount of equilibrium aggregates and shows a fast fluorescence decay. For hematoporphyrin and mesoporphyrin the appearance of the X band emission appears to be correlated with irreversible photoprocesses leading to fluorescent photoproducts. Analysis of the reported fluorescence spectra of cancer cells after incubation with hematoporphyrin derivative suggests that the fluorescent photoproducts might be formed also in vivo.     

IN VIVO FLUORESCENCE OF TUMORS AFTER TREATMENT WITH DERIVATIVES OF HEMATOPORPHYRIN

Abstract— Administration of a mixture of porphyrins termed HPD (hematoporphyrin derivative) to mice bearing the Lewis lung tumor leads to preferential accumulation of fluorescence at tumor loci in vivo after 48 h. HPLC analysis shows that the fluorescent species consist of hematoporphyrin and its dehydration products. But injection of these porphyrins does not lead to fluorescence localization. The intracellular fluorescence which is observed apparently arises from intracellular degradation of the tumor-localizing component of HPD. These fluorescent species represent only a small fraction of the total accumulated porphyrin pool; a larger weakly-fluorescent porphyrin pool is also present, and may be the major factor in tumor photosensitization.     

X-RAY INDUCED VISIBLE LUMINESCENCE OF PORPHYRINS

A concept has been presented whereby X-ray irradiation can be used to induce visible luminescence of chromophores such as porphyrins. The essential aspects of the idea have been demonstrated in a supramolecular assembly consisting of a water-dispersed polystyrene latex with an embedded scintillating compound, 2,5-diphenyloxa-zole, and an externally attached hematoporphyrin. X-ray excitation of the assembly yields an emission spectra typical for hematoporphyrin with fluorescent yields. of up to 3% with respect to 2,5-diphenyloxazole emission. Significant quenching in the presence of dioxygen indicates that singlet oxygen is formed at atmospheric conditions.     

烟酸修饰尾式卟啉的合成及其与人血清白蛋白的相互作用

合成了烟酸分子修饰的自由卟啉o-(niacin)C2O-T(3p-OCH3)PP、p-(niacin)C2O-T(3p-OCH3)PP及锌配合物o-(niacin)C2O-T(3p-OCH3)PPZn、p-(niacin)C2O-T(3p-OCH3)PPZn.经元素分析、紫外-可见光谱、核磁共振氢谱(1HNMR)、红外(IR)光谱等对结构进行了表征,并通过量子化学方法计算了锌卟啉的最低能量构型.实验结果表明:o-(niacin)C2O-T(3p-OCH3)PPZn中侧链烟酸基团处于卟啉环上方,烟酸基团中N原子与卟啉环中Zn2+存在着Zn―N间的分子内配位作用,而p-(niacin)C2O-T(3p-OCH3)PPZn中侧链烟酸基团处于卟啉环较远的位置,一个锌卟啉的中心Zn2+与另一个锌卟啉烟酸中N原子之间存在着Zn―N间的分子间配位作用.同时,为模拟金属卟啉的生物功能,采用荧光光谱滴定法测定了金属锌卟啉与人血清白蛋白相互作用的光谱性质.荧光光谱实验结果显示:金属锌卟啉与人血清白蛋白(HSA)之间发生了较强的静态荧光猝灭作用,反应机理是以氢键或van der Waals力结合反应.按照Stern-Volmer方程、Lineweaver-Burk双倒数方程分析和处理实验数据,得到了反应的猝灭常数、结合常数和热力学参数等.     

Synthesis of 5-dialkyl(aryl)aminomethyl-8-hydroxyquinoline dansylates as selective fluorescent sensors for Fe3+

A series of 5-dialkyl(aryl)aminomethyl-8-hydroxyquinoline dansylates were synthesized and their fluoroionophoric properties toward representative alkali ions, alkaline earth ions and transition metal ions were investigated. Among the selected ions, Fe3+ caused considerable quenching of the fluorescence, while Cr3+ caused quenching to some extent. The absence of any significant fluorescence quenching effects of the other ions examined, especially Fe2+, renders these compounds highly useful Fe3+-selective fluorescent sensors.     

