Copolymers containing alternating sequences of nucleic acid–base pairs. I. Monomer synthesis

To provide suitable monomers for a study designed to synthesize copolymers containing alternating sequences of nucleic acid base pairs, the following electron-donor monomers were synthesized: 9-(2-vinyloxyethyl)adenine, 1-(2-vinyloxyethyl)thymine, and 1-(2-vinyloxyethyl)-cytosine. The following electron-acceptor monomers were also synthesized: 9-(2-maleimidoethyl)adenine, 1-(2-maleimidoethyl)thymine, and 1-(2-maleimidoethyl)cytosine. The methods of synthesis are described along with their characterization by the usual methods, and their physical properties are reported. A variety of novel compounds were required as intermediates in the above identified syntheses. This paper also includes characterization of these compounds and a report of their physical properties.     

Complexation of sequence-ordered methacrylic acid copolymers with poly(4-vinylpyridine)

The complexation of three kinds of sequence-ordered acid (co)polymers with a base homopolymer was studied. The acid polymers used are poly(methacrylic acid) 1 , alternating (1:1) ethylene-methacrylic acid copolymer 2 , and periodic (2:1) ethylene-methacrylic acid copolymer 3 , and the base polymer is poly(4-vinylpyridine) 4. When mixing a methanol solution of 1, 2 , or 3 with that of 4 (0.1 M of each functional group), precipitate was formed immediately for all polymer pairs. All the precipitates contained carboxyl and pyridyl groups in ca. 1:1 molar ratio and showed IR spectra indicating the hydrogen bonding between carboxyl and pyridyl groups. When mixing dilute methanol solutions (10⁻⁴M) of the above polymer pairs, no precipitation was observed, but the extinction coefficient (ϵ_B) at 255 nm of pyridyl groups in 4 was found to increase with an increasing acid polymer concentration. This is ascribed to hydrogen bonding between carboxyl and pyridyl groups in methanol. Based on the ϵ_B variation, the order of complexation constants for acid/base polymer pairs was estimated as follows: 1/4 pair ∼ 2/4 pair ≫ 3/4 pair. © 1996 John Wiley & Sons, Inc.     

Controlled Supramolecular Architecture Transformation from Homopolymer to Copolymer through Competitive Self‐Sorting Method

Supramolecular copolymers can not only enrich the diversity of the polymer backbone but also exhibit certain special and improved properties compared with supramolecular homopolymers. However, the synthesis procedure of supramolecular copolymers is relatively complicated and time‐consuming. Herein, a simple transformation from an AB₂‐based supramolecular hyperbranched homopolymer to an AB₂+CD₂‐based supramolecular hyperbranched alternating copolymer by the “competitive self‐sorting” strategy is reported. After adding CD₂ monomer, which bears a competitive neutral guest moiety ( TAPN ) and two receptive benzo‐21‐crown‐7 host moieties ( B21C7 ), to the as‐prepared AB₂‐type supramolecular hyperbranched homopolymer constructed by the self‐assembly of dialkylammonium salt ( DAAS , A group)‐functionalized pillar[5]arene ( MeP5 , B groups) monomers, the initial homopolymer structure is disrupted and then reassemble into a new supramolecular hyperbranched alternating copolymer based on the competitive self‐sorting interaction between MeP5 ‐ TAPN and B21C7 ‐ DAAS . This study supplies a convenient approach to directly transform supramolecular homopolymers into supramolecular copolymers.

     

Functional monomers and polymers. XXXXVI. A copolymerization study of methacryloyl-type monomers containing nucleic acid bases in chloroform solution

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.     

