Process design for acidic and alcohol based deep eutectic solvent pretreatment and high pressure homogenization of palm bunches for nanocellulose production.

This research aimed to study on nanocellulose production from palm bunch using process design and cost analysis. Choline chloride based deep eutectic solvent pretreatment was selected for high-purity cellulose separation at mild condition, followed by nano-fibrillation using mechanical treatment. Three types of choline chloride-based deep eutectic solvents employing different hydrogen-bond donors (HBDs) namely lactic acid, 1,3-butanediol and oxalic acid were studied. The optimal cellulose extraction condition was choline chloride/lactic acid (ChLa80C) pretreatment of palm empty bunch at 80 °C followed by bleaching yielding 94.96%w/w cellulose content in product. Size reduction using ultrasonication and high-pressure homogenization produced nanocellulose at 67.12%w/w based on cellulose in raw material. Different morphologies of nanocellulose were tunable in the forms of nanocrystals, nano-rods and nanofibers by using dissimilar deep eutectic solvents. This work offered a sustainable and environmentally friendly process as well as provided analysis of DES pretreatment and overview operating cost for nanocellulose production. Application of nanocellulose for the fabrication of highly functional and biodegradable material for nanomedicine, electronic, optical, and micromechanical devices is achievable in the near future.

Wastewater Treatment Using Membrane Bioreactor Technologies: Removal of Phenolic Contaminants from Oil and Coal Refineries and Pharmaceutical Industries.

Huge amounts of noxious chemicals from coal and petrochemical refineries and pharmaceutical industries are released into water bodies. These chemicals are highly toxic and cause adverse effects on both aquatic and terrestrial life. The removal of hazardous contaminants from industrial effluents is expensive and environmentally driven. The majority of the technologies applied nowadays for the removal of phenols and other contaminants are based on physio-chemical processes such as solvent extraction, chemical precipitation, and adsorption. The removal efficiency of toxic chemicals, especially phenols, is low with these technologies when the concentrations are very low. Furthermore, the major drawbacks of these technologies are the high operation costs and inadequate selectivity. To overcome these limitations, researchers are applying biological and membrane technologies together, which are gaining more attention because of their ease of use, high selectivity, and effectiveness. In the present review, the microbial degradation of phenolics in combination with intensified membrane bioreactors (MBRs) has been discussed. Important factors, including the origin and mode of phenols' biodegradation as well as the characteristics of the membrane bioreactors for the optimal removal of phenolic contaminants from industrial effluents are considered. The modifications of MBRs for the removal of phenols from various wastewater sources have also been addressed in this review article. The economic analysis on the cost and benefits of MBR technology compared with conventional wastewater treatments is discussed extensively.

Scaling-up of carbon dots hydrothermal synthesis from sugars in a continuous flow microreactor system for biomedical application as in vitro antimicrobial drug nanocarrier.

Carbon dots (CDs) are a new class of nanomaterials exhibiting high biocompatibility, water solubility, functionality, and tunable fluorescence (FL) property. Due to the limitations of batch hydrothermal synthesis in terms of low CDs yield and long synthesis duration, this work aimed to increase its production capacity through a continuous flow reactor system. The influence of temperature and time was first studied in a batch reactor for glucose, xylose, sucrose and table sugar precursors. CDs synthesized from sucrose precursor exhibited the highest quantum yield (QY) (175.48%) and the average diameter less than 10 nm (~6.8 ± 1.1 nm) when synthesized at 220°C for 9 h. For a flow reactor system, the best condition for CDs production from sucrose was 1 mL min-1 flow rate at 280°C, and 0.2 MPa pressure yielding 53.03% QY and ~ 6.5 ± 0.6 nm average diameter (6.6 mg min-1 of CDs productivity). CDs were successfully used as ciprofloxacin (CP) nanocarrier for antimicrobial activity study. The cytotoxicity study showed that no effect of CDs on viability of L-929 fibroblast cells was detected until 1000 µg mL-1 CDs concentration. This finding demonstrates that CDs synthesized via a flow reactor system have a high zeta potential and suitable surface properties for nano-theranostic applications.

