In the present work, four types of newly chosen municipal solid wastes (Panax ginseng, spent tea residue, waste cotton cloth, and old corrugated cardboard) were studied as the promising sources for nanocellulose, which has efficiently re-engineered the structure of waste products into highly valuable nanocellulose materials. The nanocellulose was produced directly via a facile one-pot oxidative hydrolysis process by using H2O2/Cr(NO3)3 solution as the bleaching agent and hydrolysis medium under acidic condition. The isolated nanocellulose products were well-characterized in terms of chemical composition, product yield, morphological structure and thermal properties. The study has found that the crystallinity index of the obtained nanocellulose products were significantly higher (62.2-83.6%) than that of its starting material due to the successive elimination of lignin, hemicellulose and amorphous regions of cellulose, which were in good agreement with the FTIR analysis. The evidence of the successful production of nanocellulose was given by TEM observation which has revealed the fibril widths were ranging from 15.6 to 46.2nm, with high cellulose content (>90%), depending on the cellulosic origin. The physicochemical properties of processed samples have confirmed that the isolation of high purity nanocellulose materials from different daily spent products is possible. The comparative study can help to provide a deep insight on the possibility of revalorizing the municipal solid wastes into nanocellulose via the simple and versatile one-pot isolation system, which has high potential to be used in commercial applications for sustainable development.
Lignocellulosic biomass is a complex biopolymer that is primary composed of cellulose, hemicellulose, and lignin. The presence of cellulose in biomass is able to depolymerise into nanodimension biomaterial, with exceptional mechanical properties for biocomposites, pharmaceutical carriers, and electronic substrate's application. However, the entangled biomass ultrastructure consists of inherent properties, such as strong lignin layers, low cellulose accessibility to chemicals, and high cellulose crystallinity, which inhibit the digestibility of the biomass for cellulose extraction. This situation offers both challenges and promises for the biomass biorefinery development to utilize the cellulose from lignocellulosic biomass. Thus, multistep biorefinery processes are necessary to ensure the deconstruction of noncellulosic content in lignocellulosic biomass, while maintaining cellulose product for further hydrolysis into nanocellulose material. In this review, we discuss the molecular structure basis for biomass recalcitrance, reengineering process of lignocellulosic biomass into nanocellulose via chemical, and novel catalytic approaches. Furthermore, review on catalyst design to overcome key barriers regarding the natural resistance of biomass will be presented herein.
The present work focuses on the development of cellulose nanofibrils (CNF) film that derived from sustainable biomass resources, which potentially to work as bio-based conductive membranes that assembled into supercapacitors. The chemically purified cellulose was isolated from different parts of coconut (coconut shell and its husk) and further subjected to 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation for CNF preparation. Physicochemical properties of prepared CNFs were studied in terms of chemical characteristics & crystallinity, surface functionalities, surface morphology, and thermal properties. Both coconut shell-derived CNF and coconut husk-derived CNF fulfilled with nanocellulose's characteristics with fibres width ranged of 70-120 nm and 150-330 nm, respectively. CNF films were further prepared by solvent casting method to measure the modulus elasticity, piezoelectric and dielectric properties of the films. Mechanical study indicated that coconut shell-derived CNF film showed a higher value of elastic modulus than the coconut husk-derived CNF film, which was 8.39 GPa and 5.36 GPa, respectively. The effectiveness of electrical aspects for CNF films are well correlated with the crystallinity and thermal properties, associated with it's composition of different coconut's part.
Non-edible bio-oil derived from lignocellulosic biomass could be used as environmentally friendly lubricant-ester base stock for maritime and road-type transportations. However, the use of crude bio-oil with highly oxygenated compounds required further upgrading to yield ester that mimicked the characteristics of Group V base oil (polyolesters). In this study, bio-oil based polyolesters was produced via esterification using green biopolymer alginate acid catalyst (Al-Alg). The bio-oil compounds used were acetic acid (AcA), propionic acid (PrA) and levulinic acid (LA), while polyols such as neopentyl glycol (NPG), trimethylolpropane (TMP) and pentaerythritol (PE) were used. Optimization studies revealed that NPG-PrA ester gave the best ester purity of 100%, with 95% of diester selectivity under optimum conditions of 15 wt% Al-Alg, 8 h, 6:1 PrA:NPG and 140 °C. The produced polyolesters showed potential lube characteristics with viscosity index of 76, kinematic viscosity of 2.3 mm2 s-1 at 40 °C and oxidative induction time of 15 min at 100 °C. Furthermore, a reusability study of the Al-Alg catalyst indicated high NPG-PrA diester selectivity (above 90%) for 8 consecutive cycles. The physico-chemical properties of spent Al-Alg catalyst were also discussed.
