β-Cyclodextrin-ionic liquid polymer (CD-ILP) was first synthesized by functionalized β-cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using a toluene diisocyanate (TDI) linker to form insoluble CD-ILP (βCD-BIMOTs-TDI). The βCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native β-cyclodextrin polymer (βCD-TDI). The SEM result shows that the presence of ionic liquid (IL) increases the pore size, while the thermo gravimetric analysis (TGA) result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET) results show that βCD-BIMOTs-TDI polymer has 1.254 m(2)/g surface areas and the Barret-Joyner-Halenda (BJH) pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the βCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V).
For the first time, a highly efficient Cr(NO3)3 catalysis system was proposed for optimization the yield and crystallinity of nanocellulose end product. A five-level three-factor central composite design coupled with response surface methodology was employed to elucidate parameters interactions between three design factors, namely reaction temperature (x1), reaction time (x2) and concentration of Cr(NO3)3 (x3) over a broad range of process conditions and determine the effect on crystallinity index and product yield. The developed models predicted the maximum nanocellulose yield of 87% at optimum process conditions of 70.6°C, 1.48h, and 0.48M Cr(NO3)3. At these conditions, the obtained nanocellulose presented high crystallinity index (75.3%), spider-web-like interconnected network morphology with the average width of 31.2±14.3nm. In addition, the yielded nanocellulose rendered a higher thermal stability than that of original cellulosic source and expected to be widely used as reinforcement agent in bio-nanocomposites materials.
Response surface methodology was used to optimize preparation of biocomposites based on poly(lactic acid) and durian peel cellulose. The effects of cellulose loading, mixing temperature, and mixing time on tensile strength and impact strength were investigated. A central composite design was employed to determine the optimum preparation condition of the biocomposites to obtain the highest tensile strength and impact strength. A second-order polynomial model was developed for predicting the tensile strength and impact strength based on the composite design. It was found that composites were best fit by a quadratic regression model with high coefficient of determination (R (2)) value. The selected optimum condition was 35 wt.% cellulose loading at 165°C and 15 min of mixing, leading to a desirability of 94.6%. Under the optimum condition, the tensile strength and impact strength of the biocomposites were 46.207 MPa and 2.931 kJ/m(2), respectively.
Bacteria isolated from thermophilic environment that can produce cellulase as well as utilise agro-waste biomass have a high potential for developing thermostable cellulase required in the biofuel industry. The cost for cellulase represents a significant challenge in converting lignocellulose to fermentable sugars for biofuel production. Among three potential bacteria examined, Bacillus licheniformis 2D55 (accession no. KT799651) was found to produce the highest cellulolytic activity (CMCase 0.33 U/mL and FPase 0.09 U/mL) at 18-24 h fermentation when grown on microcrystalline cellulose (MCC) as a carbon source in shake flask at 50 °C. Cellulase production process was further conducted on the untreated and NaOH pretreated rice straw (RS), rice husk (RH), sugarcane bagasse (BAG) and empty fruit bunch (EFB). Untreated BAG produced the highest FPase (0.160 U/mL), while the highest CMCase (0.150 U/mL) was supported on the pretreated RH. The mixture of untreated BAG and pretreated RH as agro-waste cocktail has remarkably improved CMCase (3.7- and 1.4-fold) and FPase (2.5- and 11.5-fold) compared to the untreated BAG and pretreated RH, respectively. The mechanism of cellulase production explored through SEM analysis and the location of cellulase enzymes of the isolate was also presented. Agro-waste cocktail supplementation provides an alternative method for an efficient production of cellulase.
