A PORPHYRIN-DNA EXCIPLEX: RESONANCE RAMAN SPECTRA OF ELECTRONICALLY EXCITED Cu(TMpy-P4) BOUND TO POLY(dA-dT)-POLY(dA-dT)

The resonance Raman spectra of water-soluble porphyrins, Cu(TMpy-P4) and Ni(TMpy-P4), and their mixtures with DNA, Poly(dG-dC).Poly(dG-dC), and Poly(dA-dT).Poly(dA-dT) were measured using 426 nm pulsed laser excitation (and 556 nm for some applications). At high laser power, the solution of Cu(TMpy-P4) mixed with DNA or Poly(dA-dT).Poly(dA-dT) exhibits new bands at 1550 and 1349 cm-1 that are not observed for Cu(TMpy-P4) alone or for Cu(TMpy-P4) mixed with Poly(dG-dC).Poly(dG-dC). These extra bands do not appear when the resonance Raman spectra are measured by a cw laser or by a pulsed laser with low power. Similar mixtures of M(TMpy-P4) (where M = Ni, Zn, Co, Mn, and H2) with these nucleic acids exhibit no such bands even by high power pulsed laser excitation. We attribute the new resonance Raman bands to an electronically excited Cu(TMpy-P4), stabilized by forming an exciplex with the A-T site of the nucleic acid. The minimum lifetime value of such an exciplex was estimated to be on the order of 10 ps.     

The mode of binding ACMA-DNA relies on the base-pair nature

A thermodynamic and kinetic study on the mode of binding of 9-amino-6-chloro-2-methoxi-acridine (ACMA) to poly(dA-dT)·poly(dA-dT) and poly(dG-dC)·poly(dG-dC) has been undertaken at pH = 7.0 and I = 0.1 M. The spectrophotometric, kinetic (T-jump), circular dichroism, viscometric and calorimetric information gathered point to formation of a fully intercalated ACMA complex with poly(dA-dT)·poly(dA-dT) and another one only partially intercalated (7%) with poly(dG-dC)·poly(dG-dC). The ACMA affinity with the A-T bases was higher than with the G-C bases. The two polynucleotide sequences give rise to external complexes when the ACMA concentration is raised, namely, the electrostatic complex poly(dA-dT)·poly(dA-dT)-ACMA and the major groove binding complex poly(dG-dC)·poly(dG-dC)-ACMA. A considerable quenching effect of the ACMA fluorescence is observed with poly(dA-dT)·poly(dA-dT), ascribable to face-to-face location in the intercalated A-T-ACMA base-pairs. The even stronger effect observed in the presence of poly(dG-dC)·poly(dG-dC) is related to the guanine residue from on- and off-slot ACMA positions.     

Circular dichroism spectroscopic studies reveal pH dependent binding of curcumin in the minor groove of natural and synthetic nucleic acids

For the first time, an interaction between the non-toxic, cancer chemopreventive agent curcumin and both natural and synthetic DNA duplexes has been demonstrated by using circular dichroism (CD) and absorption spectroscopy techniques. Upon addition of curcumin to calf thymus DNA, poly(dG-dC).poly(dG-dC) and poly(dA-dT).poly(dA-dT) solutions, an intense positive induced CD band centered around 460-470 nm was observed depending on the actual pH and Na+ ion concentration of the medium; no CD signal was obtained, however, with single stranded poly(dC). Interaction of curcumin with calf thymus DNA was observed already at pH 6.5 in contrast with poly(dG-dC).poly(dG-dC) which induces no extrinsic Cotton effect above a pH value of 5. The protonated, Hoogsteen base-paired structure of poly(dG-dC).poly(dG-dC) is necessary for curcumin binding while the alternating AT-rich polymer formed complexes with curcumin only at certain Na+ concentrations. Evaluation of the spectral data and molecular modeling calculations suggested that curcumin, this dietary polyphenolic compound binds in the minor groove of the double helix. The mechanism of the induced CD activity, the effects of the pH and Na+ ions on the ligand binding and conformation of the double helix are discussed in detail. As well as being an essentially new phenolic minor groove binder agent curcumin is also a promising molecular probe to study biologically important, pH and cation induced conformational polymorphisms of nucleic acids.     

