The aims of this study were to fabricate cellulose acetate (CA) film from oil palm empty fruit bunch (OP-EPB), as well as to characterize and evaluate their biocompatibility. Several processes were carried out, and these included prehydrolysis-soda method, chlorine free bleaching method, including oxygen, ozone and peroxide, to produce the cellulose pulp. Then, a liquid phase acetylation method was applied through acetic acid-acetic anhydride-sulphuric acid. Triethyl citrate (TEC) ester was used as additive at different percentages of 10, 20, 30 and 40 wt%. The film produced was characterized by FTIR to identify the functional group of the CA film and their tensile properties were further characterized. Biocompatibility of the film was evaluated using cytotoxicity test. Stem cell derived from human deciduous teeth (SHED) was used with MTS assay. The results showed at 30% of TEC, the tensile strength and elongation of CA (OP-EFB) film was at the optimum and is therefore suitable to be used in dental application. The cytotoxicity evaluated showed that the fabricated CA (OP-EFB) films were non-toxic up to the concentration tested, and are thus compatible with SHED.
In this work, the oil palm empty fruit bunch (EFB) fiber was used as a source of lignocellulosic filler to fabricate a novel type of cost effective biodegradable composite, based on the aliphatic aromatic co-polyester poly(butylene adipate-co-terephtalate) PBAT (Ecoflex™), as a fully biodegradable thermoplastic polymer matrix. The aim of this research was to improve the new biocomposites' performance by chemical modification using succinic anhydride (SAH) as a coupling agent in the presence and absence of dicumyl peroxide (DCP) and benzoyl peroxide (BPO) as initiators. For the composite preparation, several blends were prepared with varying ratios of filler and matrix using the melt blending technique. The composites were prepared at various fiber contents of 10, 20, 30, 40 and 50 (wt %) and characterized. The effects of fiber loading and coupling agent loading on the thermal properties of biodegradable polymer composites were evaluated using thermal gravimetric analysis (TGA). Scanning Electron Microscopy (SEM) was used for morphological studies. The chemical structure of the new biocomposites was also analyzed using the Fourier Transform Infrared (FTIR) spectroscopy technique. The PBAT biocomposite reinforced with 40 (wt %) of EFB fiber showed the best mechanical properties compared to the other PBAT/EFB fiber biocomposites. Biocomposite treatment with 4 (wt %) succinic anhydride (SAH) and 1 (wt %) dicumyl peroxide (DCP) improved both tensile and flexural strength as well as tensile and flexural modulus. The FTIR analyses proved the mechanical test results by presenting the evidence of successful esterification using SAH/DCP in the biocomposites' spectra. The SEM micrograph of the tensile fractured surfaces showed the improvement of fiber-matrix adhesion after using SAH. The TGA results showed that chemical modification using SAH/DCP improved the thermal stability of the PBAT/EFB biocomposite.
In recent years, there has been considerable interest in the use of natural fibers as potential reinforcing fillers in polymer composites despite their hydrophilicity, which limits their widespread commercial application. The present study explored the fabrication of nanocomposites by melt mixing, using an internal mixer followed by a compression molding technique, and incorporating rice husk (RH) as a renewable natural filler, montmorillonite (MMT) nanoclay as water-resistant reinforcing nanoparticles, and polypropylene-grafted maleic anhydride (PP-g-MAH) as a compatibilizing agent. To correlate the effect of MMT delamination and MMT/RH dispersion in the composites, the mechanical and thermal properties of the composites were studied. XRD analysis revealed delamination of MMT platelets due to an increase in their interlayer spacing, and SEM micrographs indicated improved dispersion of the filler(s) from the use of compatibilizers. The mechanical properties were improved by the incorporation of MMT into the PP/RH system and the reinforcing effect was remarkable as a result of the use of compatibilizing agent. Prolonged water exposure of the prepared samples decreased their tensile and flexural properties. Interestingly, the maximum decrease was observed for PP/RH composites and the minimum was for MMT-reinforced and PP-g-MAH-compatibilized PP/RH composites. DSC results revealed an increase in crystallinity with the addition of filler(s), while the melting and crystallization temperatures remained unaltered. TGA revealed that MMT addition and its delamination in the composite systems improved the thermal stability of the developed nanocomposites. Overall, we conclude that MMT nanoclay is an effective water-resistant reinforcing nanoparticle that enhances the durability, mechanical properties, and thermal stability of composites.
