Synergistic sequential oxidative extraction for nanofibrillated cellulose isolated from oil palm empty fruit bunch.

This research presents a comprehensive study of sequential oxidative extraction (SOE) consisting of alkaline and acidic oxidation processes to extract nanocellulose from plant biomass. This proposed process is advantageous as its operation requires a minimum process with mild solvents, and yet successfully isolated high-quality nanofibrillated cellulose (NFC) from raw OPEFB. The SOE involved ammonium hydroxide (NH4OH, 2.6 M) and formic acid (HCOOH, 5.3 M) catalyzed by hydrogen peroxide (H2O2, 3.2 M). This approach was used to efficiently solubilize the lignin and hemicellulose from Oil Palm Empty Fruit Bunch (OPEFB) at the temperature of 100°C and 1 h extraction time, which managed to retain fibrous NFC. The extracted solid and liquor at each stage were studied extensively through physiochemical analysis. The finding indicated that approximately 75.3%dwb of hemicellulose, 68.9%dwb of lignin, and 42.0%dwb of extractive were solubilized in the first SOE cycle, while the second SOE cycle resulted in 92.3%dwb, 99.6%dwb and 99.8%dwb of solubilized hemicellulose, lignin, and extractive/ash, respectively. High-quality NFC (75.52%dwb) was obtained for the final extracted solid with 76.4% crystallinity, which is near the crystallinity of standard commercial NFC. The proposed process possesses an effective synergy in producing NFC from raw OPEFB with less cellulose degradation, and most of the degraded hemicellulose and lignin are solubilized in the liquor.

An alternative peptone preparation using Hermetia illucens (Black soldier fly) hydrolysis: process optimization and performance evaluation.

Background: Hermetia illucens (HI), commonly known as the black soldier fly, has been recognized for its prowess in resource utilization and environmental protection because of its ability to transform organic waste into animal feed for livestock, poultry, and aquaculture. However, the potential of the black soldier fly's high protein content for more than cheap feedstock is still largely unexplored. Methods: This study innovatively explores the potential of H. illucens larvae (HIL) protein as a peptone substitute for microbial culture media. Four commercial proteases (alkaline protease, trypsin, trypsase, and papain) were explored to hydrolyze the defatted HIL, and the experimental conditions were optimized via response surface methodology experimental design. The hydrolysate of the defatted HIL was subsequently vacuum freeze-dried and deployed as a growth medium for three bacterial strains (Staphylococcus aureus, Bacillus subtilis, and Escherichia coli) to determine the growth kinetics between the HIL peptone and commercial peptone. Results: The optimal conditions were 1.70% w/w complex enzyme (alkaline protease: trypsin at 1:1 ratio) at pH 7.0 and 54 °C for a duration of 4 h. Under these conditions, the hydrolysis of defatted HIL yielded 19.25% ±0.49%. A growth kinetic analysis showed no significant difference in growth parameters (µmax, Xmax, and λ) between the HIL peptone and commercial peptone, demonstrating that the HIL hydrolysate could serve as an effective, low-cost alternative to commercial peptone. This study introduces an innovative approach to HIL protein resource utilization, broadening its application beyond its current use in animal feed.

Evaluating the Stability of PLA-Lignin Filament Produced by Bench-Top Extruder for Sustainable 3D Printing.

As additive manufacturing continues to evolve, there is ongoing discussion about ways to improve the layer-by-layer printing process and increase the mechanical strength of printed objects compared to those produced by traditional techniques such as injection molding. To achieve this, researchers are exploring ways of enhancing the interaction between the matrix and filler by introducing lignin in the 3D printing filament processing. In this work, research has been conducted on using biodegradable fillers of organosolv lignin, as a reinforcement for the filament layers in order to enhance interlayer adhesion by using a bench-top filament extruder. Briefly, it was found that organosolv lignin fillers have the potential to improve the properties of polylactic acid (PLA) filament for fused deposition modeling (FDM) 3D printing. By incorporating different formulations of lignin with PLA, it was found that using 3 to 5% lignin in the filament leads to an improvement in the Young's modulus and interlayer adhesion in 3D printing. However, an increment of up to 10% also results in a decrease in the composite tensile strength due to the lack of bonding between the lignin and PLA and the limited mixing capability of the small extruder.