Synthesis and DNA binding of novel water-soluble cationic methylcobalt porphyrins

Organocobalt derivatives of tetracationic water-soluble porphyrins are difficult to prepare via the typical reductive alkylation of the Co(II)(por) (porH(2) = porphyrin ligand). None have been reported. The problem may arise because the porphyrin core is made relatively electron poor by the positively charged peripheral groups. We have circumvented this problem by using the [Co(III)(NH(3))(5)CH(3)](2+) reagent, which inserts the Co(III)-CH(3) moiety directly into porH(2) in water under basic conditions. The method afforded two new [CH(3)Co(por)](4+) derivatives, [CH(3)CoTMpyP(4)](4+) and [CH(3)CoTMAP](4+), where [TMpyP(4)](4+) and [TMAP](4+) are the coordinated, NH-deprotonated forms of meso-tetrakis(N-methyl-4-pyridiniumyl)porphyrin and meso-tetrakis(N,N,N-trimethylaniliniumyl)porphyrin, respectively. The binding of the two new [CH(3)Co(por)](4+) cations to DNA and to the synthetic DNA polymers [poly(dA-dT)](2) and [poly(dG-dC)](2) was studied. Using published criteria by which changes in DNA viscosity and in the visible and CD spectra in the Soret region can be used to assess DNA binding, we conclude that both are outside binders. A large hypochromicity of the Soret bands of the [CH(3)Co(por)](4+) cations observed upon outside binding to DNA may indicate a high degree of self-stacking. The visible absorption and CD spectra of the [CH(3)Co(por)](4+) cations in the presence of 1:1 mixtures of [poly(dA-dT)](2) and [poly(dG-dC)](2) are nearly identical to those with [poly(dA-dT)](2) alone and are very different from those of [poly(dG-dC)](2) alone. Thus, both cations show a high preference for outside binding at AT-rich over GC-rich DNA sites. Upon binding of each of the [CH(3)Co(por)](4+) cations to all of the DNA polymers, the Soret bands exhibit blue shifts, whereas the Soret bands of the corresponding [(H(2)O)(2)Co(por)](5+) cations exhibit red shifts. The blue shifts strongly suggest that the [CH(3)Co(por)](4+) cations, particularly [CH(3)CoTMAP](4+), become five-coordinate forms to some extent on DNA binding; this result is the first good evidence for the presence at equilibrium of five-coordinate CH(3)Co(III)(N(4)) forms in water.     

Spectroscopic study of the interaction of pazelliptine with nucleic acids

The antitumor drug pazelliptine (PZE) binds to natural and synthetic DNA sequences at 100 mM NaCl, pH 7.0, as deduced from the absorption and fluorescence data. Scatchard plots constructed from the results obtained with poly(dG-dC)-poly(dG-dC) give binding constants of base pairs in the range (2–6) × 10⁵ M⁻¹. The modifications in the absorption and fluorescence spectra observed when PZE binds to various polynucleotides, namely poly(dA-dT)-poly(dA-dT), poly(dA)-poly(dT), poly(dG-dC)-poly(dG-dC) and calf thymus DNA. reveal a change in the protonation state of the drug upon binding, increasing the apparent pK_a of its 9-N nitrogen atom. The PZE excited state properties serve as a sensitive probe to distinguish between homo and hetero A-T sites as well as between AT and GC sites. Fluorescence studies reveal that energy transfer occurs from polynucleotide bases to the bound PZE chromophore, a result consistent with an intercalative mode of binding of the drug to DNA. The emission is enhanced when PZE is bound to A-T base pairs ( 30% increase of φ_F) whereas it is quenched in the vicinity of G-C base pairs ( 90% decrease of φ_F). Furthermore, the fluorescence spectrum obtained with calf thymus DNA is hardly distinguishable from that obtained with poly(dG-dC)-polu(dG-dC), suggesting a binding of PZE to G-C rich regions.     

