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At least 973 records · Page 54Linked to original sources
PubMed1984

Interaction of electron acceptors with the excited triplet state of Zn cytochrome c.

The decay rate of the excited triplet state of Zn cytochrome c was enhanced by electron acceptors including methyl viologen and ferric complexes of cyanide, oxalate, EDTA and cytochrome c at room temperature. Ferrous compounds were several orders of magnitude less effective than the respective ferric form in quenching the phosphorescence. In the presence of ferricytochrome c and ferricyanide the semilogarithmic plots of the decay curve showed an anomalous decay profile in which the rate of interaction appeared to accelerate after excitation. One explanation is that the quenching process was accelerated by a conformational change of the polypeptide chain around the excited triplet state porphyrin. Another explanation is that quenching occurs via an intermediate.

Animals↗
PubMed1994

Formation of charge separated state P+OA- and triplet state 3P at low temperature in Rhodobacter sphaeroides (R-26) reaction centers in which bacteriopheophytin a is replaced by plant pheophytin a.

Low temperature optical and photochemical properties of Rhodobacter sphaeroides (R-26) reaction centers, in which bacteriopheophytin a has been replaced by plant pheophytin a, are reported. Modified reaction centers preserve the ability for photoinduced electron transfer from the primary electron donor P to the primary quinone acceptor QA at 80K. The triplet state ESR signal of modified reaction centers with prereduced QA at 10K shows an electron spin polarization pattern and ZFS parameters analogous to those for the triplet state 3P in non-treated reaction centers. It was found that at low temperature both P+QA- and 3P states are formed via a precursor radical pair P+I- in which I is the introduced plant pheophytin molecule. This shows that acceptor systems of bacterial and plant (photosystem II) reaction centers are mutually replacable in structural and functional aspects.

Circular Dichroism↗
PubMed1994

On the site by which alpha-dendrotoxin binds to voltage-dependent potassium channels: site-directed mutagenesis reveals that the lysine triplet 28-30 is not essential for binding.

We constructed a synthetic gene encoding the published amino acid sequence of DTx from Dendroaspis angusticeps, a ligand of voltage-dependent postassium channels that facilitates neurotransmitter release. We expressed it in Escherichia coli as a fusion protein secreted in the culture medium. The recombinant DTx was generated in vitro by chemical treatment and recovered as two isoforms. One of them (rDTx), like the venom toxin, has an N-terminal pyroglutamate whereas the other (rQDTx) has a free N-terminal glutamine. Chromatographic differences between rDTx and natural DTx led us to re-examine the amino acid sequence of natural DTx. In contrast to what was previously published, position 12 was an Asp and not Asn. Despite this difference, rDTx and DTx had similar toxicity in mice and binding affinity to synaptosomes, suggesting that residue 12 is not important for DTx function. Nor is the N-terminal residue implicated in DTx function since rDTx and rQDTx also had similar biological activities. We also synthesized and expressed a mutant of the DTx gene in which the lysine triplet 28-30 was changed into Ala-Ala-Gly. The two resulting recombinant isoforms exhibited only small decreases in biological activity, excluding the possibility that the positively charged lysine triplet 28-30 of DTx is directly involved in the toxin functional site.

Amino Acid Sequence↗
PubMed1993

Genes with triplet repeats: candidate mediators of neuropsychiatric disorders.

Recently a new form of human mutation-expansion of trinucleotide repeats-has been found to cause the diseases of fragile X syndrome, spinal and bulbar muscular atrophy, myotonic dystrophy and, most recently, Huntington's disease. We review the emerging data on the genetics and neurobiology of these disorders. Three are characterized by unusual patterns of inheritance, in particular, genetic 'anticipation', in which the severity of the disorder increases and the age of onset decreases in successive generations of a pedigree. Several idiopathic neuropsychiatric disorders have features of inheritance consistent with anticipation. In bipolar affective disorder, there is evidence for both earlier age of onset and more severe illness in the second generation of a subset of unilineal pedigrees. There is also the suggestion of anticipation in some forms of schizophrenia, spinocerebellar atrophy and autism. Triplet repeats are present in additional known genes, both in coding regions and untranslated regions. Furthermore, many novel genes with triplet repeats are expressed in the human brain, and these are candidates to cause some forms of these neuropsychiatric disorders.

Humans↗
PubMed1986

Damages induced in lambda phage DNA by enzyme-generated triplet acetone.

Exposure of lambda phage to triplet acetone, generated via the oxidation of isobutanal by peroxidase, leads to genome lesions. The majority of these lesions are detected as DNA single-strand breaks only under alkaline conditions, and so true breaks do not occur. Also, no sites sensitive to UV-endonuclease from Micrococcus luteus were found in DNA from treated phage. The participation of triplet acetone in the generation of such DNA damage is discussed.