Cellulosic fibers from kenaf bast were isolated in three distinct stages. Initially raw kenaf bast fibers were subjected to an alkali pulping process. Then pulped fibers undergone a bleaching process and finally both pulped and bleached fibers were separated into their constituent nanoscale cellulosic fibers by mechanical shearing. The influence of each treatment on the chemical composition of fibers was investigated. Moreover morphology, functional groups, crystallinity, and thermal behavior of fiber hierarchy at different stages of purification were studied using scanning and transmission electron microscopies, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA), respectively. Microscopy studies revealed that applied procedures successfully isolated nanoscale cellulosic fibers from both unbleached and bleached pulps. Chemical composition analysis and FTIR spectroscopy showed that lignin and hemicellulose were almost entirely removed by the applied treatments. XRD and TGA analyses demonstrated progressive enhancement of properties in fibers, hierarchically, in going from micro to nano scale. Interestingly no significant evolution was observed between obtained data of characterized ubnleached and bleached nanofibers.
The use of chemical modification of cellulosic fibre is applied in order to increase the hydrophobicity, hence improving the compatibility between the fibre and matrix bonding. In this study, the effect of propionic anhydride modification of kenaf fibre was investigated to determine the role of bionanocarbon from oil palm shell agricultural wastes in the improvement of the functional properties of bionanocomposites. The vinyl esters reinforced with unmodified and propionic anhydride modified kenaf fibres bio nanocomposites were prepared using 0, 1, 3, 5 wt% of bio-nanocarbon. Characterisation of the fabricated bionanocomposite was carried out using FESEM, TEM, FT-IR and TGA to investigate the morphological analysis, surface properties, functional and thermal analyses, respectively. Mechanical performance of bionanocomposites was evaluated according to standard methods. The chemical modification of cellulosic fibre with the incorporation of bionanocarbon in the matrix exhibited high enhancement of the tensile, flexural, and impact strengths, for approximately 63.91%, 49.61% and 54.82%, respectively. The morphological, structural and functional analyses revealed that better compatibility of the modified fibre-matrix interaction was achieved at 3% bionanocarbon loading, which indicated improved properties of the bionanocomposite. The nanocomposites exhibited high degradation temperature which signified good thermal stability properties. The improved properties of the bionanocomposite were attributed to the effect of the surface modification and bionanocarbon enhancement of the fibre-matrix networks.
A novel synthesis and characterization of cellulose, hydroxyapatite and chemically-modified carbon electrode (Cellulose-HAp-CME) composite was reported for the analysis of trace Pb(II) ions detection and its validation in blood serum. The Field Emission Scanning Electron Microscopy (FESEM) analyses showed that the composite retained the orderly porous structure but with scattered particle size agglomeration. The Fourier Transform Infrared Spectroscopy (FTIR) spectra suggested the presence of functional groups associated with the bending and stretching of carbon bonds and intermolecular H-bonding. X-ray Diffraction (XRD) analyses further elucidated that the crystallite size could have influenced the properties of the electrode. Based on Thermo-gravimetric Analysis (TGA/DTG), the composites showed thermal stability with more than 60% residual content at 700°C. The sensor was successfully developed for trace Pb(II) ions detection in complex medium such as blood serum, in the physiologically relevant range of 10-60ppb, with resulting Limit of Detection (LOD) of 0.11±0.36ppb and Limit of Quantification (LOQ) of 0.36±0.36ppb. The newly fabricated electrode could be advantageous as a sensing platform with favourable electrochemical characteristics for robust, in situ and rapid environmental and clinical analyses of heavy metal ions.
Polysaccharide-based magnetic nanocomposites can eminently illuminate several attractive features as anticancer drug carriers. In this study, rice straw-based cellulose nanowhisker (CNW) was used as solid support for Fe3O4 nanofillers to synthesize magnetic CNW. Then, cross-linked chitosan-coated magnetic CNW for 5-fluorouracil carrier abbreviated as CH/MCNW/5FU. Fourier-transform infrared, X-Ray diffraction, and X-ray photoelectron spectroscopy analysis indicated successful fabrication and multifunctional properties of the CH/MCNW/5FU nanocomposites. In addition, CH/MCNW/5FU nanocomposites showed hydrodynamic diameter and zeta potential value of 181.31 ± 3.46 nm and +23 ± 1.8 mV, respectively. Based on images of transmission electron microscopy, magnetic CNW as reinforcement was coated with chitosan to obtain almost spherical CH/MCNW/5FU nanocomposites with an average diameter of 37.16 ± 3.08. The nanocomposites indicated desired saturation magnetization and thermal stability, high drug encapsulation efficiency, and pH-dependent swelling and drug release performance. CH/MCNW/5FU nanocomposites showed potent killing effects against colorectal cancer cells in both 2D monolayer and 3D spheroid models. These findings suggest CH/MCNW as a potential carrier for anticancer drugs with high tumour-penetrating capacity.
