Physicochemical evolutions of starch/poly (lactic acid) composite biodegraded in real soil.

Plastic pollution is a major environmental problem and the waste disposal is a challenge in this case. Poly (lactic acid) (PLA) based biodegradable materials is one of the most attractive polymers which can fulfill the current demand. In this work, the degradation of starch/PLA composite was investigated in real soil environment. The weight loss results demonstrated that the degradation rate of PLA could be accelerated by starch. Scanning electrical microscopy (SEM) and Fourier transform infrared (FTIR) results showed that the samples degraded faster with the presence of starch. The mechanical strengths had an abrupt decrease for the starch/PLA composite while that of PLA only decreased in a low degree. The distribution of carboxyl group intensity and carbon atomic percent reflected the heterogeneity of biodegradation for starch/PLA composite in soil. Moreover, the variation of internal carbon atomic percent was higher than that on the surface, demonstrating that the degradation of starch/PLA composite was bulk degradation. Based on the role of starch played in starch/PLA composite and the physicochemical performance evolutions during biodegradation, it should create a scientific basis for people interested in studying the biodegradation of PLA, and provide some knowledge about controlling the biodegradation rate of PLA through adjusting the content of starch in the composite.

[Determination of the carboxyl content of oxidized starch by fourier transform infrared (FTIR) spectroscopy].

In the present study, the carboxyl content of oxidized starch was determined by FTIR spectroscopy. Standard curve was drawn in which the ordinate was carboxyl content determined by national standard method with the ratio of carbonyl absorbance to the key of C-H absorbance in FTIR spectroscopy as the abscissa. The ratio of absorbance of unknown oxidized starch tested by FTIR spectroscopy was obtained, The carboxyl content was calculated by standard curve, and then compared with the carboxyl content determined by national standard method, and the deviation is between 2% and 4%. In order to improve the accuracy of the experiment, standard sample was selected to draw standard curve to better ensure that the carboxyl content of the unknown oxidized starch is in the range of standard curve calculation limit, and deviates from the limit of standard curve. Compared with the carboxyl content determined by national standard method, testing with FTIR spectroscopy is simple, easy to operate, and of high efficiency and better accuracy. So, it is significant to forecast the carboxyl content of oxidized starch by FTIR spectroscopy.

Maternal autistic traits and anxiety in children with typical development in Chinese families: a moderated mediation model of mothers' negative emotional expressions and child gender.

Background: Prior studies have focused on the effects of maternal autistic traits on children with autism, but little attention has been paid to the effects of maternal autistic traits on typically developing children, while the mechanisms of the effects are not clear. Objective: Given that, a moderated mediation model was conducted to examine the association between maternal autistic traits and typically developing children's anxiety and the underlying mechanisms. Methods and results: Participants were 648 mother-child dyads in which these children had no autistic siblings. Mothers reported their autistic traits and negative emotional expressions in the family and children's anxiety. The results indicated that children's anxiety was predicted by maternal autistic traits. Mediating analysis revealed that mothers' negative emotional expressions partially mediated the association between their autistic traits and children's anxiety. The findings also indicated that child gender moderated the relationship between maternal emotional expressions and children's anxiety. Specifically, anxiety in girls was more strongly predicted by negative emotional expressions from their mothers than in boys. Conclusion: These results have important theoretical and practical implications for reducing the adverse effect of maternal autistic traits on children's anxiety, especially for girls. The present study also reveals that maternal negative emotional expression is an important mechanism. Causal conclusions cannot be drawn based on cross-sectional research design, so it is necessary to conduct longitudinal studies in the future.

Converting soy protein isolate into biomass-based polymer electrolyte by grafting modification for high-performance supercapacitors.

