This study reports on the effects of unmodified autohydrolyzed ethanol organosolv lignin (AH EOL) and modified autohydrolyzed ethanol organosolv lignin on the structural characteristics and antioxidant properties upon incorporation of p-hydroxyacetophenone (AHP EOL). The lignin samples isolated from black liquor of oil palm fronds (OPF) were evaluated and compared using various complementary analyses; FTIR, 1H and 13C NMR spectroscopy, 2D-NMR spectroscopy (HMBC and HSQC), CHN, GPC, HPLC and thermal analyses (TGA and DSC). Chemically modified organosolv lignin (AHP EOL) provided lignin with lower molecular weight (Mw), which has smaller fragments that leads to higher solubility rate in water in comparison to unmodified organosolv lignin, AH EOL (DAHP EOL: 19.8% > DAH EOL: 14.0%). It was evident that the antioxidant properties of modified organosolv lignin has better reducing power in comparison to the unmodified organosolv lignin. Therefore, the functionalization of lignin polymers enhanced their antioxidant properties and structural features towards a various alternative approach in lignin-based applications.
This study aimed to develop and characterize the calcium alginate films loaded with diclofenac sodium and other hydrophilic polymers with different degrees of cross-linking obtained by external gelation process. To the formed films different physicochemical evaluation were performed which showed an initial character of the films. The films produced by this external gelation process were found thicker (0.031-0.038 mm) and stronger (51.9-52.9 MPa) but less elastic (2.3%) than those non-cross-linked films (0.029 mm; 39.7 MPa; 4.4%). The lower water vapor permeability (WVP) values of the films were obtained where maximum level of crosslinking occurs. Composite films can be cross-linked in presence of external crosslinking agent to improve the quality of the produced matrices for various uses. The characterization of the film was performed using Differential Scanning Calorimetry (DSC) and Fourier-Transform Infrared Spectroscopy (FT-IR) analysis. The Scanning Electron Microscopy (SEM) study showed the morphology of treated composite films. The kinetic release studies showed a sustained release of the drug from the formulated films as it can be prolonged in composite film. The prepared biodegradable Ca-Alginate bio-composite film may be of clinical importance for its therapeutic benefit.
In this study, chitosan/polyvinyl alcohol/TiO2 nanofiber was fabricated via electrospinning at a pump rate of 1.5 mL/h and voltage 6 kV. Field-emission scanning electron microscopic images showed bead free finer nanofiber. Fourier transform infrared spectra proved the formation of strong bond among chitosan, polyvinyl alcohol and TiO2. X-ray powder diffraction showed that TiO2 became amorphous in the composite nanofiber. Toughness and thermal stability of the chitosan/PVA nanofibrous membrane was increased with addition TiO2. The chitosan/PVA/TiO2 nanofibrous membrane was stable at basic medium. But degraded in acidic and water medium after 93 and 162 h, respectively. The adsorption mechanism of congo red obeyed the Langmuir isotherm model. On the other hand, adsorption characteristic of methyl orange fitted well with both Langmuir and Freundlich isotherm models. The maximum adsorption capacity of the resulting membrane for congo red and methyl orange is 131 and 314 mg/g, respectively. However, a high dose of adsorbent was required for congo red.
A green regenerated superabsorbent hydrogel was fabricated with mixtures of dissolved oil palm empty fruit bunch (EFB) cellulose and sodium carboxymethylcellulose (NaCMC) in NaOH/urea system. The formation of hydrogel was aided with epichlorohydrin (ECH) as a crosslinker. The resultant regenerated hydrogel was able to swell >80,000% depending on the NaCMC concentrations. The hydrogel absorbed water rapidly upon exposure to water up to 48 h and gradually declined after 72 h. The crosslinked of covalent bond of COC between dissolved EFB cellulose (EFBC) with NaCMC was confirmed with Attenuated total reflectance Fourier transform infrared (ATR-FT-IR) spectroscopy. Crystallinity and thermal stability of the hydrogel samples were depended on the concentrations of NaCMC, crosslinking, and swelling process. The strength and stability of crosslinked network was studied by examining the gel fraction of hydrogel. This study explored the swelling ability and probable influenced factors towards physical and chemical properties of hydrogel.