Nanostructured N/S doped carbon dots/mesoporous silica nanoparticles and PVA composite hydrogel fabrication for anti-microbial and anti-biofilm application.

Regarding the convergence of the worldwide epidemic, the appearance of bacterial infection has occasioned in a melodramatic upsurge in bacterial pathogens with confrontation against one or numerous antibiotics. The implementation of engineered nanostructured particles as a delivery vehicle for antimicrobial agent is one promising approach that could theoretically battle the setbacks mentioned. Among all nanoparticles, silica nanoparticles have been found to provide functional features that are advantageous for combatting bacterial contagion. Apart from that, carbon dots, a zero-dimension nanomaterial, have recently exhibited their photo-responsive property to generate reactive oxygen species facilitating to enhance microorganism suppression and inactivation ability. In this study, potentials of core/shell mesoporous silica nanostructures (MSN) in conjugation with carbon dots (CDs) toward antimicrobial activity against Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli have been investigated. Nitrogen and sulfur doped CDs (NS/CDs) conjugated with MSN which were cost effective nanoparticles exhibited much superior antimicrobial activity for 4 times as much as silver nanoparticles against all bacteria tested. Among all nanoparticles tested, 0.40 M NS/CDs@MSN showed the greatest minimal biofilm inhibitory at very low concentration (< 0.125 mg mL-1), followed by 0.20 M NS/CDs@MSN (0.5 mg mL-1), CD@MSN (25 mg mL-1), and MSN (50 mg mL-1), respectively. Immobilization of NS/CDs@MSN in polyvinyl alcohol (PVA) hydrogel was performed and its effect on antimicrobial activity, biofilm controlling efficiency, and cytotoxicity toward fibroblast (NIH/3 T3 and L-929) cells was additionally studied for further biomedical applications. The results demonstrated that 0.40 M NS/CDs-MSN@PVA hydrogel exhibited the highest inhibitory effect on S. aureus > P. aeruginosa > E. coli. In addition, MTT assay revealed some degree of toxicity of 0.40 M NS/CDs-MSN@PVA hydrogel against L-929 cells by a slight reduction of cell viability from 100% to 81.6% when incubated in the extract from 0.40 M NS/CDs-MSN@PVA hydrogel, while no toxicity of the same hydrogel extract was detected toward NIH/3 T3 cells.

Preparation of Nanocellulose from Coffee Pulp and Its Potential as a Polymer Reinforcement.

Coffee is one of the most valued agricultural products regarding its high commercialization rate. During the production of coffee beans, coffee pulp is obtained as one of the main byproducts with a cellulose content of more than 30% of dry weight. This research focused on the value-added potential of coffee pulp fiber as the reinforcement in composite materials. The nanocellulose coffee pulp (NCP) from the coffee pulp (CP) was prepared and subsequently used as a filler to reinforce the polyvinyl alcohol (PVA) matrix for the improvement of PVA composite properties. The CP was treated via alkali and bleaching treatment before the production of NCP using the acid hydrolysis treatment. The TEM result of NCP showed the successful preparation of NCP with an average diameter of 16.03 ± 4.70 nm with increasing crystallinity size and crystallinity index. The effect of glycerol (G) in the PVA matrix was observed. The result showed that glycerol had a play-role as a plasticizer for increased flexibility and decreased hardness and brittleness of PVA nanocomposite film. The nanocomposite film of PVA/G/NCP was fabricated with various ratios of NCP through the casting method. It was shown that the physical properties were improved with the presence of NCP in the PVA matrix compared to the neat PVA film.

Fabrication and Characterization of Functional Biobased Membranes from Postconsumer Cotton Fabrics and Palm Waste for the Removal of Dyes.

