Pseudo-Eutectic of Isodimorphism to Design Biaxially-Oriented Bio-Based PA56/512 with High Strength, Toughness and Barrier Performances.

The biaxially-oriented PA56/512 has excellent mechanical strength, extensibility and water-oxygen barrier properties and has broad application prospects in green packaging, lithium battery diaphragm and medical equipment materials. The correlation between the aggregation structure evolution and macroscopic comprehensive properties of copolymer PA56/512 under biaxial stretching has been demonstrated in this work. The structure of the random copolymerization sequence was characterized by 13C Nuclear magnetic resonance (NMR). The typical isodimorphism behavior of the co-crystallization system of PA56/512 and its BOPA-56/512 films was revealed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) tests. And the aggregation structure, including the hydrogen bond arrangement, crystal structure and crystal morphology of PA56/512 before and after biaxial stretching, was investigated by XRD, Fourier-transform infrared spectroscopy (FTIR) and polarized optical microscopy (POM) tests. Furthermore, the effect of the biaxially-oriented stretching process on the mechanical properties of PA56/512 has been demonstrated. In addition, a deep insight into the influence of the structure on the crystallization process and physical-mechanical performance has been presented. The lowest melting point at a 512 content of 60 mol% is regarded as a "eutectic" point of the isodimorphism system. Due to the high disorder of the structural units in the polymer chain, the transition degree of the folded chain (gauche conformation) is relatively lowest when it is straightened to form an extended chain (trans conformation) during biaxially-oriented stretching, and part of the folded chain can be retained. This explains why biaxially stretched PA56/512 has high strength, outstanding toughness and excellent barrier properties at the pseudo-eutectic point. In this study, using the unique multi-scale aggregation structure characteristics of a heterohomodymite polyamide at the pseudo-eutectic point, combined with the new material design scheme and the idea of biaxial-stretching processing, a new idea for customized design of high-performance multifunctional polyamide synthetic materials is provided.

The Investigation of Copolymer Composition Sequence on Non-Isothermal Crystallization Kinetics of Bio-Based Polyamide 56/512.

A new bio-based polyamide 56/512 (PA56/512) has been synthesized with a higher bio-based composition compared to industrialized bio-based PA56, which is considered a lower carbon emission bio-based nylon. In this paper, the one-step approach of copolymerizing PA56 units with PA512 units using melt polymerization has been investigated. The structure of the copolymer PA56/512 was characterized using Fourier-transform infrared spectroscopy (FTIR) and Proton nuclear magnetic resonance (1H NMR). Other measurement methods, including relative viscosity tests, amine end group measurement, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), were used to analyze the physical and thermal properties of the PA56/512. Furthermore, the non-isothermal crystallization behaviors of PA56/512 have been investigated with the analytical model of Mo's method and the Kissinger method. The melting point of copolymer PA56/512 exhibited a eutectic point at 60 mol% of 512 corresponding to the typical isodimorphism behavior, and the crystallization ability of PA56/512 also displayed a similar tendency.

Developing a cerium lactate antibacterial nucleating agent for multifunctional polylactic acid packaging film.

With the rapid development of the packaging industry, people have high requirements for the functionality of packaging materials. As a representative biodegradable packaging material, polylactic acid (PLA) still has some problems. Multifunctional additives in PLA are an effective modification method. In this paper, cerium lactate (Ce-LA) was synthesized by a precipitation method and integrated into PLA to prepare a functional PLA composite. The results showed that Ce-LA not only significantly improved the crystallinity but also imparted antibacterial ability to PLA. When the concentration of Ce-LA was 0.9 %, the crystallinity of PLA reached 39.35 %, which was 77 % higher than that of pure PLA. When the addition of Ce-LA was 1.8 %, the antibacterial rates of PLA against Staphylococcus aureus and Escherichia coli reached 93 % and 85 %, respectively. This study provides a beneficial solution for the development of PLA packaging materials with high crystallinity and antibacterial properties.

Improvement of Gas Barrier Properties for Biodegradable Poly(butylene adipate-co-terephthalate) Nanocomposites with MXene Nanosheets via Biaxial Stretching.