Soy protein isolate (SPI) is one of the most abundant plant proteins in nature. Enormous studies have been carried out on SPI-based materials, however, the application for energy storage devices is still limited due to its fiddly film forming process and lack of electrochemical performance. Herein, we presented a SPI-based polymer electrolyte by grafting modification with the hydrophilic functional monomer acrylamide (AM). The optimized gel polymer electrolyte (GPE) exhibited an excellent ionic conductivity up to 5.10 mS cm-1, which was greatly higher than gel polymer electrolyte based on original pure SPI (1.84 mS cm-1). More significantly, supercapacitors constructed by grafting-modified SPI delivered a specific capacitance of 141.74 F g-1 at 1.0 A g-1 and exhibited high capacitance retention of 95% after 8000 charge-discharge cycles. Beyond that, redox-active polymer electrolyte based on grafting-modified SPI combining with KI enormously improved the energy density of supercapacitor up to 27.52 Wh kg-1 at a current density of 0.5 A g-1. This work provided a novel and facile strategy to obtain a high-performance SPI-based polymer electrolyte and laid an experimental foundation for the high-value application of SPI in the field of energy storage devices.

Novel dopamine-modified cellulose acetate ultrafiltration membranes with improved separation and antifouling performances.

Cellulose acetate (CA) is widely used in the preparation of ultrafiltration membranes due to its many excellent characteristics, especially chemical activity and biodegradability. To improve the inherent hydrophobic and antifouling properties of CA membrane, in this work, CA was successfully modified with dopamine (CA-2,3-DA) through selective oxidation and Schiff base reactions, which was confirmed by FTIR and 1H NMR measurements. Then, CA-2,3-DA membrane with high water permeability and excellent antifouling property was prepared by the phase inversion method. Compared with the original CA membrane, the CA-2,3-DA membrane maintained a higher rejection ratio for BSA (92.5%) with a greatly increased pure water flux (167.3 L m-2 h-1), which could overcome the trade-off between permeability and selectivity of the traditional CA membrane to a certain extent. According to static protein adsorption and three-cycle dynamic ultrafiltration experiments, the CA-2,3-DA membrane showed good antifouling performance and superior long-term performance stability, as supported by the experimental results, including flux recovery ratio, flux decline ratio, and filtration resistance. It is expected that this approach can greatly expand the high-value utilization of modified natural organic polysaccharides in separation engineering.

Development and investigation of novel antifouling cellulose acetate ultrafiltration membrane based on dopamine modification.

In this contribution, a novel cellulose acetate modified with dopamine (CA-DA) membrane material was designed and prepared by a two-step route consist of chlorination and further substitution reactions. The chemical structure of the prepared CA-DA material was determined by FTIR and 1H NMR, respectively. The CA-DA ultrafiltration membrane was subsequently fabricated by the scalable phase inversion process. Compared with cellulose acetate membrane as the control sample, the introduction of dopamine improved the porosity, pore size and hydrophilicity of the CA-DA membrane, which was helpful to the water permeability (181.2 L/m2h) without obviously affecting the protein rejection (93.5%). According to the static protein adsorption and dynamic cycle ultrafiltration experiments, the CA-DA membrane displayed persistent antifouling performance, which was verified by flux recovery ratio, flux decline ratio and filtration resistance. Moreover, the water flux recovery ratio of the CA-DA membrane was retained at 97.3% after three-cycles of BSA solution filtration, which was much higher than that of the reference CA membrane. This new approach provided a long life and excellent ultrafiltration performance for polymer-based membranes, which has potential application prospects in the field of separation process.

A Crosslinked Soybean Protein Isolate Gel Polymer Electrolyte Based on Neutral Aqueous Electrolyte for a High-Energy-Density Supercapacitor.

A crosslinked membrane based on renewable, degradable and environmentally friendly soybean protein isolate was formed by solution casting method. A series of gel polymer electrolytes were prepared with the crosslinked membranes saturated with 1 mol·L-1 Li2SO4. The solid-state electric double-layer capacitors were fabricated with the prepared gel polymer electrolytes and activated carbon electrodes. The optimized solid-state supercapacitor delivered a single electrode specific capacitance of 115.17 F·g-1 at a current density of 1.0 A·g-1, which was higher than the supercapacitor assembled with the commercial separator in 1 mol·L-1 Li2SO4. The solid-state supercapacitor exhibited an outstanding cycling stability, indicating that the gel polymer electrolyte based on the crosslinked soybean protein isolate membrane could be a promising separator for a solid-state supercapacitor.

