Electrospinning is widely accepted as a simple and versatile technique for producing nanofibers. The present work, however, introduces a new concept of the electrospinning method for controlling the crystal morphology and molecular orientation of the nanofibers through an illustration of a case study of polyoxymethylene (POM) nanofibers. Isotropic and anisotropic electrospun POM nanofibers are successfully prepared by using a stationary collector and a rotating disk collector. By controlling the voltage and the take-up velocity of the disk rotator, the morphology changes between an extended chain crystal (ECC) and a folded chain crystal (FCC) as clarified by a detailed analysis of the X-ray diffraction and polarized infrared spectra of the POM nanofibers. Herman's orientation function and dichroic ratio lead us to a schematic conclusion--that (i) molecular orientation is parallel to the fiber axis in both isotropic and anisotropic POM nanofibers, (ii) a single nanofiber consists of a nanofibril assembly with a size of 60-70 A and tilting at a certain degree, and (iii) the higher the take-up velocity, the smaller the nanofibril under the (9/5) helical structure of the POM chains. It should be emphasized here that the electrospinning method is no longer a single nanofiber producer but that it can be applied as a new instrument to control the morphology and chain orientation characteristics of polymer materials, opening a new research field in polymer science where we can understand the relationship between structure at the molecular level and the properties and performance at the macroscopic level.

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The Mannich reaction is detailed, which was carried out on benzoxazine dimers under various conditions, that is, temperature, reaction time, and solvents. Against our expectation, in any condition, instead of generating a disubstitution oxazine compound, the reaction gives a product with only a single oxazine ring, a mono-oxazine benzoxazine dimer, as characterized by FT-IR, 1H NMR, 13C NMR, 2D-NMR (1H-1H COSY, 1H-13C HMQC, and 1H-13C HMBC), and EA. The asymmetrical reaction is found to be based on the original structure of the benzoxazine dimer which has two phenol rings in a different stability as clarified by X-ray structure analysis of the single crystal. All types of benzoxazine dimers indicate the specific structure with a pair of inter- and intramolecular hydrogen bonds. The bond distance indicates that the intramolecular hydrogen bonding is very strong, while the packing structure emphasizes the high stability of the dimer unit and implies the deactivation of one phenol ring in the benzoxazine dimer. In this contribution, we demonstrate one of the quite rare examples, showing how the stereostructure of the reactant molecule is an important factor to control the reaction and give an asymmetric product which we never expected when considering only the chemical formula.

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A successful electrospun polyoxymethylene (POM) nanofiber using a hexafluoroisopropanol (HFIP)based solvent is reported. The nanofibers obtained show a significant nanoporous surface as a consequence of the spinning conditions, i.e. spinning voltage and relative humidity, as well as the polymer/solvent properties. The oxyethylene unit in the polyoxymethylene copolymer decreases the nanofiber surface roughness and porosity, leading to a significant change in the specific surface area. A slight change in the molecular weight of the POM after electrospinning confirms that the nanofiber with nanoporous POM barely degrades or decomposes during the spinning. The electrospun POM nanofiber gives an inevitable nanoporous structure with high specific surface area (as much as 2-3 times higher) compared to those of the nonporous electrospun nylon-6 and porous electrsopun PAN reported in the past.

A novel biopolymer-based antioxidant, chitosan conjugated with gallic acid (chitosan galloylate, chitosan– GA), is proposed. Electron paramagnetic resonance (EPR) demonstrates a wide range of antioxidant activity for chitosan–GA as evidenced from its reactions with oxidizing free radicals, that is, 1,1-diphenyl-2-picryl-hydrazyl (DPPH), horseradish peroxidase (HRP)–H2O2, carbon-centered alkyl radicals, and hydroxyl radicals. The EPR spectrum of the radical formed on chitosan–GA was attributed to the semiquinone radical of the gallate moiety. The stoichiometry and effective concentration (EC50) of the DPPH free radical with chitosan–GA show that the radical scavenging capacity is maintained even after thermal treatment at 100 °C for an hour. Although the degree of substitution of GA on chitosan was about 15%, its antioxidant capacity, that is, the reaction with carbon-centered and hydroxyl radicals, is comparable to that of GA.