In order to ease the white pollution problem, biodegradable packaging materials are highly demanded. In this work, the biodegradable poly (butylene adipate-co-terephthalate)/MXene (PBAT/Ti3C2TX) composite casting films were fabricated by melt mixing. Then, the obtained PBAT/Ti3C2TX composite casting films were biaxially stretched at different stretching ratios so as to reduce the water vapor permeability rate (WVPR) and oxygen transmission rate (OTR). It was expected that the combination of Ti3C2TX nanosheets and biaxial stretching could improve the water vapor and oxygen barrier performance of PBAT films. The scanning electron microscope (SEM) observation showed that the Ti3C2TX nanosheets had good compatibility with the PBAT matrix. The presence of Ti3C2TX acted as a nucleating agent to promote the crystallinity when the content was lower than 2 wt%. The mechanical tests showed that the incorporation of 1.0 wt% Ti3C2TX improved the tensile stress, elongation at break, and Young's modulus of the PBAT/Ti3C2TX nanocomposite simultaneously, as compared with those of pure PBAT. The mechanical dynamical tests showed that the presence of Ti3C2TX significantly improved the storage modulus of the PBAT nanocomposite in a glassy state. Compared with pure PBAT, PBAT-1.0 with 1.0 wt% Ti3C2TX exhibited the lowest OTR of 782 cc/m2·day and 10.2 g/m2·day. The enhancement in gas barrier properties can be attributed to the presence of Ti3C2TX nanosheets, which can increase the effective diffusion path length for gases. With the biaxial stretching, the OTR and WVPR of PBAT-1.0 were further reduced to 732 cc/m2·day and 6.5 g/m2·day, respectively. The PBAT composite films with enhanced water vapor and water barrier performance exhibit a potential application in green packaging.

The Effect of Stretching on the Crystal Structure and Crystal Orientation of PA510/SiO2 Films.

In order to explore the relationship between the microstructure and macroscopic properties of PA510/SiO2 films, the effect of the stretching on the crystal structure and crystal orientation of stretched PA510/SiO2 films was studied. It could be seen from the transmission electron microscopy (TEM) graphs that the layered SiO2 molecules were mainly oriented toward the machine direction (MD) and the dispersion could be improved by stretching. Through wide-angle X-ray scattering (WAXS) analysis, PA510/SiO2 stretched films only contained a γ crystal form. During uniaxial stretching, especially for 1 × 3 film, the γ1(100) crystal form was obviously oriented in the equatorial direction, and the orientation of γ2(004) and γ3(006) crystal forms could be observed in the meridian direction. According to the Herman orientation function, the orientation of the b-axis in the MD increased with the increase of the stretching ratio. It was worth noting that the orientation of the crystal region was more obvious. The addition of SiO2 and the orientation of the crystalline and amorphous regions could improve the barrier properties of the films. The changes in the optical properties of stretched films were affected by the dispersion state of SiO2 and the surface roughness.

Biodegradable Poly(butylene adipate-co-terephthalate) Antibacterial Nanocomposites Reinforced with MgO Nanoparticles.

Antibacterial packaging materials can reduce the microbial contamination of food surfaces. In this study, magnesium oxide (MgO) nanoparticles were synthesized and then coated with cetrimonium bromide (CTAB). CTAB-modified MgO (MgO@CTAB) was characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and thermogravimetric analysis. Then, different loadings of MgO@CTAB were mixed with poly(butylene adipate-co-terephthalate) (PBAT) by melt compounding. The results showed that the addition of MgO@CTAB deteriorated the thermal stability of PBAT due to MgO serving as a catalyst to promote the thermal degradation of PBAT. In addition, MgO@CTAB could serve as a nucleating agent to improve the crystallinity of PBAT. With the optimal 3 wt% of MgO@CTAB, the tensile strength of PBAT/MgO@CTAB increased from 26.66 to 29.90 MPa, with a slight enhancement in elongation at break. SEM observations and dynamical rheological measurements revealed that aggregation occurred when the content of MgO@CTAB exceeded 5 wt%. The presence of MgO@CTAB endowed PBAT with antibacterial properties. The bacterial inhibition zone increased with the increasing content of MgO@CTAB. In addition, MgO@CTAB had a better antibacterial efficiency against Gram-positive bacterial S. aureus than Gram-negative bacterial E. coli.