Base-specific and enantioselective studies for the DNA binding of iron(II) mixed-ligand complexes containing 1,10-phenanthroline and dipyrido[3,2-a:2',3'-c]phenazine

Base specificity and enantioselectivity for the DNA binding of [Fe(phen)2(dppz)]2+ (phen=1,10-phenanthroline and dppz=dipyrido[3,2-a:2',3'-c]phenazine) have been studied by determining the equilibrium binding constant (Kb) of the iron(II) complex to calf thymus DNA (ct-DNA), poly[(dA-dT)2], poly[(dG-dC)2] and poly[(dI-dC)2] using spectrophotometric titration and by monitoring the CD spectral profile of the iron(II) complex in the presence and absence of different types of DNA using circular dichroism (CD) spectroscopy, respectively. It has been shown that [Fe(phen)2(dppz)]2+ prefers to intercalate into the A-T and I-C sequences of poly[(dA-dT)2] and poly[(dI-dC)2] rather than into the G-C sequences of poly[(dG-dC)2] or into the base pairs of ct-DNA. In contrast to previous reports, it is a surprising observation that the enantioselectivity of the DNA binding for [Fe(phen)2(dppz)]2+ is base-dependent in nature. The Delta-enantiomer of [Fe(phen)2(dppz)]2+ is preferentially intercalated into the base pairs of poly[(dG-dC)2] or ct-DNA as indicated by its CD spectral profiles. On the other hand, the Lambda-enantiomer of [Fe(phen)2(dppz)]2+ is favorably intercalated into poly[(dA-dT)2] or poly[(dI-dC)2] as suggested by the opposite CD spectral profile. This preferential binding of Lambda-[Fe(phen)2(dppz)]2+)for the A-T sequence may be attributed to the fact that the binding site for the A-T sequence is relatively facile and thus the steric effect caused by the ancillary (non-intercalated) phen ligands is alleviated. The degree of enantioselectivity represented by inversion constants (Kinv) decreases as the salt concentration in the solution increases, indicating that electrostatic interaction is also operating in the ct-DNA-binding events of the iron (II) complex.     

硫堇与寡核苷酸结合序列选择性的光谱研究

用UV-Vis吸收光谱、荧光光谱、圆二色谱以及核磁共振光谱等手段研究了硫堇(TH)与两个不同序列寡核苷酸的作用。TH与寡核苷酸作用后的吸收光谱和荧光光谱产生了明显的减色红移和荧光猝灭效应。分别计算了TH与[oligo d(GC)]2和[oligo d(AT)]2作用的荧光猝灭常数和结合常数,结果表明TH与GC序列的结合能力比与AT序列更强。通过TH与[oligo d(GC)]2作用后双螺旋链构象变化以及TH质子的1HNMR谱峰明显变宽,进一步说明TH与寡核苷酸结合的序列选择性。     

Sequence-dependent interactions of cationic naphthalimides and polynucleotides

The binding interactions of three naphthalimide derivatives with heteropoly nucleic acids have been evaluated using fluorescence, absorption and circular dichroism spectroscopies. Mono- and bifunctionalized naphthalimides exhibit sequence-dependent variations in their affinity toward DNA. The heteropoly nucleic acids, [Poly(dA-dT)]2 and [Poly(dG-dC)]2, as well as calf thymus (CT) DNA, were used to understand the factors that govern binding strength and selectivity. Sequence selectivity was addressed by determining the binding constants as a function of polynucleotide composition according to the noncooperative McGhee-von Hippel binding model. Binding affinities toward [poly(dA-dT)](2) were the largest for spermine-substituted naphthalimides (Kb = 2-6 x 10(6) M(-1)). The association constants for complex formation between the cationic naphthalimides and [poly(dG-dC)]2 or CT DNA (58% A-T content) were 2-500 times smaller, depending on the naphthalimide-polynucleotide pair. The binding modes were also assessed using a combination of induced circular dichroism and salt effects to determine whether the naphthalimides associate with DNA through intercalative, electrostatic or groove-binding. The results show that the monofunctionalized spermine and pyridinium-substituted naphthalimides associate with DNA through electrostatic interactions. In contrast, intercalative interactions are predominant in the complex formed between the bifunctionalized spermine compound and all of the polynucleotides.     