Palm fatty acid distillate (PFAD), is a by-product of the crude palm oil refining process. It comprises mainly of free fatty acids-around 45% palmitic and 33% oleic acids-as the major components. Ultra-violet (UV) curable urethane acrylate (UA) oligomers could be synthesized from PFAD, by the following procedure. A hydroxyl terminated macromer was first prepared by reacting PFAD with a mixture of isophthalic acid, phthalic anhydride, neopentagylcol (NPG), and pentaerythritol. The macromer was then reacted with 2-hydroxylethylacrylate (2HEA) and toluene diisocynate (TDI) to generate a resin, containing acrylate side chains for UV curable application. A series of UA resins were prepared by using 15, 25, 45, 55, and 70% of PFAD, respectively. The UA resin has Mw in the range of 3,200 to 27,000. They could be cured by UV irradiation at an intensity of 225 mW/cm². Glass transition temperature (Tg) of the cured film was measured by differential scanning calorimeter (DSC), and hardness of the film was determined by a pendulum hardness tester, according to American Society for Testing and Materials (ASTM)4366. The resins were used in a wood-coating application. All of the cured films showed good adhesion, hardness, and chemical resistance except for the one using the 70% PFAD, which did not cure properly.
A series of ten 5-arylidene Meldrum’s acid derivatives had been synthesised in excellent yield via Knoevenagel condensation. This method does not require catalyst, or any further purification. Isopropylidene malonate (2,2-dimethyl-1,3-dioxane-4,6-dione), also known as Meldrum’s acid, is utilised as a core skeleton for various kind of reactions. Meldrum’s acid has features of a peculiar ring- opening sequences based on nucleophile-sensitive carbonyl functional groups at C-4 and C-6, which has made it possible for useful synthetic transformations, as well as its high acidity of methylene hydrogen at carbon position C-5. Hence, it allows the compound to be a flexible reagent for further reaction to prepare other derivatives. Therefore, Meldrum’s acid derivatives showed high potential of biological functions, such as antibacterial, antimalarial and antioxidant activities due to the olefinic linkage which played an important role in the enhancement of antimalarial activity. Furthermore, when arylidene Meldrum’s acid transformed to epoxide, the compound showed losses of antimalarial behaviour. Additionally, this compound has unique molecules due to the high acidity of methylene hydrogen at the carbon-5 position to initiate various reactions with different functional groups. In this research, Meldrum’s acid, 3 and ten its 5-arylidene derivatives (4a-e) and (5a-e) were synthesised by using two short and efficient reaction steps. The first step involved the condensation of malonic acid, 1 with acetone, 2 in acetic anhydride and acid via one-pot reaction to give Meldrum’s acid, 3 in 50% overall yield. Having Meldrum’s acid in hand, the reaction was proceeded with the Knoevenagel condensation reaction by using various functional groups, such as aryl aldehydes and aryl amines. All the synthesised compounds were characterised by using 1H and 13C spectroscopy.
The effect of polypropylene maleic anhydride (PPMAH) on tensile properties and morphology of polypropylene (PP)/recycled acrylonitrile butadiene rubber (NBRr)/ rice husk powder (RHP) composites has been studied. The composites were prepared through melt mixing at 180ºC for 9 minutes using 50 rpm rotor speed. The specimens were analyzed using different techniques, namely tensile test and Scanning Electron Microscopy (SEM). The results obtained showed that the tensile strength and Young’s modulus of the modified composites were increased, while the elongation at break showed the opposite trend as compared with the unmodified composites. The morphology results support the tensile properties and these indicated a better interaction between the filler and matrix with the presence of PPMAH as a compatibilizer.
