Interaction of water-soluble bridged porphyrin with DNA

A water-soluble porphyrin dimer (Por Dimer) containing eight positive charges, bridged by 4,4′-dicarboxy-2,2′-bipyridine, has been synthesized. With Meso-tetrakis(N-methyl-pyridium-4-yl)porphyrin (H₂TMPyP) as the reference compound, the water-soluble porphyrin dimer was investigated for its interaction with DNA by absorption, fluorescence, and circular dichroism (CD) spectroscopy. The apparent affinity binding constant (K _app = 1.2 × 10⁶) of Por Dimer binding to CT DNA was measured by a competition method with ethidium bromide (EB) (that of H₂TMPyP was 6.9 × 10⁶). The cleavage ability of Por Dimer to pBR322 plasmid DNA was studied by gel electrophoresis. The results suggest that the binding modes of Por Dimer were complex and involve both intercalation and outside binding. __________ Translated from Acta Chimica Sinica, 2007, 65(22): 2597–2603     

Synthesis of water-soluble porphyrin and the corresponding highly planar benzoporphyrin without meso-substituents

Water-soluble bicycloporphyrin and benzoporphyrin having octacarboxyl groups are synthesized from the corresponding octaester porphyrin by simple hydrolyzing and heating procedures. These compounds are characterized by UV-vis, NMR and mass spectroscopies. The benzoporphyrin octacarboxylic acid exhibits extremely high planarity in spite of its poly-substitution.     

Flow injection analysis combined with a hydrothermal flow reactor: application to kinetic determination of trace amounts of iridium using a water-soluble porphyrin

A new type of flow injection analysis (FIA) system combined with an extremely high temperature reactor, namely hydrothermal flow injection analysis (HT-FIA), has been successfully constructed for the first time. Fundamental characteristics of HT-FIA system, such as limit temperature, pressure, and flow rate, were examined as an analytical tool. To demonstrate the potential of HT-FIA, the catalytic activity of Ir(IV) for the degradation of a water-soluble porphyrin, 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid (TPPS), was applied for the determination of trace amounts of Ir(IV). Although the indicator reaction is very slow at room temperature, HT-FIA system enables to accelerate the reaction. A linear calibration curve was acquired at 10⁻⁸ M level of Ir(IV) and the interferences of platinum group metal ions were examined. The detection limit of Ir(IV) was 5.8 × 10⁻⁹ M and a fairly high-throughput analysis, of which more than 30 samples can be analyzed within 80 min, was achieved.     

Interaction of cationic surfactant and anionic polyelectrolytes in mixed aqueous solutions

Surfactant–polymer interactions in aqueous solutions have been studied using dynamic surface tension, polyelectrolyte titration, nephelometric turbidity, and dynamic light scattering. For the preparation of complexes, a technical cationic surfactant was used in combination with two poly(maleic acid-co-polymers) of similar structure but different hydrophobicity. The dynamic surface tensions of mixed solutions as functions of surfactant concentration at constant polyelectrolyte content, as well as changes in the surface activity due to the influence of polyanion at constant surfactant concentration are discussed in terms of a complex or aggregate formation in the bulk phase. The interaction of the surfactant with poly(maleic acid-alt-propene) (P-MS-P) and poly(maleic acid-alt--methylstyrene) (P-MS-MeSty), respectively, is strong in both cases and results in the formation of nanoparticles with properties depending on the composition of the corresponding mixture.     

