New and emerging demand for polyurethane (PU) continues to rise over the years. The harmful isocyanate binding agents and their integrated PU products are at the height of environmental concerns, in particular PU (macro and micro) pollution and their degradation problems. Non-isocyanate poly(hydroxy urethane)s (NIPUs) are sustainable and green alternatives to conventional PUs. Since the introduction of NIPU in 1957, the market value of NIPU and its hybridized materials has increased exponentially in 2019 and is expected to continue to rise in the coming years. The secondary hydroxyl groups of these NIPU's urethane moiety have revolutionized them by allowing for adequate pre/post functionalization. This minireview highlights different strategies and advances in pre/post-functionalization used in biobased NIPU. We have performed a comprehensive evaluation of the development of new ideas in this field to achieve more efficient synthetic biobased hybridized NIPU processes through selective and kinetic understanding.
As the population increases, energy demands continue to rise rapidly. In order to satisfy this increasing energy demand, biogas offers a potential alternative. Biogas is economically viable to be produced through anaerobic digestion (AD) from various biomass feedstocks that are readily available in Malaysia, such as food waste (FW), palm oil mill effluent (POME), garden waste (GW), landfill, sewage sludge (SS) and animal manure. This paper aims to determine the potential feedstocks for biogas production via AD based on their characteristics, methane yield, kinetic studies and economic analysis. POME and FW show the highest methane yield with biogas yields up to 0.50 L/g VS while the lowest is 0.12 L/g VS by landfill leachate. Kinetic study shows that modified Gompertz model fits most of the feedstock with R 2 up to 1 indicating that this model can be used for estimating treatment efficiencies of full-scale reactors and performing scale-up analysis. The economic analysis shows that POME has the shortest payback period (PBP), highest internal rate of return (IRR) and net present value (NPV). However, it has already been well explored, with 93% of biogas plants in Malaysia using POME as feedstock. The FW generation rate in Malaysia is approximately 15,000 tonnes per day, at the same time FW as the second place shows potential to have a PBP of 5.4 years and 13.3% IRR, which is close to the results achieved with POME. This makes FW suitable to be used as the feedstock for biogas production.
Transdermal drug delivery is used to deliver a drug by eliminating the first-pass metabolism, which increases the bioavailability of the drug. The present study aims to formulate the chitosan-tamarind seed polysaccharide composite films and evaluate for the delivery of protein/peptide molecules. Nine formulations were prepared and evaluated by using different parameters, such as physical appearance, folding endurance, thickness of film, surface pH, weight variation, drug content, surface morphology, percentage moisture intake and uptake, drug release kinetics, and drug permeability. The film weight variance was observed between 0.34 ± 0.002 to 0.47 ± 0.003 g. The drug level of the prepared films was found to be between 96 ± 1.21 and 98 ± 1.33μg. Their intake of moisture ranged between 2.83 ± 0.002 and 3.76 ± 0.001 (%). The moisture absorption of the films ranged from 5.33 ± 0.22 to 10.02 ± 0.61 (%). SEM images revealed a smooth film surface, while minor cracks were found in the film after permeation tests. During the first 4 days, drug release was between 13.75 ± 1.64% and 22.54 ± 1.34% and from day 5 to day 6, it was between 72.67 ± 2.13% and 78.33 ± 3.13%. Drug permeation during the first 4 days was 15.78 ± 1.23 %. Drug permeation (%) during the first 4 days was between 15.78 ± 1.23 and 22.49 ± 1.29 and from day 5 to day 6, it was between 71.49 ± 3.21 and 77.93 ± 3.20.
The adsorption of residue oil from palm oil mill effluent (POME) using chitosan powder and flake has been investigated. POME contains about 2g/l of residue oil, which has to be treated efficiently before it can be discharged. Experiments were carried out as a function of different initial concentrations of residue oil, weight dosage, contact time and pH of chitosan in powder and flake form to obtain the optimum conditions for the adsorption of residue oil from POME. The powder form of chitosan exhibited a greater rate compared to the flake type. The results obtained showed that chitosan powder, at a dosage of 0.5g/l, 15min of contact time and a pH value of 5.0, presented the most suitable conditions for the adsorption of residue oil from POME. The adsorption process performed almost 99% of residue oil removal from POME. Equilibrium studies have been carried out to determine the capacity of chitosan for the adsorption of residue oil from POME using the optimum conditions from the flocculation at different initial concentrations of residue oil. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms and isotherm constants. Equilibrium data fitted very well with the Freundlich model. The pseudo first- and second-order kinetic models and intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The experimental data fitted well with the second-order kinetic model, which indicates that the chemical sorption is the rate-limiting step, i.e. chemisorption between residue oil and chitosan. The significant uptake of residue oil on chitosan was further proved by BET surface area analysis and SEM micrographs.
