Natural hydro-low-transition-temperature mixtures (NH-LTTMs) tend to be the most favorable next-generation green solvents for biomass pretreatment, as they are cheap and environmental friendly. The amount of water bound into the NH-LTTMs greatly affected their thermal stability, whereby the highest thermal stability was observed with the water content of 7.6 wt%. It is worth noting that, the highest molar transition energy of NH-LTTMs (47.57 kcal mol-1), which indicated the highest solubility, was optimized with the molar ratio of hydrogen bond donor (HBD)-hydrogen bond acceptor (HBA)-water (2:4:3) at a temperature of 60 °C. Hydrogen bonding networks of the NH-LTTMs, which led to the dissolution of biomass, were confirmed by the alteration in the peaks of the involved bonds and resonance signal to lower field through FTIR and 1H NMR spectra, respectively. The components evidenced in high-resolution mass spectra of extracted lignin showed its high potential to be valorized into useful fuels and chemicals.
Non-healing wounds have placed an enormous stress on both patients and healthcare systems worldwide. Severe complications induced by these wounds can lead to limb amputation or even death and urgently require more effective treatments. Electrospun scaffolds have great potential for improving wound healing treatments by providing controlled drug delivery. Previously, we developed fibrous scaffolds from complex carbohydrate polymers [i.e. chitin-lignin (CL) gels]. However, their application was limited by solubility and undesirable burst drug release. Here, a coaxial electrospinning is applied to encapsulate the CL gels with polycaprolactone (PCL). Presence of a PCL shell layer thus provides longer shelf-life for the CL gels in a wet environment and sustainable drug release. Antibiotics loaded into core-shell fibrous platform effectively inhibit both gram-positive and -negative bacteria without inducting observable cytotoxicity. Therefore, PCL coated CL fibrous gel platforms appear to be good candidates for controlled drug release based wound dressing applications.
Cellulose nanocrystals (CNC) have received great research attention since the last few decades due to their extraordinary properties and wide range of applications. In this study, a sustainable and cost-effective method for the synthesis of lignin-containing cellulose nanocrystals (LCNC) from oil palm empty fruit bunch (EFB) is presented. This method is able to retain the lignin in EFB and manifest the properties of lignin. The proposed synthesis process is simpler than the conventional method of producing lignin-coated CNC by first removing the lignin to synthesize CNC followed by the re-coating of lignin on the structure. The samples of LCNC were characterized by transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy and water contact angle analysis. In addition, by altering the acid concentration during acid hydrolysis process (53% - 60% H2SO4), both surface hydrophobicity (66.0° - 75.1°) and length of LCNC (467 nm-177 nm) can be altered wherein a higher concentration of acid resulted in a greater contact angle and a shorter length of LCNC. Cost and energy analysis deduced that the proposed synthesis method saved about 62% of the total material cost and 80% less energy as compared to the synthesis of lignin-coated CNC.
The effect of corrosion inhibition of low carbon steel in water based medium containing lignin was investigated via weight loss method. The evolution of surface morphology has been carried out for 7 to 42 days via optical microscopy (OM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron microscopy (XPS). Immersion of metal specimen without lignin shows that significant increase in the surface roughness. The longer the immersion time, the more the oxide crust formed. The surface degradation of metal specimen was well protected by immersion in lignin solution. A protective layer containing of lignin was formed on the surface of metal specimens after 7 and 21 days immersion. The corrosion inhibition gives about 13 and 53% inhibition for both 7 and 21 days immersion, respectively. The protective layers were spalling and separated from the metal surface after 42 days immersion in lignin solution possibly due to the increase in corrosion attack after long time immersion according to the increase in dissolved oxygen and may also due to the thermal mismatch between oxide and substrate. The adsorption of protective layer containing lignin was temporary adsorbed on the surface.