Nanocellulose was successfully isolated from Gelidium elegans red algae marine biomass. The red algae fiber was treated in three stages namely alkalization, bleaching treatment and acid hydrolysis treatment. Morphological analysis was performed by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). TEM results revealed that the isolated nanocellulose had the average diameter and length of 21.8±11.1nm and of 547.3±23.7nm, respectively. Fourier transform infrared (FTIR) spectroscopy proved that the non-cellulosic polysaccharides components were progressively removed during the chemically treatment, and the final derived materials composed of cellulose parent molecular structure. X-ray diffraction (XRD) study showed that the crystallinity of yielded product had been improved after each successive treatments subjected to the treated fiber. The prepared nano-dimensional cellulose demonstrated a network-like structure with higher crystallinity (73%) than that of untreated fiber (33%), and possessed of good thermal stability which is suitable for nanocomposite material.
In the present study, we attempted revalorization of pear (Pyrus pyrifolia L.) peel residue into high value-added nanomaterials. A green and facile one-pot isolation procedure was designed to simplify the isolation process of nanocellulose directly from pear peel residue. The one-pot approach employed in this work is interesting as the reaction involved less harmful chemicals usage and non-multiple steps. The reaction was carried out by adding hydrogen peroxide as an oxidant and chromium (III) nitrate as catalyst in the acidic medium under mild process conditions. FTIR spectroscopy proved that the pear peel derived nanocellulose was purely cellulose phases without the presence of non-cellulosic layer. XRD study indicated that the isolated nanocellulose possessed of cellulose I polymorph with high crystallinity index of 85.7%. FESEM analysis clearly revealed that the considerable size reduction during one-pot process. Remarkably, TEM analysis revealed that the isolated nanocellulose consisted of network-liked nature and spherical shaped morphologies with high aspect ratio of 24.6. TGA showed nanocellulose has lower thermal stability compared to pear peel residue. This study provided a cost-effective method and straightforward one-pot process for fabrication of nanocellulose from pear peel residue. This is the first investigation on the nanocellulose extraction from pear fruit.
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.
Cellulose in nanostructures was successfully isolated from empty fruit bunch biomass via a novel one-pot oxidative-hydrolysis technique. The physicochemical properties of nanocellulose prepared via one-pot process have shown comparable characteristics as products isolated via conventional multistep purification approach (namely dewaxing, chlorite bleaching process, alkalization, and acid hydrolysis). The chemical composition study indicated that the one-pot oxidative-hydrolysis process successfully extracted cellulose (91.0%), with the remaining minority being hemicellulose and lignin (∼6%) in the final product. Crystallinity profile of one-pot treated product (80.3%) was higher than that of multistep isolated nanocellulose (75.4%), which indicated that the disorder region (amorphous) in cellulose fibers was successfully removed. In additional to that, the morphology study demonstrated that nanocellulose prepared by one-pot process rendered spider-web-like network nanostructure, with an average diameter of fibers at a range of 51.6±15.4nm. The nanocellulose product showed high thermal stability (320°C), which was ready for nanocomposite application. One-pot oxidative-hydrolysis technique is a simple and versatile route for the preparation of nanocellulose from complex biomass within 90°C and 6h period, with minimum wastewater as compared to the multistep process.
Boronic-acid-modified nanomaterials have inspired significant research interest owing to their unique biocompatibility and excellent reversible interaction with diol groups containing saccharides, protein, DNA, and other related glucose compounds. However, the different sources and methods change the application of nanomaterials. Thus, surface-functionalized nanomaterials are of interest as one of the best ways to improve the application of the biomedical field. In this mini-review, we summarize recent studies on boronic-acid-modified nanomaterials, based on the carbon dot group and graphene oxides, which have been used in the fields of bioimaging, biosensing, antiviral inhibitors, etc. Moreover, the multivalent interaction on boronic-acid-modified materials has become the main key improvement for targeting treatment in the future. We mainly focused on any previously reported papers for synergistic future opportunities of superior biomedical applications of carbon dots (CDs) in the management and diagnostics of nanomedicine fields.