Recently, research and development in the field of drug delivery systems (DDS) facilitating site-specific therapy has reached significant progression. DDS based on polymer micelles, coated micro- and nanoparticles, and various prodrug systems including water-soluble polymer have been prepared and extensively studied as novel drugs designed for cancer chemotherapy and brain delivery. Since polymers are going to be used in human, this study has the interest of testing two types of polymer, polyimides (PI) and polyphenylenevinylene (PPV) on neuronal cells. The objective of this study was to determine the possible neurotoxicity and potential neuroprotective effects of PI and PPV towards SH-SY5Y neuronal cells challenged by hydrogen peroxide (1120) as an oxidant. Cells were pretreated with either PI or PPV for 1 hour followed by incubation for 24 hour with 100 ,uM of 11201. MTS • assay was used to assess cell viability. Results show that PI and PPV are not harmful within the concentration up to 10 pM and 100 pM, respectively. However, PI and PPV do not protect neuronal cells against toxicity induced by H2O, or further up the cell death.
In this study, the effects of lignin modification on the properties of kenaf core fiber reinforced poly(butylene succinate) biocomposites were examined. A weight percent gain (WPG) value of 30.21% was recorded after the lignin were modified with maleic anhydride. Lower mechanical properties were observed for lignin composites because of incompatible bonding between the hydrophobic matrix and the hydrophilic lignin. Modified lignin (ML) was found to have a better interfacial bonding, since maleic anhydrides remove most of the hydrophilic hydrogen bonding (this was proven by a Fourier-transform infrared (FTIR) spectrometer-a reduction of broadband near 3400 cm-1, corresponding to the -OH stretching vibration of hydroxyl groups for the ML samples). On the other hand, ML was found to have a slightly lower glass transition temperature, Tg, since reactions with maleic anhydride destroy most of the intra- and inter-molecular hydrogen bonds, resulting in a softer structure at elevated temperatures. The addition of kraft lignin was found to increase the thermal stability of the PBS polymer composites, while modified kraft lignin showed higher thermal stability than pure kraft lignin and possessed delayed onset thermal degradation temperature.
In this study, poly(ethylene terephthalate) (PET) wastes bottle was recycled by glycolysis process using ethylene glycol. The unsaturated polyester resin (UPR) was then prepared by reacting the glycolysed product with maleic anhydride. The blend of UPR based on recycled PET wastes with liquid natural rubber (LNR) was carried out by varying the amount of LNR from 0 to 7.5 wt%. Mechanical tests such as tensile and impact were conducted to investigate the effects of LNR on the mechanical properties. Scanning Electron Microscopy (SEM) was used to analyze the morphology of the breaking area resulted from the tensile tests on the UPR and blend samples. From the results, the blend of 2.5 wt% LNR in UPR based recycled PET wastes achieved the highest strength in the mechanical properties and showed a well dispersed of elastomer particles in the sample morphology compared to other blends concentrations. This blend sample was then compared to the optimum blend of LNR with commercial resin through the glass transition temperature value Tg, mechanical strength and morphology properties. The comparison study showed that the Tg for UPR based recycled PET was higher than the value represented from commercial resin due to the degree of crystalinity in the molecular structure of the materials. LNR was found to be an effective impact modifier which gave a greater improvement in UPR from recycled PET wastes structure but not to the commercial one which needs 5% LNR to achieve the optimum properties. Thus, the compatibility between the UP resin based recycled PET and LNR was much better than with the commercial resin.