Textile industries currently face vast challenges for the active removal of colored wastewater. Indeed, sustainable, recyclable, and green approaches are still lacking to achieve this aim. Thus, the present study explored the utilization of highly functional, green, recyclable, fully bio-based, and cost-effective composite membranes from post-consumer cotton fabrics and palm waste for wastewater treatment purposes. Highly functional cellulose nanofibers (CNF) were produced from waste cotton fabrics and filter paper using an acid hydrolysis technique. The yield of nanofibers extracted from waste cotton fabrics and filter paper was 76.74 and 54.50%, respectively. The physical, chemical, and structural properties of nanofibers were studied using various advanced analytical techniques. The properties of isolated nanofibers were almost similar and comparable to those of commercial nanofibers. The surface charge densities were -94.0, -80.7, and -90.6 mV for the nanofibers of palm waste, cotton fibers, and filter paper, respectively. After membrane fabrication using vacuum and hot-pressing techniques, the characteristics of the membrane were analyzed. The results showed that the average pore size of the palm-waste membrane was 1.185 nm, while it was 1.875 nm for membrane from waste cotton fibers and filter paper. Congo red and methylene blue dyes were used as model solutions to understand the behavior of available functional groups and the surface ζ-potential of the membrane frameworks' interaction. The membrane made from palm waste had the highest dye removal efficiency, and it was 23% for Congo red and 44% for methylene blue. This study provides insights into the challenges associated with the use of postconsumer textile and agricultural waste, which can be potentially used in high-performance liquid filtration devices for a more sustainable society.

Cryo-Induced Cellulose-Based Nanogel from Elaeis guineensis for Antibiotic Delivery Platform.

Cryo-induced hydrogel from cellulose is a new class of biomaterials for drug delivery, cell delivery, bone and skin tissue engineering for cell proliferation and regeneration applications. This research aimed to synthesize cryo-induced hydrogel from cellulose and carboxymethyl cellulose (CMC) produced from empty bunch's cell wall of Elaeis guineensis. First, the experiment was to produce cellulose-rich material using hot-compressed water extraction followed by alkaline delignification and bleaching with H2O2. The obtained bleached EFB cellulose was used as the substrate for CMC, and the optimal condition with the highest degree of carboxyl substitution (DS) of 0.75 was achieved when varying NaOH and monochloroacetic acid concentration as well as etherification temperature using fractional factorial design. For cryogelation study, hydrogels were synthesized from cellulose, CMC and beta-cyclodextrin (ß-CD) by dissolving cellulose-based matrix in a NaOH/urea system, and the cellulose (CEL) solution was frozen spontaneously at -40 °C followed by high speed mixing to loosen cellulose fibrils. Epichlorohydrin (ECH) and Polyethylene glycol diglycidyl ether (PEGDE) were used as a cross-linker. First, the ratio of cellulose and CMC with different amounts of ECH was investigated, and subsequently the proper ratio was further studied by adding different crosslinkers and matrices, i.e., CMC and ß-CD. From the result, the ECH crosslinked CMC-CEL (E-CMC-CEL) gel had the highest swelling properties of 5105% with the average pore size of lyophilized hydrogel of 300 µm. In addition, E-CMC-CEL gel had the highest loading and release capability of tetracycline in buffer solution at pH 7.4 and 3.2. At pH 7.4, tetracycline loading and release properties of E-CMC-CEL gel were 65.85 mg g-1 dry hydrogel and 46.48 mg g-1 dry hydrogel (70.6% cumulative release), respectively. However, at pH 3.2, the loading and release capabilities of Tetracycline were moderately lower at 16.25 mg g-1 dry hydrogel and 5.06 mg g-1 dry hydrogel, respectively. The findings presented that E-CMC-CEL hydrogel was a suitable material for antibiotic tetracycline drug carrying platform providing successful inhibitory effect on Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa, respectively.