Copolymers containing alternating sequences of nucleic acid base pairs. II. Polymerization studies

The objective of this project was to utilize the alternating copolymerizability of electrondonor monomers with electron-acceptor monomers to selectively introduce nucleic acid bases into copolymers in a controlled sequence distribution. To this end, maleimide monomers containing the adenine, thymine, cytosine, and 6-chloropurine moieties were converted to their hompolymers. The homopolymer of 1-(vinyloxyethoxy)thymine was also prepared. Alternating copolymers of the adenine maleimide monomer and the corresponding 6-chloropurine maleimide monomer with 1-(vinyloxyethoxy)thymine were prepared. The latter copolymer was converted to the alternating adenine–thymine copolymer by reaction with ammonia. Characterization of the polymers and copolymers via spectroscopic methods and physical measurements confirm their proposed structures. Monomer syntheses and characterization, as well as studies designed to establish the extent and nature of adenine–thymine interactions in the copolymers, are reported in accompanying papers.     

Unperturbed dimensions of random and alternating styrene/n-alkyl methacrylate copolymers

The steric factors σ of homopolymers of ethyl, n-butyl, and n-octyl methacrylate, of equimolar random and alternating copolymers of these monomers with styrene, and of polystyrene, were determined by measuring intrinsic viscosities in a good solvent (butanone, 25°C) and extrapolating the data thus obtained to zero molecular weight of the polymer. For all comonomeric pairs under investigation, the σ² of an equimolar random copolymer and, particularly, of an alternating copolymer, is higher than the arithmetic mean (σ + σ)/2 of the σ² values of the parent homopolymers. The positive deviation from the linear dependence of σ² on the copolymer composition, expressed as an increment of σ², is proportional to the mole fraction of alternating dyads in the copolymer chain with in the limits of experimental error. The effect of copolymer microstructure on the unperturbed dimensions of the chains has been compared for equimolar copolymers of styrene with methyl, ethyl, n-butyl, and n-octyl methacrylate by using a relative increment ξ defined as the ratio of σ² of the alternating copolymer to (σ + σ)/2. The dependence of ξ on the number of carbon atoms in the alcohol substituent of the methacrylate component of the copolymer seems to exhibit a maximum for ethyl methacrylate.     

Synthesis and clustering of supramolecular “graft” polymers

The synthesis and melt rheology of supramolecular poly(isobutylene) polymers bearing statistically distributed hydrogen‐bonding moieties is reported, aiming at understanding the formation of the underlying supramolecular networks for self‐healing polymers. Two different hydrogen bonds were incorporated into a poly(isobutylene) (PIB) copolymer, one based on a (weak) pyridinium/pyridine interaction, the other based on a (stronger) 2,6‐diaminotriazine/thymine interaction. A direct copolymerization based on living cationic polymerization of isobutene and the comonomers 1 , 2 , and 4 in amounts of 1 mol % lead to the copolymers PIB‐ 1 , PIB‐ 2 , and PIB‐ 4 with a content of ～1 mol % of comonomer and molecular weights ranging from ～2000 to 19,000 g mol^?1 (M_w/M_n ～ 1.2–1.5). Subsequent azide/alkyne “click” chemistry enabled the attachment of 2,6‐diaminotriazine‐ and thymine‐moieties to yield the copolymers PIB‐ 5 , PIB‐ 6 , and PIB‐ 7 . Proof of the statistical incorporation of ～1 mol % of hydrogen‐bonding moieties was achieved by ¹H NMR spectroscopy and matrix‐assisted laser desorption ionization measurements. The true presence of a supramolecular network in PIB‐ 1 (pyridinium/pyridine interaction) as well as with 1/1 blends of PIBs interacting via the 2,6‐diaminotriazine/thymine interaction (PIB‐ 5 /PIB‐ 6 ) was proven via the increasing plateau modulus with increasing molecular weights (5.5k, 9.9k, 12.4k, 16k, and 19k). Dynamics of the hydrogen bonds in the melt state was investigated by determining the effective cluster lifetime ( τ ) observing a clear difference in the (weaker) pyridinium/pyridine interaction ( τ ～ 1 s) to the 2,6‐ (stronger) diamintriazine/thymine interaction ( τ ～ 100 s). The so‐generated materials will be useful as a basis for self‐healing polymers, as dynamics plays a major role in such polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Molecular weight dependence of diblock copolymer segregation at a polymer/polymer interface