Nanofibrillated cellulose (NFCs) were extracted from sugar palm fibres (SPS) in two separate stages; delignification and mercerization to remove lignin and hemicellulose, respectively. Subsequently, the obtained cellulose fibres were then mechanically extracted into nanofibres using high pressurized homogenization (HPH). The diameter distribution sizes of the isolated nanofibres were dependent on the cycle number of HPH treatment. TEM micro-images displayed the decreasing trend of NFCs diameter, from 21.37 to 5.5 nm when the number of cycle HPH was increased from 5 to 15 cycles, meanwhile TGA and XRD analysis showed that the degradation temperature and crystallinity of the NFCs were slightly increased from 347 to 347.3 °C and 75.38 to 81.19% respectively, when the number of cycles increased. Others analysis also were carried on such as FT-IR, FESEM, AFM, physical properties, zeta potential and yield analysis. The isolated NFCs may be potentially applied in various application, such as tissue engineering scaffolds, bio-nanocomposites, filtration media, bio-packaging and etc.
Fungi of the Trichoderma species are valued industrial enzymes in support of the 'zero-waste' technology to convert agro-industrial biomass into valuable products, i.e. nanocellulose (NC). In this study, an in silico approach using substrate docking and molecular dynamic (MD) simulation was used to predict the order of which the multilayers of cellulosic polymers, i.e. lignin, hemicellulose and cellulose in oil palm leaves (OPL) are degraded by fungal enzymes, endocellulase and exocellulase. The study aimed to establish the catalytic tendencies of the enzymes to optimally degrade the cellulosic components of OPL for high yield production of NC. Energy minimized endocellulase and exocellulase models revealed satisfactory scores of PROCHECK (90.0% and 91.2%), Verify3D (97.23% and 98.85%) and ERRAT (95.24% and 91.00%) assessments. Active site prediction by blind docking, COACH meta-server and multiple sequence alignment indicated the catalytic triads for endocellulase and exocellulase were Ser116-His205-Glu249 and Ser382-Arg124-Asp385, respectively. Binding energy of endocellulase docked with hemicellulose (-6.0 kcal mol-1) was the most favourable followed by lignin (-5.6 kcal mol-1) and cellulose (-4.4 kcal mol-1). Exocellulase, contrarily, bonded favorably with lignin (-8.7 kcal mol-1), closely followed by cellulose (-8.5 kcal mol-1) and hemicellulose (-8.4 kcal mol-1). MDs simulations showed that interactions of complexes, endocellulase-hemicellulose and the exocellulase-cellulose being the most stable. Thus, the findings of the study successfully identified the specific actions of sugar-acting enzymes for NC production. Communicated by Ramaswamy H. Sarma.
Poplar trees rapidly yield wood and are therefore suitable as a biofuel feedstock; however, the quality of poplar is modest, and the profitability of poplar cultivation depends on the efficiency of the harvesting process. This study offers a simple and sustainable technique to harvest lignocellulosic resources from poplar for bioethanol production. The proposed two-step pretreatment method increased the surface lignin content and decreased the surface polysaccharide content. The cellulose content increased to 54.9% and the xylan content decreased to 6.7% at 5% AC. The cellulose yield of poplar residues (Populus L.) reached 65.5% by this two-step acetic acid (AC) and sodium sulphite (SS) treatment method. Two-step pretreatment using 5% AC and 4% SS obtained a recovery of nearly 80% of the total available fermentable sugar. The surface characterization showed a higher porosity in treated samples, which improved their hydrolysability. This method decreased the amount of lignin in plant biomass, making it applicable for further wood resource recovery or waste recycling for biorefinery purposes at very low costs.
The chemical composition and anatomical characteristics on lignin distribution of rattan waste were analyzed to determine its suitability to be used in binderless board fabrication. The chemical composition was analyzed by using TAPPI methods. Observation and determination of lignin distribution and board structure were executed by using optical microscopy (OM) and scanning electron microscope (SEM). High amount of hemicellulose, cellulose and lignin content found in rattan waste chemical composition is seen to help in binderless board fabrication. The micrographs revealed that the rattan has fine structural construction that helps in producing good qualities of binderless boards with particular manufacturing parameters.
