Crystalline polymers of bis(β-chloroethyl) vinylphosphonate

The polymerization of bis(β-chloroethyl) vinylphosphonate to a crystalline solid was carried out with a Ziegler-Natta catalyst. A confirmation of the crystalline nature of the polymers was carried out by x-ray diffraction. The polymers would not melt even at temperatures up to 620°C., but instead began to char. However, they were soluble in dimethylformamide and acrylonitrile.     

Structural Characterization and Enzymatic Degradation of α‐, β‐, and γ‐Crystalline Forms for Poly(β‐propiolactone)

A structural comparison of three different crystalline forms of poly(β‐propiolactone) (PPL) was carried out by wide‐angle X‐ray diffraction, Fourier‐transform infrared spectroscopy, and differential scanning calorimetry. The α‐form in a hot‐drawn and annealed film represents a 2₁ helix conformation. The β‐form in a cold‐drawn and annealed film represents a planar zigzag conformation. The γ‐form in an oriented sedimented mat of solution‐grown chain‐folded lamellar crystals also implies a planar zigzag conformation. The solution‐cast film depicts similar outlines with the γ‐form in lamellar crystals in all the experimental measurements, suggesting that the molecular chain in the solution‐cast film has a planar zigzag conformation. While elongation at break decreased, tensile strength and Young's modulus increased with an increase in the crystallinity, independent of the crystalline forms. The influence of the enzymatic degradation of these crystal structures has been investigated by using an extracellular PHB depolymerase purified from Ralstonia pickettii T1. The rate of degradation was in the order of β‐form > α‐form > solution‐cast (γ‐form) film, and the different surface morphologies after partial enzymatic degradation were observed in scanning electron micrographs. It is suggested that the crystal structure is one of the important factors for determining the rate of degradation together with crystallinity.

Enzymatic degradation profiles of poly(β‐propiolactone) films.     

Synthesis of Poly(α‐alkyl β,L‐aspartate)s by Transesterification

A new procedure for the preparation of poly(α‐alkyl β,L ‐aspartate)s based on the transesterification of polyα‐benzyl β,L ‐aspartate) with alcohols in the presence of titanium tetrabutoxide is described. The reaction proceeded to almost total conversion without substantial racemization or imidation. Thermal properties of the resulting polymers were comparable to those of their homologues obtained by anionic ring‐opening polymerization of β‐lactams and their thermal stability is even higher.     

Self‐Assembly of Poly(γ‐benzyl L‐glutamate)‐graft‐Poly(ethylene glycol) and Its Mixtures with Poly(γ‐benzyl L‐glutamate) Homopolymer

Summary: Self‐association behaviors of poly(γ‐benzyl L ‐glutamate)‐graft‐poly(ethylene glycol) (PBLG‐graft‐PEG) and its mixtures with PBLG homopolymer in aqueous media were investigated by fluorescence spectroscopy, transmission electron microscopy (TEM), and nuclear magnetic resonance (NMR) spectroscopy. It was revealed that PBLG‐graft‐PEG could self‐assemble to form polymeric micelles with a core‐shell structure in the shape of spindle. The introduction of PBLG homopolymer not only decreases the critical micelle concentration, but also changes the morphology of the micelles.

The excitation fluorescence spectra of pyrene as a function of concentrations for the mixture of PBLG‐graft‐PEG with PBLG and a TEM image of the formed micelles.     

Monolayer properties of a fuzzy rod polymer: Poly(γ-stearyl α, L-glutamate)

Static and dynamic properties, and surface morphologies of monolayers at the air-water interface of a fuzzy rod polymer, poly(γ-stearyl α, L-glutamate), PSLG, have been examined by the Wilhelmy plate method for surface pressure, electrically induced capillary wave diffraction (ECWD), epi-fluorescence microscopy, and atomic force microscopy (AFM). The monolayers were first formed by spreading polymer solutions at the air-water interface and allowing the solvent to evaporate to obtain polymer films, i.e., spread monolayers. The surface mass density was varied by either successive additions of more solutions on a given surface area or step-wise compression of the surface barrier on a Langmuir trough. Surface pressure isotherms at 23–;60°C were confirmed to be reversible and reproducible, and an abrupt change at approximately 60°C was observed, which is reported as the melting point of crystalline stearyl side chains. By AFM, the monolayer director n by surface alignment was confirmed as perpendicular to the compression direction and certain islands of departure from the monolayer state were visualized upon transferring the monolayers horizontally to silicon wafers. Macroscopic anisotropy in the surface alignment was probed by the electrocapillary waves propagated perpendicular (⟂) and parallel (∥) to the director n; the surface tension anisotropy amount to about 7% difference, σ_⟂/σ_⟂ < 0.07, where σ is the surface tension deduced from the wave propagation characteristics. Multidomain morphologies of the monolayers were imaged by epi-fluorescence microscopy and they were found to differ according to the method of monolayer mass density variation, i.e., the successive addition and step-wise compression. © 1996 John Wiley & Sons, Inc.     