1-Propanol↗
PubMed1995

Triplet-state quenching in complexes between Zn-cytochrome c and cytochrome oxidase or its CuA domain.

The quenching of the triplet state of Zn-cytochrome c in electrostatic complexes with cytochrome oxidase and its soluble CuA domain has been studied by laser flash photolysis. The triplet state of free Zn-cytochrome c decayed with a rate of about 200 s-1. With the oxidase, biphasic decay with rate constants of 2 x 10(5) and 2 x 10(3) s-1, respectively, was observed. At high ionic strength (I = 0.2) the decay was the same as with free Zn-cytochrome c. The quenching was also eliminated by reduction of the oxidase. The decay rate in the complex with the CuA domain was 4 x 10(4) s-1. The results are interpreted in terms of rapid electron transfer to CuA and a slower one to cytochrome a. No electron transfer products were detected, because the backward reaction is faster than the forward one. This can be explained by the high driving force (1.1 eV) for the forward electron transfer, taking the system into the inverted Marcus region. The distance in the electrostatic complex between cytochrome c and the electron acceptor, presumed to be CuA, is calculated to be 16 A.

Animals↗
PubMed1990

Different lethal effects by enzyme-generated triplet indole-3-aldehyde in different Escherichia coli strains.

Strains of Escherichia coli which lack 4-thiouridine (S4U) exhibit a higher survival rate than their wild-type parents which contain S4U after treatment with enzyme-generated triplet indole-3-aldehyde. In a similar manner to results obtained with monochromatic 334 nm UV light, the survival is related to single-strand breakage of DNA in E. coli containing the pBR 322 plasmid. The effects of the excited states generated by an enzymatic system suggest that S4U is an important chromophore in the lethal effects observed. The results also suggest that the energy transferred from triplet indole-3-aldehyde to S4U may also be passed from S4U of t-RNA to DNA, possibly through a singlet oxygen intermediate generated by excited S4U, resulting in a decrease in the survival rate of E. coli containing S4U. These results emphasize the importance of excited states in biological systems.

DNA Damage↗
PubMed1994

Quenching of merocyanine 540 triplet state by nitroxyl radicals in liposomal systems: a laser flash photolysis study.

Laser flash photolysis experiments were undertaken to investigate the interaction between stearic acid nitroxide spin probes and photoexcited merocyanine 540 (MC540) in dimyristoyl-L-alpha-phosphatidylcholine liposomes (membrane model). The measurements of the paramagnetic signal decay kinetics of four different spin-labelled stearic acids (n-DSA) show that the direct interaction between the dye and the probe is affected by the position of the nitroxyl group along the carbon chain. Laser flash photolysis results reveal a significant decrease in the MC540 triplet lifetime in the presence of n-DSA, the effect depending on the depth at which the nitroxyl moiety is localized in the bilayer. Previous results on the rate of disappearance of the electron spin resonance (ESR) nitroxide signal on continuous photolysis of the same systems do not show the same dependence on the localization of the nitroxyl moiety in the liposome. Although the MC540 triplet state seems to be implicated in the reaction process, the results suggest that ESR and laser flash experiments demonstrate two different kinds of mechanism.

Dimyristoylphosphatidylcholine↗
PubMed2006

Electron-transfer mechanism of the triplet state quenching of aluminium tetrasulfonated phthalocyanine by cytochrome c.

The mechanism of electron-transfer from aluminium tetrasulfonated phthalocyanine triplet state to cytochrome c was investigated in this work. This reaction successfully quenches the dye triplet state due to the formation of complexes between the solute and the protein at the active site. The electron-transfer rate constant is around 3x10(7) s(-1), and is in accordance with previous results for the singlet excited state quenching [C.A.T. Laia, S.M.B. Costa, D. Phillips, A. Beeby. Electron-transfer kinetics in sulfonated aluminum phthalocyanines/cytochrome c complexes, J. Phys. Chem. B 108 (2004) 7506-7514.] in the framework of the Marcus theory, with a reorganization energy equal to 0.94 eV. The complex formation is diffusion controlled, but heterogeneities of the protein surface charge distribution lead to quenching rate constants smaller than predicted on a hard-spheres model with electrostatic interactions. Also the binding equilibrium constant is strongly affected by this phenomenon. Ionic strength plays an important role on the complex formation, but its effect on the unimolecular electron-transfer rate constant is negligible within experimental error.