Utilizing forward recoil spectrometry (FRES), we have determined the segregation isotherm which describes the interfacial excess z_i^* of diblock copolymers of poly (d₈-styrene-b-2-vinylpyridine) (dPS-PVP) at the interface between the homopolymers PS and PVP as a function of ?_∞, the volume fraction of diblock copolymer remaining in the host homopolymer. All the samples were analyzed after annealing at temperatures and times sufficient to achieve equilibrium segregation. The effect of the degree of polymerization of both the diblock copolymers and the host homopolymers on the segregation isotherm is investigated. When the degree of polymerization of the homopolymer is much larger than that of the diblock copolymer, the normalized interfacial excess (z_i^*/R_g), where R_g is the radius of gyration of an isolated block copolymer chain, is a universal function of that portion of the block copolymer chemical potential due to chain stretching. The existence of such a universal function is predicted by theory and its form is in good agreement with self-consistent mean field calculations. Using these results, one can predict important aspects of the block copolymer segregation (e.g., the saturation interfacial excess) without recourse to the time-consuming numerical calculations. © 1994 John Wiley & Sons, Inc.     

Amphiphilic graft copolymers with poly(oxyethylene) side chains: Synthesis via phthalimidoacrylate prepolymers

Amphiphilic graft copolymers of definite composition were obtained by grafting of amino-functionalized poly(oxyethylene) monoether (MPEO–NH₂) of M?_n = 750, 2000, and 5000 onto phthalimidoacrylate (PIA) homopolymer or its copolymer with styrene (St). The radical co-polymerization of PIA and phthalimidomethacrylate (PIMA) with St was studied in dimeth-ylformamide (DMF) at 60°C. The copolymer composition curves and the monomer reactivity ratios showed a high tendency of PIA to alternating copolymerization with St (r₁r₂ = 0.006). Hydrogen bonding between the functional groups leads to significant spectral modifications. The micellization of the graft copolymers was studied by GPC in aqueous-methanolic eluent. The aggregation behavior of the graft copolymers depended on their composition and chromato-graphic separation lead to the copolymers fractionation. © 1995 John Wiley & Sons, Inc.     

Nematogenic aromatic block copolymers of rigid and flexible units. II. Phase equilibria

The solubility and mesophase behavior are investigated for block copolymers of poly(p-benzamide) (PBA), the polyterephthalamide of p-aminobenzhydrazide (PABH-T), and PBA and poly(m-phenylene isophthalamide) (MPD-I) dissolved in N,N-dimethylacetamide (DMAc) containing 3% LiCl. The block copolymers, whose synthesis and characterization were described in the previous paper in this series, included samples prepared by the two-step and multistep copolycondensations. The first of these methods yields a considerable amount of the flexible homopolymer (PABH-T) and also some of the rigid homopolymer. The flexible homopolymer can be removed from the block copolymer by extraction with dimethyl sulfoxide (DMSO), whereas precipitation may offer a way to remove the rigid homopolymer. The results observed for the block copolymers are compared with those for the homopolymers and mixtures of homopolymers. The apparent solubility of the PBA/PABH-T block copolymers obtained by the two-step method is unusually large but decreases toward the value observed for mixtures after the flexible homopolymer had been extracted with DMSO. Labile adducts involving PABH-T and/or the block copolymer appear to be capable of forming a single mesophase. This offers a most interesting approach to the preparation of composite materials involving rigid and flexible polymers.     

Interface stabilization and micelle formation in blends with a block copolymer

The phase separation behavior of ternary blends of two homopolymers, PMMA and PS, and a block copolymer of styrene and methylmethacrylate, P(S-b-MMA), was studied. The homopolymers were of equal chain length and were kept at equal amounts. Two copolymers were used with blocks of equal length, which exceeded or equaled that of the homopolymer chains. Varied was the copolymer contentf. Films were cast from toluene, which is a nonselective solvent. The morphologies of the cast films were compared with the structure of the critical fluctuations in solution, which were calculated in mean field approximation. The axis of blend compositionsf can be divided into parts of dominating macrophase and microphase separation. Above a transition concentrationf _o, all copolymer chains are found in phase interfaces. Belowf _o, part of them form micelles within the homopolymer phases.     