Incorporation of nanocellulose could improve wear resistance of ultra-high molecular weight polyethylene (UHMWPE) for an artificial joint application. Yet, the extremely high melt viscosity of the polymer may constrict the mixing, leading to fillers agglomeration and poor mechanical properties. This study optimized the processing condition of UHMWPE/cellulose nanofiber (CNF) bionanocomposite fabrication in triple screw kneading extruder by using response surface methodology (RSM). The effect of the process parameters-temperature (150-190 °C), rotational speed (30-60 rpm), and mixing time (30-45 min)-on mechanical properties of the bionanocomposites was investigated. Homogenous filler distribution, as confirmed by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) analysis, was obtained through the optimal processing condition of 150 °C, 60 rpm, and 45 min. The UHMWPE/CNF bionanocomposites exhibited improved mechanical properties in terms of Young's and flexural modulus by 11% and 19%, respectively, as compared to neat UHMWPE. An insignificant effect was observed when maleic anhydride-grafted-polyethylene (MAPE) was added as compatibilizer. The obtained results proved that homogenous compounding of high melt viscosity UHMWPE with CNF was feasible by optimizing the melt blending processing condition in triple screw kneading extruder, which resulted in improved stiffness, a contributing factor for wear resistance.
Enzyme immobilization has been known to be one of the methods to improve the stability and reusability of enzyme. In this study, a strategy to optimize laccase immobilization on polyethylene terephthalate grafted with maleic anhydride electrospun nanofiber mat (PET-g-MAH ENM) was developed. The development involves the screening and optimization processes of the crucial factors that influence the immobilization yield such as enzyme concentration, pH values, covalent bonding (CV) time, CV temperature, crosslinking (CL) time, CL temperature and glutaraldehyde concentration using two-level factorial design and Box-Behnken design (BBD), respectively. It was found that laccase concentration, pH values and glutaraldehyde concentration play important role in enhancing the immobilization yield of laccase on PET-g-MAH ENM in the screening process. Subsequently, the optimization result showed at 0.28 mg/ml laccase concentration, pH 3 and 0.45% (v/v) glutaraldehyde concentrations gave the highest immobilization yield at 87.64% which was 81.2% increment from the immobilization yield before optimization. Under the optimum condition, the immobilized laccase was able to oxidize 2, 2-azino-bis 3-ethylbenzothiazoline-6- sulfonic acid (ABTS) in a broad range of pH (pH 3-6) and temperature (20- 70 °C). Meanwhile, the kinetic parameters for Km and Vmax were 1.331 mM and 0.041 mM/min, respectively. It was concluded that the optimization of immobilized laccase on PET-g-MAH ENM enhance the performance of this biocatalyst.
Recently, drug functionalized biodegradable polymers have been appreciated to be imperative to fabricate multi-drug delivery nanosystems for sustainable drug release. In this work, amphiphilic chitosan-grafted-(cetyl alcohol-maleic anhydride-pyrazinamide) (CS-g-(CA-MA-PZA)) was synthesized by multi-step reactions. The incorporation of rifampicin (RF) and entrapment of silver nanoparticles (Ag NPs) on CS-g-(CA-MA-PZA) polymer was carried out by dialysis technique. From the FT-IR experiment, the polymer modification, incorporation of drugs and the entrapment of Ag NPs on micelles were confirmed. The surface morphology of Ag NPs, polymeric system and drug loaded micelles was described by SEM, TEM and AFM techniques. In addition, the controlled release behaviour of CS-g-(CA-MA-PZA) micelles was studied by UV-Vis spectroscopy. In vitro cell viability, cell apoptosis and cellular uptake experiments shows that multi-drug delivery system could enhance the biocompatibility and higher the cytotoxicity effect on the cells. Since the prepared amphiphilic polymeric micelles exhibit spotty features and the system is a promising strategy for a novel candidate for immediate therapeutically effects for alveolar macrophages.
