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101.
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103.
With the objective of developing efficient DNA oxidizing agents, a new series of viologen-linked pyrene conjugates with the general formula PYLnV(2+), having a different number of methylene spacer units (Ln) was synthesized, and their interactions with nucleosides and DNA have been investigated through photophysical and biophysical techniques. The viologen-linked pyrene derivatives PYL1V(2+) (n =equals; 1), PYL7V(2+) (n = 7), and PYL12V(2+) (n = 12) exhibited characteristic fluorescence emission of the pyrene chromophore centered around 380 nm but with significantly reduced yields when compared to those of the model compound PYL1Et(3)(+). The fluorescence quenching observed in these systems is explained through an electron-transfer mechanism based on a calculated favorable change in free energy (DeltaG(ET) = -1.59 eV), and the redox species characterized through laser flash photolysis studies. Intramolecular electron-transfer rate constants (k(ET)) were calculated from the observed fluorescence yields, and the singlet lifetimes of the model compound and are found to decrease with increasing spacer length. The DNA binding studies of these systems through photophysical, chiroptical, and viscometric techniques demonstrated that these systems effectively undergo DNA intercalation with association constants (KDNA) in the range of 1.1-2.6 x 10(4) M(-1) and exhibit 2:1 sequence selectivity for poly(dG) x poly(dC) over poly(dA) x poly(dT). Photoactivation of these systems initiates electron transfer from the singlet excited state of the pyrene chromophore to the viologen moiety followed by an electron transfer from DNA to the oxidized pyrene. This results in the formation of stable charge-separated species such as radical cations of both DNA and reduced viologen as characterized by laser flash photolysis studies and subsequently the oxidized DNA modifications. These novel systems are soluble in buffer media, stable under irradiation conditions, and oxidize DNA efficiently and selectively through a cosensitization mechanism and hence can be useful as photoactivated DNA cleaving agents. 相似文献
104.
Triplet state mediated di-pi-methane rearrangements of dibenzobarrelenes give a variety of interesting synthons, formed as primary and secondary photoproducts. These synthons could find use for the synthesis of complex synthetic targets. This tutorial review highlights the photoisomerisation of some bridgehead substituted dibenzobarrelenes and the products derived from them. Selected examples of photoisomerisations proceeding through a tri-pi-methane pathway are also included. 相似文献
105.
Halogenated squaraine dyes 1 and 2 possess favorable photophysical and in vitro photobiological properties that make these new class of molecules interesting for photodynamic therapeutic applications. For a better understanding of the mechanism of their photobiological activity, we have analyzed the DNA damage and the cytotoxicity induced by these photosensitizers in mammalian cells and cell-free systems in the presence and absence of various additives and scavengers. Both photoactivated squaraines were found to be similar efficient in inducing single-strand breaks (SSB) in cell-free DNA when compared with the cellular DNA. Superoxide dismutase and catalase did not show any influence. However, the presence of tert-butanol and glutathione inhibited the formation of the DNA SSB, indicating an indirect (possibly squaraine radical mediated) mechanism under cell-free conditions. Replacing H2O in the buffer by D2O resulted in a five- to six-fold increase in the number of the SSB in cell-free DNA and a significant enhancement of the photocytotoxicity in mouse lymphoma cells. The results demonstrate that singlet oxygen is the major reactive species under cell-free and cellular conditions and confirm that squaraine-based sensitizers 1 and 2 can have potential applications in photodynamic therapy. 相似文献
106.
Catalyzed by Pd(0), trialkylsilyltrialkylstannane (R(3)Si-SnR'(3)) reagents undergo highly selective additions to 1,2-dien-7-ynes and 1,2-dien-8-ynes to give 2-vinylalkylidenecyclopentanes with silicon and tin substituents on the double bonds. Similar additions of distannanes and borostannanes show that the reactions with silylstannanes are superior in terms of ease of handling of the bifunctional reagents and the isolation of the products after the reaction. The chemo- and regioselectivities are controlled by the enhanced reactivity of the allene unit, while the (Z)-geometry of the exocyclic stannylvinylidene is a consequence of the syn-carbometalation and subsequent reductive elimination from Pd with retention of configuration at the vinyl carbon. Synthesis of highly functionalized pyrrolidines and indolizidines and the reluctance of certain kinds of allenynes and silicon-tin reagents to undergo the cyclization illustrate the scope and limitations of the reaction. Based on the isolation of intermediates, a mechanism for the formation of the cyclic compounds is proposed. Model transition states to explain the stereoselectivity in cyclization of substituted allenynes are provided. Further elaboration using the vinyltin and vinylsilane moieties should lead to highly functionalized carbocyclic and heterocyclic compounds. Under similar conditions, addition of silylstannanes to highly functionalized allenes gives E-allylstannanes with high stereoselectivity. Functional groups such as THP- and silyl-ethers, lactones, beta- and gamma-lactams, alpha,beta-unsaturated esters, olefins, and substituted acetylenes are tolerated under the reaction conditions. 相似文献
107.