Poly(β-amino acid)s. IV. Synthesis and conformational properties of poly(α-isobutyl-L-aspartate)

Poly(α-isobutyl-L -aspartate) was prepared by the polycondensation reaction of p-nitrophenyl ester of α-isobutyl-L -aspartate and the conformation of the poly(β-amino acid) was investigated by X-ray diffraction, polarized infrared, circular dichroism (CD), optical rotatory dispersion (ORD), and NMR spectroscopy. α-Isobutyl β-p-nitrophenyl-L -aspartate hydrochloride and hydrobromide were used as monomers and dimethylformamide, chloroform, and chlorobenzene, as solvents. A high-molecular-weight polymer with [η] 1.0 dl/g (dichloroacetic acid, 25°C) was formed in the polymerization of the hydrochloride in chloroform at 25°C. The X-ray diagram and polarized infrared spectrum of the stretched polymer film obtained from a chloroform solution suggested a cross-β-form as the most probable structure in the solid state. The CD spectra of the polymer in a 2,2,2-trifluoroethanol (TFE) solution and its film cast from the solution showed a peak at 205 nm and a trough at 190 nm which were assigned to a β-structure. The polymer was associated in chloroform. The NMR and ORD spectra in chloroform were similar to those in TFE, which suggests that the polymer also exists in the β-structure in chloroform. The addition of small amounts of dichloroacetic acid and sulfuric acid to chloroform and TFE solutions, respectively, destroyed the β-structure. A random copolymer of α-isobutyl-L -aspartate with β-alanine was also prepared by polycondensation reaction. The copolymer apparently did not form an ordered structure in the solid state or in solution.     

Preparation of Porous Poly(ε‐caprolactone) Structures

Porous poly(ε‐caprolactone) structures have been prepared by leaching of compression moulded salt‐containing polymer precipitates. Coagulation takes place when a PCL solution containing dispersed water‐soluble salt particles is precipitated into an excess of non‐solvent. Porous scaffolds are obtained after leaching of the compression moulded polymer‐salt precipitate. This process yields scaffolds with a very homogeneous pore morphology and independent control of pore size and porosity.     

Poly(α‐methyleneglutarimide)s from radical polymerization of α‐methyleneglutarimides

α‐Methyleneglutaric acid, a metabolite of niacin (nicotinic acid), can be easily converted to its cyclic anhydride. We report here the first conversion of α‐methyleneglutaric anhydride to (a series of) α‐methyleneglutarimides. These monomers can be radically polymerized to the title polymers. These have relatively high glass transition properties compared to the lower homologs derived from itaconimides (α‐methylenesuccinimides). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1020–1026     

Crosslinking of Poly(L‐lactide) by γ‐Irradiation

The radiation crosslinking of poly(L ‐lactide) (PLLA) was investigated using triallyl isocyanurate (TAIC) as a crosslinking agent. The gel fraction of crosslinked PLLA increased with TAIC concentration and γ‐ray dose. Crosslinking of PLLA started at low TAIC contents and low γ‐ray dosage. Differential scanning calorimetry and dynamic mechanical thermal analysis revealed that PLLA was completely crosslinked at high weight ratios and high γ‐ray doses.     

The crystal structure of tris (indenyl)uranium (β,β,β-trifluoroethanolate)

The title compound was obtained by reaction of the methyl tris(indenyl) uranium complex with trifluoroethanol. A crystal structure reveals that there are two symmetrically independent molecules in the unit cell. The coordination geometry about the uranium atom is a flattened tetrahedron with three π-bonded indenyl rings and one σ-bonded trifluoroethanol oxygen atom. The U---O bonds are remarkably short. The U---C distances indicate trihapto mode of bonding of the indenyl rings. Variation of the ligand X in the U(C₉H₇)₃X class of complexes would not affect the stereochemistry about the U atom.     

Preparation of (S,S)‐Fmoc‐β2hIle‐OH, (S)‐Fmoc‐β2hMet‐OH,and (S)‐Fmoc‐β2hTyr(tBu)‐OH for Solid‐Phase Syntheses of β2‐ and β2/β3‐Peptides

The preparation of three new N‐Fmoc‐protected (Fmoc=[(9H‐fluoren‐9‐yl)methoxy]carbonyl) β²‐homoamino acids with proteinogenic side chains (from Ile, Tyr, and Met) is described, the key step being a diastereoselective amidomethylation of the corresponding Ti‐enolates of 3‐acyl‐4‐isopropyl‐5,5‐diphenyloxazolidin‐2‐ones with CbzNHCH₂OMe/TiCl₄ (Cbz=(benzyloxy)carbonyl) in yields of 60–70% and with diastereoselectivities of >90%. Removal of the chiral auxiliary with LiOH or NaOH gives the N‐Cbz‐protected β‐amino acids, which were subjected to an N‐Cbz/N‐Fmoc (Fmoc=[(9H‐fluoren‐9‐yl)methoxy]carbonyl) protective‐group exchange. The method is suitable for large‐scale preparation of Fmoc‐β²hXaa‐OH for solid‐phase syntheses of β‐peptides. The Fmoc‐amino acids and all compounds leading to them have been fully characterized by melting points, optical rotations, IR, ¹H‐ and ¹³C‐NMR, and mass spectra, as well as by elemental analyses.