Highly stable and dispersible nanocrystalline cellulose (NCC) was successfully isolated from oil palm empty fruit bunch microcrystalline cellulose (OPEFB-MCC), with yields of 93% via a sono-assisted TEMPO-oxidation and a subsequent sonication process. The sono-assisted treatment has a remarkable effect, resulting in an increase of more than 100% in the carboxylate content and a significant increase of approximately 39% in yield compared with the non-assisted process. TEM images reveal the OPEFB-NCC to have rod-like crystalline morphology with an average length and width of 122 and 6nm, respectively. FTIR and solid-state 13C-NMR analyses suggest that oxidation of cellulose chain hydroxyl groups occurs at C6. XRD analysis shows that OPEFB-NCC consists primarily of a crystalline cellulose I structure. Both XRD and 13C-NMR indicate that the OPEFB-NCC has a lower crystallinity than the OPEFB-MCC starting material. Thermogravimetric analysis illustrates that OPEFB-NCC is less thermally stable than OPEFB-MCC but has a char content of 46% compared with 7% for the latter, which signifies that the carboxylate functionality acts as a flame retardant.
In current practice, oil palm frond leaflets and stems are re-used for soil nutrient recycling, while the petioles are typically burned. Frond petioles have high commercialization value, attributed to high lignocellulose fiber content and abundant of juice containing free reducing sugars. Pressed petiole fiber is the subject of interest in this study for the production of lignocellulolytic enzyme. The initial characterization showed the combination of 0.125 mm frond particle size and 60% moisture content provided a surface area of 42.3 m2/g, porosity of 12.8%, and density of 1.2 g/cm3, which facilitated fungal solid-state fermentation. Among the several species of Aspergillus and Trichoderma tested, Aspergillus awamori MMS4 yielded the highest xylanase (109 IU/g) and cellulase (12 IU/g), while Trichoderma virens UKM1 yielded the highest lignin peroxidase (222 IU/g). Crude enzyme cocktail also contained various sugar residues, mainly glucose and xylose (0.1-0.4 g/L), from the hydrolysis of cellulose and hemicellulose. FT-IR analysis of the fermented petioles observed reduction in cellulose crystallinity (I900/1098), cellulose-lignin (I900/1511), and lignin-hemicellulose (I1511/1738) linkages. The study demonstrated successful bioconversion of chemically untreated frond petioles into lignin peroxidase and xylanase-rich enzyme cocktail under SSF condition.
A laboratory-scale study of bioconversion of local lignocellulosic material, oil palm biomass (OPB) was conducted by evaluating the enzyme production through microbial treatment in solid state bioconversion (SSB). OPB in the form of empty fruit bunches (EFB) was used as a solid substrate and treated with the white-rot fungus, Phanerochaete chrysosporium, to produce ligninase. The results showed that the highest ligninase activity of 400.27 U/liter was obtained at day 12 of fermentation. While the optimum study indicated the enzyme production of 1472.8 U/liter with moisture content of 50%, 578.7 U/liter with 10% v/w of inoculum size, and 721.8 U/liter with co-substrate concentration of 1% (w/w) at days 9, 9 and 12 of fungal treatment, respectively. The parameters glucosamine and reducing sugar were observed to evaluate the growth and substrate utilization in the experiment.