Study on spectroscopic characterization of Cu porphyrin/Co porphyrin and their interactions with ctDNA

The luminescence behaviors of Cu(II) meso-tetrakis (4-N-methyl-pyridiniumyl) porphyrin (Cu(II)TMPyP) and Co(II) meso-tetrakis (4-N-methyl-pyridiniumyl) porphyrin (Co(II)TMPyP) are investigated, and their interactions with calf thymus DNA (ctDNA) are studied by UV-vis, fluorescence and resonance light scattering (RLS) and based on the changes of UV-vis spectra, fluorescence and RLS spectra, the intrinsic binding constants of Cu(II)TMPyP/Co(II)TMPyP with ctDNA are obtained in the case of phosphate buffer solution (pH 7.2), respectively. According to the experimental results, it can be inferred that the interaction model of Cu(II)TMPyP with ctDNA is intercalative binding, while Co(II)TMPyP is the long-range assembly on the molecular surface of ctDNA.     

EXCITED STATE PROPERTIES OF THE N-(DEOXYGUANOSIN-8-YL)-2-AMINOFLUORENE ADDUCTS

The spectroscopic characteristics of adducts derived from the covalent binding of the carcinogen 2-aminofluorene to the C8 position of deoxyguanosine [N-(deoxyguanosin-8-yl)-2-amino-fluorene, dGuo-C8-AF], and from an adduct of similar structure formed with the synthetic polynucleotide poly(dG-dC).poly(dG-dC), were investigated. At 77 K both adducts are characterized by well-defined and rather narrow fluorescence emission spectra with maxima at 370 and 390 nm characteristic of the aromatic, monomolecular 2-aminofluorene (AF) residue. In contrast, at room temperature, the fluorescence is characterized by a broad, structureless emission band with a maximum at 460 nm in aqueous mixtures, shifting to 415 nm in solvents of lower polarity (100% propanol); the maxima are located at intermediate wavelengths in solutions of different propanol/water compositions, and this emission is attributed to an excited state complex (exciplex). The fluorescence quantum yield decreases when either the solvent polarity or the temperature are increased, varying from 5.4% (100% propanol) to 0.04-0.05% (100% H2O). The fluorescence decay profiles of dGuo-C8-AF adducts (measured at the National Synchrotron Light Source facility at the Brookhaven National Laboratory) can be roughly, but not exactly, modeled in terms of two exponential decay components in the range of about 0.3-1.0 ns with the propanol concentration greater than 60%; at lower propanol concentrations, a single short lifetime is observed and in 100% water solutions its value is 0.08 ns. The shorter lifetime, favored in solvent mixtures of higher polarities, is attributed to an exciplex with significant charge-transfer character.(ABSTRACT TRUNCATED AT 250 WORDS)     

Time-dependent binding mode of a cationic porphyrin dimer to poly[d(G-C)2] and Poly[d(A-T)2

The time-dependent binding mode of a porphyrin dimer to poly[d(G-C)2] and poly[d(A-T)2] was investigated by spectroscopic methods including absorption and circular and linear dichroism (CD and LD) spectroscopy. Immediately after mixing with poly[d(G-C)2], the porphyrin dimer exhibited red-shift and hypochromism in the absorption spectrum and negative CD and LD spectra. With further red-shift in absorption, the CD and LD magnitude in the Soret region became increasingly negative over time. After it was stabilized, the magnitude of the reduced LD (LDr) in the Soret region was larger than that in the DNA absorption region, indicating that the second porphyrin was also intercalated. Following the rapid intercalation of the first porphyrin, the very slow intercalation of the second followed with first-order kinetics. In the poly[d(A-T)2] case, a bisignate CD spectrum was observed in the Soret region suggesting stacking of the porphyrins. The small alteration in the CD spectrum and increased absorbance, which followed the initial rapid spectral change, was of the second order. This alteration in the spectral properties was attributed to the conformational change of poly[d(A-T)2] near the binding site because the overall shape of the CD spectrum was conserved in spite of the changes in the absorption spectrum.     