Platinum/carbon dots nanocomposites from palm bunch hydrothermal synthesis as highly efficient peroxidase mimics for ultra-low H2O2 sensing platform through dual mode of colorimetric and fluorescent detection.

Detection of hydrogen peroxide and glucose in nanomolar level is crucial for point-of-care medical diagnosis. It has been reported that human's central nervous system diseases such as Alzheimer's disease, Parkinson's disease, and even amyotrophic lateral sclerosis, are presumably caused H2O2 or reactive radical species (ROS). Sensing of H2O2 released from human biofluids, tissues, organ from metabolism disorder at ultra-low concentration assists for early identification of severe diabetis mellitus related to glucose, and heart attack, as well as stroke related to cholesterol. In this work, carbon dots (CDs) having an average diameter at 6.99 nm with highly photoluminescence performance were successfully synthesized from palm empty fruit bunch (EFB) using green and environmentally friendly process via hydrothermal condition. CDs acted well on peroxidase-like activity for H2O2 detection at room temperature, however their sensitivity on ultra-low H2O2 concentration needed to be improved. To enhance their reactivity on H2O2 nanozyme activity at room temperature, synthesis of hybrid metal nanoparticles (AgNPs and PtNPs) on CDs surface was established. The findings exhibited that CDs/PtNPs was the most suitable nanozyme achieving highly efficient peroxidase mimic for dual mode of colorimetric and fluorescent H2O2 sensing platform at very low limit of detection of 0.01 mM (10 nM) H2O2.

The Role of N and S Doping on Photoluminescent Characteristics of Carbon Dots from Palm Bunches for Fluorimetric Sensing of Fe3+ Ion.

This work aims to enhance the value of palm empty fruit bunches (EFBs), an abundant residue from the palm oil industry, as a precursor for the synthesis of luminescent carbon dots (CDs). The mechanism of fIuorimetric sensing using carbon dots for either enhancing or quenching photoluminescence properties when binding with analytes is useful for the detection of ultra-low amounts of analytes. This study revealed that EFB-derived CDs via hydrothermal synthesis exceptionally exhibited luminescence properties. In addition, surface modification for specific binding to a target molecule substantially augmented their PL characteristics. Among the different nitrogen and sulfur (N and S) doping agents used, including urea (U), sulfate (S), p-phenylenediamine (P), and sodium thiosulfate (TS), the results showed that PTS-CDs from the co-doping of p-phenylenediamine and sodium thiosulfate exhibited the highest PL properties. From this study on the fluorimetric sensing of several metal ions, PTS-CDs could effectively detect Fe3+ with the highest selectivity by fluorescence quenching to 79.1% at a limit of detection (LOD) of 0.1 µmol L-1. The PL quenching of PTS-CDs was linearly correlated with the wide range of Fe3+ concentration, ranging from 5 to 400 µmol L-1 (R2 = 0.9933).

Lignin-Derived Syringol and Acetosyringone from Palm Bunch Using Heterogeneous Oxidative Depolymerization over Mixed Metal Oxide Catalysts under Microwave Heating.

Biomass valorization to building block chemicals in food and pharmaceutical industries has tremendously gained attention. To produce monophenolic compounds from palm empty fruit bunch (EFB), EFB was subjected to alkaline hydrothermal extraction using NaOH or K2CO3 as a promotor. Subsequently, EFB-derived lignin was subjected to an oxidative depolymerization using Cu(II) and Fe(III) mixed metal oxides catalyst supported on γ-Al2O3 or SiO2 as the catalyst in the presence of hydrogen peroxide. The highest percentage of total phenolic compounds of 63.87 wt% was obtained from microwave-induced oxidative degradation of K2CO3 extracted lignin catalyzed by Cu-Fe/SiO2 catalyst. Main products from the aforementioned condition included 27.29 wt% of 2,4-di-tert-butylphenol, 19.21 wt% of syringol, 9.36 wt% of acetosyringone, 3.69 wt% of acetovanillone, 2.16 wt% of syringaldehyde, and 2.16 wt% of vanillin. Although the total phenolic compound from Cu-Fe/Al2O3 catalyst was lower (49.52 wt%) compared with that from Cu-Fe/SiO2 catalyst (63.87 wt%), Cu-Fe/Al2O3 catalyst provided the greater selectivity of main two value-added products, syringol and acetosyrigone, at 54.64% and 23.65%, respectively (78.29% total selectivity of two products) from the NaOH extracted lignin. The findings suggested a promising method for syringol and acetosyringone production from the oxidative heterogeneous lignin depolymerization under low power intensity microwave heating within a short reaction time of 30 min.

