Shilin Cao

Preparation of Microfibrillated Cellulose/Chitosan–Benzalkonium Chloride Biocomposite for Enhancing Antibacterium and Strength of Sodium Alginate Films

The nonantibacterial and low strength properties of sodium alginate films negatively impact their application for food packaging. In order to improve these properties, a novel chitosan-benzalkonium chloride (C-BC) complex was prepared by ionic gelation using tripolyphosphate (TPP) as a coagulant, and a biocomposite obtained through the adsorption of C-BC complex on microfibrillated cellulose, MFC/C-BC, was then incorporated into a sodium alginate film. The TEM image showed that the C-BC nanoparticles were spherical in shape with a diameter of about 30 nm, and the adsorption equilibrium time of these nanoparticles on the surface of MFC was estimated to be 6 min under the driving forces of hydrogen bonds and electrostatic interactions. According to the disc diffusion method, the MFC/C-BC biocomposite-incorporated sodium alginate film exhibited remarkable antibacterial activity against Staphylococcus aureus and certain antibacterial activity against Escherichia coli . The strength tests indicated that the tensile strength of the composite sodium alginate film increased about 225% when the loading of MFC/C-BC biocomposite was 10 wt %. These results suggested that the MFC/C-BC biocomposite-incorporated sodium alginate film with excellent antibacterial and strength properties would be a promising material for food packaging, and the MFC/C-BC may also be a potential multifunctional biocomposite for other biodegradable materials.

Degradation and dissolution of hemicelluloses during bamboo hydrothermal pretreatment.

To elucidate the hemicelluloses degradation and dissolution during hydrothermal pretreatment, hemicelluloses separated from both hydrolysate and pretreated substrate were investigated. Along with the pretreatment proceeding, some hemicelluloses fractions dissolved and diffused into the bulk liquor; MW (molecular weight) of these hemicelluloses fractions increased first and then decreased as well as amount of the fractions. Based on the definition of MW of the soluble hemicellulose, it has been concluded that some insoluble hemicellulose fractions appeared in the hydrolysate. In contrast, the hemicellulose degradation occurred continually and had been observed by the gradual decrease of MW of the hemicellulose isolated from pretreated substrate. Lingering dissolution at the later stage might attribute to the facts that some soluble fractions were still entrapped in the substrate. 5-15% hemicellulose fractions remained in the pretreated substrate at the later stage were composed of soluble species.

Hydrothermal pretreatment of bamboo and cellulose degradation

A systematic hydrothermal pretreatment of bamboo chips had been conducted with an aim to trace the cellulose degradation. The results showed that cellulose chain cleavage basically occurred when the temperature exceeded 150°C. A slightly higher DP (degree of polymerization) than starting material had been observed at low temperature pretreatment. Treatment at higher temperature (≥ 170°C) caused severe cleavage of cellulose and therefore gave rise to low DP with more soluble species. DP of cellulose declined drastically without additional hemicelluloses dissolution when hemicelluloses removal reached to the limit level. Cellulose degradation under hydrothermal pretreatment generally followed the zero reaction kinetics with the activity energy of 121.0 kJ/mol. Besides, the increase of cellulose crystalline index and the conversion of Iα-Iβ had also observed at the hydrothermal pretreatment.

Effect of the degree of substitution on the hydrophobicity of acetylated cellulose for production of liquid marbles

Acetylated cellulose powders with varying degree of substitution (DS) were prepared by reacting cellulose with acetic anhydride. The effect of DS on the hydrophobic properties of acetylated cellulose was examined based on contact angle and mechanical stability measurements. The surface energy of the acetylated cellulose decreases with increasing DS, and for DS of 0.39, the acetylated cellulose was able to encapsulate a water droplet to form a liquid marble. The corresponding cellulose acetate powder-over-water spreading coefficient was ca. 8.9. Increasing DS also improved the mechanical stability of the liquid marble. This study opens important perspectives for the precise control of DS of cellulose acetate for various practical applications in membranes, filters, scaffolds, and textiles.

Surface characterizations of bamboo substrates treated by hot water extraction

Environment Scanning Electron Microscopy (ESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface morphology and chemical changes on both the interior and exterior surface of bamboo (Dendrocalamopsis oldhami) substrates treated by hot water extraction. ESEM results showed the visible changes between exterior and interior surface of the treated substrates, in where spherical droplets did not extensively appear on both the surfaces at start of the pretreatment; nevertheless the droplets formation on the exterior surface occurred more rapidly than that of the interior surface. Results from XPS examination that the increase of C1 (C-C, C-H) concentration and decrease of O/C ratio and O1 (C=O) concentration of the samples on the both surfaces further demonstrated that both surfaces consisted of increasing amount of lignin as the extraction continued, especially for exterior surface. The O/C ratios finally reached to a level-off value with exterior surface 0.34 and interior surface 0.37.