三维有序金掺杂纳米TiO_2修饰电极用于抗肿瘤药物与DNA相互作用的研究

利用模板法在氧化铟锡(ITO)电极表面制备了三维有序多孔结构的金掺杂纳米Ti O2薄膜修饰电极(3DOM GTD/ITO),并在此修饰电极上成功固定小牛胸腺DNA(ct DNA),从而构建了一种新型的DNA生物传感器(DNA/3DOM GTD/ITO),并通过透射电镜(TEM)、扫描电镜(SEM)对修饰电极的表面形貌进行表征。采用电化学交流阻抗(EIS)法研究了ct DNA在3DOM GTD/ITO修饰电极表面的固定情况,结果表明,ct DNA已被成功地固定在3DOM GTD/ITO修饰电极表面。采用循环伏安法、微分脉冲伏安法等电化学方法研究了抗肿瘤药物槲皮素(Qu)在3DOM GTD/ITO修饰电极表面的电化学性质及与ct DNA的相互作用。结果表明,Qu在3DOM GTD/ITO修饰电极表面有1对准可逆的氧化还原峰,其氧化还原反应为2电子和2质子的转移过程。Qu可与固定在修饰电极上的ct DNA发生较强的结合作用,其结合常数(K)为3.61×106L/mol。循环伏安实验、紫外-可见吸收光谱、分子荧光光谱、圆二色性光谱均表明Qu与ct DNA之间的相互作用模式为嵌插作用。Qu与ct DNA的碱基结合具有序列选择性,对Qu与聚(d G-d C)及聚(d A-d T)的结合常数进行计算,得到结合常数比K(d G-d C)/K(d A-d T)=3.5,表明Qu与ct DNA发生嵌插作用时更倾向于结合在GC富集区域。     

Calorimetric and thermal analysis studies on the binding of phenothiazinium dye thionine with DNA polynucleotides

Binding of the phenothaizinium dye thionine with four sequence specific deoxyribopolynucleotides, poly(dG-dC).poly(dG-dC), poly(dG).poly(dC), poly(dA-dT).poly(dA-dT), and poly(dA).poly(dT) has been investigated by means of thermal helix melting, isothermal titration calorimetry, and differential scanning calorimetry experiments. The binding affinity values evaluated from isothermal titration calorimetry suggests that thionine exhibits the highest binding affinity to poly(dG-dC).poly(dG-dC). The binding to poly(dG-dC).poly(dG-dC), poly(dA-dT).poly(dA-dT), and poly(dG).poly(dC) is exothermic and favoured by negative enthalpy changes while binding to poly(dA).poly(dT) is endothermic and anomalous. The values of heat capacity changes of the interaction are negative and in the range (?0.4 to ?0.5) kJ · K^?1 · mol^?1. The binding is characterized by strong stabilization of the polynucleotides against thermal strand separation. The binding affinity values derived from thermal melting data are in excellent agreement with those obtained from isothermal titration calorimetry data. Insights into the energetic aspects and guanine–cytosine selectivity of the DNA interaction of thionine have been obtained from these studies.     

Base-specific Photocleavage of DNA Induced by Pazelliptine Sensitization: Study of the Mechanism by Time-resolved Absorption and Fluorescence

The intercalating antitumoral drug pazelliptine (PZE) is able to photosensitize the formation of single- and double-strand breaks in supercoiled plasmid DNA and selective photocleavage at guanine residues is observed. In order to understand the mechanisms of DNA cleavage mediated by the photoexcited drug, singlet and triplet excited-state processes in PZE complexed with poly(dA-dT)-poly(dA-dT), poly(dG-dC)-poly(dG-dC) and calf thymus DNA have been investigated by means of single photon counting fluorescence decay and transient absorption techniques. For each complex, three different binding sites have been identified, due to the existence of different geometric structures of the drug in the ground state. For one type of binding site, a proton transfer reaction occurs in the singlet excited state whatever the nucleic acid environment. In contrast, the relaxation dynamics for the other two sites are found to depend widely upon the type of polynucleotide in which the drug has been intercalated. From the results of this study, we suggest that the photodynamic action of PZE does not originate from excitation of the drug in the environment of G-C base pairs but is initiated from its triplet state that reacts by electron transfer with the adenine bases. The specificity of cleavage could be the result of subsequent reactions leading to guanine oxidation.     