Fe3+存在下磺胺甲恶唑与牛血清白蛋白相互作用的光谱学研究

在模拟生理条件下,应用荧光光谱、紫外吸收光谱以及傅立叶变换红外光谱研究Fe3+存在下磺胺甲恶唑(Sulfamethoxazole,SMZ)与牛血清白蛋(Bovine Serum Albumin,BSA)的相互作用.结果表明,Fe3+存在时SMZ与BSA结合常数增大,作用力类型由疏水作用力转变为氢键和范德华力.无论Fe3...     

FEMTOSECOND STUDIES OF HEMATOPORPHYRIN DERIVATIVE IN SOLUTION: EFFECT OF pH AND SOLVENT ON THE EXCITED STATE DYNAMICS

Abstract We report direct femtosecond measurements of the excited state dynamics of hematoporphyrin derivative (HpD) in solution. The dynamics are found to be very sensitive to the solvent and pH of aqueous solutions. The decay of the excited singlet states is much faster in acidic and pH 7 buffer aqueous solutions (<230 ps) than in basic aqueous solutions or organic solvents (> 10 ns). The dynamical results show strong correlation with static fluorescence measurements: weaker fluorescence in acidic and pH 7 buffer solutions corresponding to shorter-lived excited states. A new fast decay component with a time constant around 5 ps is identified both in acidic aqueous solutions and in organic solvents such as acetone and attributed to internal conversion from the second to the first excited singlet state of aggregates or certain oligomers in HpD, in accord with the observation that the fast decay component is larger at a higher concentration. Oxygen is found to have no effect on the dynamics on the time scale investigated, 1 ns, indicating that oxygen quenching of the singlet excited states is insignificant on this time scale. The sensitive solvent and pH dependence of the excited state dynamics has important clinical implications in the use of HpD as a photosensitizing agent.     

Electrofluorescence of MEH-PPV and its oligomers: evidence for field-induced fluorescence quenching of single chains

Electrofluorescence (Stark) spectroscopy has been used to measure the trace of the change in polarizability (trDeltaalpha) and the absolute value of the change in dipole moment (|Deltamu|) of the electroluminescent polymer poly[2-methoxy,5-(2'-ethyl-hexoxy)-1,4-phenylene vinylene] (MEH-PPV) and several model oligomers in solvent glass matrixes. From electrofluorescence, the measured values of trDeltaalpha increase from 500 +/- 60 A(3) in OPPV-5 to 2000 +/- 200 A(3) in MEH-PPV. The good agreement found between these values and those measured by electroabsorption suggests the electronic properties do not differ strongly between absorption and emission, in contrast to earlier predictions. Evidence of electric-field-induced fluorescence quenching of MEH-PPV in dilute solvent glasses was found. When normalized to the square of the applied electric field, the magnitude of quench is comparable to that reported in the literature for thin films of MEH-PPV. In addition, fluorescence quenching was also observed in the oligomers with a magnitude that increases with increasing chain length. By using the values of trDeltaalpha measured by electrofluorescence, a model is developed to qualitatively explain the chain length dependence to the fluorescence quench observed in the oligomers as a function of exciton delocalization along the oligomer backbone. Various explanations for the origin of this quenching behavior and its chain length dependence are considered.     

Influence of the solvent on the quenching of the fluorescence of anthracene by aromatic amines

The influence of the solvent on the quenching of the fluorescence of anthracene by diethylaniline (DEA) and aniline has been investigated. Fluorescence quenching in these systems obeys the equation of Stern and Volmer. A transition from kinetics-controlled to diffusion-controlled processes takes place with the increase in viscosity () in nonpolar solvents. In polar solvents the quenching rate is limited by diffusion over the whole viscosity range investigated. These peculiar effects of the solvent can be explained by the traditional three-stage quenching scheme of the singlet-excited anthracene by electron donors. It is also possible that the increase in the quenching constant () in polar as compared to nonpolar solvents with the same is related to an increase in the rate constant of non-emitting deactivation in polar media, induced by the quenching agent. In the case of the quenching of fluorescence of anthracene by aniline the process is diffusion-controlled, regardless of the nature of the solvent.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 3, pp. 370–374, May–June, 1985.     

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.     