Interaction and photodynamic activity of cationic porphyrin derivatives bearing different patterns of charge distribution with GMP and DNA

The interaction of amphiphilic cationic porphyrins, containing different patterns of meso-substitution by 4-(3-N,N,N-trimethylammoniumpropoxy)phenyl (A) and 4-(trifluoromethyl)phenyl (B) groups, with guanosine 5′-monophosphate (GMP) and calf thymus DNA have been studied by optical methods in phosphate buffer solution. The properties of these synthetic porphyrins were compared with those of representative standard of anionic 5,10,15,20-tetra(4-sulphonatophenyl)porphyrin (TPPS₄⁴⁻) and cationic 5,10,15,20-tetra(4-N,N,N-trimethylammonium phenyl)porphyrin (TMAP⁴⁺). Stable complexes with GMP were found for cationic porphyrins, except for monocationic AB₃⁺. The binding constant (K_GMP  10⁴ M⁻¹) follows the order: A₃B³⁺  ABAB²⁺ > A₄⁴⁺  TMAP⁴⁺. Also, interaction with DNA was observed for all evaluated cationic porphyrins. For these related cationic porphyrins, the binding constant (K_DNA  10⁵ M⁻¹) increases with the number of cationic charges. On the other hand, the photodynamic activity of porphyrins was analyzed in solution of GMP and DNA. Monocationic AB₃⁺ is a less effective sensitizer to oxidize GMP in comparison with the other cationic porphyrins, in agreement with the lack of detected interaction with this nucleotide. The electrophoretic analysis of DNA indicates that photocleavage takes place when the samples are exposed to photoexcited tricationic and tetracationic porphyrins. In the presence of sodium azide the DNA decomposition was diminished. Also, reduction in the DNA photocleavage was observed under anoxic condition, indicating that oxygen is essential for DNA photocleavage sensitized by these cationic porphyrins. In addition, an increase in DNA degradation was not observed in deuteriated water. Therefore, an important contribution of type I photoreaction processes could be occurring in the DNA photodamage sensitized by these cationic porphyrins. These results provide a better understanding of the characteristics needed for sensitizers to produce efficient DNA photocleavage.     

水溶性金属卟啉与DNA相互作用的微量热法研究

叶琳化合物以其对肿瘤组织的特殊亲和性和光动力学效应受到广泛的重视，国内外研究报导甚多·自D79年nel等人山证实水溶性四一K甲基毗陡基）叶咐及其金属配合物能嵌入＊＊A的碱基之间后，人们以这类水溶性叶琳为模型利用各种物理和化学手段研究它们与＊NA相互作用［2，3］．但用微量热法进行研究尚未见报导．我们曾报导用共振拉曼光谱研究图1所示的二个水溶性金属叶琳ru（＊A仰）」和卜i（N＊＊刊I同＊＊A的作用＊‘］，本文进一步报导用微量热法和紫外可见光谱研究的结果．1实验部分1．1试剂将小牛胸腺DN以华美生物工程公司产品）直接…     

cis-Pyridyl core-modified porphyrins for the synthesis of cationic water-soluble porphyrins and unsymmetrical non-covalent porphyrin arrays

Synthesis of a series of 21-thia and 21-oxoporphyrin building blocks containing two pyridyl functional groups at the meso positions in a cis fashion is reported. The building blocks were used to synthesize a series of cationic water-soluble 21-thia and 21-oxoporphyrins. An unsymmetrical non-covalent trimer containing two dissimilar porphyrin cores such as one N₃S and two N₄ porphyrins cores was also constructed using the pyridyl porphyrin building blocks reported here.     

H-aggregation of cationic palladium-porphyrin as a function of anionic surfactant studied using phosphorescence, absorption and RLS spectra

Room temperature phosphorescence (RTP) was used as a useful analytical tool to investigate the interaction behavior between tetracationic meso-tetrakis (4-trimethylaminophenyl) porphyrin palladium (Pd-TAPP) and anionic sodium dodecyl sulfate (SDS). UV-vis absorption and resonance light scattering (RLS) were further applied to characterize the system. It was presumably suggested that nonspecific self-aggregates among porphyrins formed considering the relatively high concentration of Pd-TAPP. Furthermore, Pd-TAPP changed from free monomer/nonspecific aggregate to H-aggregate and then to out-micellized monomer/nonspecific aggregate as a function of SDS concentration. The fact that RTP signal enhanced obviously and excitation spectrum was blue-shifted by 1580cm(-1) in energy with respect to energy of free Pd-TAPP monomer demonstrated that 1:4 electrostatic interaction between Pd-TAPP and SDS led to the formation of the premicellar porphyrin-surfactant H-aggregates. The RLS spectrum reviewed that the formed H-aggregates were multiple porphyrin units, and UV-vis spectra revealed that cationic groups of monomers/nonspecific aggregates of Pd-TAPP were electrostatically attracted in favor of the surface of anionic micelles but were not encapsulated within apolar regions of SDS micelles when the concentration of SDS was above its critical micelle concentration (CMC).     