The presence of heavy metal and radionuclides in water bodies has been a long-lasting environmental problem which results in many undesirable consequences. In this framework, the biosorption process, which uses inexpensive and naturally produced material such as alginate, is an alternative technology in the environmental remediation. This review provides relevant and recent literature regarding the application of alginate and its derivatives on removal of various heavy metal ions and radionuclides. The effects of process variables such as solution pH, adsorbent dosage, metal ion concentration, contact time, temperature and co-existing ions used in batch studies in addition to kinetic, isothermal models as well as thermodynamic that fit the adsorption experimental data are critically discussed. This review also includes mechanisms involved during adsorption process. Furthermore, future research needs for the removal of contaminants by alginate-based materials with the aims of improving their adsorption performance and their practical applications are commented.
Multi-particulate Dome matrix with sustained-release melatonin and delayed-release caffeine was designed to restore jet lag sleep-wake cycle. The polymeric pellets were produced using extrusion-spheronization technique and fluid-bed coated when applicable. The compact and Dome module were produced by compressing pellets with cushioning agent. Dome matrix was assembly of modules with pre-determined compact formulation and drug release characteristics. The physicochemical and in vivo pharmacokinetics of delivery systems were examined. Melatonin loaded alginate/chitosan-less matrix exhibited full drug release within 8 h gastrointestinal transit with low viscosity hydroxypropymethylcellulose as cushioning agent. The cushioning agent reduced burst drug release and omission of alginate-chitosan enabled full drug release. Delayed-release alginate-chitosan caffeine matrix was not attainable through polymer coating due to premature coat detachment. Admixing of cushioning agent high viscosity hydroxypropylmethylcellulose and high viscosity ethylcellulose (9:1 wt ratio) with coat-free caffeine loaded particulates introduced delayed-release response via hydroxypropylmethylcellulose swelled in early dissolution phase and ethylcellulose sustained matrix hydrophobicity at prolonged phase. The caffeine was released substantially in colonic fluid in response to matrix polymers being degraded by rat colonic content. Dome matrix with dual drug release kinetics and modulated pharmacokinetics is produced to introduce melatonin-induced sleep phase then caffeine-stimulated wake phase.
The mode of action and activities of guava leaf extracts against various food pathogens were studied. The killing kinetics, viability and cell leakage of Kocuria rhizophila, Salmonella typhimurium, Listeria monocytogenes and Escherichia coli O157:H7, measured after exposure to guava methanolic extracts (GME) revealed a significantly higher (p≤0.05) release of bacterial nucleic acids, K+ ions and protein than that of untreated microbes, indicating disruption of the bacterial membrane. GME caused a significantly higher (p≤0.05) release of RNA in gramnegatives compared to gram-positives. GME caused a relatively small but significant release of pyrines and pyrimidines in all organisms investigated. GME probably disrupted the integrity of the Gram-negative microorganism lipopolysaccharide (LPS) layer. Unlike all the other microorganisms tested, E. coli O157:H7, demonstrated the lowest protein leakage, the highest K+ leakage, the highest pyrines and pyrimidines leakage within the first 10 min of extract exposure, but the lowest after 30 minutes, which may indicate their good homeostasis ability or adaptability. Understanding the mode of action of this flavonoid rich guava leaf extract, would help develop it as an alternative biodegradable and safe, antimicrobial for food and medicine, and as a by-product of the guava industry.