This study aimed to develop a sustainable and bio-based nano-additive (sodium caseinate/cellulose nanofibers (SC/CNF) complex) to modulate liquid-based oil-in-water (O/W) colloid interfaces, which function as a fat control agent to slow lipid digestion. Edible protein (SC) was grafted onto CNF through facile electrostatic attraction, which reduces solvent and chemical usage for greener process. The physicochemical properties of SC/CNF showed that adding SC increased the interfacial bonding between CNF particles, resulting in higher interfacial pressure by forming dense and compact layers of SC/CNF. This characteristic improves the mechanical strength and colloidal stability of SC/CNF during water-oil stabilization. Further preparation of O/W Pickering emulsions stabilized by SC/CNF complexes was conducted using different parameters (such as SC concentration, dosage of SC/CNF, and O/W ratio) to investigate profile of free fatty acid (FFA) released during lipid digestion via simulated in vitro gastrointestinal tract (GIT) model. The results showed that the optimized emulsion stabilized by the SC/CNF complex rendered a lower value of free fatty acids (FFA) after undergoing in vitro simulated digestion. The lowest FFA release (31.18 %) was achieved under the following conditions: 1 % w/v (SC concentration), 1 % w/w (dosage of SC/CNF), and 20/80 (O/W) ratio. Low FFA release within the digestive system indicated that the nano-emulsions effectively regulated lipid digestion. The changes in physicochemical characteristics in terms of colloidal stability (particle size, microstructure, and surface charge) of the stabilized emulsions corresponding to the FFA released were studied during each digestion phase (including mouth, stomach, and small intestine). This study revealed that the SC/CNF complex is a promising nano-biomaterial that can function as a bio-functional food additive, particle stabilizer, and fat digestion controller. The unique characteristics of SC/CNF complexes in stabilizing oil-water emulsions present a potential interfacial mechanism for modulating lipid bioavailability. The innovation approach allows for the demand for green-label products, promote development of healthier food options, and the pursuit of sustainable food solutions.
Transesterification catalyzed by solid base catalyst is a brilliant technology for the noble process featuring the fast reaction under mild reacting condition in biodiesel production. Heterogeneous base catalysts are generally more reactive than solid acid catalysts which require extreme operating condition for high conversion and biodiesel yield. In the present study, synthesis of biodiesel was studied by using edible (palm) or non-edible (Jatropha) feedstock catalyzed by heterogeneous base catalysts such as supported alkali metal (NaOH/Al2O3), alkaline-earth metal oxide (MgO, CaO and SrO) and mixed metal oxides catalysts (CaMgO and CaZnO).
In the past few years, the research on particle-stabilized emulsion (Pickering emulsion) has mainly focused on the usage of inorganic particles with well-defined shapes, narrow size distributions, and chemical tunability of the surfaces such as silica, alumina, and clay. However, the presence of incompatibility of some inorganic particles that are non-safe to humans and the ecosystem and their poor sustainability has led to a shift towards the development of materials of biological origin. For this reason, nano-dimensional cellulose (nanocellulose) derived from natural plants is suitable for use as a Pickering material for liquid interface stabilization for various non-toxic product formulations (e.g., the food and beverage, cosmetic, personal care, hygiene, pharmaceutical, and biomedical fields). However, the current understanding of nanocellulose-stabilized Pickering emulsion still lacks consistency in terms of the structural, self-assembly, and physio-chemical properties of nanocellulose towards the stabilization between liquid and oil interfaces. Thus, this review aims to provide a comprehensive study of the behavior of nanocellulose-based particles and their ability as a Pickering functionality to stabilize emulsion droplets. Extensive discussion on the characteristics of nanocelluloses, morphology, and preparation methods that can potentially be applied as Pickering emulsifiers in a different range of emulsions is provided. Nanocellulose's surface modification for the purpose of altering its characteristics and provoking multifunctional roles for high-grade non-toxic applications is discussed. Subsequently, the water-oil stabilization mechanism and the criteria for effective emulsion stabilization are summarized in this review. Lastly, we discuss the toxicity profile and risk assessment guidelines for the whole life cycle of nanocellulose from the fresh feedstock to the end-life of the product.