Interactions of temperature-responsive anionic polyelectrolytes with a cationic surfactant

The interactions of temperature-responsive copolymers of sodium 2-acrylamido-2-methyl-1-propanesulfonate (AMPS) and N-isopropylacrylamide (NIPAM) with a cationic surfactant, dodecyltrimethylammonium chloride (DTAC), have been studied. The content of AMPS in the copolymers ranged from 1.1 to 9.6 mol%. The surface activity was higher for the polymers with lower AMPS content. It was found that DTAC undergoes association with the polymer chain, forming mixed polymer-surfactant micelles. The values of cac for the polymers were found in fluorescence studies using pyrene as the fluorescent probe. They were in the range 0.9-3.6x10(-3) M and were lower for polymers with higher AMPS content. An increase in DTAC concentration up to about its cmc results in a decrease of the LCST (lower critical solution temperature) of the copolymers, while further increase above the cmc results in an increase of the LCST. The minimum value of LCST in the presence of the surfactant is lower than the LCST of NIPAM homopolymer.     

Interaction of sodium ions with cationic surfactant interfaces

The thermodynamically stable microemulsion and lamellar phases in the didodecyldimethylammonium bromide/water/n-decane ternary system were explored in the presence of NaBr to gain information on sodium ion-interface interactions. Experimental results, obtained by different NMR techniques, strongly suggest accumulation of sodium ions at the cationic interface. This apparently counterintuitive result is explained by invoking the dispersion potential experienced by the ions near the interface. A mechanism is proposed that can account for the dramatic shrinkage of the microemulsion phase region when an electrolyte is added.     

Synthesis and characterization of a novel double-tailed cationic surfactant

A novel double-tailed cationic surfactant, N,N′-didodecylacetamidinium bicarbonate, was prepared by reacting dimethylacetamide dimethyl acetal with dodecylamine, followed by reacting with dry ice. MSD, FTIR, ¹H NMR, ¹³C NMR, 2D-NMR were used to confirm its structure. The surfactant reduced the surface tension of pure water to 24.7 mN m⁻¹ and its critical micelle concentration was 8.75 × 10⁻⁵ M. Formation of vesicle was also observed.     

Solubilization of phenols in anionic polyelectrolyte gels with adsorbed cationic surfactant

Solubilization isotherms for various phenols in cetylpyridinium chloride (CPC)-polyelectrolyte gel aggregates have been determined in order to compare solubilization within these aggregates with that in free micelles and to examine the effects of gel chemistry and structure on solubilization. The isotherms describing solubilization are quite similar to those found for free surfactant in solution. Solutes that are more hydrophobic give rise to larger solubilization constants with trends similar to what is seen for hydrophobic effects in adsorption from aqueous solutions onto hydrophobic solids. The solubilization constants decrease as the fraction of solute in the aggregates increases, indicating that the solutes partition into the palisade region of the aggregates. Solubilization is found to be quite insensitive to changes in gel structure (cross-linker varying from 1% to 3%) and chemistry (poly(acrylic acid) versus poly(methacrylic acid) and neutralization from 50% to 100%). However, the switch from poly(acrylic acid) to poly(methacrylic acid) did give rise to a slight decrease in magnitude of the slope of the isotherm. The most significant factors appear to be the initial concentration of surfactant in solution and the ratio of surfactant solution to gel amount. A decrease in surfactant concentration (especially combined with an increase in solution volume) gives rise to a decrease in solubilization constants.     