Linear density polyethylene (LDPE)/thermoplastic sago starch (TPSS), blended with and without the addition of compatibilizer [Polyethylene-grafted-Maleic Anhydride, (PE-g-MA)] were prepared for soil burial test. The test was conducted in the natural soil environment for 3 and 6 months. Different loading of TPSS (10, 20, 30, 40, and 50 wt. %) were used in this study. After soil burial, the blends were evaluated for their tensile properties and scanning electron microscopy (SEM) to observe the surface morphology properties after the test. For LDPE/TPSS, it was observed that the tensile strength decreased with the increase of soil burial time, as well as Young modulus and elongation at break (EB). The LDPE/TPSS/PE-g-MA also showed the same trend for the tensile properties, but with higher properties as compared to uncompatibilized blends. The tensile properties also decreased with the increase in the TPSS loading for both the LDPE/TPSS and LDPE/TPSS/PE-g-MA. Meanwhile,
the scanning electron microscopy (SEM) on the blend surfaces after the soil burial test showed that degradability increased with the increase in the exposure time as well as the TPSS loading.
Chitosan was chemically modified with bulky structure, cis-5-norbornene-2, 3-dicarboxylic anhydride and the characteristic of this modified chitosan was studied. The resulting material was analyzed by FTIR, TGA, DSC, XRD and SEM to study the effect of N-acylation to the polysaccharide structure. FTIR results show that the anhydride monomer was successfully bound to amine group of chitosan. Thermal analysis of the modified structure provides the chitosan fibers with thermal stability while XRD and SEM show the lost of crystallinity of modified chitosan. XRD of modified chitosan shows broader peak pattern and a considerable increase in a dimension while SEM of chitosan presented the single particle morphology while norbornene-chitosan shows aggromolarate behaviour due to the hydrophobic nature of norbornene pendant group which induced aggromolaration of the particles in modified structure.
In this research work, graphene nanoplatelets (GNP) were selected as alternative reinforcing nanofillers to enhance the properties of polypropylene (PP) using different compatibilizers called polypropylene grafted maleic anhydride (PP-g-MA) and ethylene-octene elastomer grafted maleic anhydride (POE-g-MA). A twin screw extruder was used to compound PP, GNP, and either the PP-g-MA or POE-g-MA compatibilizer. The effect of GNP loading on mechanical and thermal properties of neat PP was investigated. Furthermore, the influence and performance of different compatibilizers on the final properties, such as mechanical and thermal, were discussed and reported. Tensile, flexural, impact, melting temperature, crystallization temperature, and thermal stability were evaluated by using a universal testing system, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). For mechanical properties, it was found that increasing GNP content from 1 wt.% to 5 wt.% increased tensile strength of the neat PP up to 4 MPa. The influence of compatibilizers on the mechanical properties had been discussed and reported. For instance, the addition of PP-g-MA compatibilizer improved tensile strength of neat PP with GNP loading. However, the addition of compatibilizer POE-g-MA slightly decreased the tensile strength of neat PP. A similar trend of behavior was observed for flexural strength. For thermal properties, it was found that both GNP loading and compatibilizers have no significant influence on both crystallization and melting temperature of neat PP. For thermal stability, however, it was found that increasing the GNP loading had a significant influence on improving the thermal behavior of neat PP. Furthermore, the addition of compatibilizers into the PP/GNP nanocomposite had slightly improved the thermal stability of neat PP.
A new heterocyclic coupling agent has been produced from the reaction of maleic anhydride and p-aminophenol, namely N-(4-hydroxylpheneyl)maleimide. The coupling agent underwent azo coupling reaction with aromatic amine, which is p-aminophenol to produce a new heterocyclic azo pigment. The pigment was then subjected to solubility, hiding power and light fastness test. Fourier Transform Infrared Spectroscopy (FTIR), Ultraviolet/Visible (UV/Vis) Spectroscopy, and Nuclear Magnetic Resonance Spectroscopy (1H-NMR, 13C-NMR) were used to obtain the characteristics and structural features of the pigment.