Nanocellulose-Based Biomaterial Ink Hydrogel for Uptake/Release of Bovine Serum Albumin.

This study explores the potential of using nanocellulose extracted from oil palm empty fruit bunch (OPEFB) as a biomaterial ink for 3D printing. The research focuses on using nanocellulose hydrogels for the controlled uptake and release of proteins, with the specific protein solution being Bovine Serum Albumin (BSA). To provide a suitable material for the bioprinting process, the study examines the characteristics and properties of the printed hydrogels through various analyses, such as morphology, functional group, crystallinity, and compression test. Several parameters, such as initial concentration, temperature, and the presence of calcium chloride as an additional crosslinker, affect the protein uptake and release capabilities of the hydrogel. The study is important for biomedicine as it explores the behavior of protein uptake and release using nanocellulose and 3D printing and can serve as a preliminary study for using hydrogels in biological materials or living cells.

3D Printed Functionalized Nanocellulose as an Adsorbent in Batch and Fixed-Bed Systems.

Nanocellulose, a refined form of cellulose, can be further functionalized on surface-active sites, with a catalyst as a regenerative agent. Newly developed adsorbents are expected to have the characteristics of good and rapid adsorption performance and regeneration properties with flexible structure using 3D printing technology. In this work, the adsorption performance of 3D printed functionalized nanocellulose was investigated using batch and fixed-bed column adsorption. Kinetics adsorption studies were divided into different adsorption models, with the pseudo-second order model showing a better correlation coefficient than the pseudo-first order and intraparticle diffusion models. The Langmuir and Thomas models were used to calculate the adsorption performance of batch and fixed-bed columns. Given the catalytic activity of Fenton oxidation, the fixed-bed column was regenerated up to five adsorption-desorption cycles, suggesting satisfactory performance of the column, with a slightly reduced adsorption capacity.

A novel chitinous nanoparticles prepared and characterized with black soldier fly (Hermetia illucens L.) using steam flash explosion treatment.

This is the first report of the use of steam flash explosion (SFE) to prepare chitinous nanoparticles from black soldier fly (BSF). SFE treatment was performed at a steam pressure of 0.45 to 1.60 MPa with a holding time of 60 s. As the pressure increased, the particle size of the chitinous particles decreased. Under SFE at 1.60 MPa, chitinous nanoparticles with sizes ranging from 59 to 162 nm were produced. SEM, AFM, Raman spectroscopy, FT-IR spectroscopy, 1H NMR, TGA, and DSC were used to characterize the BSF chitin materials. It was demonstrated that SFE treatment deacetylated chitin to obtain chitosan with 91.24 % deacetylation. In addition, the polymer backbone was maintained, and the degree of polymerization of chitosan nanoparticles was reduced. The activity of the cationic groups of chitosan nanoparticles was improved, thereby enhancing the temperature sensitivity of the polymeric material. It can be concluded that the SFE one-step processing method is a simple and efficient way to prepare homogeneous biomaterial nanoparticles. This study has implications for the development of chitosan nanomaterials for biomedical applications.

Correlation Study between the Organic Compounds and Ripening Stages of Oil Palm Fruitlets Based on the Raman Spectra.