Superhydrophobic magnetic poly(DOPAm-co-PFOEA)/Fe3O4/cellulose microspheres for stable liquid marbles

Novel magnetic superhydrophobic cellulose-based microspheres were fabricated using poly(DOPAm-co-PFOEA), which provide remarkable stability to liquid marbles with various liquids for liquid droplet transportation and manipulation.

Synergistic effects of guanidine-grafted CMC on enhancing antimicrobial activity and dry strength of paper.

In order to improve the strength property and antimicrobial activity of paper simultaneously, we prepared a novel multifunctional agent based on carboxymethyl cellulose (CMC) by a simple two-stage method. The first stage was the oxidation of CMC to obtain the dialdehyde CMC (DCMC), and the second stage was the graft of guanidine hydrochloride (GH) onto DCMC to obtain DCMC-GH polymer. The strength property and antimicrobial activity of DCMC-GH-coated copy paper have been studied by the tensile test and inhibition zone method, respectively. The results showed that the dry strength index could increase about 20% after the paper was coated with DCMC-GH. The coating of DCMC-GH on paper also resulted in excellent antimicrobial activities against Escherichia coli and Staphylococcus aureus, and the inhibition zone became larger as the GH content grafted on DCMC increased. The novel DCMC-GH polymer would be a multifunctional coating agent for food packaging paper.

Lignin removal and benzene-alcohol extraction effects on lignin measurements of the hydrothermal pretreated bamboo substrate.

Lignin content of hydrothermal pretreated bamboo chips was determined by the two methods: TAPPI standard method (222om-06) and TAPPI standard method without benzene-alcohol extraction (BAE). The results showed that including BAE resulted in lower Klason lignin (KL) and acid soluble lignin (ASL) measurements in the prehydrolyzed substrate, that is to say, BAE removed parts of KL and ASL. Therefore, the TAPPI standard method should be modified by omitting the BAE for lignin measurements of pretreated substrate. The following lignin removal analysis suggested that lignin was removed from the bamboo substrate during pretreatment by a combination of degradation reaction and deconstruction; thereafter the pseudo lignin generated in the hydrothermal pretreatment and condensation reaction between the lignin fragments accounted for the later KL increase.

Kinetic study of pentosan solubility during heating and reacting processes of steam treatment of green bamboo

Green bamboo was hydrolyzed over a range of durations at different temperatures. A simple pseudo-homogeneous irreversible first order kinetic model was developed to describe pentosan solubility during steam treatment of green bamboo. To avoid the influence of soluble pentosan during heating process, kinetic parameters were effectively dissolved based on the data in the reacting process. Moreover, the pentosan solubility during heating process was also well modeled by numerical algorithm method. According to the origin of H factor, a modified parameter called steam treatment factor (f(P)) was proposed in this paper based on the determined kinetic constants. Finally, residual pentosan in whole process could be predicted properly based on the f(P) and the introducing of potential hydrolysis degree (h(d)). After using f(P) to combine reaction temperature and time into a single factor, comparative result showed that steam treatment is more effective for removing pentosan compared with hot water extraction.

Preparation and Characterization of Antibacterial Cellulose/Chitosan Nanofiltration Membranes

Presently, most nanofiltration membranes are prepared with non-biodegradable petrochemical materials. This process is harmful to the ecosystem and consumes a large amount of non-renewable energy. In this study, biodegradable and biocompatible antibacterial cellulose/chitosan nanofiltration membranes (BC/CS-NFMs) were fabricated and characterized for their mechanical strength, antimicrobial activity, salt and dye filtration performance, and polyethylene glycol (PEG) retention using Thermal gravimetric analysis (TGA), Field emission scanning electron microscopy(FE-SEM), Fourier transform infrared spectroscopy(FT-IR), and X-ray diffraction (XRD). The BC/CS-NFMs were obtained by the hydrolysis and carboxymethylation of dense cellulose/chitosan membranes (BC/CSMs). The tensile strength of the BC/CS-NFMs decreased as the chitosan content increased. In addition, the thermal stability and antibacterial ability of the BC/CS-NFMs improved. The pore size is less than 1 nm, and a spongy, layered structure is observed in the cross-sectional FE-SEM images. FT-IR analysis shows that a part of the hydroxyl in cellulose transforms to carboxymethyl during the hydrolysis and carboxymethylation of the BC/CSMs. No obvious changes can be observed in the cellulose and chitosan after the blend membrane formation from the XRD measurements. Based on the experimental results on the permeation and rejection of BC/CS-NFMs, different proportions of cellulose and chitosan nanofiltration membranes almost did not affect the water flux and rejection rate. The BC/CS-NFMs showed better water flux and a higher rejection rate in aqueous dye-salt solutions.