Four cocrystals of thymine with phenolic coformers: influence of the coformer on hydrogen bonding

Cocrystals are molecular solids composed of at least two types of neutral chemical species held together by noncovalent forces. Crystallization of thymine [systematic name: 5‐methylpyrimidine‐2,4(1H,3H)‐dione] with four phenolic coformers resulted in cocrystal formation, viz. catechol (benzene‐1,2‐diol) giving thymine–catechol (1/1), C₅H₆N₂O₂·C₆H₆O₂, (I), resorcinol (benzene‐1,3‐diol) giving thymine–resorcinol (2/1), 2C₅H₆N₂O₂·C₆H₆O₂, (II), hydroquinone (benzene‐1,4‐diol) giving thymine–hydroquinone (2/1), 2C₅H₆N₂O₂·C₆H₆O₂, (III), and pyrogallol (benzene‐1,2,3‐triol) giving thymine–pyrogallol (1/2), C₅H₆N₂O₂·2C₆H₆O₃, (IV). The resorcinol molecule in (II) occupies a twofold axis, while the hydroquinone molecule in (III) is situated on a centre of inversion. Thymine–thymine base pairing is common across all four structures, albeit with different patterns. In (I)–(III), the base pair is propagated into an infinite one‐dimensional ribbon, whereas it exists as a discrete dimeric unit in (IV). In (I)–(III), the two donor N atoms and one carbonyl acceptor O atom of thymine are involved in thymine–thymine base pairing and the remaining carbonyl O atom is hydrogen bonded to the coformer. In contrast, in (IV), just one donor N atom and one acceptor O atom are involved in base pairing, and the remaining donor N atom and acceptor O atom of thymine form hydrogen bonds to the coformer molecules. Thus, the utilization of the donor and acceptor atoms of thymine in the hydrogen bonding is influenced by the coformers.     

Chain center‐functionalized amphiphilic block polymers: Complementary hydrogen bond self‐assembly in aqueous solution

Hydrogen bonding self‐assemblies were formed in an aqueous medium from a pair of an amphiphilic ABA triblock copolymer and a hydrophobic homopolymer, both with a triple hydrogen bonding site that was complementary to each other and precisely placed at the main‐chain center: (PEGMA)_m–(MMA)_n– ADA –(MMA)_n–(PEGMA)_m and (MMA)_p– DAD –(MMA)_p ( A = hydrogen acceptor; D = hydrogen donor; PEGMA: PEG methacrylate; MMA: methyl methacrylate). The polymers were synthesized by the ruthenium‐catalyzed living radial polymerization with bifunctional initiators (Br– ADA –Br and Cl– DAD –Cl) aiming at pinpoint chain center functionalization to give a symmetric segmental sequence; ADA and DAD initiators were derived from 2,6‐diaminopyridine and thymine, respectively. On mixed equimolar in tetrahydrofuran (THF), both polymers spontaneously associated, and the apparently 1:1 assembly further grew into higher aggregate particles on subsequent addition of water. The aggregates in water/THF were relatively stable and uniform in size, which most likely stems from the intermolecular complementary hydrogen bond interaction at polymer chain centers. In sharp contrast, an equimolar mixture of ADA ‐block polymer and DAD ‐free poly(MMA) in water/THF resulted in larger and irregular particles, and thus short‐lived to eventually collapse. These results indicate that, however structurally marginal, precise pinpoint functionalization of macromolecular chains allows stable self‐assemblies via complementary hydrogen bond interaction even in aqueous media. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4498–4504     

Theoretical investigation on the structural and electronic properties of complexes formed by thymine and 2′-deoxythymidine with different anions