The utilization of renewable and functional group enriched nano-lignin as bio-additve in fabricating composite has become the focus of attention worldwide. Herein, lignin nanoparticles in the form of hollow spheres with the diameter of the order of 138 ± 39 nm were directly prepared from agro-industrial waste (palm kernel shell) using recyclable tetrahydrofuran in an acidified aqueous system without any chemical modification steps. We then fabricated a new chitosan/nano-lignin composite material as highly efficient sorbent, as demonstrated by efficient removal (~83%) of methylene blue (MB) dye under natural pH conditions. The adsorption process obeyed pseudo-second-order kinetics and adequate fitting of the adsorption data using Langmuir model suggested a monolayer adsorption with a maximum adsorption capacity of 74.07 mg g-1. Moreover, thermodynamic study of the system revealed spontaneous and endothermic nature of the sorption process. Further studies revealed that chitosan composite with nano-lignin showed better performance in dye decontamination compared to native chitosan and chitosan/bulk lignin composite. This could essentially be attributed to synergistic effects of size particularity (nano-effect) and incorporated functionalities due to lignin nanoparticles. Recyclability study performed in four repeated adsorption/regeneration cycles revealed recyclable nature of as-prepared composite, whilst adsorption experiments using spiked real water samples indicated recoveries as high as 89%. Based on this study, as-prepared bio-nanocomposite may thus be considered as an efficient and reusable adsorptive platform for the decontamination of water supplies.
This research aimed to improve the stability of Chlorella-Alginate Beads (CABs) by zeolite molecular sieves 13X. Dissolution time of synthesized Zeolite-Algal-Alginate Beads (ZABs) in a chelating agent revealed a significant improvement on the beads stability (78.5 ± 0.5 min) compared to the control beads (51.5 ± 0.5 min) under the optimum conditions of zeolite/alginate (1.5:1), pH 5 and 2% of beads. Monitoring cell growth during 5 days of incubation showed good biocompatibility of zeolite 13X. Scanning electron microscopy (SEM) indicated rough surface and spherical shapes of ZABs. Energy dispersive X-ray spectroscopy (EDX) and Fourier transform infrared spectroscopy (FTIR) of ZABs confirmed the presence of zeolite 13X within the matrix. The zeta potential value of ZABs indicated that the beads were relatively stable. The findings of this research showed that zeolite molecular sieves 13X have the potential to improve the stability of algal-alginate beads compared to common beads.
In this work, a chitosan-modified nanofiber membrane was fabricated and used to examine the permeation characteristics of C-phycocyanin (CPC) obtained from Spirulina platensis. The effects of NaCl concentration (0.1-1.0 M), chitosan coupling pH (6-8), chitosan coupling concentration (0.1-3.0%), algal solution pH (6-8), algal mass concentration (0.1-1.0% dw/v), and membrane flux (4.08 × 10-2-2.04 × 10-1 mL/min·cm2) on the penetration performance of the membrane for CPC were investigated. The results show that the order of binding selectivity of the membrane for these proteins is contaminating proteins (TP) > allophycocyanin (APC) > CPC. TP and APC molecules were more easily adsorbed by the chitosan-modified membrane, and the CPC molecules most easily penetrated the membrane without being adsorbed, enhancing CPC purity. The purification factor and total mass flux were 3.3 fold and 66%, respectively, in a single step.
Silver nanoparticle was synthesized using D-glucosamine chitosan base as green reducing agent at elevated temperature in alkaline pH ranges. The excess of D-glucosamine chitosan base was used as it is both stabilizing and reducing agent at different pHs, regulates the shape and size of the silver nanoparticles. The progressive growth of silver nanoparticles was monitored by UV-Visible spectral studies. A sharp peak at 420 nm indicates the formation of spherical silver nanoparticles. The size and shape of silver nanoparticles were observed from Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) methods. The anisotropically grown nanoparticles were used as probe for Surface Enhanced Raman Studies (SERS) using ATP (4-aminothiophenol) as a model system. The catalytic behavior of silver nanoparticles was exploited for 4-nitrophenol reduction and observed that the reduction reaction follows pseudo first order kinetics with a rate constant 0.65 min. The antibacterial activity of silver nanoparticles was also tested for both gram-positive and -negative microorganisms, in which higher zone of inhibition was observed for gram negative microorganism.
