Functional monomers and polymers. CXLVII. Inclusion compounds of poly(1,3-butadiyne) in deoxycholic acid and apocholic acid canals: Synthesis and characterization

The inclusion polymerization of 1,3-butadiyne was studied at different temperatures using deoxycholic acid and apocholic acid as the host molecules. The polymers that resulted consist of predominantly 1,4-structure rather than 1,2 or acene structure as confirmed by both IR and Raman spectroscopies. The poly(1,3-butadiyne)s were found to possess unique optical properties and high electric conductivity as compared with those prepared by the usual polymerization methods.     

Inclusion polymerization of various diene monomers in apocholic acid canals

The inclusion polymerization of diene monomers with different sizes and shapes in apocholic acid canals was studied under -ray irradiation. It was found that the sizes and shapes of monomers profoundly influenced the microstructures of the corresponding polymers obtaied. Thus, polybutadiene contained a significant amount of 1,2-units like usual radical polymerization in solution. Polyisoprene consisted of a mixture of head-to-tail and head-to-head (tail-to-tail) addition. The introduction of two methyl groups into butadiene led to the synthesis of polymers with almost exclusively head-to-tail, 1,4-trans structure.     

Radiation-induced polymerization of 2,3-dimethyl-1,3-butadiene clathrate in deoxycholic acid

Poly(dimethylbutadiene) (PDMB) was synthesized through the inclusion polymerization technique, by γ-irradiation of a clathrate of 2,3-dimethyl-1,3-butadiene in deoxycholic acid (DOCA) at 75, 150, 320 and 430 kGy. The resulting inclusion complexes PDMB@DOCA were studied by FTIR spectroscopy and by thermal analysis (DTA, TGA and DTG). Pure PDMB was isolated by extracting the complex PDMB@DOCA with ethanol. The best sample in terms of purity was that prepared at 75 kGy, while the other samples prepared at higher doses suffered of DOCA grafting on PDMB chains. Pure PDMB isolated from PDMB@DOCA complex was studied by FT-IR spectroscopy and by thermal analysis in comparison to a reference highly crystalline and ≈=100% trans-1,4-PDMB prepared by inclusion polymerization in thiourea and in comparison to PDMB prepared by emulsion polymerization. A lower degree of regularity and crystallinity has been found on the PDMB sample prepared as inclusion compound in DOCA in comparison to the reference PDMB obtained by inclusion polymerization in thiourea.     

Functional monomers and polymers. XXXVIII. Postirradiation polymerization of 2,3-dimethylbutadiene in deoxycholic acid canal complexes

Postirradiation polymerization of 2,3-dimethylbutadiene in deoxycholic acid canal complexes was studied under various reaction conditions. The polymerization was carried out in degassed sealed tubes since the atmosphere had a large effect upon the polymer yield. Addition of 2,3-dimethylbutane led to a sharp drop in polymer yield, while hydroquinone showed little effect on the polymerization. The rate of postirradiation polymerization was found to increase with increase in reaction temperature and irradiation dose. The apparent activation energy was obtained as 13.7 kcal/mole in a temperature range between ?14 and 30°C. Existence of living free radicals having a long lifetime, the gradual change of the monomer into the polymer within the canals, and the effective spatial control in canals are discussed on the basis of the postirradiation polymerization behavior, nature of the adducts, and the structure of the polymers.     

Inclusion polymerization of isoprene in deoxycholic acid

The radiation-induced polymerization of isoprene was made on its inclusion (or clathrate) complex with deoxycholic acid (DOCA) at 150 and 300 kGy. The microstructure of the resulting polyisoprene (PIP) was studied by FTIR spectroscopy and found fully comparable to that of PIP prepared by emulsion polymerization by a free radical initiator. Thus, the 1,4-trans content was found to be 48% and that of 1,4-cis units was 28% of the polymer structure; the remaining are being 1,2 and 3,4 units. The PIP irregular microstructure was justified in terms of monomer dynamics inside the DOCA channels. PIP from inclusion polymerization is fully amorphous as studied by differential thermal analysis (DTA) in comparison to an authentic sample of trans-1,4-polyisoprene, which instead has a crystalline melting point of 71.5 °C. The inclusion complex of PIP with DOCA (PIP@DOCA) shows a DTA melting point of 194.4 °C, 12.4 °C higher than the melting point of pure DOCA. PIP isolated from inclusion polymerization from DOCA and its complex PIP@DOCA was studied also by thermogravimetry (TGA) and differential thermogravimetry (DTG).Isoprene does not form inclusion complexes with urea and thiourea. When irradiated with these two compounds it produces an oily PIP oligomer whose microstructure was found by FTIR spectroscopy analogous to that of PIP prepared by emulsion polymerization by a free radical initiator.     

Functional monomers and polymers. CXXXII. Template polymerization of methacrylamide derivatives containing nucleic acid bases

Free-radical polymerizations of methacrylamide derivatives containing nucleic acid bases were studied in the presence of the polymethacrylamide having complementary nucleic acid bases as template polymers. The rate of the polymerization did not show remarkable difference in the presence or the absence of the template polymer. A stable polymer complex, however, was precipitated from the polymerization system, and was found to be different in a thermal analysis from the polymer complex which was obtained by mixing of the complementary polymers in solution. Free-radical copolymerizations in the presence of the template polymers also supported the template polymerization.     

