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1.
The photodimerization reaction of pendant thymine bases in thymine-containing poly-lysine derivatives was studied over a wide range in aqueous solution. It was found that the quantum yield of the photodimerization of pendant thymine bases is affected mainly by the conformation of the polymers in solution. The differences in photoreaction behavior were discussed for poly-D -, poly-L -, and poly-DL -lysine derivatives.  相似文献   

2.
The photodimerization reaction between thymine bases in thymine-grafted poly-D - and poly-L -lysine derivatives was studied in an alkaline, aqueous, buffered solution. It was found that the helix content of the polymers changes by photodimerization. The result was discussed in terms of conversion, the rate of photodimerization, and the helix content of the polymers.  相似文献   

3.
The photodimerization reaction of thymine bases incorporated in the modified oligo- and polyethyleneimines, in which α-alanine or ß-alanine unit was inserted between the main chain and the pendant thymine bases, was studied both in aqueous and in dimethyl sulfoxide solutions. It was found that the quantum yields for the photodimerization for the oligomers were closely related to the intramolecular interaction in the ground state, while those of the copolymers were not related to the ground state interaction. It was suggested that the singlet energy migration was present in the case of the polyethyleneimine derivatives. This result is discussed in terms of the effects of the nearest-neighboring thymine units, the structure of the side chain, and the singlet energy migration, particularly for the copolymers.  相似文献   

4.
Photodimerization of Polyacrylic and polymethacrylic derivatives with different pendant thymine unit content was studied in dimethylformamide solution. The quantum efficiency of thymine base for the photodimerization increased with increasing thymine content in the copolymers. The quenching study, which used isoprene as the quencher, revealed that the photodimerization resulted from excited singlet state increases with increasing thymine content. The photochemical results were discussed in terms of self-association of thymine bases in the polymer chain.  相似文献   

5.
Photodimerization of N-2-isobutyloxyethyl thymine (T-M), bis[2-(5-methyl-1-primidinyl)-ethyl] glutarate (T-T), poly(N-2-methacryloyloxyethyl thymine) (polyMAOT), and poly(N-2-acryloyloxyethyl thymine) (poly AOT) was studied in dimethylformamide solution. The rate of intramolecular photodimerization of polyMAOT and polyAOT was 5.7 and 7.2 times faster, respectively, than that of T-T. In T-M, however, intermolecular photodimerization did not occur under the reaction condition used. Quenching studies with isoprene suggest that the photodimerization of T-T occurs predominantly in an excited triplet state, whereas that of polyMAOT and polyAOT occur in singlet and triplet states. It was concluded that the photodimers of T-T, polyMAOT, and polyAOT are two syn-fused cyclobutane-type dimers (cis-syn and trans-syn). Quantum efficiencies of thymine base disappearance were determined by ultraviolet (UV) analysis to be 0.0012 for T-T, 0.0084 for polyMAOT, and 0.010 for polyAOT.  相似文献   

6.
Photodimerization reactions of polyacrylate and polymethacrylate derivatives and the dimer model compound containing thymine bases were studied in the presence of adenine derivatives in dimethyl sulfoxide; N,N-dimethylformamide; and dimethyl sulfoxide–ethylene glycol solutions. The photodimerization of thymine bases both in the polymers and in the dimer model compound was found to be quenched by the addition of adenine derivatives. Base-base interaction in the ground state was also studied by ultraviolet (UV) spectroscopy in the three solvents. The quenching of the photodimerizationof thymine bases in the presence of adenine derivatives was discussed in terms of the specific interaction between adenine and thymine bases both in ground and excited states.  相似文献   

7.
The photodimerization reaction of synthetic polymers which contain thymine bases was studied in polymethyl methacrylate film. The quantum efficiency for the photodimerization of the thymine bases of polyacrylate and polymethacrylate, fixed in the polymethyl methacrylate film was measured. The value of the film was higher than those measured in solution.  相似文献   

8.
Irradiation of UV light to the solution of gold nanoparticles modified with thymine units resulted in the formation of aggregates comprising chemical cross-linking gold nanoparticles through the photodimerization of the thymine units. Transmission electron microscopy and UV-visible absorption measurement showed the aggregates consisting of the gold nanoparticles. The effect of thymine unit density on the nanoparticle surface and the concentration of the gold nanoparticles in solution to the aggregation process were studied by UV-visible absorption measurement.  相似文献   