Crystal Structure and Mechanical Properties of Uniaxially Stretched PA612/SiO2 Films.

Stretching has a significant effect on the microstructure and ultimate performance of semi-crystalline polymers. To investigate the effect of stretching on structure and mechanical properties of uniaxial stretched PA612/SiO2, PA612 and PA612/SiO2 films were prepared at four temperatures close to the glass transition temperature at various strain. The samples were characterized by a transmission electron microscope (TEM), wide-angle X-ray diffractometer (WAXD), Two-dimensional wide-angle X-ray Scattering (2D-WAXS), differential scanning calorimeter (DSC), dynamic mechanical analyzer (DMA), and stretching tests. The results showed that the α phase was the dominant phase in PA612 casting film, no obvious γ phase was observed, while both stretching and the presence of SiO2 can induce the generation of α phase and improve the crystallinity of PA612. Crystals were oriented along the stretching direction and the b axis was parallel to the equatorial direction after stretching. The interplanar spacing of (010/110) decreased with the increasing stretching temperature and expanded with the increasing strain, while stretching temperature and strain present negligible effect on the interplanar spacing of (100). The grain size increased with the stretching temperature while decreased with strain. The presence of SiO2 led to reduce the yield stress and the stress drop beyond yielding of the composite. Uniaxial stretching gave rise to a significant improvement in the fracture stress and the glass transition temperature.

Molecular functional analysis of auxin/indole-3-acetic acid proteins (Aux/IAAs) in plant disease resistance in cassava.

Auxin/indole-3-acetic acid proteins (Aux/IAAs) play important roles in auxin signaling pathways, with extensive involvement in plant development and plant response to abiotic and biotic stresses. Manihot esculenta (Cassava) is one of the most important biomass energy crops in tropical regions; however, the information about Aux/IAA proteins remain limited in cassava. In this study, 37 MeAux/IAA gene family members were identified in cassava and a phylogenetic analysis was performed. The transcript levels of MeAux/IAAs were commonly regulated by the pathogen Xanthomonas axonopodis pv manihotis (Xam), and some of them were specifically localized to the nucleus. Moreover, the overexpression of MeAux/IAAs confers an improved disease resistance against Xam in Nicotiana benthamiana, while MeAux/IAAs-silenced plants show disease sensitivity against Xam in cassava, as evidenced by the leaf phenotype and leaf bacterial population. Consistent with the disease resistance, MeAux/IAAs regulated the transcript levels of PATHOGENESIS-RELATED GENES (MePRs), reactive oxygen species accumulation and callose development in the plants' defense response. Taken together, gene profile and functional analysis identified several MeAux/IAAs as novel members in plant disease resistance, providing important information for further utilization of MeAux/IAAs.

Two Cassava Basic Leucine Zipper (bZIP) Transcription Factors (MebZIP3 and MebZIP5) Confer Disease Resistance against Cassava Bacterial Blight.

Basic domain-leucine zipper (bZIP) transcription factor, one type of conserved gene family, plays an important role in plant development and stress responses. Although 77 MebZIPs have been genome-wide identified in cassava, their in vivo roles remain unknown. In this study, we analyzed the expression pattern and the function of two MebZIPs (MebZIP3 and MebZIP5) in response to pathogen infection. Gene expression analysis indicated that MebZIP3 and MebZIP5 were commonly regulated by flg22, Xanthomonas axonopodis pv. manihotis (Xam), salicylic acid (SA), and hydrogen peroxide (H2O2). Subcellular localization analysis showed that MebZIP3 and MebZIP5 are specifically located in cell nucleus. Through overexpression in tobacco, we found that MebZIP3 and MebZIP5 conferred improved disease resistance against cassava bacterial blight, with more callose depositions. On the contrary, MebZIP3- and MebZIP5-silenced plants by virus-induced gene silencing (VIGS) showed disease sensitive phenotype, lower transcript levels of defense-related genes and less callose depositions. Taken together, this study highlights the positive role of MebZIP3 and MebZIP5 in disease resistance against cassava bacterial blight for further utilization in genetic improvement of cassava disease resistance.