Hydrogen bonding interactions between thymine nucleobase and 2′-deoxythymidine nucleoside (dT) with some biological anions such as F⁻ (fluoride), Cl⁻ (chloride), OH⁻ (hydroxide), and NO₃ ⁻ (nitrate) have been explored theoretically. In this study, complexes have been studied by density functional theory (B3LYP method and 6-311++G (d,p) basis set). The relevant geometries, energies, and characteristics of hydrogen bonds (H-bonds) have been systematically investigated. There is a correlation between interaction energy and proton affinity for complexes of thymine nucleobase. The nature of all the interactions has been analyzed by means of the natural bonding orbital (NBO) and quantum theory atoms in molecules (QTAIM) approaches. Donors, acceptors, and orbital interaction energies were also calculated for the hydrogen bonds. Excellent correlations between structural parameter (δR) and electron density topological parameter (ρ _b) as well as between E(2) and ρ _b have been found. It is interesting that hydrogen bonds with anions can affect the geometry of thymine and 2′-deoxythymidine molecules. For example, these interactions can change the bond lengths in thymine nucleobase, the orientation of base unit with respect to sugar ring, the furanose ring puckering, and the C1′–N1 glycosidic linkage in dT nucleoside. Thus, it is necessary to obtain a fundamental understanding of chemical behavior of nucleobases and nucleosides in presence of anions.     

Asymmetric induction copolymerization. Cationic copolymerization of l-menthyl vinyl ether with indene and acenaphthylene

l-Menthyl vinyl ether (l-MVE) was homopolymerized and copolymerized with the monomers indene (IN) and acenaphthylene (ANp) by BF₃OEt₂ as a catalyst. The chiral menthyl substituent was cloven from the homopolymers and copolymers using dry-hydrogen bromide gas. After the removal of optically active menthyl group, poly(vinyl alcohol) (PVA) from l-MVE homopolymer was optically inactive, and copolymers (VA-IN, VA-ANp) from l-MVE-IN and l-MVE-ANp copolymers were still optically active. Hence, in the case of l-MVE homopolymer, it was concluded that asymmetric induction in the polymer main chain can only produce pseudoasymmetry. In the case of l-MVE-IN and l-MVE-ANp copolymers, it was found that asymmetric induction proceeded in the copolymer main chain and was caused by the influence of chiral menthyl group.     

Five pseudopolymorphs of 6‐amino‐2‐thiouracil: absence of N—H...S hydrogen bonds

In order to study the preferred hydrogen‐bonding pattern of 6‐amino‐2‐thiouracil, C₄H₅N₃OS, (I), crystallization experiments yielded five different pseudopolymorphs of (I), namely the dimethylformamide disolvate, C₄H₅N₃OS·2C₃H₇NO, (Ia), the dimethylacetamide monosolvate, C₄H₅N₃OS·C₄H₉NO, (Ib), the dimethylacetamide sesquisolvate, C₄H₅N₃OS·1.5C₄H₉NO, (Ic), and two different 1‐methylpyrrolidin‐2‐one sesquisolvates, C₄H₅N₃OS·1.5C₅H₉NO, (Id) and (Ie). All structures contain R₂¹(6) N—H...O hydrogen‐bond motifs. In the latter four structures, additional R₂²(8) N—H...O hydrogen‐bond motifs are present stabilizing homodimers of (I). No type of hydrogen bond other than N—H...O is observed. According to a search of the Cambridge Structural Database, most 2‐thiouracil derivatives form homodimers stabilized by an R₂²(8) hydrogen‐bonding pattern, with (i) only N—H...O, (ii) only N—H...S or (iii) alternating pairs of N—H...O and N—H...S hydrogen bonds.     

Tuning block copolymer phase behavior with a selectively associating homopolymer additive

We use polymer random phase approximation (RPA) theory to calculate the microphase separation transition (MST) spinodal for an AB + C diblock copolymer–homopolymer blend where the C homopolymers are strongly attracted to the A segment of the copolymers. Our calculations indicate that one can shift the MST spinodal value of the A ? B segmental interaction parameter (χ_ABN)_S to significantly lower values [i.e., (χ_ABN)_S < 10.5] upon the addition of a selectively attractive C homopolymer. For a sufficiently attractive C homopolymer, (χ_ABN)_S can be pushed to negative values, indicating microphase separation in what would appear to be a completely miscible diblock copolymer. Furthermore, we show that microphase separation can occur in diblock copolymer–homopolymer blends where the segmental interactions between all polymer constituents are attractive. By tuning the value of (χ_ABN)_S with a homopolymer additive, one is therefore able to tune the effective copolymer segregation strength and thus dramatically affect the blend phase behavior. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2083–2090, 2009     

