Liqing Wei

Grafting of Bacterial Polyhydroxybutyrate (PHB) onto Cellulose via In Situ Reactive Extrusion with Dicumyl Peroxide

Polyhydroxybutyrate (PHB) was grafted onto cellulose fiber by dicumyl peroxide (DCP) radical initiation via in situ reactive extrusion. The yield of the grafted (cellulose-g-PHB) copolymer was recorded and grafting efficiency was found to be dependent on the reaction time and DCP concentration. The grafting mechanism was investigated by electron spin resonance (ESR) analysis and showed the presence of radicals produced by DCP radical initiation. The grafted copolymer structure was determined by nuclear magnetic resonance (NMR) spectroscopy. Scanning electronic microscopy (SEM) showed that the cellulose-g-PHB copolymer formed a continuous phase between the surfaces of cellulose and PHB as compared to cellulose-PHB blends. The relative crystallinity of cellulose and PHB were quantified from Fourier transform infrared (FTIR) spectra and X-ray diffraction (XRD) results, while the absolute degree of crystallinity was evaluated by differential scanning calorimetry (DSC). The reduction of crystallinity indicated the grafting reaction occurred not just in the amorphous region but also slightly in crystalline regions of both cellulose and PHB. The smaller crystal sizes suggested the brittleness of PHB was decreased. Thermogravimetric analysis (TGA) showed that the grafted copolymer was stabilized relative to PHB. By varying the reaction parameters the compositions (%PHB and %cellulose) of resultant cellulose-g-PHB copolymer are expected to be manipulated to obtain tunable properties.

Interfacial improvements in biocomposites based on poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) bioplastics reinforced and grafted with α-cellulose fibers

In this study, α-cellulose fibers reinforced green biocomposites based on polyhydroxybutyrate (PHB) and the copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) were prepared and characterized. The α-cellulose fibers were isolated from at-risk intermountain lodgepole pine wood by successive removal of extractives, lignin and hemicellulose. Grafting of PHB or PHBV onto cellulose was conducted using reactive extrusion with dicumyl peroxide free radical initiation at high temperature. It is postulated that the grafted copolymers at the interfaces of cellulose and the polymer matrix performed as an interfacial coupling agent. Grafting tended to interact with both the hydrophilic fibers and the hydrophobic PHB or PHBV matrix. The biocomposites were characterized by scanning electron microscopy (SEM) and dynamic mechanical analysis (DMA) and indicated good interfacial bonding and compatibility between the two phases. The mechanical properties of the biocomposites were improved by grafting due to improved stress transfer between the two interphases of the fiber/polymer matrix as compared to the blend control composite. The crystallinity of PHB, PHBV and cellulose in the biocomposite were reduced as determined by Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC) analyses. This in situ reactive extrusion process offers an effective approach to improve the properties of biocomposite materials from sustainable resources.

A Review on Grafting of Biofibers for Biocomposites

A recent increase in the use of biofibers as low-cost and renewable reinforcement for the polymer biocomposites has been seen globally. Biofibers are classified into: lignocellulosic fibers (i.e., cellulose, wood and natural fibers), nanocellulose (i.e., cellulose nanocrystals and cellulose nanofibrils), and bacterial cellulose, while polymer matrix materials can be petroleum based or bio-based. Green biocomposites can be produced using both biobased fibers and polymers. Incompatibility between the hydrophilic biofibers and hydrophobic polymer matrix can cause performance failure of resulting biocomposites. Diverse efforts have focused on the modification of biofibers in order to improve the performances of biocomposites. “Grafting” copolymerization strategy can render the advantages of biofiber and impart polymer properties onto it and the performance of biocomposites can be tuned through changing grafting parameters. This review presents a short overview of various “grafting” methods which can be directly or potentially employed to enhance the interaction between biofibers and a polymer matrix for biocomposites. Major grafting techniques, including ring opening polymerization, grafting via coupling agent and free radical induced grafting, have been discussed. Improved properties such as mechanical, thermal, and water resistance have provided grafted biocomposites with new opportunities for applications in specific industries.