The present study is aimed at optimizing the in vitro culture protocol for generation of rat bone marrow- (BM-) derived mesenchymal stem cells (MSCs) and characterizing the culture-mediated cellular senescence. The initial phase of generation and characterization was conducted using the adherent cells from Sprague Dawley (SD) rat's BM via morphological analysis, growth kinetics, colony forming unit capacity, immunophenotyping, and mesodermal lineage differentiation. Mesenchymal stem cells were successfully generated and characterized as delineated by the expressions of CD90.1, CD44H, CD29, and CD71 and lack of CD11b/c and CD45 markers. Upon induction, rBM-MSCs differentiated into osteocytes and adipocytes and expressed osteocytes and adipocytes genes. However, a decline in cell growth was observed at passage 4 onwards and it was further deciphered through apoptosis, cell cycle, and senescence assays. Despite the enhanced cell viability at later passages (P4-5), the expression of senescence marker, β-galactosidase, was significantly increased at passage 5. Furthermore, the cell cycle analysis has confirmed the in vitro culture-mediated cellular senescence where cells were arrested at the G0/G1 phase of cell cycle. Although the currently optimized protocols had successfully yielded rBM-MSCs, the culture-mediated cellular senescence limits the growth of rBM-MSCs and its potential use in rat-based MSC research.
Cassava starch was used as feedstock for production of bioethanol by Saccharomyces cerevisiae. The cassava starch was hydrolyzed using commercial α-amylase and glucoamylase enzymes followed by a batch ethanol fermentation process using saccharified starch slurry. By using 110 g/L of reducing sugar from saccharified starch slurry, the ethanol yield was promising with maximum ethanol concentration of 20.6 g/L recorded after 55 hours of cultivation process. Three different models - the Logistic model, Luedeking-Piret-like equation and Gompertz equation - were used to characterize and explain the cell growth, reducing sugar consumption and production formation, respectively. The kinetic parameters were estimated by fitting the experimental data to the proposed models using non-linear regression analysis. The correlation coefficient r2 values for the Logistic model, Luedeking-Piret-like equation and the Gompertz equation were 0.994, 0.996 and 0.990, respectively. The high correlation coefficient values indicate that the proposed models were able to describe the ethanol fermentation process.
Multiwall carbon nanotubes (MWCNTs) were synthesized using a tubular microwave chemical vapor deposition technique, using acetylene and hydrogen as the precursor gases and ferrocene as catalyst. The novel MWCNT samples were tested for their performance in terms of Pb(II) binding. The synthesized MWCNT samples were characterized using Fourier Transform Infrared (FT-IR), Brunauer, Emmett and Teller (BET), Field Emission Scanning Electron Microscopy (FESEM) analysis, and the adsorption of Pb(II) was studied as a function of pH, initial Pb(II) concentration, MWCNT dosage, agitation speed, and adsorption time, and process parameters were optimized. The adsorption data followed both Freundlich and Langmuir isotherms. On the basis of the Langmuir model, Qmax was calculated to be 104.2mg/g for the microwave-synthesized MWCNTs. In order to investigate the dynamic behavior of MWCNTs as an adsorbent, the kinetic data were modeled using pseudo first-order and pseudo second-order equations. Different thermodynamic parameters, viz., ∆H(0), ∆S(0) and ∆G(0) were evaluated and it was found that the adsorption was feasible, spontaneous and endothermic in nature. The statistical analysis revealed that the optimum conditions for the highest removal (99.9%) of Pb(II) are at pH5, MWCNT dosage 0.1g, agitation speed 160r/min and time of 22.5min with the initial concentration of 10mg/L. Our results proved that microwave-synthesized MWCNTs can be used as an effective Pb(II) adsorbent due to their high adsorption capacity as well as the short adsorption time needed to achieve equilibrium.
To assess stress level induced by multiple stressors in aquatic organism, biomarkers have been adopted as early warning indicator due to their high accuracy, rapidity, and sensitivity. We investigated the effects of ectoparasitic isopod infection on heavy metal bioaccumulation (Fe, Cu, Zn, and Cd) in the fish Nemipterus furcosus and profiled the expression of metallothionein (MT) and heat shock proteins 70 (HSP70) genes of the fish host. Sixty individuals (parasitized and nonparasitized with Cymothoa truncata) were collected from three sites differing in the levels of anthropogenic activities off the South China Sea. Our results revealed no significant difference in heavy metal concentrations between infected and nonparasitized fish. We observed a positive correlation between heavy metal bioaccumulation in the fish host and anthropogenic activities. Accordingly, expression analysis of MT genes in fish liver showed significant differences in expression level between sampling sites, with lowest level in the least exploited site (Batu Rakit). A reverse pattern in HSP70 gene expression was demonstrated in fish muscle, showing the highest expression at Batu Rakit. While cymothoid infection in N. furcosus had no significant impact on fish MT gene expression, it resulted in a reduction of HSP70 level in liver of parasitized fish. These findings highlight the putative roles of MT in heavy metal assessment. Future studies should determine the kinetics of cymothoid infection and other potential stressors in characterizing the HSP70 gene expression profile.
