Growth stages in epitaxial crystallization of poly(γ-benzyl L-glutamate)

The electron microscope study of the isothermal epitaxial crystallization of PBLG on 001 cleavage surface of NaCl or KCl from 0.01% chloroform solution with various n-octane contents has shown that the epitaxial growth process could be divided in two stages. In the first stage a rapid growth of a lamellar layer 20–40 Å thick could be observed; the PBLG molecules in αhelix conformation are oriented along <110> substrate directions. The dimensions and perfectness of alignment of these lamellae along the <110> direction depends on the molecular weight of the PBLG. In the second stage of PBLG epitaxial crystallization the relatively slow thickening of some initial lamellae takes place and one can observe many types of secondary structures. With increasing thickness of the epitaxial structures and increasing molecular weight of the PBLG the degree of orientation in relation to <110> substrate direction diminishes. The two growth stages in PBLG epitaxial crystallization are related to different kinds of orienting and attracting forces of the alkali halide substrate.     

A crystal transition in poly(γ-n-alkyl L-glutamate)s

A thermally reversible crystal transition was found for γ-helical poly(γ-n-alkyl L -glutamate)s (alkyl = ethyl, propyl, butyl, and amyl). The transition temperature is higher than that of the side-chain mechanical dispersion, and decreases from 115 to ?5°C, as the alkyl groups become longer. The transition in poly(γ-n-propyl L -glutamate) is clearly first order. The structures were analyzed by x-ray diffraction at various temperatures. It is noteworthy that the pseudohexagonal form observed below the transition temperature is less ordered than the hexagonal form at higher temperatures. The mechanism of this transition is discussed.     

A structure with an irregular layer lattice in poly(γ-methyl L-glutamate-co-γ-benzyl L-glutamate) film

Two types of films showing different characteristic x-ray equatorial patterns were prepared from chloroform and N,N-dimethylformamide solutions of poly(γ-methyl L -glutamate-co-γ-benzyl L -glutamate). In the film cast from chloroform solution, the x-ray pattern on the equator consisted of a remarkable mixture of sharp and diffuse reflections, with the sharp reflections corresponding to integral values of 1/3k. On the other hand, in the film cast from N,N-dimethylformamide solution, a well-defined x-ray pattern was observed. An explanation for this characteristic pattern of chloroform-cast film was made on the basis of a structural model wherein stacking faults or dislocations are incorporated into the ordered structure characteristic of N,N-dimethylformamide-cast film. Two domains divided by a stacking fault are mutually displaced along the (100) crystal planes, but the shape and size of the unit cell is everywhere the same. The intensity distribution of x-ray diffraction was calculated as a function of the probability of a stacking fault occurring in a regular sequence of (100) planes. The best correspondence with observation was obtained with a stacking fault in every three layers, on the average.     

Conformational transitions of poly(β-benzyl L-aspartate)

Conditions that affect the conformation of poly(β-benzyl L-aspartate) in films have been studied. A slow transition from the left-handed to the right-handed α-helical form is observed under certain conditions in half-dried film cast from chloroform solutions and after exposure of amorphous films of the left-handed β-helical form to chloroform vapor. This transition is caused by adsorption of moisture. Thermal transitions of these films were examined by differential scanning calorimetry and infrared spectroscopy. The right-handed α-helices change to left-handed ω-helices around 140°C, and sharp exothermic peak is observed in this region for some films.     

Novel core-shell type thermo-sensitive nanoparticles composed of poly(γ-benzyl L-glutamate) as the core and poly(N-isopropylacrylamide) as the shell

AB diblock copolymers consisting of PBLG as the hydrophobic part and PNIPAAm as the hydrophilic one were prepared by polymerization of BLG-NCA with semitelechelic PNIPAAm with amino end group as initiator. The core-shell type nanoparticles of the block copolymers were obtained by the diafiltration method. The sizes of the nanoparticles were from about 73 to 359 nm and the shapes of them were spherical. The release for indomethacin (IN) from the nanoparticles was faster at 28°C than at 34°C due to the conformational change of PNIPAAm by temperature.     