Grafting of crosslinked chitosan with monomer, N-vinyl-2-pyrrolidone, has been carried out to investigate its adsorption capacity toward Orange G (OG) from aqueous solutions. The adsorption performance of modified chitosan (cts(x)-g-PNVP) was examined and compared with that of the unmodified chitosan. The effects of initial pH, contact time and initial dye concentration were investigated in a batch system. The experimental data were correlated with the Langmuir and Freundlich isotherm models. The maximum adsorption capacity of cts(x)-g-PNVP (63.7mgg-1) based on Langmuir equation was relatively higher than that of the unmodified chitosan (1.7mgg-1). The kinetic studies showed that the adsorption process was consistent with the pseudo-second order kinetic model. Interaction mechanisms between OG and cts(x)-g-PNVP were also proposed. The overall results suggested that the prepared cts(x)-g-PNVP stands a good candidate as adsorbent for removal of anionic dye from aqueous solutions.
A report on the de novo Whole Genome Sequence (WGS) of Marinobacter litoralis SW-45, a moderately salt-tolerant bacterium isolated from the seawater in Malaysia is presented. The strain has a genome size of 3.45 Mb and is capable of producing halophilic lipase, protease and esterase enzymes. Computational prediction of non-coding RNA (ncRNA) genes in M. litoralis SW-45 was performed using standalone software known as the non-coding RNA characterization (nocoRNAc). In addition, a phylogenetic tree showing the evolutionary relationship between the strain and other members of the genus Marinobacter was constructed using 16SrRNA sequence information. A total of 385 ncRNA transcripts, 1124 terminator region, and 2350 Stress Induced Duplex Destabilization sites were predicted. The current WGS shotgun project has provided the relevant genetic information that may be useful for the strain's improvement studies. This manuscript gives the first description of M. litoralis with a complete genome.
In the present study, high-methoxyl pectin (HMP) was extracted from Hylocereus polyrhizus peel's using physico-chemical process. In addition, the hypolipidemic activity of HMP was investigated at different concentration and time corresponding to its adsorption ability. FTIR and contact angle analysis were used to determine the sorbent characterization. A high degree of esterification (63.8%) and the contact angle (95.5°) confirmed hydrophobic nature and resulting bad wetting of the HMP extract, respectively. The methoxyl content in the pectin acted as an affinity-precursor of the pectin towards cholesterol due to its increased hydrophobicity. The maximum equilibrium uptake capacity of cholesterol of 370.5mg/g (0.96mmol/g) was observed by HMP. The experimental data showed good fitting for Freundlich isotherm equation and followed pseudo-first-order kinetic model with a correlation coefficient (R2) of 0.89-0.97 due to physisorption mechanism. Intra-particle model confirmed that the cholesterol sorption rate by HMP was significantly influenced by external mass transfer (surface diffusion) and intra-particle diffusion (diffusion control). It was also revealed that the HMP extracted from Hylocereus polyrhizus peels possess a high affinity towards cholesterol, making it an ideal hypolipidemic agent.
Nanofiber membrane chromatography integrates liquid membrane chromatography and nanofiber filtration into a single-step purification process. Nanofiber membrane can be functionalised with affinity ligands for promoting binding specificity of membrane. Dye molecules are a good affinity ligand for nanofiber membrane due to their low cost and high binding affinity. In this study, a dye-affinity nanofiber membrane (P-Chitosan-Dye membrane) was prepared by using polyacrylonitrile nanofiber membrane modified with chitosan molecules and immobilized with dye molecules. Reactive Orange 4, commercially known as Procion Orange MX2R, was found to be the best dye ligand for membrane chromatography. The binding capacity of P-Chitosan-Dye membrane for lysozyme was investigated under different operating conditions in batch mode. Furthermore, desorption of lysozyme using the P-Chitosan-Dye membrane was evaluated systematically. The recovery percentage of lysozyme was found to be ~100%. The optimal conditions obtained from batch-mode study were adopted to develop a purification process to separate lysozyme from chicken egg white. The process was operated continuously using the membrane chromatography and the characteristic of the breakthrough curve was evaluated. At a lower flow rate (i.e., 0.1 mL/min), the total recovery of lysozyme and purification factor of lysozyme were 98.59% and 56.89 folds, respectively.