Photophysical Properties of Safranine T in Aqueous Glycol Oligomer Mixtures

The photophyscial behavior of the dye Safranine T in the ground and excited states in aqueous mixtures of glycol oligomers was investigated by absorption and fluorescence spectroscopic techniques. The formation of a 1:1 complex in the excited state was inferred from fluorescence studies. The calculated equilibrium constants of the complex are directly proportional to the molar mass of the glycol. Microviscosity values of the aqueous glycol mixtures were determined by employing Auromine O as a fluorescence probe. Stokes shift values were correlated with the bulk dielectric constant and the microviscosity of the media. Also employing Stokes shifts, solvent parameters such as the Kowoser Z values and the intramolecular charge transfer energy, E _T (30), were evaluated. The fluorescence quenching of Safranine T by the inorganic ions [Fe(CN)₆]³⁻, [Fe(CN)₆]⁴⁻, and [I]⁻ in aqueous oligomer mixtures at a fixed concentration was investigated. The ions influenced the quenching process to different extents, and the efficiency of quenching of the dye in the glycol media for [Fe(CN)₆]⁴⁻ and [I]⁻ ions follows the order EG > DEG > TEG > TTEG. In the case of ferricyanide ion the reverse order was observed. The microviscosity and bulk dielectric constant of the media played a major role in the collisional quenching process.     

Spectroscopic investigations in molecularly organized solvent media. Part 3. Examination of the nitromethane selective quenching rule in aqueous anionic + cationic and anionic + nonionic mixed surfactant solutions

Applicability of the nitromethane selective quenching rule for discriminating between alternant versus nonalternant polycyclic aromatic hydrocarbons (PAHs) is examined for 20 representative PAH solutes dissolved in micellar sodium dodecylsulfate (SDS) + cetyltrimethylammonium bromide (CTAB), SDS + dodecyltrimethylammonium bromide (DTAB), SDS + Brij-35, and SDS + sodium octanoate (SO) mixed surfactant solvent media. Experimental results show that nitromethane quenched fluorescence of all 8 alternant PAHs studied in the four different solvent systems. Unexpected quenching behavior was observed, however, in the case of nonalternant PAHs. Nitromethane quenched fluorescence emission of nonalternant PAHs dissolved in the SDS + SO solvent media, which is contrary to the selective quenching rule. In the case of the mixed anionic + cationic surfactant solvent media, nitromethane quenching selectivity was restored at concentration ratios of approximately 4 : 1 (anionic:cationic) or less. Received: 22 May 1997 / Revised: 29 September 1997 / Accepted: 3 October 1997     

以共价键相连的卟啉-酞菁化合物分子内能量传递及光诱导电子转移

合成了叶啉与酞菁以共价键连接起来的双发色团分子。测定了它们的吸收光谱,荧光光谱,荧光寿命等。计算了分子内能量传递过程的效率(φ_EnT)及速率常数(κ_EnT)。结果表明:在稀溶液中,卟啉与酞菁等克分子混合时,观察不到分子间能量传递过程现象的发生;而双发色团分子的分子内能量传递过程则明显发生了,其效率(φ_EnT=13～70%)与速率常数(κ_EnT=1.2×10⁷～2.0×10⁸s^-1)取决于分子的结构类型。电子转移与能量传递过程与介质性质有关。在极性溶剂中有利于电子转移过程的进行,而不利于能量传递过程;在非极性溶剂中,则有利于能量传递过程的进行,而不利于电子转移。 选择性激发酞菁发色团,观测到了只有电子转移发生的过程,其电子转移效率达到38%。     

Spectroscopic investigations in molecularly organized solvent media. Part 3. Examination of the nitromethane selective quenching rule in aqueous anionic + cationic and anionic + nonionic mixed surfactant solutions

Applicability of the nitromethane selective quenching rule for discriminating between alternant versus nonalternant polycyclic aromatic hydrocarbons (PAHs) is examined for 20 representative PAH solutes dissolved in micellar sodium dodecylsulfate (SDS) + cetyltrimethylammonium bromide (CTAB), SDS + dodecyltrimethylammonium bromide (DTAB), SDS + Brij-35, and SDS + sodium octanoate (SO) mixed surfactant solvent media. Experimental results show that nitromethane quenched fluorescence of all 8 alternant PAHs studied in the four different solvent systems. Unexpected quenching behavior was observed, however, in the case of nonalternant PAHs. Nitromethane quenched fluorescence emission of nonalternant PAHs dissolved in the SDS + SO solvent media, which is contrary to the selective quenching rule. In the case of the mixed anionic + cationic surfactant solvent media, nitromethane quenching selectivity was restored at concentration ratios of approximately 4?:?1 (anionic:cationic) or less.     