Chemical modification of nanocellulose with canola oil fatty acid methyl ester

Cellulose nanocrystals (CNCs), produced from dissolving wood pulp, were chemically functionalized by transesterification with canola oil fatty acid methyl ester (CME). CME performs as both the reaction reagent and solvent. Transesterified CNC (CNCFE) was characterized for their chemical structure, morphology, crystalline structure, thermal stability, and hydrophobicity. Analysis by Fourier transform infrared (FTIR) and FT-Raman spectroscopies showed that the long chain hydrocarbon structure was successfully grafted onto CNC surfaces. After transesterification the crystal size and crystallinity of nanocrystals were not changed as determined by Raman spectroscopy and wide angle X-ray diffraction (XRD). CNCFE showed higher thermal stability and smaller particle size than unmodified CNCs. Water contact angle measurement indicated the CNCFE surface has significantly higher hydrophobicity than unmodified CNCs. The transesterified CNCs could be potentially used as hydrophobic coatings and reinforcing agents to hydrophobic polymer for nanocomposites.

Valorization of residual bacterial biomass waste after polyhydroxyalkanoate isolation by hydrothermal treatment.

Hydrothermal treatment (HTT) was used to convert residual bacterial biomass (RBB), recovered from poly(3-hydroxybutyrate-co-3-hydroxyvalerate) production, into valuable bioproducts. The effect of processing temperatures (150, 200, and 250°C) on the bioproducts (water-solubles (WSs), bio-oil, insoluble residue, and gas) was investigated. The yields of bio-oil and gas were higher at higher temperatures. The maximum WS content (28 wt%) was obtained at 200°C. GCMS analysis showed higher content of aromatics and N-containing compounds with increasing temperature. ESI-MS revealed chemical compounds (e.g. protein, carbohydrate, lipids, and lignin) associated with RBB are fragmented into smaller molecules (monomers) at higher HTT temperatures. The WS fraction contained totally 838, 889 and 886mg/g acids and 160, 31 and 21 mg/g carbohydrate for HTT at 150, 200, and 250°C, respectively. The solid residues contain unconverted compounds, especially after HTT at 150°C. The WS products (acids and carbohydrates) could be used directly for PHA biosynthesis.

Preparation and characterization of the nanocomposites from chemically modified nanocellulose and poly(lactic acid)

Cellulose nanocrystals (CNCs) are renewable and sustainable filler for polymeric nanocomposites. However, their high hydrophilicity limits their use with hydrophobic polymer for composite materials. In this study, freeze-dried CNCs were modified by transesterification with canola oil fatty acid methyl ester to reduce the hydrophilicity. The transesterified CNCs (CNCFE) were compounded with PLA into nanocomposites. CNCFE with long-chain hydrocarbons plays a role as plasticizer. Increasing CNCFE loadings resulted in clear plasticizing effects. Lower Tg and Tm were achieved for CNCFE-based nanocomposites. Plasticizing nanocomposite melt with CNCFE can mitigate the degradation of CNCs during thermal processing. The elongation at break of nanocomposites containing 5% CNCFE was increased. Dynamic rheological study showed the highest elastic and viscous moduli (G′ and G′′) and complex viscosity (G*) of nanocomposites with addition of 2% CNCFE. By tailoring the loadings of the transesterified CNCs, tunable structure and properties of nanocomposites can be obtained.

Phytochemical Analyzes from the Leaves of Bryophyllum pinnatum

Aims: To identify extractable components in the traditional medicinal plant, Bryophyllum pinnatum (BP). Methodology: The leaves of BP were sequentially extracted with non-polar (CH2Cl2) and polar (CH3OH) solvents. The extracts were derivatized to their volatile fatty acid methyl esters (FAME) and trimethylsilyl (TMS) esters/ethers and characterized by gas chromatography mass spectrometry (GC-MS). Results: GC-MS analysis revealed the presence of sterols, fatty acids, monoarylphenolics, sugars, alcohols, sugar alcohols, sugar acids, carboxylic acids, dicarboxylic acids, tricarboxylic acids, vitamin, alkanes and alkenes. Conclusion: Compounds identified (e.g. tocopherol) in the extracts are most likely responsible for its antimicrobial, antifungal, anticancer, antitumour and insecticidal activities. Original Research Article Faboro et al.; EJMP, 14(3): 1-10, 2016; Article no.EJMP.26156 2