Human papillomavirus (HPV) is a double-standard DNA virus, as well as the source of infection to the mucous membrane. It is a sexually transmitted disease that brings the changes in the cervix cells. Oncogenes, E6 and E7 play a pivotal role in the HPV infection. Identifying these genes to detect HPV strains, especially a prevalent HPV16 strain, will bring a great impact. Among different sensing strategies for pathogens, the dielectric electrochemical biosensor shows the potential due to its higher sensitivity. In this research, HPV16-E7 DNA sequence was detected on the carbodiimidazole-modified interdigitated electrode (IDE) surface with the detection limit of 1 fM. To enhance the sensitivity, the target sequence was conjugated on gold nanoparticle (GNP) and attained detection to the level of 10 aM. This produced ~100 folds improvement in detecting HPV16-E7 gene and 4 folds increment in the current flow. The stability of HPV16-E7 DNA sequences on GNP was verified by the salt-induced GNP aggregation. The current system has shown the higher specificity by comparing against non-complementary and triple-mismatched DNA sequences of HPV16-E7. This demonstration in detecting HPV16-E7 using dielectric IDE sensing system with a higher sensitivity can be recommended for detecting a wide range of disease-causing DNA-markers.
The current study is motivated by the strict environmental regulations regarding the utilization and consumption of ecofriendly materials. In this context, the aim of this study has been to prepare and characterize different date palm tree (Phoenix dactylifera L.) fibers processed through the conventional water retting method. The chemical, elemental, crystallinity, thermal and morphological characterization of trunk (DPTRF), leaf stalk (DPLST), sheath or leaf sheath (DPLSH) and fruit bunch stalk (DPFBS) fibers was carried out. Chemical analysis revealed that the four types of date palm fibers display noteworthy differences in the content of cellulose, hemicellulose and lignin. Also, the amount of calcium is relatively high in all the date palm fibers; besides this, DPTRF exhibited 69.2% crystallinity, which is lower than that of DPLSH with 72.4% crystallinity. Moreover, DPLST and DPFBS fibers are more thermally stable (higher thermal degradation temperature) than DPTRF and DPLSH samples. Morphological analysis revealed that the fracture surface of DPFBS was relatively rougher, which would probably lead to increased bonding strength with polymers in composites. Overall, we conclude that DPFBS would be promising alternative sustainable and biomass material for the isolation of respective cellulose nanofibers and cellulose nanocrystals as potential reinforcement in polymer composites.
Silylated cellulose has been successfully synthesized using TEMPO-oxidized nanocellulose (TEMPO-NC) from oil palm empty fruit bunch and 3-aminopropyltriethoxysilane (APS) in an ethanol/water medium at a low curing temperature of 40 °C as compared to those reported in the literature of above 100 °C. Confirmation of the grafting process can be seen from the new FTIR peaks at 810 cm-1 and 749 cm-1 which are attributed to the SiC stretching and SiC, and new 13C NMR signals at 10.3, 21.7 and 42.7 ppm which are assigned to C7, C8, and C9 of the silylated TEMPO-NC. The decrease in the intensities of the cellulose peaks of C2, C3, C6 and C6' in the 13C NMR indicates that silylation not only occurs on the hydroxyls, but more importantly on the TEMPO-NC carboxylic moiety of C6', which is postulated as being the primary factor for this successful modification. This is further corroborated by the emergence of three signals at 43, 61, and 69 ppm in the 29Si NMR spectrum which corresponds to Si(OSi)(OR)2R', Si(OSi)2(OR)R', and Si(OSi)3R' units respectively. Additional evidence is provided by the EDX which shows an increase in Si weight percent of 1.94 after reaction. This silylated cellulose from OPEFB has the potentials to be used as bionanocomposite reinforcing elements.
In this work, chitosan (Chi) was cross-linked with glyoxal (Gly) and deposited onto glass plate to be a superior adsorbent film for two structurally different reactive orange 16 (RO-16) and methyl orange (MO) dyes by using non-conventional adsorption system without filtration process. The characterizations indicate that the cross-linked chitosan-glyoxal (Chi-Gly) film has a low swelling index, high adherence strength on glass plate, amine group (NH2) content was 32.52%, and pHpzc of ∼6.0 indicating a negative surface charge occurs above pHpzc. The adsorption isotherm data of RO-16 and MO by Chi-Gly film were in agreement with Langmuir isotherm, with maximum adsorption capacities of 1554.3 mg/g and 1451.9 mg/g, respectively. The pseudo-first-order kinetic model best described the kinetic data. The adsorption process was spontaneous and exothermic in nature at Chi-Gly film thickness of 8.55 μm, and pH ~3. The mechanism of adsorption included mainly electrostatic attractions, dipole-dipole hydrogen bonding interactions, n-π stacking attractions, and Yoshida H-bonding. This study reveals that immobilized Chi-Gly film as a good candidate for adsorption of reactive and acid dyes as it does not require any filtration process and adsorbent recovery during and post-adsorption process.