Because chiral liquid chromatography (LC) could become a powerful tool to estimate racemic atenolol quantity, excellent enantiomeric separation should be produced during data acquisition for satisfactory observation of atenolol concentrations throughout the racemic resolution processes. Selection of chiral LC column and analytical protocol that fulfill demands of the ultra fast LC analysis is essential. This article describes the characteristics of atenolol chromatographic separation that resulted from different resolution media and analytical protocols with the use of a Chiralcel® OD column. The chromatograms showed quite different characteristics of the separation process. The single enantiomer and racemic atenolol could be recognized by the Chiralcel® OD column in less than 20 min. Symmetrical peaks were obtained; however, several protocols produced peaks with wide bases and slanted baselines. Observations showed that efficient enantioresolution of racemic atenolol was obtained at slow mobile phase flow rate, decreased concentration of amine-type modifier but increased alcohol content in mobile phase and highest ultraviolet detection wavelength were required. The optimal ultra fast LC protocol enables to reduce and eliminate the peaks of either the atenolol solvent or the buffers and provided the highest peak intensities of both atenolol enantiomers.
Acacia mangium, a fast growing tree is widely planted in Malaysia. Converting Acacia wood into nanocellulose could create new value added products for forest-based industry. Nanocrystalline cellulose (NCC) was prepared from Acacia mangium wood pulp via 64wt% sulfuric acid hydrolysis. Prior to acid hydrolysis, Acacia mangium was subjected to pulping followed by bleaching in order to remove non-cellulosic fragments. Acid hydrolysis was carried out on bleached pulp to produce the needle-like NCC with 79% crystallinity and aspect ratio of 26. The resulting NCC was mixed with PVA as a reinforcement material. Incorporation of 2% NCC improved the tensile of the NCC-PVA film by 30%.
Novel bio-based polyurethane (PU) nanocomposites composed of cellulose nanofiller extracted from the rachis of date palm tree and polycaprolactone (PCL) diol based PU were prepared by casting/evaporation. Two types of nanofiber were used: cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs). The mechanical and thermal properties of the nanocomposite films were studied by DMA, DSC, and tensile tests and the morphology was investigated by SEM. Bionanocomposites presented good mechanical properties in comparison to neat PU. While comparing both nanofillers, the improvement in mechanical and thermal properties was more pronounced for the nanocomposites based on CNF which could be explained, not only by the higher aspect ratio of CNF, but also by their better dispersion in the PU matrix. Calculation of the solubility parameters of the nanofiller surface polymers and of the PU segments portend a better interfacial adhesion for CNF based nanocomposites compared to CNC.
The current research discusses the development of poly (lactic acid) (PLA) and poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) reinforced nanocrystalline cellulose bionanocomposites. The nanocrystalline cellulose was derived from waste oil palm empty fruit bunch fiber by acid hydrolysis process. The resulting nanocrystalline cellulose suspension was then surface functionalized by TEMPO-mediated oxidation and solvent exchange process. Furthermore, the PLA/PHBV/nanocrystalline cellulose bionanocomposites were produced by solvent casting method. The effect of the addition of nanocrystalline cellulose on structural, morphology, mechanical and barrier properties of bionanocomposites was investigated. The results revealed that the developed bionanocomposites showed improved mechanical properties and decrease in oxygen permeability rate. Therefore, the developed bio-based composite incorporated with an optimal composition of nanocrystalline cellulose exhibits properties as compared to the polymer blend.
