Synthesis and conformation of asymmetric rigid polyamides

Asymmetric polyamides from the reaction of either optically active trans-1,2-cyclopropanedicarboxylic acid (C3) or trans-1,2-cyclohexanedicarboxylic acid (C6) with 2,7-diazaspiro[4,4]nonane(DSN) were synthesized. The possible conformations of these polymers and their model compounds in 2,2,2-trifluoroethanol (TFE), water, methanesulfonic acid (MSA), and sulfuric acid were examined by circular dichroism (CD), NMR, viscosity, and dipole moment measurements. The racemic polyamides (±)C3·(±)DSN and (±)C6·(±)DSN exist in extended forms. No intrinsic viscosity changes were observed for these two polymers in TFE and MSA. Certain viscosity and spectral changes have been observed for the optically active polyamides, although no specific ordered conformations can be assigned. The optically active diacid units incorporated into the polymer give a conformation unique from the totally extended chain. CD studies seem to evidence some conformational differences among the polyamide derived from (+)C6 diacid and the optically active DSN. By changing the solvent from TFE to MSA a blue shift of the trough was observed for (+)C6·(±)DSN, a red shift for (+)C6·(?)DSN, and an inversion of the CD spectrum for (+)C6·(+)DSN polyamides. The results of the work with (+)C6·(?)DSN in dilute acid solution suggest that the rotation around the C–N bond is a relatively low-energy process. The spectral and intrinsic viscosity data are consistent with this suggestion. No drastic spectral changes have been observed for the C3·DSN polyamides by changing the solvent from TFE to MSA. The amide group in the C3·DSN polyamide and the corresponding model compound prefer a similar conformation with the carbonyl group bisecting the cyclopropane ring. The C3·DSN polyamide seems to exist in an extended form.     

Conformational properties of structurally rigid polyamides. I. Conformation of polyamides and model diamides derived from optically active cyclic 1,2-dicarboxylic acids

The conformational equilibria of piperidine diamides derived from five cyclic 1,2-dicarboxylic acids (I–V) have been investigated by dipole moment measurements and a priori conformational energy estimates. Since these diamides represent the building blocks of the polyamides derived from the above cyclic diacids and piperazine or trans-2,5-dimethylpiperazine, the results obtained in the study of the models have been used to investigate the conformation of the polymers. The overall evidence suggests that cyclopentane, cyclohexane, and bicyclooctane piperazine polymers behave as rigid rods in which the structural units possess approximately the same conformational preference exhibited by the respective model diamides.     

Synthesis and solution properties of poly(trans-5-ethylproline). A slow mutarotating substituted polyproline

An optically active polypeptide, poly(trans-5-ethylproline) (PT5EP) was synthesized and its solution properties were observed to investigate the conformational changes with various conditions. The trans-5-ethyl substitution on polyproline showed noticeable perturbed effects on the conformations of the polypeptide as well as mutarotation of the polypeptide in solution. Circular dichroism (CD) spectra suggested that the polypeptide existed in a poly(L -proline) form-I-type helix and mutarotated slowly to an intermediate conformation in which some of the amide bonds had rotated to a trans conformation. In trifluoroethanol (TFE) solution the polymer took more than 20 days to change from a form-I-type helix conformation, in which CD bands for D -PT5EP are at 199.5 ± 1.0 (positive), 115.5 ± 0.5 (negative), and around 238 nm (positive), to an intermediate conformation. Upon addition of trifluoroacetic acid (TFA) to a TFE solution, the polymer was transformed to form-II-type polymers. Even a greater change in conformation was observed in a solution of TFA or in LiClO₄-TFE. The overall change of the intensity ratio R_CD of positive to negative CD bands of D -PT5EP was from 0.6–0.7 to 30. Reverse mutarotation toward the original form I was observed when n-butyl alcohol, water, or THF was added to a solution containing the form II polymer. A blue shift of the UV spectra and a change in the NMR spectrum also supported the concept of this conformational change.     