Lignosulfonate (LS) is a by-product obtained during sulfite pulping process and is commonly used as a growth enhancer in plant growth. However, the underlying growth promoting mechanism of LS on shoot growth remains largely unknown. Hence, this study was undertaken to determine the potential application of eco-friendly ion-chelated LS complex [sodium LS (NaLS) and calcium LS (CaLS)] to enhance recalcitrant indica rice MR 219 shoot growth and to elucidate its underlying growth promoting mechanisms. In this study, the shoot apex of MR 219 rice was grown on Murashige and Skoog medium supplemented with different ion chelated LS complex (NaLS and CaLS) at 100, 200, 300 and 400 mg/L The NaLS was shown to be a better shoot growth enhancer as compared to CaLS, with optimum concentration of 300 mg/L. Subsequent comparative proteomic analysis revealed an increase of photosynthesis-related proteins [photosystem II (PSII) CP43 reaction center protein, photosystem I (PSI) iron-sulfur center, PSII CP47 reaction center protein, PSII protein D1], ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco), carbohydrate metabolism-related proteins (glyceraldehyde-3-phosphate dehydrogenase 3, fructose-bisphosphate aldolase) and stress regulator proteins (peptide methionine sulfoxide reductase A4, delta-1-pyrroline-5-carboxylate synthase 1) abundance in NaLS-treated rice as compared to the control (MSO). Consistent with proteins detected, a significant increase in biochemical analyses involved in photosynthetic activities, carbohydrate metabolism and protein biosynthesis such as total chlorophyll, rubisco activity, total sugar and total protein contents were observed in NaLS-treated rice. This implies that NaLS plays a role in empowering photosynthesis activities that led to plant growth enhancement. In addition, the increased in abundance of stress regulator proteins were consistent with low levels of peroxidase activity, malondialdehyde content and phenylalanine ammonia lyase activity observed in NaLS-treated rice. These results suggest that NaLS plays a role in modulating cellular homeostasis to provide a conducive cellular environment for plant growth. Taken together, NaLS improved shoot growth of recalcitrant MR 219 rice by upregulation of photosynthetic activities and reduction of ROS accumulation leading to better plant growth.
This study demonstrated the effect of two-pot sequential pretreatment, comprising of ultrasound assisted deep eutectic solvent (DES) with the aim to investigate the effects of ultrasound amplitude and duration in enhancing delignification. Oil palm fronds (OPF) were ultrasonicated in a water medium, followed by a pretreatment using DES (choline chloride:urea). Fourier transform infra-red spectroscopy, X-ray diffraction, field emission scanning electron microscope, Brunauer-Emmet-Teller and solubilised lignin concentration were conducted to confirm the effectiveness of ultrasound assisted DES on the pretreatment of OPF. The recommended ultrasound conditions were determined to be 70% amplitude and duration of 30 min, where the sequential DES pretreatment was able to reduce lignin content of OPF to 14.01%, while improving xylose recovery by 58%.
In this study, a novel Type II deep eutectic solvent (DES) namely, choline chloride:copper(II) chloride dihydrate (ChCl:CuCl2·2H2O) was used to pretreat oil palm fronds (OPFs). The sequential pretreatment with alkaline hydrogen peroxide (0.25 vol%, 90 min) at ambient conditions and a Type II DES (90 °C, 3 h) at a later stage resulted in a delignification of 55.14% with high xylan (80.79%) and arabinan (98.02%) removals. The characterizations of pretreated OPFs confirmed the excellent performance of DES in OPF fractionation. Thus, the application of a Type II DES at ambient pressure and relatively lower temperature was able to improve the lignin and hemicellulose removals from OPFs.
Recently, second-generation bio-ethanol (SGB), which utilizes readily available lignocellulosic biomass has received much interest as another potential source of liquid biofuel comparable to biodiesel. Thus the aim of this paper is to determine the exergy efficiency and to compare the effectiveness of SGB and palm methyl ester (PME) processes. It was found that the production of bio-ethanol is more thermodynamically sustainable than that of biodiesel as the net exergy value (NExV) of SGB is 10% higher than that of PME. Contrarily, the former has a net energy value (NEV) which is 9% lower than the latter. Despite this, SGB is still strongly recommended as a potential biofuel because SGB production can help mitigate several detrimental impacts on the environment.
Sago pith residue is one of the most abundant lignocellulosic biomass which can serve as an alternative cheap substrate for fermentable sugars production. This residue is the fibrous waste left behind after the starch extraction process and contains significant amounts of starch (58%), cellulose (23%), hemicellulose (9.2%) and lignin (3.9%). The conversion of sago pith residue into fermentable sugars is commonly performed using cellulolytic enzymes or known as cellulases. In this study, crude cellulases were produced by two local isolates, Trichoderma asperellum UPM1 and Aspergillus fumigatus, UPM2 using sago pith residue as substrate. A. fumigatus UPM2 gave the highest FPase, CMCase and β-glucosidase activities of 0.39, 23.99 and 0.78 U/ml, respectively, on day 5. The highest activity of FPase, CMCase and β-glucosidase by T. asperellum UPM1 was 0.27, 12.03 and 0.42 U/ml, respectively, on day 7. The crude enzyme obtained from A. fumigatus UPM2 using β-glucosidase as the rate-limiting enzyme (3.9, 11.7 and 23.4 IU) was used for the saccharification process to convert 5% (w/v) sago pith residue into reducing sugars. Hydrolysis of sago pith residue using crude enzyme containing β-glucosidase with 23.4 IU, produced by A. fumigatus UPM2 gave higher reducing sugars production of 20.77 g/l with overall hydrolysis percentage of 73%.