The degree of maturity of oil palm fresh fruit bunches (FFB) at the time of harvest heavily affects oil production, which is expressed in the oil extraction rate (OER). Oil palm harvests must be harvested at their optimum maturity to maximize oil yield if a rapid, non-intrusive, and accurate method is available to determine their level of maturity. This study demonstrates the potential of implementing Raman spectroscopy for determining the maturity of oil palm fruitlets. A ripeness classification algorithm has been developed utilizing machine learning by classifying the components of organic compounds such as ß-carotene, amino acid, etc. as parameters to distinguish the ripeness of fruits. In this study, 47 oil palm fruitlets spectra from three different ripeness levels-under ripe, ripe, and over ripe-were examined. To classify the oil palm fruitlets into three maturity categories, the extracted features were put to the test using 31 machine learning models. It was discovered that the Medium, Weighted KNN, and Trilayered Neural Network classifier has a maximum overall accuracy of 90.9% by using four significant features extracted from the peaks as the predictors. To conclude, the Raman spectroscopy method may offer a precise and efficient means to evaluate the maturity level of oil palm fruitlets.

Oil Palm Fruits Ripeness Classification Based on the Characteristics of Protein, Lipid, Carotene, and Guanine/Cytosine from the Raman Spectra.

The capacity of palm oil production is directly affected by the ripeness of the fresh fruit bunches (FFB) upon harvesting. Conventional harvesting standards rely on rigid harvesting scheduling as well as the number of fruitlets that have loosened from the bunch. Harvesting is usually done every 10 to 14 days, and an FFB is deemed ready to be harvested if there are around 5 to 10 empty sockets on the fruit bunch. Technology aided by imaging techniques relies heavily on the color of the fruit bunch, which is highly dependent on the surrounding light intensities. In this study, Raman spectroscopy is used for ripeness classification of oil palm fruits, based on the molecular assignments extracted from the Raman bands between 1240 cm-1 and 1360 cm-1. The Raman spectra of 52 oil palm fruit samples which contain the fingerprints of different organic compounds were collected. Signal processing was applied to perform baseline correction and to reduce background noises. Characteristic data of the organic compounds were extracted through deconvolution and curve fitting processes. Subsequently, a correlation study between organic compounds was developed and eight hidden Raman peaks including protein, beta carotene, carotene, lipid, guanine/cytosine, chlorophyll-a, and tryptophan were successfully located. Through ANOVA statistical analysis, a total of six peak intensities from proteins through Amide III (ß-sheet), beta-carotene, carotene, lipid, guanine/cytosine, and carotene and one peak location from lipid were found to be significant. An automated oil palm fruit ripeness classification system deployed with artificial neural network (ANN) using the seven signification features showed an overall performance of 97.9% accuracy. An efficient and accurate ripeness classification model which uses seven significant Raman peak features from the correlation analysis between organic compounds was successfully developed.

Recent Advances in 3D Bioprinting: A Review of Cellulose-Based Biomaterials Ink.

Cellulose-based biodegradable hydrogel proves to be excellently suitable for the medical and water treatment industry based on the expressed properties such as its flexible structure and broad compatibility. Moreover, their potential to provide excellent waste management from the unutilized plant has triggered further study on the advanced biomaterial applications. To extend the use of cellulose-based hydrogel, additive manufacturing is a suitable technique for hydrogel fabrication in complex designs. Cellulose-based biomaterial ink used in 3D bioprinting can be further used for tissue engineering, drug delivery, protein study, microalgae, bacteria, and cell immobilization. This review includes a discussion on the techniques available for additive manufacturing, bio-based material, and the formation of a cellulose-based hydrogel.

Facile Synthesis of 3D Printed Tailored Electrode for 3-Monochloropropane-1,2-Diol (3-MCPD) Sensing.