Upgrading of Light Bio-oil from Solvothermolysis Liquefaction of an Oil Palm Empty Fruit Bunch in Glycerol by Catalytic Hydrodeoxygenation Using NiMo/Al2O3 or CoMo/Al2O3 Catalysts.

Hydrodeoxygenation (HDO) of bio-oil derived from liquefaction of a palm empty fruit bunch (EFB) in glycerol was investigated. To enhance the heating value and reduce the oxygen content of upgraded bio-oil, hydrodeoxygenation of light bio-oil over Ni- and Co-based catalysts on an Al2O3 support was performed in a rotating-bed reactor. Two consecutive steps were conducted to produce bio-oil from EFB including (1) microwave-assisted wet torrefaction of EFB and (2) solvothermolysis liquefaction of treated EFB in a Na2CO3/glycerol system. The HDO of as-prepared bio-oil was subsequently performed in a unique design reactor possessing a rotating catalyst bed for efficient interaction of a catalyst with bio-oil and facile separation of the catalyst from upgraded bio-oil after the reaction. The reaction was carried out in the presence of each mono- or bimetallic catalyst, namely, Co/Al2O3, Ni/Al2O3, NiMo/Al2O3, and CoMo/Al2O3, packed in the rotating-mesh host with a rotation speed of 250 rpm and kept at 300 and 350 °C, 2 MPa hydrogen for 1 h. From the results, the qualities of upgraded bio-oil were substantially improved for all catalysts tested in terms of oxygen reduction and increased high heating value (HHV). Particularly, the NiMo/Al2O3 catalyst exhibited the most promising catalyst, providing favorable bio-oil yield and HHV. Remarkably greater energy ratios and carbon recovery together with high H/O, C/O, and H/C ratios were additionally achieved from the NiMo/Al2O3 catalyst compared with other catalysts. Cyclopentanone and cyclopentene were the main olefins found in hydrodeoxygenated bio-oil derived from liquefied EFB. It was observed that cyclopentene was first generated and subsequently converted to cyclopentanone under the hydrogenation reaction. These compounds can be further used as a building block in the synthesis of jet-fuel range cycloalkanes.

Fabrication and Characterization of Lignin Particles and Their Ultraviolet Protection Ability in PVA Composite Film.

Recently, lignin utilization in advanced applications has gained much interest. Due to the limitation of the current use of standard lignin, lignin particles have recently gained attention in overcoming the challenge. In this work, the spherical lignin particles obtained from organosolv lignin (OL) were prepared using the dialysis method with tetrahydrofuran (THF) or ethanol as the solvent. From the result, it was found that the types of lignin and solvent, initial lignin concentration, and stirring rate strongly affected the size of fabricated particles. Moreover, the preparation of lignin particles using THF as a solvent showed more uniform and symmetric spherical lignin particles. The stability of the particle dispersion was examined under various pH conditions. Moreover, lignin samples were also introduced into the poly(vinyl alcohol) (PVA) for the production of ultraviolet (UV)-blocking composite film. Mechanical and optical properties of composite film were also observed. As a result, the prepared lignin-PVA composite film showed great ultraviolet (UV) protective potential in both UVA and UVB regions.