[en] (1-Chloro-2,2-dicyanovinyl)benzene or 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene was reacted with 2-amino-phenol to give the model compound, hydroxy enaminonitrile, which was found to undergo thermal cyclization reaction to form the corresponding benzoxazole. This intramolecular cyclization reaction is expected to occur through nucleophilic attack to electropositive enamine carbon by ortho-hydroxy group on the phenyl ring, which is accompanied by the release of neutral malononitrile through rearrangement. From each bifunctional monomer, o-hydroxy substituted polyenaminonitrile was prepared and characterized as a new precursor polymer for well-known aromatic polybenzoxazole. Also the unusual macrocyclic dimer formation from the 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane polymerization reaction system was discussed. The thermal cyclization reactions and the properties of polymers were investigated using FR-IR and thermal analysis (DSC and TGA)

[en] Novel copolymers consisting of poly(2-hydroxyethyl aspartamide-co-N,N'-dimethyl-1,3-propane aspartamide) (PHEA-DPA) were prepared from polysuccinimide (PSI), which is the thermal polycondensation product of aspartic acid, via a ring-opening reaction with N,N'-dimethyl-1,3-propane diamine (DPA) and ethanolamine. The prepared water-soluble copolymer was then crosslinked by reacting it with hexamethylene diisocyanate to provide the corresponding gel. The swelling behavior and morphology of the crosslinked hydrogels were investigated. The degree of swelling decreased with increasing crosslinking reagent due to the higher crosslinking density. It was also confirmed that the swelling property is affected by pH. At low pH (< pH 4), swelling is increased due to the ionization of DPA with a tertiary amine moiety. In addition, a reversible swelling and de-swelling behavior was demonstrated by adjusting the pH of the solution. The prepared hydrogels showed a well-interconnected microporous structure with regular 5-20 μm sized pores

[en] Stimuli-responsive and self-healing materials have a wide range of potential uses, and some significant research has focused on cross-linking of hydrogel materials by means of reversible coordination bonding. The resulting materials, however, tend to have poor mechanical properties with pronounced weakness and brittleness. In this work, we present a novel mussel-inspired graphene oxide(GO)–containing hydrogel based on modified polyaspartamide with γ-amino butyric acid (GABA), 3.4-dihydroxyphenethylamine (DOPA), and ethanolamine (EA), termed PolyAspAm(GABA/DOPA/EA). Here both GO nanosheets and boric acid (H₃BO₃) act as cross-linkers, interacting with polar functional groups of the PolyAspAm(GABA/DOPA/EA). Compared to PolyAspAm(GABA/DOPA/EA)/B³⁺ gel without GO, the same containing 5 wt% of GO yielded a 10-fold increase in both the storage and loss moduli, as well as 134% and 104% increases in the tensile and compressive strengths, respectively. In addition, the GO-containing polyaspartamide hydrogel exhibited rapid and autonomous self-healing property. Two types of bonding, boron–catechol coordination and strong hydrogen bonding interactions between PolyAspAm side chains and GO nanosheets, would impart the enhanced mechanical strength and good reversible gelation behavior upon pH stimulation to the hydrogel, making this biocompatible hydrogel a promising soft matter for biomedical applications. - Highlights: • Novel GO-containing nanocomposite hydrogels based on dopamine-conjugated polyaspartamide derivative was prepared. • Improvement in the mechanical property of composite gel by GO incorporation was elucidated. • The “smart” characteristics of pH-responsive gelation and rapid self-healing were demonstrated.

[en] The reduced graphene oxide (rGO) aerogels are particularly attractive owing to their ultralight-weight, high surface area and interconnected macroporosity for energy storage applications. However, pure rGO aerogels are generally weak and brittle to limit their practical applications. To overcome this drawback, a small amount of synthetic dopamine-conjugated poly(aspartic acid) was mixed with graphene oxide to fabricate ultralight rGO aerogels with high porosity and mechanical integrity via hydrothermal reactions at 80 °C and freeze-drying process. In addition, the Fe³⁺ ionic species was chosen for an additional cross-linker to further strengthen the ultralight poly(aspartic acid/dopamine) functionalized rGO aerogel, abbreviation for PAAD/rGO, through the coordination bonding between Fe³⁺ and carboxylic acid or catechol groups of both polymer and rGO sheets at pH 9 (PAAD/rGO-Fe❾). The hybrid electrodes of PAAD/rGO-Fe❾ showed the reversible transformation of the Fe³⁺ tris-catecholate complexes into mono-catecholate promoting Quinone (Q)-hydroquinone (QH₂) in 1.0 mol L⁻¹ H₂SO₄ electrolyte, thus delivering a high specific capacitance of 276.4 F g⁻¹ at 0.5 A g⁻¹ and capacitance retention of 88.2% after 5000 cycles. Moreover, this compressible aerogel provided high strength with 150 kPa without noticeable structural fracture after 80% compression and repeated deformation processes suggesting applications in energy storage and absorption.

[en] Hydrophobicity-enhanced poly(L-lactide-co-ε-caprolactone) (PLCL) (50:50) films were cast by using the solvent–nonsolvent casting method. PLCL (50:50) was synthesized by the well-known random copolymerization process and confirmed by ¹H NMR analysis. The molecular weight of the synthesized PLCL was measured by gel permeation chromatography (GPC). Number-average (Mn), weight-average (Mw) molecular weights and polydispersity (Mw/Mn) were 7 × 10⁴, 1.2 × 10⁵, and 1.7, respectively. PLCL films were cast in vacuum condition with various nonsolvents and nonsolvent ratios. Tetrahydrofuran (THF) was used as the solvent and three different alcohols were used as the nonsolvent: methanol, ethanol, and isopropyl alcohol (IPA). Surface hydrophobicity was confirmed by water contact angle. The water contact angle was increased from 81° ± 2° to 107° ± 2°. Water contact angle was influenced by surface porosity and topography. The prepared film surfaces were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The change of crystalline property was characterized by X-ray diffraction (XRD). Platelet adhesion tests on the modified PLCL film surfaces were evaluated by platelet-rich plasma (PRP). The modified film surface exhibited enhanced hydrophobicity and reduced platelet adhesion ratio depending on the surface topography. One of the candidate products proposed as a potential blood compatible material showed a markedly reduced platelet adhesion property.