Linear‐dendritic block copolymer hosts for the encapsulation of electro‐optic chromophores via H‐Bonding

Linear‐dendritic block copolymer hosts were synthesized by end‐functionalizing poly(methylmethacrylate) with dendrons that acted as hydrogen‐bonding acceptors for nonlinear optical chromophores. Second harmonic generation experiments indicate that the d₃₃ coefficients and maximum chromophore loading are increased in linear‐dendritic block copolymer hosts over comparable homopolymer hosts. Transmission electron microscopy shows 5–10 nm chromophore domains, confirming the effective spatial dispersion of the chromophores. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5017–5026, 2009     

带电组氨酸侧链与DNA碱基间非键作用强度的理论研究

采用MP2方法和6-31+G(d,p)基组优化得到了带有一个正电荷的组氨酸侧链与4个DNA碱基间形成的18个氢键复合物的气相稳定结构, 从文献中获取了组氨酸侧链与DNA碱基间形成的12个堆积和T型复合物的气相稳定结构, 使用包含基组重叠误差(BSSE)校正的MP2方法和aug-cc-pVTZ基组及密度泛函理论M06-2X-D3方法和aug-cc-pVDZ基组计算了这些复合物的结合能. 研究结果表明, 包含BSSE校正的M06-2X-D3方法和aug-cc-pVDZ基组能够给出较准确的结合能; 气相条件下, 组氨酸侧链与同种DNA碱基间的离子氢键作用明显强于堆积作用和T型作用, 组氨酸侧链最易通过离子氢键与胞嘧啶C和鸟嘌呤G作用形成氢键复合物, 组氨酸与胞嘧啶C和鸟嘌呤G间的T型作用强于与腺嘌呤A和胸腺嘧啶T间的离子氢键作用; 水相条件下, 组氨酸侧链与同种DNA碱基间的离子氢键作用仍明显强于堆积作用和T型作用, 组氨酸侧链更易与胞嘧啶C和鸟嘌呤G相互作用形成氢键复合物, 但是最强的组氨酸侧链与胞嘧啶C间的T型作用明显弱于与腺嘌呤A和胸腺嘧啶T间的离子氢键作用, 说明水相条件下组氨酸侧链与DNA碱基间主要通过离子氢键作用形成氢键复合物.     

Triarylamine N‐functionalized 3,6‐linked carbazole main chain polymers and copolymers: Preparation and physical properties

The preparation of triarylamine N‐functionalized 3,6‐linked carbazole homopolymers as well as alternating copolymers with 2,5‐diphenyl‐[1,3,4]oxadiazole and benzo[1,2,5]thiadiazole was undertaken using Suzuki cross‐coupling polymerization procedures associating 3,6‐bis(4,4,5,5‐tetramethyl‐[1,3,2]dioxaborolan‐2‐yl)‐9‐(bis[4‐(2‐butyl‐octyloxy)‐phenyl]‐amino‐phen‐4‐yl)‐carbazole and, respectively, 3,6‐dibromo‐9‐(bis[4‐(2‐butyl‐octyloxy)‐phenyl]‐amino‐phen‐4‐yl)‐carbazole, 2,5‐bis(4‐bromo‐phenyl)‐[1, 3,4]oxadiazole, and 4,7‐dibromo‐benzo[1,2,5]thiadiazole. Both the carbazole homopolymer and alternating copolymer with 2,5‐diphenyl‐[1,3,4]oxadiazole were found as wideband gap materials emitting in the blue part of the electromagnetic spectrum while the carbazole alternating copolymer with 4,7‐benzo[1,2,5]thiadiazole had a narrower band gap and emitted in the orange part of the electromagnetic spectrum. The new polymers are thermally stable up to 300 °C. A discussion of the electrochemical and optical properties of the new polymers is presented. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5957–5967, 2007.