Optical properties and conformations of asymmetric polyamides derived from optically active trans-1,2-cyclopropanedicarboxylic acid

Optical properties and conformations, in solution, of optically active polyamides derived from (+)(S)-trans-1,2-cyclopropanedicarboxylic acid with secondary diamines such as trans-2,5-dimethylpiperazine (DMPIP), piperazine (PIP), or N,N′-dimethylethylenediamine (DMED) have been investigated and compared with the corresponding diamide model compounds. The results suggest that the rigid DMPIP and PIP polyamides may exist in ordered conformations in 2,2,2-trifluoroethanol (TFE) and tetramethylene sulfone (TMS), while reversible conformational transitions to highly extended forms may be induced by the addition of methanesulfonic acid (MSA). In MSA/TMS mixtures, a change in the optical properties, and thus possibly in the conformations, can be observed around 0.5 mole fraction of MSA. A study of CD at higher temperature indicates that the conformations of the DMPIP and PIP polymides tend to be randomized on heating in TMS and probably also in MSA. No evidence for salt effects on conformation has been observed. Possible ordered conformations have been proposed.     

Synthesis and properties of polyamides of p-phenylenedioxydiacetic acid

Several polyamides of p-phenylenedioxydiacetic acid (PDDA) were synthesized by the low-temperature solution polycondensation techniques. Six different diamines were condensed independently with p-phenylenedioxydiacetyl chloride (PDC) in a mixture of N-methyl pyrolidone (NMP) and hexamethyl phosphoramide (HMPA). The polymers were obtained in 80–95% yield and possessed inherent viscosities in the range 0.32–0.81 dL/g. The polymers were characterized by infrared (IR) and H¹-NMR spectra. The solubility, density, crystallinity, and thermal stability of the polyamides were also determined. A model diamide (MDA-1) was also synthesized from aniline and PDC to confirm the formation of polyamides from diamines.     

Optical properties of inherently dissymmetric polyamides

A study of the optical rotatory dispersion (ORD), circular dichroism (CD), and ultraviolet spectra (UV) of polyamides derived from optically active biphenyl acid chlorides, and aromatic, and aliphatic diamines, was made. The optically active monomers were (–)-(S)-2,2′-dinitro-6,6′-dimethylbiphenyl-4,4′-dicarbonyl chloride and (–)-(S)-2,2′-dichloro-6,6′-dimethylbiphenyl-4,4′-dicarbonyl chloride. The diamines were o-, m-, and p-phenylenediamine, piperazine, trans-2,5-dimethylpiperazine, and 1,2-pyrazolidine. The ORD spectra of the o-phenylenediaminepolyamide taken in different solvents indicated the existence of some ordered structure in the least polar solvent. All other polyamides existed in a random coil conformation in the solvents employed.     

Conformation and Optical Activity of all-trans,mono-cis,and di-cis Carotenoids: Temperature Dependent Circular Dichroism

The CD. spectra of carotenoids with an asymmetric centre at C(3) have the following unusual features: (1) All-trans and di-cis compounds with two end-rings, at least one of which possesses an asymmetric C-atom, have very similar CD. spectra, whereas the corresponding mono-cis compounds give mirror-image CD. spectra; (2) In carotenoids or apocarotenoids with only one end-ring all-trans and mono-cis compounds have the same CD. spectra; (3) The CD. spectra of such carotenoids are strongly temperature dependent either increasing in magnitude or completely changing in sign upon cooling. These properties have been rationalized with the aid of a model with takes the total chromophore of the carotenoid as being intrinsically chiral with symmetry C₂. It seems that the chirality arises not only from the presence of the hydroxyl group of an asymmetric carbon atom, C(3), which occupies an equatorial position thereby locking the conformation of the end-ring, but also from the steric hindrance across the formal single bond C(6), C(7), linking the end-ring to the chain and thus creating a chiral π-system. (The twist about the C(6), C(7)-bond acquires a handedness because of the predominance of one conformational form of the end-ring. In this way, the double bonds of the end-ring become twisted out of the plane of the chain with one hand predominating. Thus the whole conjugated system becomes chiral). The reversal of sign between the trans (and di-cis) and mono-cis compounds is due to a tilt of the 2-fold symmetry axis and thereby a change of chirality. The temperature dependence stems from the varying population of forms of different twist of the end-group relative to the chain. Compounds with 7, 8-triple bonds also show distinct CD. spectra and a sign change between all-trans and mono-cis isomers in addition to temperature dependence. The latter property demonstrates that some steric hindrance between the end-ring and the main chain is present in these compounds. Some suggestions for the origins of the sign patterns and band intensities of the CD. and absorption spectra are included.     