Additive manufacturing (AM) has allowed enormous advancement in technology and material development; thus, it requires attention in developing functionalized printed materials. AM can assist in efficiently manufacturing complex tailored electrodes for electrochemical sensing in the food industry. Herein, we used a commercial fused deposition modeling (FDM) filament of acrylonitrile butadiene styrene (ABS) for FDM 3D printing of a self-designed electrode with minimal time and cost compared to a commercial electrode. A graphene-based ABS conductive filament (ABS-G) was used to fabricate the conductive electrode in a dual-nozzle FDM 3D printer. The electrochemically conductive 3D printed electrode was characterized using cyclic voltammetry and tested against standard 3-monochloropropane-1,2-diol (3-MCPD) with known concentrations using an amperometric detection method. Results showed a basis for promising application to detect and quantify 3-MCPD, a food contaminant known for its carcinogenic potential. The fabrication of functionalized 3D printed polymer electrodes paves way for the development of complete 3D printable electrochemical sensors. Under optimal conditions, this newly synthesized electrochemical sensor exhibited sensitivity with a linear response range from 6.61 × 10-4 to 2.30 × 10-3 µg/mL with an estimated limit of detection of 3.30 × 10-4 µg/mL against 3-MCPD.

Production of Rigid Polyurethane Foams Using Polyol from Liquefied Oil Palm Biomass: Variation of Isocyanate Indexes.

Development of polyurethane foam (PUF) containing bio-based components is a complex process that requires extensive studies. This work reports on the production of rigid PUFs from polyol obtained via liquefaction of oil palm empty fruit bunch (EFB) biomass with different isocyanate (NCO) indexes. The effect of the NCO index on the physical, chemical and compressive properties of the liquefied EFB-based PUF (EFBPUF) was evaluated. The EFBPUFs showed a unique set of properties at each NCO index. Foaming properties had affected the apparent density and cellular morphology of the EFBPUFs. Increasing NCO index had increased the crosslink density and dimensional stability of the EFBPUFs via formation of isocyanurates, which had also increased their thermal stability. Combination of both foaming properties and crosslink density of the EFBPUFs had influenced their respective compressive properties. The EFBPUF produced at the NCO index of 120 showed the optimum compressive strength and released the least toxic hydrogen cyanide (HCN) gas under thermal degradation. The normalized compressive strength of the EFBPUF at the NCO index of 120 is also comparable with the strength of the PUF produced using petrochemical polyol.

Intact Fibrillated 3D-Printed Cellulose Macrofibrils/CaCO3 for Controlled Drug Delivery.

The tendency to use cellulose fibrils for direct ink writing (DIW) of three-dimensional (3D) printing has been growing extensively due to their advantageous mechanical properties. However, retaining cellulose in its fibrillated forms after the printing process has always been a challenge. In this study, cellulose macrofibrils (CMFs) from oil palm empty fruit bunch (OPEFB) fibers were partially dissolved for consistent viscosity needed for DIW 3D printing. The printed CMF structure obtained from optimized printing profiles (volumetric flow rate, Qv = 9.58 mm/s; print speed, v = 20 mm/s), exhibited excellent mechanical properties (tensile strength of 66 MPa, Young's modulus of 2.16 GPa, and elongation of 8.76%). The remarkable structural and morphological effects of the intact cellulose fibrils show a homogeneous distribution with synthesized precipitated calcium carbonate (CaCO3) nanoparticles. The shear-aligned CMF/CaCO3 printed composite exhibited a sustained therapeutic drug release profile that can reduce rapid release that has adverse effects on healthy cells. In comparison with the initial burst release of 5-fluorouracil (5-FU) by CaCO3, the controlled release of 5-fluorouracil can be varied (48 to 75%) with the composition of CMF/CaCO3 allowing efficient release over time.

A Revisit to the Formation and Mitigation of 3-Chloropropane-1,2-Diol in Palm Oil Production.

Process-based contaminants in food-particularly in vegetable oils-have been a topic of interest due to their potential health risk on humans. Oral consumption above the tolerable daily intake might result in health risks. Therefore, it is critical to correctly address the food contaminant issues with a proper mitigation plan, in order to reduce and subsequently remove the occurrence of the contaminant. 3-monochloropropane-1,3-diol (3-MCPD), an organic chemical compound, is one of the heat- and process-induced food contaminants, belonging to a group called chloropropanols. This review paper discusses the occurrence of the 3-MCPD food contaminant in different types of vegetable oils, possible 3-MCPD formation routes, and also methods of reduction or removal of 3-MCPD in its free and bound esterified forms in vegetable oils, mostly in palm oil due to its highest 3-MCPD content.