Oil palm empty fruit bunch (EFB) was pretreated by Formiline process to overcome biomass recalcitrance and obtain hemicellulosic syrup and lignin. Higher formic acid concentration led to more lignin removal but also higher degree of cellulose formylation. Cellulose digestibility could be well recovered after deformylation with a small amount of lime. After digested by enzyme loading of 15 FPU+10 CBU/g solid for 48 h, the polysaccharide conversion could be over 90%. Simultaneous saccharification and fermentation (SSF) results demonstrated that ethanol concentration reached 83.6 g/L with approximate 85% of theoretic yield when performed at an initial dry solid consistency of 20%. A mass balance showed that via Formiline pretreatment 0.166 kg of ethanol could be produced from 1 kg of dry EFB with co-production of 0.14 kg of high-purity lignin and 5.26 kg hemicellulosic syrup containing 2.8% xylose. Formiline pretreatment thus can be employed as an entry for biorefining of EFB.
The potential for the transformation of lignocellulosic biomass into valuable commodities is rapidly growing through an environmentally sustainable approach to harness its abundance, cost-effectiveness, biodegradability, and environmentally friendly nature. Ionic liquids (ILs) have received considerable and widespread attention as a promising solution for efficiently dissolving lignocellulosic biomass. The fact that ILs can act as solvents and reagents contributes to their widespread recognition. In particular, ILs are desirable because they are inert, non-toxic, non-flammable, miscible in water, recyclable, thermally and chemically stable, and have low melting points and outstanding ionic conductivity. With these characteristics, ILs can serve as a reliable replacement for traditional biomass conversion methods in various applications. Thus, this comprehensive analysis explores the conversion of lignocellulosic biomass using ILs, focusing on main components such as cellulose, hemicellulose, and lignin. In addition, the effect of multiple parameters on the separation of lignocellulosic biomass using ILs is discussed to emphasize their potential to produce high-value products from this abundant and renewable resource. This work contributes to the advancement of green technologies, offering a promising avenue for the future of biomass conversion and sustainable resource management.
Oil palm (Elaeis guineensis Jacq.) is one of the most planted trees in Malaysia for the palm oil production. Thus, solid biomass had been generated from this industry such as empty fruit bunch, shell, mesocarp fibre, frond and trunk produced that causes problematic to the nation and expected to escalate up to 85-110 million tonnes by 2020. Besides that, palm oil mill effluent and excessive steam also generated from the production of palm oil. In situ hydrothermal pretreatment means the utilisation of excessive steam produced by the oil palm mill and at the same time, generating value added product as well as reducing the biomass. Oil palm biomass is rich in lignocellulosic materials which comprised of lignin, hemicellulose and cellulose. Refinement of lignocellulosic from oil palm biomass can be utilised to form fermentable sugar, bioethanol and other potential chemicals. Recalcitrant property of lignocellulosic reduces the ability of enzymes to penetrate, thus pretreatment is required prior to hydrolysis process. Pretreatment can be either physical, chemical, biological or combined. In this review paper, three types of hydrothermal pretreatment were discussed as suitable in situ pretreatment process for oil palm biomass; in palm oil mill. The suitability was measured based on the availability of excess steam and energy in the mill. Furthermore, physicochemical pretreatment also facilitate the saccharification process, whereby it loosened the lignocellulose structure and increase the surface area. The effects and factors in choosing right pretreatment are highlighted in this paper.
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.