Construction of Polymer Electrolyte Based on Soybean Protein Isolate and Hydroxyethyl Cellulose for a Flexible Solid-State Supercapacitor.

Supercapacitors are a very active research topic. However, liquid electrolytes present several drawbacks on security and packaging. Herein, a gel polymer electrolyte was prepared based on crosslinked renewable and environmentally friendly soybean protein isolate (SPI) and hydroxyethyl cellulose (HEC) with 1.0 mol L-1 Li2SO4. Highly hydrophilic SPI and HEC guaranteed a high ionic conductivity of 8.40 × 10-3 S cm-1. The fabricated solid-state supercapacitor with prepared gel polymer electrolyte exhibited a good electrochemical performance, that is, a high single electrode gravimetric capacitance of 91.79 F g-1 and an energy density of 7.17 W h kg-1 at a current density of 5.0 A g-1. The fabricated supercapacitor exhibited a flexible performance under bending condition superior to liquid supercapacitor and similar electrochemical performance at various bending angles. In addition, it was proved by an almost 100% cycling retention and a coulombic efficiency over 5000 charge-discharge cycles. For comparison, supercapacitors assembled with commercial aqueous PP/PE separator, pure SPI membrane, and crosslinked SPI membrane were also characterized. The obtained gel polymer electrolyte based on crosslinked SPI and HEC may be useful for the design of advanced polymer electrolytes for energy devices.

Soil burial-induced chemical and thermal changes in starch/poly (lactic acid) composites.

Soil burial degradation was confirmed to be an efficient waste disposal method for the biodegradable materials with short service life, such as starch/poly (lactic acid) (PLA) composite. The biodegradation behavior about chemical and thermal properties of starch/PLA composite was analyzed by using X-ray photoelectron spectroscopy (XPS), infrared microscopy (IRM), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). XPS and IRM results indicated that the biodegradation of PLA occurred at the ester groups in PLA chains. XPS demonstrated the cleavage of CO linkages between glucose rings in starch. DSC and TGA results showed that the starch/PLA composite degraded faster than the pure PLA. During the soil burial degradation, the glass transition temperature of starch/PLA composite exhibited an obviously decrease while it had a slight variation for PLA. The thermal stability of starch/PLA composite shifted towards to that of PLA when they were subjected to soil burial for the same time. It is established that the starch can accelerate the degradation of PLA-based materials, which will enlarge the markets of biodegradable PLA materials used for short service life products.

Vitamin E Encapsulation in Plant-Based Nanoemulsions Fabricated Using Dual-Channel Microfluidization: Formation, Stability, and Bioaccessibility.

In this study, vitamin E was encapsulated in oil-in-water nanoemulsions fabricated using a dual-channel microfluidizer. A long chain triacylglycerol (corn oil) was used as a carrier oil and a biosurfactant (quillaja saponin) was used as a natural emulsifier. The impact of vitamin-to-carrier oil ratio on the formation, storage stability, and bioaccessibility of the nanoemulsions was determined. The lipid droplet size formed during homogenization increased with increasing vitamin content, which was attributed to a large increase in lipid phase viscosity. The storage stability of the nanoemulsions decreased as the vitamin content increased because the larger lipid droplets creamed faster. The rate and extent of lipid hydrolysis in the small intestine decreased as the vitamin content increased, probably because the vitamin molecules inhibited the ability of lipase to reach the triacylglycerols inside the lipid droplets. Vitamin bioaccessibility decreased as the vitamin level in the lipid phase increased, which was attributed to the reduced level of mixed micelles available to solubilize the tocopherols. The optimized nanoemulsion-based delivery system led to a relatively high vitamin bioaccessibility (53.9%). This research provides valuable information for optimizing delivery systems to increase the bioaccessibility of oil-soluble vitamins.