Supramolecular structure investigation of poly(γ-benzyl, α-l-glutamate)-benzyl alcohol system by static light scattering

The cholesteric mesophase of the PBLG-BA system in concentrated solutions and in the gel phase has been investigated by static laser light scattering. The observed ‘distortion’ of the patterns in terms of their dependence on the azimuthal angle was studied. Effect of form-optical rotation on the pattern is discussed. The manner of distortion in the H_v pattern determines the sense of cholesteric twisting. The observed scattering patterns are analogous to those obtained by previous investigators in other solvents. Quantitative measurements of the intensity as a function of scattering vector provide information on the sense and pitch of the cholesteric twisting, as a function of temperature and concentration. Optical microscopy studies reveal onset and build-up of the cholesteric structure. Optical rotation and differential scanning calorimetry (DSC) studies support the conclusions obtained from light-scattering experiments.     

Crystallinity and conformational changes in poly(β-benzyl L-aspartate)

The crystallinity of poly(β-benzyl L -aspartate) is highly variable, in a series of specimens prepared under various conditions: films cast from chloroform solutions at various evaporation rates, films cast comparatively slowly from chloroform–trifluoroacetic acid solutions, films prepared from dichloroacetic acid solution by treatment with ethyl alcohol, precipitates formed from trifluoroacetic acid solution by addition of ether. Film cast slowly from chloroform is in the highly crystalline ω form. In contrast, the conformation of the benzene rings in the ω helix obtained from the α helix by heating is distorted to some extent in comparison with the structure of the highly crystalline ω form. Crystallization and conformational changes from the α to the ω form, and from the ω to the β form upon heating, are correlated with the dispositions of the side chains, the packing of the benzene rings, and the motion of the side chains. The main chain of the α helix is distorted into the ω form when its side chains are in a favorable conformation. The α helix is stable in the disordered conformation, and it is distorted to some extent at high temperature.     

Crystal structure of poly(γ-methyl L-glutamate) at high temperature

A unique crystal structure of the α-helical form of poly(γ-methyl L -glutamate) appearing above 170°C is analyzed by x-ray diffraction. At room temperature, the unit cell determined for a well-annealed sample is hexagonal with dimension a = 11.8₂ Å and contains one α helix with pitch P = 5.42 Å and unit height p = 1.493 Å. This form is reversibly transformed at about 170°C into a modification characterized by a trigonal unit cell (a = 21.2₇ Å) having three times the cross section of the single-chain unit cell and containing three α helices with P = 5.50 Å and p = 1.504 Å. In a narrow temperature range below 180°C, the three chains in the unit cell are not interrelated by any crystallographic symmetry element, but they are reasonably associated with one another so that all helices are surrounded by other helices in the same way. The axial and azimuthal displacements between neighboring chains are expressed by z = ±4p/3 and ? = ± (2π/3)(4p/P ? 1), respectively. The segmental main-chain motion, which becomes appreciable above 150°C, is composed of screw-type motion along the α-helix fold and correlated P/3 axial jumps. The relation between the structural transition and thermal motion is discussed.     

Clonazepam release from core-shell type nanoparticles composed of poly(γ-benzyl L-glutamate) as the hydrophobic part and poly(ethylene oxide) as the hydrophilic part