Extending Cellulose-Based Polymers Application in Additive Manufacturing Technology: A Review of Recent Approaches.

The materials for additive manufacturing (AM) technology have grown substantially over the last few years to fulfill industrial needs. Despite that, the use of bio-based composites for improved mechanical properties and biodegradation is still not fully explored. This limits the universal expansion of AM-fabricated products due to the incompatibility of the products made from petroleum-derived resources. The development of naturally-derived polymers for AM materials is promising with the increasing number of studies in recent years owing to their biodegradation and biocompatibility. Cellulose is the most abundant biopolymer that possesses many favorable properties to be incorporated into AM materials, which have been continuously focused on in recent years. This critical review discusses the development of AM technologies and materials, cellulose-based polymers, cellulose-based three-dimensional (3D) printing filaments, liquid deposition modeling of cellulose, and four-dimensional (4D) printing of cellulose-based materials. Cellulose-based AM material applications and the limitations with future developments are also reviewed.

3D Printed Laminated CaCO3-Nanocellulose Films as Controlled-Release 5-Fluorouracil.

Drug delivery constitutes the formulations, technologies, and systems for the transport of pharmaceutical compounds to specific areas in the body to exert safe therapeutic effects. The main criteria for selecting the correct medium for drug delivery are the quantity of the drug being carried and the amount of time required to release the drug. Hence, this research aimed to improve the aforementioned criteria by synthesizing a medium based on calcium carbonate-nanocellulose composite and evaluating its efficiency as a medium for drug delivery. Specifically, the efficiency was assessed in terms of the rates of uptake and release of 5-fluorouracil. Through the evaluation of the morphological and chemical properties of the synthesized composite, the established 3D printing profiles of nanocellulose and CaCO3 took place following the layer-by-layer films. The 3D printed double laminated CaCO3-nanocellulose managed to release the 5-fluorouracil as an effective single composition and in a time-controlled manner.

3D Printing of UV-Curable Polyurethane Incorporated with Surface-Grafted Nanocellulose.

The recognition of nanocellulose has been prominent in recent years as prospect materials, yet the ineffectiveness of nanocellulose to disperse in an organic solvent has restricted its utilization, especially as a reinforcement in polymer nanocomposite. In this study, cellulose has been isolated and defibrillated as cellulose nanofibrils (CNF) from oil palm empty fruit bunch (EFB) fibers. Subsequently, to enhance its compatibility with UV-curable polyurethane (PU)-based resin, the surface hydrophilicity of CNF has been tailored with polyethylene glycol (PEG), as well as reduced graphene oxide (rGO). The dispersibility of reinforced modified CNF in UV-curable PU was examined through the transmittance interruption of resin, chemical, and mechanical properties of the composite printed using the stereolithographic technique. Evidently, the enhanced compatibility of modified CNF and UV-curable PU was shown to improve the tensile strength and hardness of the composites by 37% and 129%, respectively.

Evaluation of the Compatibility of Organosolv Lignin-Graphene Nanoplatelets with Photo-Curable Polyurethane in Stereolithography 3D Printing.

In this study, lignin has been extracted from oil palm empty fruit bunch (EFB) fibers via an organosolv process. The organosolv lignin obtained was defined by the presence of hydroxyl-containing molecules, such as guaiacyl and syringyl, and by the presence of phenolic molecules in lignin. Subsequently, the extracted organosolv lignin and graphene nanoplatelets (GNP) were utilized as filler and reinforcement in photo-curable polyurethane (PU), which is used in stereolithography 3D printing. The compatibility as well as the characteristic and structural changes of the composite were identified through the mechanical properties of the 3D-printed composites. Furthermore, the tensile strength of the composited lignin and graphene shows significant improvement as high as 27%. The hardness of the photo-curable PU composites measured by nanoindentation exhibited an enormous improvement for 0.6% of lignin-graphene at 92.49 MPa with 238% increment when compared with unmodified PU.