Circular Dichroism↗
PubMed2006

Frequent recovery of triplet mutations in UVB-exposed skin epidermis of Xpc-knockout mice.

Mutations of the Xpc gene cause a deficiency in global genome repair, a subpathway of nucleotide excision repair (NER), in mammalian cells. We used transgenic mice harboring the lambda-phage-based lacZ mutational reporter gene to study the effect of an Xpc null mutation (Xpc-/-) on damage induction, repair and mutagenesis in mouse skin epidermis after UVB irradiation. UVB induced equal amounts of cyclobutane pyrimidine dimers (CPDs) and pyrimidine(6-4)pyrimidone photoproducts (64PPs) in mouse skin epidermis of Xpc-/- and wild-type mice. CPDs were not significantly removed in either of the mouse genotypes by 12h after irradiation, whereas removal of 64PPs was observed in the wild-type. Irradiation with 300 and 400J/m2 UVB increased the lacZ mutant frequency in the Xpc-/- epidermis to at least twice as high as in the wild-type. Ninety-nine lacZ mutants isolated from the UVB-exposed epidermis of Xpc(-/-)mice were analyzed and compared with mutant sequences from irradiated wild-type mice. The spectra of the mutations in the two genotypes were both highly UV-specific and similar in the dominance of C-->T transitions at dipyrimidine sites; however, Xpc-/- mice had a higher frequency of two-base tandem substitutions, including CC-->TT mutations, three-base tandem substitutions and double base substitutions that were separated by one unchanged base in a three-base sequence (alternating mutations). These tandem/alternating mutations included a remarkably large number of triplet mutations, a recently reported, novel type of UV-specific mutation, characterized by multiple base substitutions or frameshifts within a three-nucleotide sequence containing a dipyrimidine. We concluded that the triplet mutation is a UV-specific mutation that preferably occurs in NER deficient genetic backgrounds.

Animals↗
PubMed2005

Identification and reactivity of the triplet excited state of 5-hydroxytryptophan.

Both the neurotransmitter serotonin and the unnatural amino acid 5-hydroxytryptophan (5HT), contain the 5-hydroxyindole chromophore. The photochemistry of 5HT is being investigated in relation to the multiphoton excitation of this chromophore to produce a characteristic photoproduct with green fluorescence ('hyperluminescence'). Laser flash photolysis (308 nm) of 5HT in aqueous solution at neutral pH produces both the neutral 5-indoloxyl radical (lambda(max) 400-420 nm) and another transient absorption with lambda(max) 480 nm and lifetime of 2 micros in deaerated solutions. Based on quenching by oxygen and beta-carotene, the species at 480 nm is identified as the triplet excited state of 5HT. In acidic solution a new oxygen-insensitive intermediate with lambda(max) 460 is assigned to the radical cation of 5HT. Time-resolved measurements of luminescence at 1270 nm have shown that the triplet state of 5HT is able to react with oxygen to form singlet excited oxygen (1O2*) with a quantum yield of approximately 0.1. However, 5HT has also been found to be an effective quencher of singlet oxygen with a second order rate constant of 1.3 x 10(8) dm3 mol(-1) s(-1). The results are discussed in the light of recent observations on the multiphoton-excited photochemistry of serotonin.

5-Hydroxytryptophan↗
PubMed2006

Triplet photosensitization in cyercene A and related pyrones.

Mollusks of the Sacoglossa order contain a variety of polypropionate metabolites that are characterized by a pyrone chromophore, such as cyercene A and 9,10-deoxytridachione. Most often the pyrone is a 2-methoxy-gamma-pyrone but occasionally is a 4-methoxy-alpha-pyrone or hydropyrone. Members of this class of metabolites have been shown to undergo photochemical reactions of biosynthetic importance. An example is the photochemical conversion of 9,10-deoxytridachione to photodeoxytridachione, which has been observed in several mollusks. In this report, a series of gamma-pyrones and their alpha-pyrone analogs were synthesized and analyzed for photosensitizing activity. In all cases studied, the gamma-pyrone was a more efficient triplet sensitizer than the corresponding alpha-pyrone. Included in this set of molecules was the Sacoglossan metabolite cyercene A and its alpha-pyrone isomer. When irradiated in the presence of oxygen, cyercene A produced singlet oxygen at significantly higher rate than the corresponding alpha-pyrone isomer. Furthermore, the photoisomerization of cyercene A was quenched by piperylene with con-committant isomerization of the piperylene indicating that the isomerization proceeded through a triplet excited state. In contrast, the isomerization of the alpha-pyrone analog was not quenched. The implications of these photochemical results in terms of the biosynthesis and biological activity of Sacoglossan polypropionate metabolites are discussed.