The objective of this study is to investigate the effects of limited moisture content and storing temperature on the retrogradation of rice starch. Starch was gelatinized in various moisture contents (30-42%) and rice paste was stored at different temperatures (4 °C, 15 °C, 30 °C, -18/30 °C and 4/30 °C). X-ray diffraction (XRD) analysis revealed that after retrogradation, the crystalline type of rice starch changed from A-type to B + V type. The B-type crystallinity of retrograded rice starch under 30 °C was the highest among the five temperature conditions, and an increase in B-type crystallinity with increasing moisture content was observed. Differential scanning calorimetry (DSC) results revealed that rice starch retrogradation consists of recrystallization of amylopectin and amylose, and is mainly attributed to amylopectin. The higher moisture content was favorable for amylopectin recrystallization, whereas the moisture content had little effect on the amylose recrystallization. The optimal temperature for amylopectin and amylose recrystallization was 4 °C and 15 °C, respectively. The amylopectin recrystallization enthalpy of rice starch stored at 4/30 °C was mediated between 4 °C and 30 °C but always higher than that at -18/30 °C. On the whole, after being heated at 42% moisture content and stored at 4 °C, rice starch showed the maximum total retrogradation enthalpy (8.44 J/g).
The cellulose microfibers (CMF) from water hyacinth (WH) fiber as a filler in sago starch (SS) biocomposites was investigated. The CMF was isolated by pulping, bleaching and acid hydrolysis methods. The addition of CMF in sago matrix was varied i.e. 0, 5, 10, 15 and 20 wt%. Biocomposites were made by using solution casting and glycerol as a plasticizer. The biocomposites were also determined by tensile test, FTIR, X-Ray, thermogravimetric, SEM, and soil burial tests. The results show that the SS15CMF sample has the highest tensile strength of 10.23 MPa than those other samples. Scanning Electron Microscope (SEM) images show that the strong interaction was formed between CMF WH and matrix. Fourier Transform Infra-red (FTIR) indicated that the functional group of biocomposites was a hydrophilic cluster. The addition of CMF WH in sago starch biocomposites lead to the moisture barrier, crystallinity, and thermal stability increased; it is due to the pure sago starch film was more rapidly degraded than its biocomposites.
Rod-shape particles have been a good drug carrier due to the long circulatory time, tumor accumulation and high cellular uptake in body. Acid-hydrolysed nanocrystalline cellulose (NCC) from empty fruit bunch exhibited a width of 13-30nm and a length of 150-360nm in rod-shape structure. NCC holds good potential as a bio-based drug carrier owing to its biodegradability and biocompatibility. Fourier-transform infrared spectroscopy results confirmed the binding of curcumin onto the NCC modified with tannic acid (TA) and decylamine (DA). TA-DA modification rendered NCC with a higher level of hydrophobicity, as evidenced by a substantial increase in contact angle from 45° to 73°. The modified NCC had the curcumin-binding efficiency in the range of 95-99%, which is at least twofold higher than the unmodified NCC at any curcumin concentration tested. This remarkable curcumin-binding effciency was comparable to that of commercialized NCC from wood-based origin. This work suggests NCC as a superior and sustainable drug carrier, while TA-DA modification is a promising approach to alter the surface property of NCC for an efficient binding of curcumin.
Fucoidan is a marine sulfated polysaccharide, which is extracted from brown seaweed that has a wide range of bioactivities including anti-cancer properties. However, the underlying mechanism of fucoidan on its anti-cancer and apoptotic activity against colon cancer cell line Caco-2 remains to be elucidated. Hence, the present study evaluated the cytotoxicity, apoptotic and anti-cancer activity of fucoidan extracted from brown seaweed Sargassum cinereum against Caco-2 cell line. Cytotoxicity, morphological examination of nuclei, mitochondrial membrane potential, flow cytometry, reactive oxygen species (ROS) formation and detection of apoptotic efficacy of fucoidan were assessed by different assay protocols. Fucoidan inhibited growth of Caco-2 cells in a dose-dependent manner. IC50 concentration of fucoidan was found to be 250 μg/ml. AO/EB, Hoechst and Annexin V/PI staining confirmed the apoptosis induced by fucoidan in Caco-2 cells. Fucoidan was also found to increase ROS production and augment mitochondrial membrane permeability. The findings of the study suggest that fucoidan exerts potent anti-cancer and apoptotic effect on Caco-2 cells by enhancing ROS production. Thus, fucoidan may be used as a promising therapeutic regimen against various cancer cell types.