Functional monomers and polymers. XXXXI. Template polymerization of methacryloyl-type monomers containing nucleic acid bases

In due consideration of the specific base–base interaction that exists between nucleic acid molecules, the free radical polymerization of N-β-methacryloyloxyethyl derivatives of adenine, thymine, and theophylline initiated by azobisisobutyronitrile (AIBN) was studied in the presence of N-β-methacryloyloxyethyl-type polymers which have complementary nucleic acid bases as template polymers. The rate of polymerization of N-β-methacryloyloxyethyladenine was accelerated when poly(N-β-methacryloyloxyethyluracil) or -thymine was present in the polymerization system. The effect of the stereoregularity of the template polymers, as well as polymerization temperature and the sort of solvents used on the rate of polymerization, was studied and discussed in some detail. The results suggest that the interaction between complementary bases plays a role in template polymerization behavior.     

Inclusion polymerization of 1-chlorobutadiene in a deoxycholic acid canal

Inclusion polymerization of 1-chlorobutadiene was studied using 3α,12α-dihydroxy-5β-cholan-24-oic acid (deoxycholic acid, DCA) as host molecules. It was found that the poly(1-chlorobutadiene) had almost 100% of head to tail, trans-1,4-structure on the basis of ¹³C-NMR and IR spectroscopies. This was the first example of preparing the highly regulated poly(1-chlorobutadiene) by using the inclusion polymerization technique. The polymers obtained were optically active and the maximum value of specific rotation was [α]_D-41.9°. Both the rate constants and the value of activation energy of the elementary reactions of inclusion polymerization of 1-chlorobutadiene were determined by graphical evaluation. The activation energy of propagation and termination was 11.7 and 11.1 kcal/mol, respectively.     

Functional monomers and polymers. LXXI. Conformation and interaction studies of poly-L-lysine derivatives with pendant nucleic acid bases

Copolymers of L -lysine and L -lysine derivatives which contained nucleic acid bases substituted on the N^ε position were synthesized by grafting nucleic acid derivatives onto poly-L -lysine. The conformation and interaction of these copolymers in solution were studied by using spectroscopic measurements. They existed in helical conformation at neutral pH values, and the polymer complex formation among them was examined by ultraviolet (UV) measurements in organic solvents. A decrease in the nucleic acid base content of the copolymers resulted in a decrease in helical structures and also in interactions with the polymer-containing complementary bases.     

Functional monomers and polymers. XIX. Copolymerization of vinyl monomers containing nucleic acid bases

Taking into account the specific base–base interaction existing between nucleic acid molecules, we studied the free-radical copolymerization of N-β-methacryloyloxyethyl derivative of uracil with that of adenine at 60°C in various solvents. N-β-Methacryloyloxyethyltheophylline as well as methyl methacrylate were used also as comonomers. From the data on the rates in different comonomer feed ratios and the r₁ and r₂ values obtained, copolymerizability was discussed in some detail. The results suggest that the interaction between uracil and adenine bases plays a role in the copolymerization behavior.     

Functional monomers and polymers. CIV. Synthesis and properties of oligomer models of polyethyleneimine derivatives with spacer-separated nucleic acid bases

A series of polyethyleneimine derivatives and their oligomer models with pendant thymine or adenine bases separated by β-alanyl groups as spacers were prepared by an activated ester method. To elucidate the nature of intramolecular interaction of thymine and adenine bases ultraviolet (UV) spectrophotometric studies were undertaken for the series of compounds and the results were compared with those obtained for the corresponding oligomers without spacers. In the thymine derivatives, the nature of the intramolecular interaction resembled that of the corresponding compounds without β-alanyl units, although larger hypochromicities were found in the series with β-alanyl units. In the adenine derivatives, contrary to the corresponding thymine systems, UV hypochromicities of the compounds decreased by incorporation of the spacer group into side chains. It became evident that the intramolecular interaction of adenine bases was due to stacking neutral species, hydrogen bonding, and residual hypochromicity for the protonated species.     

Functional monomers and polymers. CXIII. Photoinduced conformational change of thymine containing poly-lysine derivatives

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.     

Functional monomers and polymers. CX. Methylation and interaction studies on uracil-containing polymethacrylate derivatives

A polymethacrylate derivative containing uracil bases was methylated by using methyl iodide or dimethyl sulfate to give polymers containing 3-methyluracil derivatives. In the case of methylation with dimethyl sulfate, sulfonation at 5-position of the bases occurred in addition to the methylation at N-3 position. The methylated polymers thus obtained were used further for the study of polymer complex formation with polymethacrylate containing adenine base.     

Functional monomers and polymers. XXXXVII. Complex formation of stereoregular methacryloyl-type polymers containing nucleic acid bases

The complex formation between a poly(N-β-methacryloyloxyethyl) derivative of adenine with one of thymine or uracil was studied in dimethyl sulfoxide and ethylene glycol mixture by ultraviolet (UV) spectroscopy. For the polymer pairs containing complementary nucleic acid bases both hypochromicity and hyperchromicity were found. Stereoregularity of the polymers, as well as the conditions for measurement of, for example, solvent, temperature, and time, affected the complex formation. Both inter- and intramolecular interaction of polymers in solution were discussed in some detail.