Surface properties of mixed anionic/cationic surfactant solutions

Summary Published experimental surface pressures for mixtures of anionic and cationic surfactants are compared to what can be predicted from the surface behaviour of the separate constituents. Simple theory correctly predicts, for soluble surfactants, a large increase of surface pressure upon mixing an anionic and a cationic solution having the same surface pressure, and, for insoluble surfactants, a decrease of surface pressure upon mixing at a given area per long chain ion. These effects are due to the different adsorption characteristics of the four electroneutral combinations involved, and will occur even in the absence of specific surface interactions.

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Zusammenfassung Es wurden bekannte Oberflächendrucke für Mischfilme von Aniontensiden und Kationtensiden mit theoretischen Voraussagen, begründet auf dem Grenzflächenverhalten der einzelnen Komponenten, verglichen. Die einfache Theorie sagt richtig voraus, daß die Mischung zweier wäßriger Lösungen von Aniontensid bzw. Kationtensid mit gleichem Oberflächendruck, eine starke Erhöhung des Oberflächendruckes zur Folge haben muß, während die Mischung zweier unlöslicher Filme bei gegebener Tensidadsorption den Oberflächendruck herabsetzt. Dieses Verhalten wird aufgrund der verschiedenen Adsorptionseigenschaften der vier betreffenden Salze gedeutet, und ist von spezifischen Oberflächenwechselwirkungen unabhängig.

     

Synergism in mixtures of cationic surfactant and anionic copolymers

Surface tension measurements have been made in aqueous solutions of anionic hemiesters of an alternating copolymer of maleic acid and styrene, MAS-n with n=0-12, in the presence of dodecyltrimethylammonium bromide, DTAB. A synergistic aspect of surface tension reduction efficiency was observed for all systems studied. The pseudo-phase separation approach and regular solution approximation have been applied, and the interaction parameter, beta, and the mole fraction of DTAB in the adsorbed layer (on a surfactant/repetitive unit basis), X, were obtained. Negative values of beta, ranging from -3 to -11, were calculated. On the other hand, the molar fraction of DTAB varies from 0.52 to 0.26. These results are discussed in terms of hydrophobic effects on the distribution of the aggregates between the interface and the bulk of the solution. The conditions predicted by the model to obtain synergism in the tension reduction efficiency are completely satisfied in all cases.     

Interaction of chromophores in cationic/anionic dyes

The spectral properties of dyes containing colored organic cations and anions have been investigated in solvents differing in polarity. It has been established that the color of cationic/anionic dyes in low-polarity solvents is governed by the properties of the ion pairs that are formed. The chromophores in the ion pairs of cationic/anionic dyes interact, and this moves the absorption bands away from each other and redistributes their intensities.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 1, pp. 47–53, January–February, 1989.     

Interaction of surfactant with antistatic polymer thin layers

Thin layers made from three kinds of hydrophilic polymer were coated onto poly(ethylene terephthalate)(PET) fibers to study the interaction of an anionic surfactant, sodiumn-dodecyl benzenesulfonate, with the polymer layers. The coated layers include a) poly(vinyl alcohol) (PVA) crosslinked with glutaraldehyde [nonionic], b) crosslinked, sulfated PVA [anionic], and c) polyethyleneimine crosslinked with poly(ethyleneglycol diglycidylether) [cationic]. All of these coatings were found to reduce the electrostatic charging of the PET cloths, indicating that they were effectively coated with the hydrophilic polymers. The PET cloth coated with the thin layers was immersed in the aqueous solution of surfactant at 40°C for different durations and the electrostatic voltage as well as the weight change were determined after drying. When the cloth coated with the nonionic or the anionic layer was brought into contact with the surfactant, neither the electrostatic voltage nor the weight of PET changed. On the contrary, immersion in the surfactant solution brought about an increase in both the electrostatic voltage and the weight for the PET coated with the cationic layer. This suggested that the surfactant molecules were bound to the cationic layer, in contrast to the nonionic and the anionic layer. It was concluded that the binding was due to ion complexing between the cationic groups in the polymeric layer and the sulfate groups in the surfactant molecules.     