60Co γ-ray Irradiation Crosslinking of Chitosan/Graphene Oxide Composite Film: Swelling, Thermal Stability, Mechanical, and Antibacterial Properties.

In this paper, chitosan (CS)/graphene oxide (GO) composite films were prepared, and the effect of γ-ray irradiation on the properties of composite films was investigated. The irradiation crosslinking reaction occurred in composite films with the existence of acetic acid, and the properties changed upon the various irradiation dose. The swelling degree of the composite film with 0 wt % GO decreased with the increasing of the irradiation dose, but the swelling degree of which with GO increased instead. The thermal stability increased with the increasing of the irradiation dose, but the effect of the irradiation on the thermal stability weakened as the increasing of the content of GO, due to the enhanced irradiation resistance performance. The tensile strength increased firstly and decreased subsequently with the increasing of the irradiation dose and the content of GO. Composite films showed the enhanced antibacterial activity against Bacillus subtilis, compared to Escherichia coli and Staphylococcus aureus. The antibacterial activity weakened with the increasing of the content of GO. The antibacterial activity was relatively stronger when the irradiation dose was 20 KGy. In addition, the structural, crystal, and morphological properties of composite films were characterized by FT-IR, XRD, and SEM. It is worth noting that the GO was pre-functionalized via KH560 for the better compatibility with CS matrix.

Effect of Shell Growth on the Morphology of Polyvinyl Acetate/Polystyrene Inverted Core-Shell Latex Fabricated by Acrylonitrile Grafting.

A novel strategy for fabricating inverted core-shell structured latex particles was implemented to investigate the morphology and properties of polyvinyl acetate (PVAc)-based latex. In this study, active grafting points were synthesized onto the surface of PVAc latex cores via grafting acrylonitrile (AN) to obtain a controllable coating growth of the shell monomer, styrene (St). The effect of shell growth on the morphological evolvement was explored by tuning the time of shell monomer polymerization. Unique particle morphologies, transferring from "hawthorn" type, over "peeled pomegranate" type, to final "strawberry-like" type, were observed and verified by electron microscopy. The morphological structure of latex particles exerted a significant effect on the particle size, phase structure, and mechanical properties of the obtained emulsions. The water-resistance of PVAc-based latex was also evaluated by the water absorption of latex films. More importantly, the experimental results provided a reasonable support for the controlled growth of St monomer, that is, the self-nucleation of dispersive St monomer can be transformed to in-situ coating growth on the PVAc core surface depending on the AN-active grafting points. This fabricating approach provides a reference for dynamical design and control of the latex particle morphology.

Physicochemical properties of starch adhesives enhanced by esterification modification with dodecenyl succinic anhydride.

Starch-based adhesives were prepared by esterification modification with dodecenyl succinic anhydride (DDSA) and polyaryl polymethylene isocyanate (PAPI) as a crosslinking agent. DDSA modified starch (DMS) adhesives could significantly enhance the viscosity and adhesion strength of starch adhesives, making it beneficial to be applied in the field of plywood industry. This paper investigated the physicochemical properties of starch modified by dodecenyl succinic anhydride. Solid content, viscosity, adhesion, structural change and morphological features were characterized in detail. Viscosity and solid content of the modified starch (MF) adhesives was improved remarkably when DDSA was introduced. Three-ply plywood was fabricated with DMS adhesives, and its wet shear strength was measured. The results showed that the water resistance of the adhesive with 6wt% DDSA improved by 72.4% compared to that without DDSA. The wet shear strength plywood bonded by the adhesive reached 1MPa and could meet the requirement set by the China National Standard. Incorporating DDSA into the starch adhesive formed a dense crosslinking structure due to chemical reactions between DDSA and active groups on the starch molecules and thus improve the water resistance of the cured adhesives. The introduction of DDSA improving the viscosity and solid content remarkably, which increased the amount of the adhesive that penetrated the wood surface and formed more interlocks. Using DDSA promoted a smooth and homogeneous fracture surface of cured adhesive, which effectively prevented water intrusion and improved water resistance. The modified adhesive proved practical as a plywood adhesive for industrial application.