Ravlee I Sivakumar R Muruganantham N Anbalagan N Gunasekaran V Thomas Leonard J 《Chemical & pharmaceutical bulletin》2003,51(2):162-170
In the present study, a series of 2-substituted-pyridines were synthesized and characterized by IR, (1)H-NMR and Elemental Analysis. The compounds were assayed against seizures induced by maximal electro shock (MES) and pentylenetetrazole (scMet). Neurologic deficit was evaluated by the rotarod test. The decrease in the elevated motor activity by introceptive chemical stimuli (amphetamine antagonistic activity) was studied at the dose level of 25 and 50 mg/kg, antihistaminic and cardiac activity were also studied. All the compounds exhibited significant anticonvulsant activity. Compounds 2-(2-hydroxy-3-piperazinopropylamino)-6-aminopyridine, 2-[2-hydroxy-3-(1-imidazolyl)propylamino]-6-aminopyridine, 2-[2-(1-imidazolyl)ethylamino]-6-methylpyridine and 2-[2-(methylamino)ethylamino]-6-methylpyridine were most active of the series against MES-induced seizures. Compounds 2-[2-(phenylamino)ethylamino]-6-aminopyridine, 2-[2-[bis(2-hydroxyethyl)amino]ethylamino]-6-aminopyridine, 2-[2-(diethylamino)ethylamino]-6-methylpyridine and 2-[2-hydroxy-3-(1-imidazolyl)propylamino]-6-methylpyridine exhibited significant decrease in the elevated motor activity at the dose of 50 mg/kg. Remarkable sympathetic blocking activity was observed with 2-(2-hydroxy-3-piperazinopropylamino)-6-aminopyridine, 2-(2-hydroxy-3-morpholinopropylamino)-6-methylpyridine and 2-(2-hydroxy-3-piperazinopropylamino)-6-methylpyridine only. Compounds 2-[2-(diethylamino)ethylamino]-6-aminopyridine, 2-[2-[bis(2-hydroxyethyl)amino]ethylamino]-6-aminopyridine, and 2-[2-(diethylamino)ethylamino]-6-methylpyridine exhibited significant blocking of histamine induced contraction on guinea pig ileum. 相似文献
108.
Danaboyina Ramaiah Abraham Joy Nese Chandrasekhar Nadukkudy V. Eldho Suresh Das Manapurathu V. George 《Photochemistry and photobiology》1997,65(5):783-790
Abstract— We describe the synthesis and photophysical studies, including measurements of quantum yields of triplet excited states and singlet oxygen generation of bis(3,5-dibromo-2,4,6-trihydroxyphenyl)squaraine (2) and bis(3,5-diiodo-2,4,6-trihydroxyphenyl)squaraine (3). These dyes exist in solution in the protonated, neutral, single and double depro-tonated forms, depending on pH. The pKa values of these dyes were found to be relatively lower than those of the parent bis(2,4,6-trihydroxyphenyl)squaraine (1). Only the single deprotonated forms (Sq) of 2 and 3 showed measurable fluorescence. In microheterogeneous media such as in the presence of β-cyclodextrin, cetyltrunethylammonium bromide and polyvinylpyrrolidone), bathochromic shifts in the absorption and emission spectra of Sq were observed with a substantial enhancement in their fluorescence yields. Triplet excited states are the main transient intermediates obtained upon 532 nm laser excitation of the various forms of 2 and 3 in methanol. These triplets have lifetimes in the range from 0.061 to 132 μs. The triplet quantum yields of double deprotonated forms are low (φT = <0.01), whereas the neutral and Sq?forms of 2 (φr = 0.12 and 0.22) and 3 (φT= 0.24 and 0.5), respectively, exhibited significant triplet yields. Quantum yields of singlet oxygen generation by Sq?forms of 2 and 3 were determined in methanol and were found to be 0.13 and 0.47, respectively, which are in good agreement with the triplet yields obtained in these systems. 相似文献
109.
P. V. Krishna Rao M. S. Frank A. Kodanda Ramaiah 《Reaction Kinetics and Catalysis Letters》1978,9(2):159-164
The title reaction was studied in aqueous hydrochloric acid at high iodide concentations. The reaction is first order with respect to both oxidant and substrate though diisonicotinoyl hydrazines are the products apart from nitrogen. The reaction is markedly inhibited by H+ and I– ions. An I– ion independent path is also noticed.
Part II: Indian J. Chem. (In press) 相似文献
. , , -() , . H+ I–. , , I–.
Part II: Indian J. Chem. (In press) 相似文献
110.
Acridine-viologen dyads: selective recognition of single-strand DNA through fluorescence enhancement
Tolylacridine-viologen dyads show distinct fluorescence emission changes in the presence of double-strand DNA (dsDNA) and single-strand DNA (ssDNA) depending on the position of the linkage. The para isomer shows fluorescence quenching in the presence of both dsDNA and ssDNA, while the ortho isomer interacts selectively with ssDNA with enhancement in fluorescence intensity. 相似文献