Synthesis and chiroptical properties of optically active polymer liquid crystals containing azobenzene chromophores

A series of optically active methacrylic homopolymers, poly[(4‐{4′‐[(S)‐2‐methyl‐1‐butyloxycarbonyl]phenylazo}phenoxyl)x‐methylene methacrylate] (x = 0, 2, 6, or 11), were synthesized. The structures of the polymers were characterized by IR, ¹H NMR, UV, differential scanning calorimetry, and gel permeation chromatography. The chiroptical properties of the polymers in films were investigated with circular dichroism (CD) measurements. The CD and UV spectra of the films suggested that CD absorptions occurred in the films of the polymers with long spacers (x = 6 or 11) but not in the films of the polymers with short spacers (x = 0 or 2). After irradiation with linearly polarized light at 442 nm, the CD values were amplified in all the polymeric films. The amplificatory values of the CD bands in the absorption region (260–360 nm) of azobenzene chromophores suggested that the spacer length had an effect on both the transfer of chirality and photoinduced chirality in the polymeric films. The largest level of photoinduced chirality was induced in the polymer containing six methylene units. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3210–3219, 2006     

Synthesis and optical properties of asymmetric polyamides derived from cyclopropyl diacids and diamines

The polyamides were prepared from the dicarbonyl chloride of (+) (S)- or (?)(R)-trans-1,2-cyclopropanedicarboxylic acid (C3A) with either the dihydrochloride salt of (+)(S)- or (?)(R)-trans-1,2-diaminocyclopropane (C3B) or the dihydrobromide salt of (+)(S)- or (?)(R)-trans-1,2-bis(methylamino)cyclopropane (C3MB) by interfacial polycondensation. Several diamide model compounds composed of these monomers were also synthesized. The polyamides [poly(C3A-C3B)] derived from C3A and C3B have the capability of hydrogen bonding, while the polyamides [poly-(C3A-C3MB)] derived from C3A and C3MB do not. Poly(C3A-C3B) were insoluble in common organic solvents except strong acids. Poly(C3A-C3MB) were soluble in common organic solvents. Poly(C3A-C3B) had melting points higher than 300°C. Poly(C3A-C3MB) melted at 180–235°C. The ORD and CD study has shown that poly(+)C3A(+)C3B in methane sulfonic acid (MSA), 2,2,2-trifluoroethanol (TFE) (5 v % MSA), and tetramethylenesulfone (TMS) (5 v % MSA) exhibits a very strong Cotton effect or CD peak at 212–218 mμ, attributable to a component of the split π–π^* transition of the amide chromophores. Poly(+)C3A(+)C3MB in MSA and TFE (5 v % MSA) shows a strong Cotton effect or CD peak at 217–223 mμ and an intermediate Cotton effect or CD trough at 202–204 mμ as well as an intermediate Cotton effect or CD trough at 220–222 mμ and an intermediate Cotton effect or CD peak at 202–204 mμ in TFE and TMS. These peaks and troughs may be assigned to splitting of the π–π^* transition. The CD spectra of poly(+)C3A(+)C3MB in nonacidic media are quite different from those in acidic media: they are almost mirror images. The CD spectra in this transition induced by MSA suggests that a transition from a compact helix to another more extended helix with opposite handedness occurs similar to poly-L-proline I ? II. This transition may be explained by electrostatic repulsion between protonated amide groups. Viscosity data have shown that the conformation is changed to a highly extended from in acidic media. The polyamides and diamides derived from enantiomers exhibit mirror image spectra. Poly(+)C3A(+)C3B and poly(+)C3A(+)C3MB in every solvent studied exhibit a marked enhancement of the rotatory strength of ORD and CD with respect to the corresponding diamide models.     

