Bio-based Pickering emulsifier from mangosteen residues-derived sodium caseinate grafted spherical cellulose nanocrystals: Stability, rheological properties and microstructure studies.

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.

Surface Functionalization of Sugarcane-Bagasse-Derived Cellulose Nanocrystal for Pickering Emulsion Gel: Microstructural Properties and Stability Efficiency.

An environmentally friendly Pickering stabilizer was developed by upcycling sugarcane bagasse (SCB) into a cellulose nanocrystal (CNC), which was subjected to surface modification by using quaternary ammonium compound to enhance its amphiphilic characteristics. The changes in microstructural properties of modified cellulose nanocrystal (m-CNC), such as surface functional group, thermal stability, surface morphology, elemental composition, and particle size distribution were investigated. Results indicated the success of quaternary ammonium compound grafting with the presence of a trimethyl-alkyl chain on the cellulose structure, while the m-CNC preserves the needle-like nanoparticles in length of ~534 nm and width of ~20 nm. The colloidal profile of m-CNC-stabilized oil-water emulsion gels with different concentrations of m-CNC (1-5 wt%), and oil:water (O:W) ratios (3:7, 5:5, 7:3) were examined. The emulsion gel stability study indicated that the optimal concentration of m-CNC (3 wt%) was able to stabilize all the emulsion gels at different O:W ratios with an emulsion index of >80% for 3 months. It is the minimum concentration of m-CNC to form a robust colloidal network around the small oil droplets, leading to the formation of stable emulsion gels. The emulsion gel with O:W ratio (3:7) with 3 wt% of m-CNC rendered the best m-CNC-oil-droplets dispersion. The m-CNC effectively retained the size of oil droplets (<10 µm for 3 months storage) against coalescence and creaming by creating a steric barrier between the two immiscible phases. Furthermore, the emulsion gel exhibited the highest viscosity and storage modulus which was able to prevent creaming or sedimentation of the emulsion gels.

In vivo Study of Chalcone Loaded Carbon Dots for Enhancement of Anticancer and Bioimaging Potencies.

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.

Review of Functional Aspects of Nanocellulose-Based Pickering Emulsifier for Non-Toxic Application and Its Colloid Stabilization Mechanism.

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.

Environment-friendly deoxygenation of non-edible Ceiba oil to liquid hydrocarbon biofuel: process parameters and optimization study.

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.

Boronic-Acid-Modified Nanomaterials for Biomedical Applications.

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.

Environmentally adapted bio-oil compounds-derived polyolesters synthesis: Optimization and properties of base fluids.

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.

Production of green biofuel by using a goat manure supported Ni-Al hydrotalcite catalysed deoxygenation process.

The high oxygen content in natural biomass resources, such as vegetable oil or biomass-pyrolysed bio oil, is the main constraint in their implementation as a full-scale biofuel for the automotive industry. In the present study, renewable fuel with petrodiesel-like properties was produced via catalytic deoxygenation of oleic acid in the absence of hydrogen (H2). The deoxygenation pathway of oleic acid to bio-hydrocarbon involves decarboxylation/decarbonylation of the oxygen content from the fatty acid structure in the form of carbon dioxide (CO2)/carbon monoxide (CO), with the presence of a goat manure supported Ni-Al hydrotalcite (Gm/Ni-Al) catalyst. Goat manure is an abundant bio-waste, containing a high mineral content, urea as well as cellulosic fiber of plants, which is potentially converted into activated carbon. Synthesis of Gm/Ni-Al was carried out by incorporation of pre-activated goat manure (GmA) during co-precipitation of Ni-Al catalyst with 1 : 3, 1 : 1 and 3 : 1 ratios. The physico-chemical properties of the catalysts were characterized by X-ray diffractometry (XRD), Brunauer-Emmet-Teller (BET) surface area, field emission surface electron microscopy (FESEM) and temperature program desorption ammonia (TPD-NH3) analysers. The catalytic deoxygenation reaction was performed in a batch reactor and the product obtained was characterized by using gas chromatography-mass spectroscopy (GCMS) for compound composition identification as well as gas chromatography-flame ionisation detector (GC-FID) for yield and selectivity determination. The optimization and evaluation were executed using response surface methodology (RSM) in conjunction with central composite design (CCD) with 5-level-3-factors. From the RSM reaction model, it was found that the Gm/Ni-Al 1 : 1 catalysed deoxygenation reaction gives the optimum product yield of 97.9% of hydrocarbon in the range of C8-C20, with diesel selectivity (C17: heptadecane and heptadecene compounds) of 63.7% at the optimal reaction conditions of: (1) reaction temperature: 327.14 °C, (2) reaction time: 1 h, and (3) catalyst amount: 5 wt%.