9.
Photodimerization of thymine bases present on the side chain of acryloyl and methacryloyl-type polymers was studied in dimethyl sulfoxide, dimethylformamide, and dimethyl sulfoxide—ethylene glycol mixture. Quantum efficiencies for photodimerization and quenching with isoprene were influenced by the solvents. The self-association of thymine bases estimated from their ultraviolet (UV) spectra and intrinsic viscosity were related to the effect of solvent on the photodimerization.  相似文献   

10.
A polymethacrylate derivative containing 6-cyanouracil was prepared, and its photochemical reaction was studied. The 6-cyanouracil derivative was found to show high reactivity for the photochemiccal reaction. The photochemical-reaction product was identified as a cyclobutanetype photodimer, and the photodimer was formed in high yield even from the monomeric compound of 6-cyanouracil under UV irradiation in low concentration. The quantum yield of the photodimerization of the 6-cyanouracil derivative was greater than that of the thymine derivative. The photodimerization of the 6-cyanouracil derivative could not be quenched by usual triplet quenchers, but was found to be quenched by the polymeric derivative of adenine, suggesting a specific interaction.  相似文献   

11.
In order to prepare water soluble natural and synthetic polymers, which contain nucleic acid base units as the functional side groups, a different sort of polymers, such as poly(ethyleneimine), poly(amino acids) and so on were used as the base materials. The properties of the polymers derived, in particular the specific interaction between nucleic acid base containing complementary polymers was studied in detail. Introduction of the base units onto hyaluronic acid was also carried out. Applicabilities of these polymers obtained, for example as the controlled release system by using reversible photodimerization reaction of thymine bases were also shown.  相似文献   

12.
Polyamides containing thymine photodimer units in the main chain were synthesized, and their photolysis by ultraviolet irradiation below 260 nm were studied in film state. Photodimers of thymine derivatives were obtained by photochemical reaction of the carboxylic acid derivatives of thymine in aqueous solution irradiated above 270 nm. An attempt was made to resolve the isomers of the photodimers, and the two kinds of cis isomers [cis–syn(head to head), and cis–anti(head to tail)] were isolated successfully. The polyamides were prepared by condensation of the photodimers with diamine using an activated ester method. The photodissociation of the thymine photodimer in the polymer main chain caused the breakage of the polymer chains, leading to the production of oligomers and dimer compounds containing thymine bases at the ends of the molecule. The dissociation rate of the polymer did not depend on the kind of the thymine photodimer which was in the main chain of the polymer.  相似文献   

13.
As a model for DNA damage by photodimerization of its thymine component, a new [2 + 2] photodimerization of 5-chloro and 5-methyl-2-pyridone to the corresponding cis-anti-dimers as their inclusion complexes with 1,1'-biphenyl-2,2'-dicarboxylic acid was found, and the mechanism of this stereoselective solid state reaction was studied by X-ray analysis.  相似文献   

14.
Abstract. Photodimerization of thymine in aqueous solution in the presence of tyrosine was studied with monochromatic UV irradiation. The total dimer formation was sensitized in the presence of tyrosine. The action spectrum of sensitized total dimer formation has a peak near 280 nm corresponding to the absorption maximum of tyrosine. Triplet quenchers reduced the sensitization substantially. It seems probable that tyrosine-sensitized photodimerization of thymine occurred via triplet-triplet energy transfer from tyrosine to thymine.  相似文献   

15.
Terpolymers of vinylbenzylthymine, vinylbenzyltriethylammonium chloride, and N‐butyl‐N,N‐dimethyl‐(4‐vinylbenzyl)ammonium chloride with different monomer ratios have been prepared, and the effect of the monomer ratios on the properties of the terpolymers has been investigated. These polymers are water‐soluble and, when irradiated with low levels of UV light, undergo a 2π+2π photodimerization reaction of thymine. This photodimerization significantly reduces the water solubility, immobilizing the polymer to the substrate, and shows potential for water‐soluble photoresists. Thermogravimetric analysis has revealed that the terpolymers have two degradation stages corresponding to the quaternary ammonium pendant groups and to the thymine. An evaluation of the contact‐angle measurements has shown that the surface properties and hydrophobicity can be controlled by the variation of the monomer ratios. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1296–1303, 2007  相似文献   