Magnetic circular dichroism studies of aromatic polymers

The magnetic circular dichroism (MCD) spectra of syndiotactic and isotactic polymers which contain aromatic chromophores have been found to be sensitive to configurational and conformational differences. For isotactic polymers it was determined that as the aromatic ring moved farther from the main chain the ration of B terms of the polymers to those of their model compounds reached a minimum but increased significantly when the aromatic ring was separated from the main chain by four atoms. This enhancement of MCD is believed to be caused by the alignment of the more flexible side chains which would allow the interaction of the aromatic rings with neighboring groups and could result in a favorable mixing of the ester electronic transition with the aromatic ¹A_1g?¹B_2u transition. This effect was not felt to any great extent by the syndiotactic polymers because the necessary nearest-neighbor interaction was sterically unfavorable. The ratio of the B terms of isotactic poly(phenyl methacrylate) to its model compound decreased as the polymer coil expanded, whereas it increased for the syndiotactic polymer. This effect reflects the different changes that the side chain interaction and orientations undergo in these polymers during coil expansion. The MCD ratios for iso- and syndiotactic poly(phenylethyl methacrylate) were not so sensitive during coil expansion. The ratio of the dipole strengths of the polymers and model compounds paralleled the MCD results, but the ultraviolet (UV) technique was less sensitive than MCD to subtle conformational differences. Poly(benzyl methacrylate) and benzyl pivalate were unsuitable systems for studying the MCD effect because the B terms of these materials approached zero.     

Lower-frequency infrared spectra and structures of some typical aliphatic polyamides

The Polarized lower-frequency infrared spectra (800–33 cm^-1) of nylon 66 (α form), nylon 77 (γ form), and nylon 6 (both α and γ form) have been examined. The spectral changes which occur on complex formation of the polyamides with iodine-potassium iodide solution and on subsequent iodine desorption have been studied in relation to the changes in the polymer structures. On the basis of these results, most of the stronger bands have been reasonably assigned to the vibrations characteristic of the amide group and the methylene chain of the polyamides, and some new structure–frequency correlations have been established for the polymers.     

Synthesis,thermal and optical properties of new nanosized polyamides containing N-phenyl- and O-naphthyl-s-triazine rings; part 2

We report the chemistry and properties of two new series of well-defined nano sized spheres aramides-containing N- and O-naphthyl-s-triazines. The polymers were carefully characterized by different techniques including infrared, ultraviolet, fluorescent emission, elemental, thermal analyses and scanning electron microscopy (SEM). The polymers were readily soluble in polar aprotic solvents while insoluble neither in water nor halogenated solvents. Thermal analyses data up to 900°C showed high thermal behavior and the polymers were classified either as “slow burning polymers” or “self-extinguishing polymers” based on their calculated the limiting oxygen index. Interestingly, the naphthyl / phenyl interchange has dramatic improvement on the thermal properties. Obviously, the pyridine / phenylene interchange has no influence on the thermal properties of the addressed polymers. Thermal stability of the aniline-containing polymers proved to be comparable to their naphthylamine analogues. Polymers containing p-phenylene moieties exhibited better thermal results compared to their analogues containing m-phenylene moieties. Benzidine containing polymers and sulfone containing polymers exhibited better thermal stabilities than their analogues containing either ether or methylene flexible linkages. The kinetic data obtained from the nonisothermal decomposition of the prepared polyamides series were also studied. The polymers exhibited emissions ranging from blue to orange wavelength depending on the nature of the signaling unit. The naphthyl / phenyl interchange led to either appreciable red-shifted absorptions in some cases or blue-shifted absorptions in other cases and this behavior may be attributed to the contorted, twisted structural nature of the naphthalene ring. Such attracting properties make these polymers good candidates for applications such as processable high-temperature materials and also as heat-resistant polymeric materials.     