Pyrus pyrifolia fruit peel as sustainable source for spherical and porous network based nanocellulose synthesis via one-pot hydrolysis system.

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.

Revalorization of selected municipal solid wastes as new precursors of "green" nanocellulose via a novel one-pot isolation system: A source perspective.

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.

Development of catalyst complexes for upgrading biomass into ester-based biolubricants for automotive applications: a review.

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.

Investigation of optimal conditions for production of highly crystalline nanocellulose with increased yield via novel Cr(III)-catalyzed hydrolysis: Response surface methodology.

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.

Easy Fabrication of Highly Thermal-Stable Cellulose Nanocrystals Using Cr(NO3)3 Catalytic Hydrolysis System: A Feasibility Study from Macro- to Nano-Dimensions.

This study reported on the feasibility and practicability of Cr(NO3)3 hydrolysis to isolate cellulose nanocrystals (CNCCr(NO3)3) from native cellulosic feedstock. The physicochemical properties of CNCCr(NO3)3 were compared with nanocellulose isolated using sulfuric acid hydrolysis (CNCH2SO4). In optimum hydrolysis conditions, 80 °C, 1.5 h, 0.8 M Cr(NO3)3 metal salt and solid-liquid ratio of 1:30, the CNCCr(NO3)3 exhibited a network-like long fibrous structure with the aspect ratio of 15.7, while the CNCH2SO4 showed rice-shape structure with an aspect ratio of 3.5. Additionally, Cr(NO3)3-treated CNC rendered a higher crystallinity (86.5% ± 0.3%) with high yield (83.6% ± 0.6%) as compared to the H2SO4-treated CNC (81.4% ± 0.1% and 54.7% ± 0.3%, respectively). Furthermore, better thermal stability of CNCCr(NO3)3 (344 °C) compared to CNCH2SO4 (273 °C) rendered a high potential for nanocomposite application. This comparable effectiveness of Cr(NO3)3 metal salt provides milder hydrolysis conditions for highly selective depolymerization of cellulosic fiber into value-added cellulose nanomaterial, or useful chemicals and fuels in the future.

Facile production of nanostructured cellulose from Elaeis guineensis empty fruit bunch via one pot oxidative-hydrolysis isolation approach.

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.

Production of new cellulose nanomaterial from red algae marine biomass Gelidium elegans.

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.

Heterogeneous base catalysts for edible palm and non-edible Jatropha-based biodiesel production.

BACKGROUND: 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). RESULTS: The chemical characteristic, textural properties, basicity profile and leaching test of synthesized catalysts were studied by using X-ray diffraction, BET measurement, TPD-CO2 and ICP-AES analysis, respectively. Transesterification activity of solid base catalysts showed that > 90% of palm biodiesel and > 80% of Jatropha biodiesel yield under 3 wt.% of catalyst, 3 h reaction time, methanol to oil ratio of 15:1 under 65°C. This indicated that other than physicochemical characteristic of catalysts; different types of natural oil greatly influence the catalytic reaction due to the presence of free fatty acids (FFAs). CONCLUSIONS: Among the solid base catalysts, calcium based mixed metal oxides catalysts with binary metal system (CaMgO and CaZnO) showed capability to maintain the transesterification activity for 3 continuous runs at ~ 80% yield. These catalysts render high durability characteristic in transesterification with low active metal leaching for several cycles.