Most substrate for esterification has the inherent problem of low miscibility which requires addition of solvents into the reaction media. In this contribution, we would like to present an alternative and feasible option for an efficient solvent-free synthesis of menthyl butyrate using a novel thermostable crude T1 lipase. We investigated the effects of incubation time, temperature, enzyme loading and substrate molar ratio and determined the optimum conditions. The high conversion of menthyl butyrate catalyzed by crude T1 lipase in a solvent-free system is greatly affected by temperature and time of the reaction media. The highest yield of menthyl butyrate was 99.3% under optimized conditions of 60 °C, incubation time of 13.15 h, 2.53 mg, 0.43% (w/w) enzyme to substrate ratio and at molar ratio of butyric anhydride/menthol 2.7:1. Hence, the investigation revealed that the thermostable crude T1 lipase successfully catalyzed the high-yield production of menthyl butyrate in a solvent-free system. The finding suggests that the crude T1 lipase was a promising alternative to overcome shortcomings associated with solvent-assisted enzymatic reactions.
This work investigates a new interrogation method of a fiber Bragg grating (FBG) sensor based on longer and shorter wavelengths to distinguish between transversal forces and temperature variations. Calibration experiments were carried out to examine the sensor's repeatability in response to the transversal forces and temperature changes. An automated calibration system was developed for the sensor's characterization, calibration, and repeatability testing. Experimental results showed that the FBG sensor can provide sensor repeatability of 13.21 pm and 17.015 pm for longer and shorter wavelengths, respectively. The obtained calibration coefficients expressed in the linear model using the matrix enabled the sensor to provide accurate predictions for both measurements. Analysis of the calibration and experiment results implied improvements for future work. Overall, the new interrogation method demonstrated the potential to employ the FBG sensing technique where discrimination between two/three measurands is needed.
Thermal characterization of sugar palm fibre (SPF), reinforced high impact polystyrene (HIPS)
composites, was studied by means of thermogravimetric analysis. The effects of alkaline treatment and compatibilizing agent on the thermal stability of the composites were evaluated. Alkaline treatment was carried out by soaking the fibres in 4 and 6% of NaOH solution, while treatment with compatibilizing agent was employed by adding 2 and 3% maleic anhydride-graft-polystyrene (MA-g-PS) to the composites. Both the treatments were aimed to improve the mechanical performance of the composites. From the study, the thermal stability of the treated composites was found to be higher than that of untreated composites. It is shown that the incorporation of sugar palm fibre influences the degree of thermal stability of the composites. The treatments on composites also contributed to shifting the peak temperature of degradation of the composites. In other words, there are strong chemical reactions between the components of the treated composites. The thermal stability of the composites, with alkaline treatment and compatibilizing agent, was found to be better as compared to those of the untreated composites.
The bottleneck of conventional polymeric membranes applied in industry has a tradeoff between permeability and selectivity that deters its widespread expansion. This can be circumvented through a hybrid membrane that utilizes the advantages of inorganic and polymer materials to improve the gas separation performance. The approach can be further enhanced through the incorporation of amine-impregnated fillers that has the potential to minimize defects while simultaneously enhancing gas affinity. An innovative combination between impregnated Linde T with different numbers of amine-functional groups (i.e., monoamine, diamine, and triamine) and 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA)-derived polyimide has been elucidated to explore its potential in CO2/CH4 separation. Detailed physical properties (i.e., free volume and glass transition temperature) and gas transport behavior (i.e., solubility, permeability, and diffusivity) of the fabricated membranes have been examined to unveil the effect of different numbers of amine-functional groups in Linde T fillers. It was found that a hybrid membrane impregnated with Linde T using a diamine functional group demonstrated the highest improvement compared to a pristine polyimide with 3.75- and 1.75-fold enhancements in CO2/CH4 selectivities and CO2 permeability, respectively, which successfully lies on the 2008 Robeson's upper bound. The novel coupling of diamine-impregnated Linde T and 6FDA-derived polyimide is a promising candidate for application in large-scale CO2 removal processes.