咔唑基四苯乙烯多功能发光材料的合成与性能

设计合成了一个以四苯乙烯为核心,四端连接长烷基链的咔唑基四苯乙烯衍生物(TPECz),该化合物具有典型的聚集诱导发光(AIE)特性.紫外光谱(UV-Vis)、荧光光谱(PL)、热重(TG)和示差扫描量热(DSC)研究表明,该化合物属于深蓝光材料、具有较好的热稳定性,并且对金属Fe3+具有很好的识别作用,有望用于金属离子检测;同时,该化合物外围的咔唑基团具有电化学活性,采用电化学聚合方法可制备其聚合物交联荧光薄膜,扫描电镜(SEM)和原子力显微镜(AFM)研究表明,该荧光薄膜表面平整,有望用于制备有机电致发光器件(OLED),可见该化合物是一种多功能材料.     

Role of hydrogen bonding in the photophysical properties of isomeric tetrapyridylporphyrins in aprotic solvent

Extensive photophysical properties of isomeric tetra-2-pyridylporphyrin (TpyP(2)), tetra-3-pyridylporphyrin (TpyP(3)), and tetra-4-pyridylporphyrin (TpyP(4)) have been studied in the presence of a series of phenols of increasing hydrogen bonding power in dichloromethane solution by employing UV/vis spectroscopy; steady-state, time-resolved fluorescence spectroscopy; and transient absorption spectroscopic techniques. The change of absorption spectra of all three porphyrins as a function of different phenol concentrations established the preference of hydrogen bonded complex formation to the peripheral pyridyl nitrogen rather than the pyrrole nitrogen of the porphyrin macrocycle. The fluorescence behaviors of the porphyrins which were observed upon addition of different phenols point to a marked dependence on the nature of the added phenols. Phenols with an electron withdrawing group do not quench the fluorescence of porphyrins, whereas phenols with an electron donating group quench the singlet porphyrin both in static and dynamic pathways. A remarkable difference in quenching behaviors of singlet excited porphyrin by 4-methylphenol (4-MePhOH) and 4-MeOPhOH/4-EtOPhOH (4-EtOPhOH = 4-ethoxyphenol) are observed. The quenching of singlet excited porphyrins by 4-MePhOH is attributed to be purely static in nature, and the H-bond provides a strong nonradiative channel to singlet excited porphyrins. However, the quenching of singlet excited porphyrins by 4-MeOPhOH/4-EtOPhOH is mostly dynamic, and it is ascribed to be the reductive quenching of single excited porphyrins. Picosecond transient absorption study with TpyP(2) and 4-MeOPhOH provides the evidence of porphyrin radical anion and phenol radical cation of equal lifetime, which indicates the fact that electron transfer occurs from phenol to singlet excited porphyrin. The temperature effect on dynamic quenching by 4-MeOPhOH/4-EtOPhOH and kinetic deuterium isotope effect established the reaction to be a photoinduced concerted proton coupled electron transfer.     

Coordination Studies of Iron(II) Protoporphyrin IX and Iron(II) Hematoporphyrin IX with 4,4′-Dipyridyl and other Nitrogenous Bases

Abstract

The results of spectral studies of iron(II) protopor-phyrin IX and iron(II) hematoporphyrin IX with several substituted pyridines are reported. The existence in solution of an iron(II) porphyrin complex coordinated to a water molecule and to a substituted pyridine was shown by isolation of the complex from solution. The complex isolated was dimeric inono-4,4′-dipyridyl diaquo iron(II) hematoporphyrin. Addition of ethanol to the aqueous solvent inhibits coordination of iron(II) porphyrins with substituted pyridines. The protoporphyrin ring enhances coordination relative to the hematoporphyrin ring.