Novel biosensor architecture based on nanocrystalline cellulose (NCC)/CdS quantum dots (QDs) nanocomposite was developed for phenol determination. This nanocomposite was prepared with slight modification of nanocrystalline cellulose (NCC) with cationic surfactant of cetyltriammonium bromide (CTAB) and further decorated with 3-mercaptopropionic acid (3-MPA) capped CdS QDs. The nanocomposite material was then employed as scaffold for immobilization of tyrosinase enzyme (Tyr). The electrocatalytic response of Tyr/CTAB-NCC/QDs nanocomposite towards phenol was evaluated using differential pulse voltammetry (DPV). The current response obtained is proportional to the concentration of phenol which attributed to the reduction of o-quinone produced at the surface of the modified electrode. Under the optimal conditions, the biosensor exhibits good linearity towards phenol in the concentration range of 5-40 μM (R2 = 0.9904) with sensitivity and limit of detection (LOD) of 0.078 μA/μM and 0.082 μM, respectively.
A very simple and low-cost procedure has been adopted to synthesize efficient copper (Cu), silver (Ag) and copper-silver (Cu-Ag) mixed nanoparticles on the surface of pure cellulose acetate (CA) and cellulose acetate-copper oxide nanocomposite (CA-CuO). All nanoparticles loaded onto CA and CA-CuO presented excellent catalytic ability, but Cu-Ag nanoparticles loaded onto CA-CuO (Cu0-Ag0/CA-CuO) exhibited outstanding catalytic efficiency to convert 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) in the presence of NaBH4. Additionally, the Cu0-Ag0/CA-CuO can be easily recovered by removing the sheet from the reaction media, and can be recycled several times, maintaining high catalytic ability for four cycles.
Nanocrystalline cellulose (NCC) was isolated from oil palm empty fruit bunch pulp (EFBP) using ultrasound assisted acid hydrolysis. The obtained NCC was analysed using FESEM, XRD, FTIR, and TGA, and compared with raw empty fruit bunch fibre (REFB), empty fruit bunch pulp (EFBP), and treated empty fruit bunch pulp (TEFBP). Based on FESEM analysis, it was found that NCC has a spherical shaped after acid hydrolysis with the assistance of ultrasound. This situation was different compared to previous studies that obtained rod-like shaped of NCC. Furthermore, the crystallinity of NCC is higher compared to REFB and EFBP. According to thermal stability, the NCC obtained shows remarkable sign of high thermal stability compared to REFB and EFBP.
Various concentrations of Mg into fixed amount of cellulose nanocrystals (CNC)-doped ZnO were synthesized using facile chemical precipitation. The aim of present study is to remove dye degradation of methylene blue (MB) and bactericidal behavior with synthesized product. Phase constitution, functional group analysis, optical behavior, elemental composition, morphology and microstructure were examined using XRD, FTIR, UV-Vis spectrophotometer, EDS and HR-TEM. Highly efficient photocatalytic performance was observed in basic medium (98%) relative to neutral (65%), and acidic (83%) was observed upon Mg and CNC co-doping. Significant bactericidal activity of doped ZnO nanoparticles depicted inhibition zones for G -ve and +ve bacteria ranging (2.20 - 4.25 mm) and (5.80-7.25 mm) for E. coli and (1.05 - 2.75 mm) and (2.80 - 4.75 mm) for S. aureus at low and high doses, respectively. Overall, doped nanostructures showed significant (P
In the present study, the novel Ag/cellulose nanocrystal (CNC)-doped CeO2 quantum dots (QDs) with highly efficient catalytic performance were synthesized using one pot co-precipitation technique, which were then applied in the degradation of methylene blue and ciprofloxacin (MBCF) in wastewater. Catalytic activity against MBCF dye was significantly reduced (99.3%) for (4%) Ag dopant concentration in acidic medium. For Ag/CNC-doped CeO2 vast inhibition domain of G-ve was significantly confirmed as (5.25-11.70 mm) and (7.15-13.60 mm), while medium- to high-concentration of CNC levels were calculated for G + ve (0.95 nm, 1.65 mm), respectively. Overall, (4%) Ag/CNC-doped CeO2 revealed significant antimicrobial activity against G-ve relative to G + ve at both concentrations, respectively. Furthermore, in silico molecular docking studies were performed against selected enzyme targets dihydrofolate reductase (DHFR), dihydropteroate synthase (DHPS), and DNA gyrase belonging to folate and nucleic acid biosynthetic pathway, respectively to rationalize possible mechanism behind bactericidal potential of CNC-CeO2 and Ag/CNC-CeO2.
