Synthesis and ¹⁵N NMR characterization of 4‐vinylbenzyl substituted bases of nucleic acids

Abstract

The following substances have been synthesized and characterized as monomers or intermediates for syntheses of new polymers: 1-(4-vinylbenzyl)uracil (1a), 1-(4-vinylbenzyl)thymine (1b), N-4-acetyl-1-(4-vinylbenzyl)cytosine (1 c), 1-(4-vinylbenzyl)cytosine (1 d), 9-(4-vinylbenzyl)adenine (2 a), 2-amino-9-(4-vinylbenzyl)-6-chloro-9H-purine (2b), and 9-(4-vinylbenzyl)-guanine (2c). The alkylation reactions with 4-vinylbenzyl chloride were catalyzed with anhydrous sodium iodide. The substitution at position 9 in substances 2a-c was confirmed by 15 N NMR.

Synthesis and photochromic behavior of some azo-polysiloxanes modified with nucleobases or donor-acceptor groups

“…The modified polysiloxanes were obtained in two-steps reactions, according to Figure 1. To obtain modified azo-polysiloxanes containing uracil, cytosine or nitro-phenolic groups in the side-chain, the polysiloxane was modified in the first step with 4-hydroxyazobenzene (60 − 80% substitution degree) and, in the second one, the unreacted chlorobenzyl groups were modified with uracil, cytosine or nitro-phenols, according to the procedures found in literature [19]. In the case of the nucleobase modified azo-polysiloxanes, the polymer substitution degree was monitored by using the signals corresponding to the -CH 2 Cl groups (4.5 ppm), that shift to 5.0 ppm after the connection of the azobenzene, and 4.85 ppm or 4.8 ppm, after the connection of the uracil or cytosine, respectively.…”

“…Brought to you by | MIT Libraries Authenticated Download Date | 5/9/18 8:13 PM From the point of view of practical application, one of the most interesting azopolysiloxanes' properties is the possibility to use these materials in the field of biomolecules immobilization and nano-manipulation [19]. For this reason, it is important to know the photochromic behavior of the synthesized azo-polymers following UV irradiation, especially in the solid state.…”

Preparation by controlled radical polymerization and self‐assembly via base‐recognition of synthetic polymers bearing complementary nucleobases

“…1‐(4‐vinylbenzyl)thymine,41, 42 9‐(4‐vinylbenzyl) adenine,42 1‐(4‐vinylbenzyl)uracil,42 and N,N ′‐bis (pyridin‐2‐ylmethyl 3‐hexoxo‐3‐oxopropyl)ethane‐1,2‐diamine46 were prepared according to procedures reported in the literature. Ethyl 2‐chloropropionate (97%) and dodecyl methacrylate (96%) were both purchased from Aldrich and used as received.…”

“…These monomers were selected, since recently very efficient synthetic pathways for preparing them were reported in the literature 42. The article of Sedlak and coworkers elegantly described the preparation of a complete family of five monomers bearing either one of the four bases of nucleic acids of DNA (T, A, C, and G) or uracil (U), the specific base of ribonucleic acid (RNA): 1‐(4‐vinylbenzyl)thymine, 9‐(4‐vinylbenzyl)adenine (VBA), 1‐(4‐vinylbenzyl)cytosine, 9‐(4‐vinylbenzyl)guanine and 1‐(4‐vinylbenzyl)uracil (VBU) 42. Among this family, only VBT was already polymerized by either conventional radical polymerization43–45 or CRP 41.…”

Macroscopic Self‐Assembly Based on Complementary Interactions between Nucleobase Pairs

“…As EB becomes fluorescent when bound to DNA, [40] the observed fluorescence indicates successful introduction of the oligonucleotides into DNA gels. The nucleobase gels (Scheme 1 b) were prepared by homogeneous radical terpolymerization of styrene (St), styrene-based St-A/St-T/St-G/St-C monomers (see also Table S1 in the Supporting Information), [37][38][39] and p-divinylbenzene (DVB), a process that was initiated by 2,2'-azobis(isobutyronitrile) (AIBN) in N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) (Schemes S2 and S4 in the Supporting Information). First, the adhesion test between DNA gels was carried out.…”