Block copolymers consisting of poly(γ-benzyl L -glutamate) (PBLG) as the hydrophobic part and poly(ethylene oxide) (PEO) as the hydrophilic part were synthesized and characterized. Core shell type nanoparticles of the block copolymers (abbreviated GEG) were prepared by the dialysis method. Under fluorescence spectroscopy measurement, the GEG block copolymers were associated in water to form core shell type nanoparticles as polymeric micelles and the critical micelle concentrations (CMC) values of the block copolymers decreased with increasing PBLG chain length in the block copolymers. Transmission electron microscopy (TEM) observations revealed nanoparticles of spherical shapes. From dynamic light scattering (DLS) study, sizes of nanoparticles of GEG-1 and GEG-2 copolymer were 64.3 ± 28.7 nm and 28.9 ± 7.0 nm. The drug-loading contents of GEG-1 and GEG-2 nanoparticles were 15.2 and 8.3 wt %, respectively. These results indicated that the drug-loading contents were dependent on PBLG chain length in the copolymer. Then, the longer the PBLG chain length, the more the drug-loading contents. Release of clonazepam (CNZ) from the nanoparticles was slower in higher loading contents of CNZ than lower loading contents due to the hydrophobic interaction between PBLG core and CNZ. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 415–423, 1998     

Temperature variation of piezoelectric moduli in oriented poly(γ-methyl L-glutamate)

The real and imaginary components of the complex piezoelectric strain constant, which relates the polarization to the applied stress, have been determined for elongated films of poly(γ-methyl L -glutamate) over the temperature range ?170°C to +170°C at a frequency of 20 Hz. The variation of the piezoelectric constant with temperature is similar for both α-helical and β-form molecular conformations. The sign of piezoelectric polarization is opposite for L and D polymers. A simple model, representing the piezoelectric crystallites as embedded in nonpiezoelectric amorphous regions, is proposed to account for the piezoelectric temperature dispersion curves.     

Reactive polypeptides. II. Photochemistry of poly(γ-cinnamyl L-glutamate)

Poly(γ-cinnamyl L -glutamate) was irradiated in the presence and absence of benzophenone in dichloroethane. The irradiated polymers were analyzed by gas chromatography after hydrolysis. It was possible to assign the transformation in the presence of benzophenone to trans-cis photoisomerization by comparing the effects with those observed for a model compound cinnamyl acetate. The equilibrium composition of cis and trans isomers in the photostationary state was similar for the model compound and the polypeptide. Photoisomerization was found to be accompanied by marked side reactions for the direct irradiation. Circular dichroism spectra were empolyed to study the structure, and no changes in the structure were found for the irradiated polymers.     

Synthesis of poly(γ-methoxypropylmethylsilylene) and poly(γ-methoxypropylmethylsilylene-co-di-n-hexylsilylene)

The synthesis of γ;-methoxypropylmethyldichlorosilane, and its subsequent polymerization and copolymerization with di;-n;-hexyldichlorosilane through the reductive coupling with sodium has been accomplished. The resulting polymers contain methyl ether side groups that allow further synthetic transformations on the polysilane backbone. For poly (γ;-methoxypropylmethylsilylene) these groups impart solubility characteristics different than typical alkyl and aryl substituted polysilanes. These new polymers and copolymers have been characterized by GPC and ¹H-, ¹³C-, and ²⁹Si-NMR. © 1994 John Wiley & Sons, Inc.     

Preparation and mechanical properties of poly(γ-benzyl l-glutamate) modified nano-silica reinforced polyurea composites

To improve the mechanical properties of polyaspartate polyurea (PAEP), functionalized nano-silica reinforced polyurea composites were prepared. The original nano-silica (O-SiO₂) was treated with 3-aminopropyltriethoxysilane (APTES), and the amino group at the end of APTES was used as the initiation site to realize the coating modification of poly(γ-benzyl l -glutamate) (PBLG) onto O-SiO₂. The dispersion, wettability, and interfacial properties of functionalized nano-silica (PBLG-SiO₂) in PAEP were analyzed. The tensile and tear properties of PBLG-SiO₂/PAEP composites were tested, and the reinforcement mechanism was revealed. The results showed the dispersibility of PBLG-SiO₂ in PAEP had been improved markedly. The contact angle of PBLG-SiO₂ with PAEP was 29.31°, which was significantly lower than that of O-SiO₂ (76.48°). The adhesion work between PBLG-SiO₂ and PAEP was 97.16 mJ/m², an increase of 51.7% compared with O-SiO₂. When the content of PBLG-SiO₂ was 2 phr, the tensile strength, Young's modulus, and tear strength of PAEP composites reached the maximum of 17.43 MPa, 157.12 MPa, and 127.38 N/mm, an increase of 33.6%, 77.9%, and 71.3%, respectively, compared with pure PAEP. The analysis of cross-section showed that the strengthening mechanism of PBLG-SiO₂ on PAEP was mainly manifested by non-planar cracks, deflection and bifurcation of cracks, and plastic deformation of PAEP matrix caused by peeling of PBLG-SiO₂ from matrix.     