Immobilization of porphyrins in poly(hydroxymethylsiloxane)

Three tetracationic porphyrins differing in the position of charged nitrogen atoms on the peripheral substituents — 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP4), 5,10,15,20-tetrakis(N-methylpyridinium-2-yl)porphyrin (TMPyP2), 5,10,15,20-tetrakis(4-trimethylammoniophenyl) porphyrin (TMAPP), and hydrophobic 5,10,15,20-tetraphenylporphyrin (TPP), were immobilized by adsorption and encapsulation in poly(hydroxymethylsiloxane) (PHOMS). The so prepared porphyrin-PHOMS composites were characterized by porosimetry, scanning electron microscopy, fluorescence and diffuse reflectance UV-VIS spectroscopy. It was found that porphyrins are immobilized in the PHOMS matrix in the free base monomer form Their irradiation produced singlet oxygen O₂(¹Δ_g) with the lifetime of 10–30 μs.     

Singlet and triplet energy transfers in tetra-(meso-truxene)zinc(II)- and tetra-(meso-tritruxene)zinc(II) porphyrin and porphyrin-free base dendrimers

The synthesis, optical properties, and energy transfer features of four dendrimers composed of meso-tetrasubstituted zinc(II) porphyrin (ZnP) or a free base (P) central core, where the substituents are four truxene (Tru) or four tritruxene dendrons (TriTru), TruP, TriTruP, TruZnP, and TriTruZnP, are reported. Selective excitation of the truxene donors results in a photoinduced singlet energy transfer from the truxenes to the porphyrin acceptor. The rates for singlet energy transfer (k(ET)), evaluated from the change in the fluorescence lifetime of the donors (Tru and TriTru) in the presence and absence of the acceptor (P or ZnP) for TruP, TruZnP, TriTruP, and TriTruZnP, are 5.9, 1.2, 0.87, and 0.74 (ns)(-1) at 298 K and 2.6, 2.6, 2.7, and 1.2 (ns)(-1) at 77 K, respectively. A slow triplet-triplet energy transfer from truxene to porphyrin cores in glassy 2MeTHF at 77 K is also reported with rates of 1.3 × 10(3) and 0.10 × 10(2) s(-1) for TruZnP and TriTruZnP, respectively. If the Dexter mechanism for the triplet energy transfers is considered, these slow rates are easily explained by a poor orbital overlap between the truxene and porphyrin π systems. The fluorescence quantum yields (Φ(F)) are 0.20 and 0.16 for TruP and TriTruP and 0.08 and 0.10 for TruZnP and TriTruZnP, respectively at 298 K. At 298 K, a phosphorescence from TruZnP at 795 nm was also observed and is associated with the ZnP chromophore.     

Thermodynamic profiles of the DNA binding of benzophenanthridines sanguinarine and ethidium: A comparative study with sequence specific polynucleotides

Energetics of the binding of two known classical DNA intercalating molecules, ethidium and sanguinarine with four sequence specific polynucleotides, poly(dG-dC).poly(dG-dC), poly(dG).poly(dC), poly(dA-dT).poly(dA-dT), and poly(dA).poly(dT) have been compared under identical conditions. The binding of both the molecules was characterized by strong stabilization of the polynucleotides against thermal strand separation in optical melting as well as differential scanning calorimetry studies. Isothermal titration calorimetry results revealed that the binding of both sanguinarine and ethidium to poly(dG-dC).poly(dG-dC), poly(dA-dT).poly(dA-dT), and poly(dG).poly(dC) was exothermic and favoured by negative enthalpy changes. On the other hand, the binding of both molecules to poly(dA).poly(dT) was endothermic and entropy driven. The binding affinity values obtained from isothermal titration calorimetry data was in close proximity to that derived from thermal melting data. The heat capacity changes obtained from temperature dependence of the enthalpy change gave negative values in the range (?0.4 to 1.25) kJ · mol^?1 · K^?1 for the binding of ethidium and sanguinarine to these polynucleotides. The variations in the values indicate important differences in the formation of the complexes. New insights into the energetics and specificity aspects of interaction of these molecules to DNA have emerged from these studies.     