Modification of montmorillonite with cationic surfactant and application in electrochemical determination of 4-chlorophenol

Herein, montmorillonite calcium was exchanged with a cationic surfactant: cetyltrimethylammonium bromide (CTAB). The resulting CTAB-modified montmorillonite calcium (CTAB-MMT) shows higher accumulation efficiency to 4-chlorophenol compared with the unmodified MMT. At the CTAB-MMT-modified carbon paste electrode, the oxidation peak current of 4-chlorophenol remarkably increases. Based on this, a novel, sensitive and convenient electrochemical method was developed for the determination of 4-chlorophenol. The oxidation peak current of 4-chlorophenol is proportional to its concentration over the range from 5.0 x 10(-8) to 1.0 x 10(-5) mol L(-1). The limit of detection is evaluated to be 2.0 x 10(-8) mol L(-1) for 2 min accumulation. Finally this newly proposed method was successfully applied to determine 4-chlorophenol in water samples.     

Copolymerization of styrene and reactive surfactants in a microemulsion: control of copolymer composition by addition of nonreactive surfactant

The γ-ray-induced copolymerization of styrene and the surfactant monomer (surfmer) (11-acryloyloxy)undecyltrimethylammonium bromide, 1, – with and without the presence of the nonreactive surfactant N-dodecyltrimethyammonium bromide, 2, – was studied in a single-phase (1Φ) oil-in-water microemulsion. Upon exchange of 50 weight percent of 1 against 2 the 1Φ region could be increased to higher styrene content. Upon γ-ray irradiation a copolymer is formed: this copolymer exhibits a larger styrene-to-surfmer ratio than the original monomer mixture. This allowed the styrene-to-surfmer molar ratio in the resulting polymer to be varied from 0:1 to 4.3:1. The larger styrene-to-surfmer ratio originates from the simultaneous formation of homopolymer P-1, which is in accordance with the Candau–Leong–Fitch model of polymerization. Further information on particle size and material properties of the copolymers, which is not accessible by other preparation methods, is also given. Received: 30 July 1999 /Accepted: 24 November 1999     

Rigid films of an anionic porphyrin and a dialkyl chain surfactant

The 2D complex formed at the air-water interface between the dialkyl chain cationic surfactant, dihexadecyldimethylammonium bromide, and the anionic porphyrin, tetrakis-(4-sulfonatophenyl) porphine, was studied using surface pressure-area isotherms as well as X-ray and neutron reflection measurements. The surface structure of these films was determined by the use of simultaneously constrained analysis of the neutron and X-ray reflectometry data and BAM images. Isotopic contrast variation methods were employed to enhance the information content of the neutron reflection data. The rigid complex forms at the interface due to the electrostatic interaction between the cationic headgroups of the surfactant and the anionic functional groups at the meso position of the porphyrin. The surface pressure-area isotherms show three distinct regions on compression: an initial condensed phase that ends with a pressure peak at 36 mN m-1, a second plateau region of high compressibility, and a final condensed phase. BAM images show that at the beginning of the plateau region in the isotherm there is complete surface coverage by a monolayer. The constrained simultaneous fitting of neutron and X-ray data measured just prior to and after the pressure peak shows a structurally similar 2D complex at the interface. Modeling of X-ray reflectometry data also reveals that in the final high-pressure phase the film has folded to form a trilayer. The conclusion is that the plateau region of the isotherm is due to the formation of trilayer surface coverage through localized buckling or folding, and that after this is complete there is some condensation before final film collapse.