Preparation of plasticized poly (lactic acid) and its influence on the properties of composite materials.

Plasticized poly (lactic acid) (PPLA) was prepared by melt blending poly (lactic acid) (PLA) with 10 wt% of poly (ethylene glycol) (PEG), with varied molecular weights range from 400 to 4000. The structure, thermal property, morphology, and surface free energy of the PPLA were investigated by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and contact angles (CA). The resulting PPLA results indicated that the introduction of PEG to the blend systems resulted in a ductile fracture, a decrease in the melt temperature (Tm) and glass transfer temperature (Tg), and an increase in the degree of crystallization (χc), which indicated an improved flexibility. In addition, the polarity of the PPLA increased and the surface free energy decreased. The resulting PPLA was subsequently used as matrix to blend with wood flour to prepare composites. The mechanical strength, melting behavior, thermal stability, and microscopy of the PPLA/wood flour composites were also evaluated. These results illustrated that the plasticized PPLA matrix was beneficial to the interfacial compatibility between the polar filler and the substrate.

Bio-based reactive diluents as sustainable replacements for styrene in MAESO resin.

Four different biorenewable methacrylated/acrylated monomers, namely, methacrylated fatty acid (MFA), methacrylated eugenol (ME), isobornyl methacrylate (IM), and isobornyl acrylate (IA) were employed as reactive diluents (RDs) to replace styrene (St) in a maleinated acrylated epoxidized soybean oil (MAESO) resin to produce bio-based thermosetting resins using free radical polymerization. The curing kinetics, gelation times, double bond conversions, thermal-mechanical properties, and thermal stabilities of MAESO-RD resin systems were characterized using DSC, rheometer, FT-IR, DMA, and TGA. The results indicate that all four RD monomers possess high bio-based carbon content (BBC) ranging from 63.2 to 76.9% and low volatilities (less than 7 wt% loss after being held isothermally at 30 °C for 5 h). Moreover, the viscosity of the MAESO-RD systems can be tailored to acceptable levels to fit the requirements for liquid molding techniques. Because of the introduction of RDs to the MAESO resin, the reaction mixtures showed an improved reactivity and an accelerated reaction rate. FT-IR results showed that almost all the C[double bond, length as m-dash]C double bonds within MAESO-RD systems were converted. The glass transition temperatures (T g) of the MAESO-RDs ranged from 44.8 to 100.8 °C, thus extending the range of application. More importantly, the T g of MAESO-ME resin (98.1 °C) was comparable to that of MAESO-St resin (100.8 °C). Overall, this work provided four potential RDs candidates to completely replace styrene in the MAESO resin, with the ME monomer being the most promising one.

Exploration of zwitterionic cellulose acetate antifouling ultrafiltration membrane for bovine serum albumin (BSA) separation.

This study focused on the preparation of a new kind of membrane material, zwitterionic cellulose acetate (ZCA), via a three-step procedure consist of oxidization, Schiff base and quaternary amination reaction, and the fabrication of antifouling ZCA ultrafiltration membrane by the non-solvent-induced phase separation method (NIPS). The morphologies, surface chemical structures and compositions of the obtained CA and ZCA membranes were thoroughly characterized by field emission scanning electron microscopy (FE-SEM) with energy dispersive X-ray (EDX) spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), respectively. Meanwhile, the thermal stability, porosity and average pore size of two investigated membranes were also studied. As a result, the ZCA membrane displayed significantly improved hydrophilicity and water permeability compared with those of the reference CA membrane, despite a slight decrease in the protein rejection ratio. According to the cycle ultrafiltration performance of bovine serum albumin (BSA) solution and protein adsorption experiment, ZCA membrane exhibited better flux recovery property and fouling resistant ability, especially irreversible fouling resistant ability, suggesting superior antifouling performance. This new approach gives polymer-based membrane a long time life and excellent ultrafiltration performance, and seems promising for potential applications in the protein separation.

Biodegradation behavior and modelling of soil burial effect on degradation rate of PLA blended with starch and wood flour.