Simultaneous binding of meso-tetrakis(N-methylpyridinium-4-yl)porphyrin and 4',6-diamidino-2-phenylindole at the minor grooves of poly(dA).poly(dT) and poly[d(A-T)(2)]: fluorescence resonance energy transfer between DNA bound drugs

The spectral properties of meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP) bound to poly(dA).poly(dT) and poly[d(A-T)(2)] in the presence and in the absence of 4',6-diamidino-2-phenylindole (DAPI) have been studied. DAPI fits deeply into the minor groove of both poly(dA).poly(dT) and poly[d(A-T)(2)], and TMPyP is also situated at the minor groove. The nature of the absorption, circular dichroism (CD), and flow linear dichroism (LD) spectra of the TMPyP-poly(dA).poly(dT) and -poly[d(A-T)(2)] complexes in the Soret band is essentially unaffected whether the minor groove is blocked by DAPI or not, although small variations been noticed in the presence of DAPI. Furthermore, a close analysis of the reduced LD spectrum in the Soret band results in angles of approximately 80 degrees and 55 degrees between transition moments of the TMPyP and DNA helix axes in the absence of DAPI. All these observations indicate that the side of TMPyP whose structure resembles that of classical minor groove binding drugs does not fit deeply into the minor groove. This suggests that TMPyP binds across the minor groove: two positively charged pyridiniumyl rings interact electrostatically with negatively charged phosphate groups of DNA. When DAPI and TMPyP are simultaneously bound to poly(dA).poly(dT) or poly[d(A-T)(2)], the fluorescence intensity of DAPI decreases as TMPyP concentration increases, indicating that the excited energy of DAPI is transferred to TMPyP.     

Ground- and excited-state properties of Zn(II) tetrakis(4-tetramethylpyridyl) pophyrin specifically encapsulated within a Zn(II) HKUST metal-organic framework

We have examined the photophysical properties of Zn(II) tetramethylpyridyl porphyrin (ZnT4MPyP) specifically encapsulated within the cubioctahedral cavities of a ZnHKUST metal- organic framework. The encapsulated ZnT4MPyP exhibits a Soret maxima at ～458 nm that is bathochromically shifted relative to ZnT4PyP in ethanol solution (Soret maxima centered at 440 nm). The corresponding emission spectra of the encapsulated porphyrin exhibit resolvable bands centered at 636 and 677 nm relative to a single broad emission band of the ZnT4MPyP in ethanol solution centered at 636 nm with a shoulder situated near ～660 nm. The fluorescence lifetime of the encapsulated porphyrin is also perturbed relative to that of the free porphyrin in solution (1.88 ns for the encapsulated porphyrin relative to 1.2 ns in solution). These results are consistent with the ZnT4MPyP being in a more constrained environment in which the peripheral pyridyl groups have restricted rotational motion. The ZnT4MPyP triplet lifetime is also affected by encapsulation, giving rise to a longer lifetime (τ ≈ 3.3 ms) relative to that for the free porphyrin in solution (τ ≈ 1 ms). The triplet-state results indicate that nonplanar vibrational modes of the porphyrin leading to intersystem crossing are retained by encapsulation of the porphyrin but that either the density of vibrational states or the specific nonplanar modes coupling the singlet and triplet states may be perturbed, resulting in the longer observed lifetime.     

Sugar-poly(para-phenylene ethynylene) conjugates as sensory materials: efficient quenching by Hg2+ and Pb2+ ions

Three polar poly(para-phenylene ethynylene)s (PPE) were synthesized by utilizing the Heck-Sonogashira protocol. Two of the PPEs carry beta-glucopyranose substituents. Depending upon the linker used between the glycol units and the backbone, the fluorescence of these PPEs can be quenched by Hg2+ and Pb2+ to a varying degree. Monomeric model compounds that are substituted with only one glucose unit are not efficiently quenched. The presence of many glucose substituents in one PPE assembly led to a large increase in the binding constant to Hg2+ and quenching of the fluorescence was amplified.