On the Interfacial Behavior of Catenated Poly(l-lactide) at the Air-Water Interface.

Interfacial properties of polymeric materials are significantly influenced by their architectural structures and spatial features, while such a study of topologically interesting macromolecules is rarely reported. In this work, we reported, for the first time, the interfacial behavior of catenated poly(l-lactide) (C-PLA) at the air-water interface and compared it with its linear analogue (L-PLA). The isotherms of surface pressure-area per repeating unit showed significant interfacial behavioral differences between the two polymers with different topologies. Isobaric creep experiments and compression-expansion cycles also showed that C-PLA demonstrated higher stability at the air-water interface. Interestingly, when the films at different surface pressures were transferred via the Langmuir-Blodgett method, successive atomic force microscopy imaging displayed distinct nanomorphologies, in which the surface of C-PLA exhibited nanofibrous structures, while that of the L-PLA revealed a smoother topology with less fiber-like structures.

Electropolymerized-molecularly imprinted polymers (E-MIPS) as sensing elements for the detection of dengue infection.

A straightforward in situ detection method for dengue infection was demonstrated through the molecular imprinting of a dengue nonstructural protein 1 (NS1) epitope into an electropolymerized molecularly imprinted polyterthiophene (E-MIP) film sensor. The key enabling step in the sensor fabrication is based on an epitope imprinting strategy, in which short peptide sequences derived from the original target molecules were employed as the main template for detection and analysis. The formation of the E-MIP sensor films was facilitated using cyclic voltammetry (CV) and monitored in situ by electrochemical quartz crystal microbalance (EC-QCM). Surface properties were analyzed using different techniques including atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and polarization modulation-infrared reflection-adsorption (PM-IRRAS). The standard calibration curve (R = 0.9830) was generated for the detection of the epitope, Ac-VHTWTEQYKFQ-NH2, with a linear range of 0.2 to 30 µg/mL and detection limit of 0.073 µg/mL. A separate calibration curve (R = 0.9786) was obtained using spiked buffered solutions of dengue NS1 protein, which resulted in a linear range of 0.2 to 10 µg/mL and a detection limit of 0.056 µg/mL. The fabricated E-MIP sensor exhibited long-term stability, high sensitivity, and good selectivity towards the targeted molecules. These results indicated that the formation of the exact and stable cavity imprints in terms of size, shape, and functionalities was successful. In our future work, we aim to use our E-MIP sensors for NS1 detection in real-life samples such as serum and blood.

Cellulose nanocrystals-reinforced waterborne epoxy coatings with enhanced corrosion resistance for steel.

The practical applications of waterborne epoxy coatings are limited due to their poor barrier properties caused by the formation of numerous micropores and defects during the curing process. Herein, cellulose nanocrystals (CNCs)-reinforced waterborne epoxy coatings were fabricated by the direct addition of 0.2-1.0 wt% CNCs to waterborne epoxy emulsion followed by amine curing agent addition and spray coating. The incorporation of 0.2-0.5 wt% CNCs had no discernible impact on the stability of the waterborne epoxy emulsion. This led to the uniform dispersion of CNCs in the cured coating matrix, as evidenced by differential scanning calorimetry analysis. Because of the good compatibility, 0.2-0.5 wt% CNCs-reinforced epoxy coatings exhibited superior corrosion protection performance for steels. The impedance modulus of these coatings remained at 108 Ω cm2 after being immersed in a 3.5 wt% NaCl solution for 21 d. The hydroxyl groups present on the CNC surface undergo a reaction with the epoxy group, enhancing intermolecular interaction and leading to the formation of a defect-free dense structure that improves coating barrier properties. However, the incorporation of an excessive amount of CNCs (i.e., 0.8 and 1.0 wt%) significantly compromised the corrosion resistance of epoxy coatings due to aggregation-induced coating defects. Overall, this study provides a facile and green strategy for corrosion resistance improvement of waterborne epoxy coatings.

Anticorrosive epoxy coatings from direct epoxidation of bioethanol fractionated lignin.

The development of lignin-based anticorrosive epoxy coatings for steel protection is beneficial for both alleviating the fossil resource depletion and value-added utilization of lignin but remains a challenge due to the inherent heterogeneous structure of lignin. Here, we selectively extract the low molecular weight (MW) fraction of a crop residue-derived enzymatic hydrolysis lignin (EHL) through a bioethanol fractionation process and prepare epoxy resin by direct epoxidation of the bioethanol fractionated lignin (BFL). The coatings are then fabricated using 20-100 wt% of BFL-based epoxy resin (LEp) as the commercial epoxy resin substitute. The low MW and high p-hydroxyphenyl content of the BFL offer high solubility and good workability for BFL and LEp during epoxidation and coating production, respectively. Lignin-based coatings with 20-40 wt% LEp exhibit good adhesion property (5B) and superior corrosion resistance, compared to the commercial epoxy coating. Although coating with high LEp concentrations (i.e., 60-100 wt%) resulted in decreased adhesion strength, the coating with 100 wt% LEp still displayed corrosion protection performance comparable to that of the commercial epoxy coating. Overall, this study provides a simple and effective approach to converting lignin to epoxy resins for a wide variety of surface coating applications.