Soluble and fusible polyamides and polyimides containing pyrazoline moieties and their crosslinking to heat-resistant resins

3-(4-Aminophenyl)-5-(3-aminophenyl)-2-pyrazoline as well as the 1-acetyl- or 1-benzoyl-substituted derivatives of this compound were synthesized and used for preparing a new series of polyamides and polyimides. Characterization of polymers was accomplished by inherent viscosity, ¹H-NMR, ¹³C-NMR, x-ray, DTA, TMA, TGA, and isothermal gravimetric analysis. The properties of polymers were correlated with their chemical structures. They were amorphous or microcrystalline and soluble in polar aprotic solvents, CCl₃COOH, and m-cresol. The polyamides showed an excellent solubility being soluble even in o-dichlorobenzene, 1,2-dichloroethane, and chloroform. The polymers displayed T_g at 127–163°C and softening at 150–195°C. The polyamide bearing unsubstituted pyrazoline moieties was remarkably more hydrophilic than those containing 1-acetyl- or 1-benzoyl-substituted pyrazoline segments. Upon curing, crosslinked polymers were obtained and their thermal stability was evaluated. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1353–1361, 1997     

Optically Pure,Monodisperse cis‐Oligodiacetylenes: Aggregation‐Induced Chirality Enhancement

Conformational changes in the conjugated backbone of poly‐ and oligodiacetylenes (PDAs and ODAs) play an important role in determining the electronic properties of these compounds. At the same time, conformational changes can also result in a folded structure that shows helical chirality. Using D ‐camphor as a chiral building block, we have designed a high‐yielding, iterative synthesis of monodisperse, optically pure cis‐oligodiacetylenes (ODAs). cis‐ODAs up to the tridecamer have been formed, which is the longest monodisperse cis‐ODA reported to date. UV/Vis spectroscopy suggests a large effective conjugation length in THF, likely the result of a linear, planar conformation in this solvent. High‐resolution STM/AFM measurements of the nonamer cast from THF onto HOPG show a linear structure. In iPrOH, circular dichroism (CD) spectra suggest the formation of chiral aggregates for ODAs with at least nine D ‐camphor units, based on a strong CD response.     

Chiroptical properties and enantioselectivity in hydrogenation with rhodium(I) complexes of chiral bis-diphenylphosphines derived from -glucose and -galactose

(2R,3S)-2-Diphenylphosphinomethyl-3-diphenylphosphinotetrahydropyran (3) has been prepared in 64% yield from the dimesylate 5, derived from -galactose. The surprisingly different reactivities of dimesylates 2 and 5 towards diphenylphosphide anion are considered and the conformational properties of 1–6 discussed in terms of their CD spectra. The rhodium(I) complexes 9 and 10 exhibit low to relatively high enantioselectivities in hydrogenation of Z-α-acetylaminocinnamic acid and α-acetylaminoacrylic acid. The chiroptical and conformational properties of the bidentate ligands (3, 6), and their rhodium(I) complexes (9, 10) are correlated with the observed enantioselectivities.     

Binding Mode Multiplicity and Multiscale Chirality in the Supramolecular Assembly of DNA and a π-Conjugated Polymer

Water-soluble π-conjugated polymers are increasingly considered for DNA biosensing. However, the conformational rearrangement, supramolecular organization and dynamics upon interaction with DNA have been overlooked, which prevents the rational design of such detection tools. To elucidate the binding of a cationic polythiophene (CPT) to DNA with atomistic resolution, we performed molecular simulations of their supramolecular assembly. Comparison of replicated simulations show a multiplicity of CPT binding geometries that contribute to the wrapping of CPT around DNA. The different binding geometries are stabilized by both electrostatic interactions between CPT lateral cations and DNA phosphodiesters and van der Waals interactions between the CPT backbone and the DNA grooves. Simulated circular dichroism (CD) spectra show that the induced CD signal stems from a conserved geometrical feature across the replicated simulations, i. e. the presence of segments of syn configurations between thiophene units along the CPT chain. At the macromolecular scale, we inspected the different shapes related to the CPT binding modes around the DNA through symmetry metrics. Altogether, molecular dynamics (MD) simulations, model Hamiltonian calculations of the CD spectra, and symmetry indices provide insights into the origin of induced chirality from the atomic to the macromolecular scale. Our multidisciplinary approach points out the hierarchical aspect of CPT chiral organization induced by DNA.     