Non-edible Ceiba oil has the potential to be a sustainable biofuel resource in tropical countries that can replace a portion of today's fossil fuels. Catalytic deoxygenation of the Ceiba oil (high O/C ratio) was conducted to produce hydrocarbon biofuel (high H/C ratio) over NiO-CaO5/SiO2-Al2O3 catalyst with aims of high diesel selectivity and catalyst reusability. In the present study, response surface methodology (RSM) technique with Box-Behnken experimental designs (BBD) was used to evaluate and optimize liquid hydrocarbon yield by considering the following deoxygenation parameters: catalyst loading (1-9 wt. %), reaction temperature (300-380 °C) and reaction time (30-180 min). According to the RSM results, the maximum yield for liquid hydrocarbon n-(C8-C20) was found to be 77% at 340 °C within 105 min and 5 wt. % catalyst loading. In addition, the deoxygenation model showed that the catalyst loading-reaction time interaction has a major impact on the deoxygenation activity. Based on the product analysis, oxygenated species from Ceiba oil were successfully removed in the form of CO2/CO via decarboxylation/decarbonylation (deCOx) pathways. The NiO-CaO5/SiO2-Al2O3 catalyst rendered stable reusability for five consecutive runs with liquid hydrocarbon yield within the range of 66-75% with n-(C15 + C17) selectivity of 64-72%. Despite this, coke deposition was observed after several times of catalyst usage, which is due to the high deoxygenation temperature (> 300 °C) that resulted in unfavourable polymerization side reaction.
Biomass-derived oils are recognised as the most promising renewable resources for the production of ester-based biolubricants due to their biodegradable, non-toxic and metal adhering properties. Homogeneous acid catalysts have been conventionally used in catalytic esterification and transesterification for the synthesis of ester-based biolubricants. Although homogeneous acid catalysts encounter difficulty during phase separation, they exhibit superior selectivity and good stereochemistry and regiochemistry control in the reaction. Consequently, transition metal complex catalysts (also known as homogeneous organometallic catalysts) are proposed for biolubricant synthesis in order to achieve a higher selectivity and conversion. Herein, the potential of both homogeneous transition metal complexes and heterogeneous supported metal complexes towards the synthesis of biolubricants, particularly, in esterification and transesterification, as well as the upgrading process, including hydrogenation and in situ hydrogenation-esterification, is critically reviewed.
This study focuses on the preparation of mangosteen rind-derived nanocellulose via green ascorbic acid hydrolysis. Subsequently, milk protein-grafted nanocellulose particles were developed as a renewable Pickering emulsifier for water-oil stabilization. The stabilizing efficiency of modified nanocellulose (NC-S) at different caseinate (milk protein) concentrations (1.5, 3.0, and 4.0 % w/v) was tested in a water-in-oil emulsion (W/O ratio of 40:60). At a concentration 3.0 % w/v of caseinate (3.0NC-S), the emulsion exhibited a stronger network of adsorption between water, Pickering emulsifier, and oil. This resulted in reduced oil droplet flocculation, increased stability over a longer period, and favorable emulsifying properties, as depicted in the creaming index profile, oil droplet distribution, and rheology analysis. Since 3.0NC-S demonstrated the best colloidal stability, further focus will be placed on its microstructural properties, comparing them with those of mangosteen rind (MG), cellulose, and nanocellulose (NC-L). The XRD profile indicated that both NC-L and NC-S possessed a cellulose nanocrystal structure characterized as type I beta with a high crystallinity index above 60 %. Morphology investigation shown that the NC-L present in the spherical shape of particles with nanosized ranging at diameters of 11.27 ± 0.50 nm and length 11.76 ± 0.46 nm, while modified NC-S showed increase sized at 14.26 ± 4.60 nm and length 14.96 ± 4.94 nm. The increment of particle sizes from NC-L to NC-S indicated 2.82 × 10-15 mg/m2 of surface protein coverage by caseinate functional groups.
The fluorescent imaging and drug delivery utilizing carbon dots nanomaterials (CDs) have attracted tremendously due to their unique optical ability and outstanding biocompatibility. Herein, we reported a new design of chalcone-loaded carbon dots (Chalcone-APBA-CDs) to serve chalcone transport onto cancer cells and enhance the CDs bioimaging and antitumor activity. The boronic acid was directly introduced to carbon dots (CDs) via pyrolysis process to drive CDs specifically to the cancer cell, and chalcone was mediated on CDs by ultrasonication to perform facile release of the drug delivery model. The successfully synthesized Chalcone-APBA-CDs were proved by their chemical structure, fluorescent activities, in vitro and in vivo analyses, and drug release systems using different pH. In addition, flow cytometry and confocal fluorescent imaging proved CDs' cellular uptake and imaging performance. In vitro analyses further proved that the Chalcone-APBA-CDs exhibited a higher toxicity value than bare CDs and efficiently inhibited the proliferation of the HeLa cells depending on their dose-response. Finally, the performance of Chalcone-APBA-CDs on cancer healing capability was examined in vivo with fibrosarcoma cancer-bearing mice, which showed a remarkable ability to reduce the tumor volume compared with saline (control). This result strongly suggested that the Chalcone-APBA-CDs appear promising simultaneously as cancer cell imaging and drug delivery.