Effect of molecular weight on conformation of poly(β-benzyl L-aspartate) in films

In order to study the effect of the molecular weight on the crystallinity and conformational changes of poly(β-benzyl L aspartate) in films, a previous study on high molecular weight samples has been extended to included polymers of low molecular weight, about 3.3 × 10³. Films were prepared from chloroform solution by quick or slow evaporation at room temperature. The conformation and the thermal behavior were studied by means of infrared spectroscopy and differential scanning calorimetry. All films dried quickly are composed of polymer in the left-handed α-helical form. All samples studied which have molecular weights above 2.3 × 10⁴ are similar in crystallinity and the left-handed α-helices in them crystallize to ω-helices during slow evaporation. In the low molecular weight region, however, the left-handed α-helices reverse to right-handed α-helices during slow evaporation, and the right-handed α-helices, in turn, reverse and crystallize to highly ordered ω-helices upon heat treatment, although there is some simultaneous conversion to the β-form. The transition temperatures of the quick-dried films for conversion from the left-handed α-helix to the ω-helix and from the ω-helix to the β-form increase linearly with increasing molecular weight up to about 2 × 10⁴, but no large molecular weight dependence is observed beyond that region.     

Phase separation of poly(γ-benzyl L-glutamate) to liquid crystal and isotropic solution in various helicogenic solvents

Solvent effects on the phase separation of poly(-benzyl L-glutamate) to liquid crystal and isotropic solution have been observed in various helicogenic solvents. The temperature-composition phase diagrams have been determined for each solution. The critical concentrations, ₂ ^* , at which the phase separation occours have been compared in various solvents. In dimethylformamide in which the polymer is molecularly dispersed, the observed ₂ ^* value has agreed with that calculated by Flory's theory. In some solvents in which the polymer aggregates in a head-to-tail mode such as chloroform, the observed ₂ ^* values have been considerably small. It is assumed that the polymer aggregates behave as longer particles than the original particles. In dioxane in which the polymer aggregates highly both in a head-to-tail and a side-by-side modes, the ₂ ^* value has been a little larger than that in chloroform. In this case the relationship between the aggregation and the liquid crystal formation is so complicated that further investigation is necessary. In aromatic solvents such asm-cresol that dissolves the polymer almost molecularly, the ₂ ^* is smaller than that in dimethylformamide. Therefore, the intermolecular interactions between the phenyl groups in the side groups of the polymer and those in solvent molecules must be considered.The author is grateful to Mr. K. Sano and Mr. M. Watanabe for their observation of the liquid crystal formation.     

Nuclear magnetic relaxation of α-13C nuclei of helical poly(γ-hexyl-L-glutamate) and poly(γ-benzyl-L-glutamate)

Spin-lattice relaxation times (T₁), spin-spin relaxation times (T₂), and nuclear Overhauser enhancements (NOE), at 75.5 MHz are reported for α-¹³C nuclei of poly (γ-benzyl-L -glutamate) in deuterated dimethylformamide at 60°C and of poly(γ-hexyl-L -glutamate) in cyclohexanone at 48 and 79°C. It is shown that for molecular weights above 10⁵, the polypeptides cannot be considered as essentially rigid helices with internal librational motions; additional backbone flexing motions contribute to the relaxation behavior.