The biodegradation behavior of Poly (lactic acid) (PLA) blended with starch and wood flour in outdoor soil was investigated comprehensively. As a result, starch provided a biological fuel for the growth of microorganisms in the soil which accelerated the degradation rate of PLA more obviously than wood flour. With the increase of starch content, the weight loss increased and the morphology exhibited more gullies and cavities. X-ray Photoelectron Spectroscopy (XPS) analysis indicated that the variation of O/C ratio was controlled by starch biodegradation and PLA hydrolysis and they were a concomitant process. The mechanical strengths of all the blends showed similar trend and fitted a first-order exponential decay model. The model is shown in good agreement with experimental results as the correlation coefficient is higher than 0.99, and the model can support an efficient method to estimate the durability of starch/wood flour/PLA blends.

A Rapid and Efficient Route to Preparation of Isocyanate Microcapsules.

In this paper, polyaryl polymethylene isocyanates (PAPI) were used as an innovative alternative material to prepare isocyanate microcapsules. PAPI could be used as core materials, which would react with small molecules containing active hydrogen (1,4-butanediol, ethylene glycol, 1,2-diaminoethane etc.). The reaction products of PAPI and active hydrogen would form a shell by interfacial polymerization reaction in an oil-in-water emulsion. Smooth spherical microcapsules of 70 ~ 180 µm in diameter were produced by controlling agitation rate (600 ~ 1200 rpm). High yields (~80%) of a free-flowing powder of PAPI/polyurethane and polyurea capsules were produced with a high isocyanate groups (⁻NCO) content of 23 wt % as determined by titration analysis. Structural analysis and quality assessments of each batch of microcapsules were performed by using thermogravimetric analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. Preliminary results indicated the microcapsules were stable with only about 20% loss of ⁻NCO detected after one month storage under ambient conditions. This work showed the great potential of novel microencapsulation technique in development of protection of ⁻NCO and in aspects of micro- and nano-structure construction materials.

Preparation and properties of a starch-based wood adhesive with high bonding strength and water resistance.

A Highly efficient method was developed for preparing starch-based wood adhesives with high performance, using H2O2, a silane coupling agent and an olefin monomer as an oxidant, cross-linking agent and comonomer, respectively. The effects of various parameters on the shear adhesive strength were investigated in the dry state (DS) and wet state (WS). The results indicated that the bonding strength of starch-based wood adhesives could reach 7.88 MPa in dry state and 4.09 MPa in wet state. The oxidation could reduce the content of the hydroxyl transforming into carboxyl and aldehyde groups, and the graft copolymerization enhanced the thermal stability, which improved the bonding strength and water resistance. The starch-based adhesive and the fractures in the bonded joints were analyzed via Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The improved properties were attributed to the modified of microstructure of the graft-copolymerized starch-based adhesive.

Effect of annealing on the thermal properties of poly (lactic acid)/starch blends.

A comparative study of the thermal behavior of PLA/starch blends annealed at different temperatures has been conducted. Annealing was found to be beneficial to weaken and even eliminate the enthalpy relaxation near Tg. The degree of crystallinity was evaluated by means of DSC, and the results showed that the crystallinity of the samples increased as the annealing temperatures were increased. It was observed that, during the annealing process, the disorder α (α') crystal modification tended to transform into the order α crystal modification. All of the PLA/starch blends showed a double melting behavior. With the increase of annealing temperatures, the lower Tm1 increased, while the Tm2 showed no evident change. The XRD patterns also showed that annealing was beneficial to the samples to form higher crystallinity. The TGA results indicated that the annealed samples did not show any higher thermal stability than the virgin samples. The activation energy calculated by the Flynn-Wall-Ozawa method at lower conversion degrees confirmed that the annealing slightly slowed the degradation. The activation energy did not show any dependence on the conversion degree, which indicated that there existed a complex degradation process of the PLA/starch blends. The average activation energy did not show obvious differences, indicating that the annealing treatment had little influence on the degradation activation energy.