Synthesis and properties of aromatic polyamides with oligobenzamide pendent groups. I. Poly-5-(4-benzoylamino-1-benzoylamino)isophthalamides

A series of polyisophthalamides having pendent oligomeric benzamide groups were prepared by the Yamazaki reaction from common aromatic diamines and 5-(4-benzoylamino-1-benzoylamino)isophthalic acid. The latter was synthesized from 5-aminoisophthalic acid in a three-step synthesis by successive incorporation of benzamido groups. The new polymers were characterized by NMR, DSC, TGA, and WAXD and the properties were compared to those of corresponding unsubstituted polyisophthalamides. All of the polymers were essentially amorphous and their T_gs were about 20°C higher than the reference polymers. Initial thermal decomposition temperatures ranged from 375 to 420°C. All of the polymers were soluble in aprotic polar solvents without added salts. Properties of particular note were: the water uptake, which was particularly high, ranging from 7.5 to 18.2%, and the temporary insolubilization in concentrated sulfuric acid of films of the polymers heated for a short time to ≥ 200°C. © 1995 John Wiley & Sons, Inc.     

CHIRAL CONJUGATED OLIGOMER BASED ON 1,1’-BINOL WITH 3,3’-ACETYLENE-PHENYLENE-ACETYLENE SPACER

The 1,1'-binaphthol based oligomers 3 and 7 with 3, 3'-acetylene-phenylene-acetylene spacer were prepared fromBINOL 1. The high optical rotation value and CD spectra demonstrated the main chain chirality of the oligomer molecule.The UV-VIS and fluorescent spectra evidence the characteristics of conjugated structure. In comparison with oligomer 2bearing 3,3'-acetylene spacer, the oligomers 3 and 7 have longer efficient conjugation segment, and their fluorescent quantumyields (φ) increased (0.60-0.65 versus 0.14). Extending the effective conjugation segment would improve the photophysicalproperties of chiral conjugated polymers.     

Synthesis and Asymmetric Enantioselective Addition of Chiral Polybinaphthyl and Polybinaphthol I.igands

Four chiral polymers P-1, P-2, P-3 and P-4 were synthesized by the polymerization of （S）-2,2＇-dioctoxy-1,1＇- binaphthyl-6,6＇-boronic acid （S-M-3） with （S）-6,6＇-dibromo-1,1＇-binaphthol （S-M-1）, （R）-6,6＇-dibromo-1,1＇- binaphthol （R-M-1）, （S）-3,3＇-diiodo-1,1＇-binaphthol （S-M-2） and （R）-3,3＇-diiodo-1,1＇-binaphthol （R-M-2） under Pd-catalyzed Suzuki reaction, respectively. All four polymers can show good solubility in some common solvents due to the nonplanarity of the polymers in the main chain backbone and flexible alkyl groups in the side chain. The analysis results indicate that specific rotation and circular dichroism （CD） spectral signals of the alternative S-S chiral polymers P-1 and P-3 are larger than those of S-R chiral polymers P-2 and P-4, but their UV-Vis and fluorescence spectra are almost similar. The results of asymmetric enantioselectivity of four polymers for diethylzinc addition to benzaldehyde indicate that catalytically active center is （R） or （S）-1, 1＇-binaphthol moieties.     

Application of fourier transform infrared spectroscopy to the study of semicrystalline polymers: Poly(ethylene terephthalate)

An infrared absorbance subtraction technique has been used to “isolate” bands in the composite spectrum of semicrystalline polymers according to their crystalline or amorphous character. Amorphous and crystalline spectra for annealed, melt-quenched, and solution-cast poly(ethylene terephthalate) have been separated. The spectra of the amorphous component show an increased intensity of bands associated with the trans configuration of oxygen about the C? C bond when the polymer is annealed. This increased “trans” band intensity reflects the increased proportion of trans structures as a result of annealing. The amorphous trans bands are shifted approximately 1–3 cm^?1 from their positions in the crystalline “trans” spectrum. The frequency shift of these bands can be attributed to the differences in chain interactions that exist in the amorphous phase and the crystalline lattice. We have also found that under identical anealing conditions the amorphous phase of the melt-quenched polymer contains an increased intensity of conformational trans bands compared to the sample cast from solution.