Telescopic synthesis of cellulose nanofibrils with a stable dispersion of Fe(0) nanoparticles for synergistic removal of 5-fluorouracil.

The recognition of cellulose nanofibrils (CNF) in the past years as a high prospect material has been prominent, but the impractical cellulose extraction method from biomass remained as a technological barrier for industrial practice. In this study, the telescopic approach on the fractionation of lignin and cellulose was performed by organosolv extraction and catalytic oxidation from oil palm empty fruit bunch fibers. The integration of these techniques managed to synthesize CNF in a short time. Aside from the size, the zeta potential of CNF was measured at -41.9 mV, which allow higher stability of the cellulose in water suspension. The stability of CNF facilitated a better dispersion of Fe(0) nanoparticles with the average diameter size of 52.3-73.24 nm through the formulation of CNF/Fe(0). The total uptake capacity of CNF towards 5-fluorouracil was calculated at 0.123 mg/g. While the synergistic reactions of adsorption-oxidation were significantly improved the removal efficacy three to four times greater even at a high concentration of 5-fluorouracil. Alternatively, the sludge generation after the oxidation reaction was completely managed by the encapsulation of Fe(0) nanoparticles in regenerated cellulose.

Superabsorbent hydrogel from oil palm empty fruit bunch cellulose and sodium carboxymethylcellulose.

A green regenerated superabsorbent hydrogel was fabricated with mixtures of dissolved oil palm empty fruit bunch (EFB) cellulose and sodium carboxymethylcellulose (NaCMC) in NaOH/urea system. The formation of hydrogel was aided with epichlorohydrin (ECH) as a crosslinker. The resultant regenerated hydrogel was able to swell >80,000% depending on the NaCMC concentrations. The hydrogel absorbed water rapidly upon exposure to water up to 48 h and gradually declined after 72 h. The crosslinked of covalent bond of COC between dissolved EFB cellulose (EFBC) with NaCMC was confirmed with Attenuated total reflectance Fourier transform infrared (ATR-FT-IR) spectroscopy. Crystallinity and thermal stability of the hydrogel samples were depended on the concentrations of NaCMC, crosslinking, and swelling process. The strength and stability of crosslinked network was studied by examining the gel fraction of hydrogel. This study explored the swelling ability and probable influenced factors towards physical and chemical properties of hydrogel.

Chemically crosslinked hydrogel and its driving force towards superabsorbent behaviour.

Dissolved oil palm empty fruit bunch (EFB) cellulose in NaOH/urea solvent was mixed with sodium carboxymethylcellulose (NaCMC) to form a green regenerated superabsorbent hydrogel. The effect of concentration of epichlorohydrin (ECH) as the crosslinker on the formation, physical, and chemical properties of hydrogel was studied. Rapid formation and higher gel content of hydrogel were observed at 10% concentration of ECH. The superabsorbent hydrogel was successfully fabricated in this study with the swelling ability >100,000%. Hydrogel with higher concentration of ECH showed opposite trend by having higher superabsorbent property than that of lower concentration. The covalent bond of COC was observed with Attenuated total reflectance fourier transform infrared (ATR-FT-IR) spectroscopy to confirm the occurrence of crosslinking. The physical and chemical properties of hydrogel were affected by swelling phenomenon. Hydrogel with higher degree of swelling exhibited lower moisture retention and higher transparency. Moreover, the weight of the superabsorbent hydrogel increased with the decrement of pH value of external media (distilled water). This study provided substantial information on the effect of different percentage of ECH as crosslinker on hydrogel basic properties. Furthermore, this study affords correlation of many essential driving forces that affected hydrogel superabsorbent property.