16.
The colloid stability of thymine-coated gold nanoparticles under light irradiation as a function of particle size, surface charge, and exposure time was investigated in alkaline, aqueous solutions as well as in a 0.5 vol % of DMF in H(2)O mixture. With increasing exposure to light irradiation at 280 nm, more and more particles coagulated. Light-induced aggregation of colloidal gold nanoparticles was attributed to reorientation of thymine terminal groups tethered on gold particle surfaces. A smaller particle size and negatively charged surface reduced the rate of photodimerization or even inhibited the photoreaction. UV-vis and FTIR spectroscopy confirmed the photodimerization of terminal thymine molecules under 280 nm light irradiation. The reaction kinetics of thymine photodimerization appears to be a combination of first-order reactions, each having different rates, reflecting the inhomogeneity and high curvature of the gold nanoparticle surfaces.  相似文献   

17.
《中国化学快报》2022,33(12):5124-5127
Challenges of achieving efficient photodimerization of azaanthracene derivatives remain due to the low selectivity and slow reaction rate. In this paper, cucurbit[10]uril (CB[10]), with the largest rigid and hydrophobic cavity among CB[n]s, was used to affect the photodimerization reaction of four water-soluble 1-(2-)substituted azaanthracene derivatives (1-4). It revealed that 1-4 could form 1:2 host-guest complexes with CB[10] in aqueous solution. Irradiation of 1 in the presence of 0.5 equiv. of CB[10] selectively produced a head-to-tail (anti-HT) photodimer product. As for 2-4, CB[10] acted as a nanoreactor accelerating their photodimerization reaction in water. Our results suggest that photodimerization of azaanthracene derivatives could be promoted by the CB[10]-based host-guest strategy with high efficiency and selectivity.  相似文献   

18.
Behavior of the free radical copolymerization of N-β-methacryloyloxyethyl derivatives of adenine with that of thymine was studied in chloroform solution, taking account of the specific base-base interaction of these monomers. Hydrogen bonding interaction between such monomers was observed by NMR spectroscopy. The acceleration of copolymerization was found to be greater either at lower monomer concentration or at lower polymerization temperature. When N-β-methacryloyloxyethylcarbazole was used as a comonomer, the rate of copolymerization showed a similar trend as in the case of usual free radical copolymerizations. From r1 and r2 values obtained, the copolymerization was found to be alternating, particularly in the case of copolymerization between monomers having complementary nucleic acid bases. The results suggest that the hydrogen bonding interaction between adenine and thymine plays a role in the propagation step.  相似文献   

19.
《Tetrahedron》1987,43(7):1485-1494
The photodimerization of anthracene derivatives such as 2-anthracenesulfonate or 2-anthracenecarboxylate in aqueous solution was found to proceed regio- and stereoselectively in the presence of β-CyD and γ-CyD, respectively. These reaction selectivities were explained in terms of specific inclusion of these compounds into CyDs.  相似文献   

20.
The synthesis of various 1,8-diaza-4,5-dialkoxy-2,7-anthracene dicarboxylic acid derivatives and their incorporation into cyclic and helically folded aromatic oligoamides are reported. The ability of the diaza-anthracene monomers to undergo photoaddition or head-to-tail photodimerization was investigated in the solid state and in solution. Quantitative conversion of a monomer diester to the corresponding head-to-tail photodimer could be achieved in the solid state without protection from oxygen. The formation of an emissive excimer between two diaza-anthracene units appended at the end of a helically folded oligomer was demonstrated. Intramolecular photodimerization was not observed in this compound, possibly due to the low thermal stability of the head-to-head photoadduct. A cyclic oligoamide composed of two diaza-anthracene and two pyridine units was shown to adopt a flat conformation and to form columnar stacks in the solid state. Longer, noncyclic oligoamides composed of one or two diaza-anthracene units were shown to adopt helical conformations that exist preferentially as double helical dimers.  相似文献   

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