This work aimed to study an integrated pretreatment technology employing p-toluenesulfonic acid (TsOH)-catalyzed liquid hot water (LHW) and short-time ball milling for the complete conversion of poplar biomass to xylooligosaccharides (XOS), glucose, and native-like lignin. The optimized TsOH-catalyzed LHW pretreatment solubilized 98.5% of hemicellulose at 160 °C for 40 min, releasing 49.8% XOS. Moreover, subsequent ball milling (20 min) maximized the enzymatic hydrolysis of cellulose from 65.8% to 96.5%, owing to the reduced particle sizes and cellulose crystallinity index. The combined pretreatment reduced the crystallinity by 70.9% while enlarging the average pore size and pore volume of the substrate by 29.5% and 52.4%, respectively. The residual lignin after enzymatic hydrolysis was rich in β-O-4 linkages (55.7/100 Ar) with less condensed structures. This lignin exhibited excellent antioxidant activity (RSI of 66.22) and ultraviolet absorbance. Thus, this research suggested a sustainable waste-free biorefinery for the holistic valorization of biomass through two-step biomass fractionation.
Bionanocomposite films based on regenerated cellulose (RC) and incorporated with zeolite at different concentrations were fabricated by dissolving cellulose in 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic liquid using a simple green method. The interactions between the zeolite and the cellulose matrix were confirmed by Fourier transform infrared spectra. Mechanical properties of the nanocomposite films significantly improved as compared with the pure regenerated cellulose film, without the loss of extensibility. Zeolite incorporation enhanced the thermal stability and char yield of the nanocomposites. The scanning electron microscopy and transmission electron microscopy showed that zeolite was uniformly dispersed in the regenerated cellulose matrix. In vitro cytotoxicity test demonstrated that both RC and RC/zeolite nanocomposite films are cytocompatible. These results indicate that the prepared nanocomposites have potential applications in biodegradable packaging, membranes and biomedical areas.
In this study, microcrystalline cellulose (MCC) was extracted from roselle fiber through acid hydrolysis treatment and its properties were compared with those of commercially available MCC. The physicochemical and morphological characteristics, elemental composition, size distribution, crystallinity and thermal properties of the obtained MCC were analyzed in this work. Fourier transform infrared spectroscopy (FTIR) analysis provided clear evidence that the characteristic peak of lignin was absent in the spectrum of the MCC prepared from roselle fiber. Rough surface and slight aggregation of MCC were observed by scanning electron microscopy (SEM). Energy dispersive X-ray (EDX) analysis showed that pure MCC with small quantities of residues and impurities was obtained, with a similar elemental composition to that of commercial MCC. A mean diameter of approximately 44.28μm was measured for MCC by using a particle size analyzer (PSA). X-ray diffraction (XRD) showed the crystallinity increased from 63% in roselle pulp to 78% in roselle MCC, the latter having a slightly higher crystallinity than that of commercial MCC (74%). TGA and DSC results indicated that the roselle MCC had better thermal stability than the roselle pulp, whereas it had poorer thermal stability in comparison with commercial MCC. Thus, the isolated MCC from roselle fibers will be going to use as reinforcing element in green composites and may be a precursor for future roselle derived nanocellulose, and thus a promising subject in nanocomposite research.