Animals↗
PubMed2005

Resonance Raman spectra of n-pi* singlet-triplet transition of p-benzoquinone at low concentrations.

A weak visible absorption spectrum of p-benzoquinone (p-BQ) in CS2 due to n-pi* singlet-triplet transition was measured. Using the resonance Raman (RR) effect in liquid-core optical fiber (LCOF), we have obtained the 514.5 nm excited RR spectra of p-benzoquinone near 1445 cm(-1) and have demonstrated that the new characteristic RR band is attributed to the symmetric C=O stretch (nu(C=O)) of n-pi* singlet-triplet transition of p-BQ. The effect of solution concentration on the RR band was investigated at very low concentrations. The RR peak spreads toward short wavelength side with decreasing solution concentration ranging from 10(-7) to 10(-11) mol L(-1), whereas the blue-shift isn't obvious when the concentration is, at single molecule level, lower than 10(-11) mol L(-1). Our result is useful for single molecule detection to some extent.

Benzoquinones↗
PubMed2006

Reactivity of aromatic amines with triplet 1,8-dihydroxyanthraquinone: a laser flash photolysis study.

The property of the lowest excited triplet states of 1,8-dihydroxyanthraquinone (DHAQ) was investigated by using time-resolved laser flash photolysis at 355nm in organic solvents, i.e. acetonitrile and cyclohexane. The transient absorption spectra of the excited triplet DHAQ were obtained in acetonitrile, which have an absorption maximum at 480nm and two broad absorption bands around 350 and 650nm. 3DHAQ(*) is efficiently quenched by triphenylamine (TPA) via photoinduced electron transfer pathway, which was testified by the finding of TPA radical cation. In addition, aniline derivatives such as N,N-dimethylaniline (DMA), 3,5,N,N-tetramethylaniline (TMA), 4-dimethylaminobenzoic acid (DMABA) and dimethyl-p-toluidine (DMT) could also quench 3DHAQ(*) rapidly. Evidence for electron transfer interaction with anilines in acetonitrile was obtained from transient spectral characterization of formed radicals. Experimental k(q) values approach the diffusion-controlled rate limit, and decrease significantly from DMT (1.85x10(10)M-1s-1) to DMABA (1.95x10(9)M-1s-1). These k(q) values depend on the charge density on the "N" atom of anilines, which could be quantified by Hammett sigma constant.

Aniline Compounds↗
PubMed2004

Herpes simplex virus 1 infection is required to produce ICP27 immunoreactive triplet forms when ribosomal aminoacyl-tRNA translocation is blocked by cycloheximide.

Infected cell protein (ICP) 27 is an essential herpes simplex virus type 1 (HSV-1) phosphoprotein required for optimal viral DNA and early or late gene synthesis. Three slow-migrating immunoreactive species were detected using multiple anti-ICP27 antibodies following HSV-1 infection of HEp-2 and Vero cells in the presence of cycloheximide (CHX). Generation of the protein triplet moieties required transcription of the alpha27 gene. These forms were observed following infection with a series of recombinant viruses that produce truncated ICP27 polypeptides, suggesting that alternative splicing is not involved in the process. These ICP27 species were not observed following translation inhibition by puromycin (PUR). Synthesis of the triplet occurred by 6 hpi and CHX addition as late as 3 hpi still enabled their production. That the ICP27 species were detected in uninfected ICP27-expressing cells without CHX, but not in its presence, suggests a mechanism in which virus infection is required to produce the forms when ribosomal aminoacyl-transfer RNA (tRNA) translocation is blocked.

Animals↗
PubMed1989

Monomeric bacteriochlorophyll is required for the triplet energy transfer between the primary donor and the carotenoid in photosynthetic bacterial reaction centers.

Reaction centers from the carotenoidless mutant Rb. sphaeroides R26 were treated with sodium borohydride which is known to remove one of the accessory monomeric bacteriochlorophylls (BB). Subsequently, the carotenoid, spheroidene, was incorporated into the modified reaction centers. It is demonstrated by optical absorption and circular dichroism experiments that spheroidene, reconstituted into the sodium borohydride-treated Rb. sphaeroides R26 reaction centers, is bound in a single site, in the same environment and with the same structure as spheroidene reconstituted into untreated (native) Rb. sphaeroides R26 reaction centers. Transient optical and electron spin resonance spectroscopic data indicate that unless the accessory BB is present, the primary donor-to-carotenoid triplet energy transfer reaction is inhibited. These observations provide direct evidence for the involvement of the accessory BB in the triplet energy transfer pathway.

Bacterial Proteins↗