The effect of chamber pressure of a freeze dryer on essential oil contents, drying kinetics, drying characteristics lemon balm leaves and morphology of lemon balm glandular trichomes (oil reservoirs) were investigated. It was found that overall freeze drying (FD) carried out at high (FD-HP) and low pressure (FD-LP) settings consist of sublimation rate, first falling rate and second falling rate periods. Drying rate of FD-LP dried Lemon Balm leaves are higher than FD-HP dried samples, where the drying rates ranged from 0.063 to 0.449 g H2O/ g DM. s and 0.0365 to 0.395 g H2O/ g DM. s, respectively. 3rd order Polynomial model was found to be the best fit model for both drying kinetics. In terms of product quality, eight (8) major constituents of lemon balm leaves essential oil were quantified. Further to this, electro-microscope was used to observe the peltate glandular hairs structure. Product quality analysis showed that FD-HP retained higher amount of essential oil, shape of glandular hairs, but no positive effect on the freeze drying duration.
Honey is usually subjected to filtration and heating for bottling before commercialization. However, there is no standard procedure available for thermal treatment on honey. Honey is thermally heated at various temperature and duration based on individual experience to prolong the shelf life of honey in the market. The heating methods might decrease the biochemical components such as nutrients, enzymatic activities and vitamins to certain extent. In addition to water reduction, thermal treatment on sugar rich honey usually accompanied by the formation of 5-hydroxymethylfurfural (HMF). In the present study, the biochemical components in three commonly consumed honey in Malaysia, namely tualang, gelam and acacia honey were investigated before and after thermal treatment at 90oC for 30 min. The short period of heating time was found to degrade nutrients, enzymatic activities and water soluble vitamins in honey. The degradation of protein and enzyme via proteolytic digestion had attributed to the increase of free amino acids in honey. Based on the multivariate analysis, the most thermally affected biochemical components are crude fat, panthotenic acid (Vitamin B5) and diastase activity which explain for 86.4% of the total variance. The kinetic studies on the HMF formation revealed that the honey samples followed zero order kinetic model for the first 60 min of heating at 90oC. The findings indicate that the temperature and duration of heating during honey processing is essential to be investigated according to the honey origin. The initial biochemical composition of honey would affect the kinetic profile of HMF formation.
A radiotracer study was conducted to investigate the removal characteristics of cadmium (109Cd) from aqueous solution by polypyrrole/ sawdust composite. Several factors such as solution pH, sorbent dosage, initial concentration, contact time, temperature and interfering metal ions were found to have influence on the adsorption process. The kinetics of adsorption was relatively fast, reaching equilibrium within 3 hours. A lowering of the solution pH reduced the removal efficiency from 99.3 to ~ 46.7% and an ambient temperature of 25°C was found to be optimum for maximum adsorption. The presence of sodium and potassium ions inhibited 109Cd removal from its aqueous solution. The experimental data for 109Cd adsorption showed a very good agreement with the Langmuir isotherm and a pseudo-first order kinetic model. The surface condition of the adsorbent before and after cadmium loading was investigated using BET, FESEM and FTIR. Considering the low cost of the precursor's materials and the toxicity of 109Cd radioactive metal, polypyrrole synthesized on the sawdust of Dryobalanops aromatic could be used as an efficient adsorbent for the removal of 109Cd radioisotope from radionuclide-containing effluents.
The presence of Cs(I) ions in nuclear wastewater becomes an important issue for the reason of its high toxicity. The development of adsorbent embedded metal-based catalysts that has sufficient adsorption capacity is expected for the removal of Cs(I) ions from contaminated water. This study tested the use of maghemite, titania and combined maghemite-titania polyvinyl alcohol (PVA)-alginate beads as an adsorbent to remove Cs(I) ions from aqueous solution with the variables of pH and initial concentration using batch experiments under sunlight. The results showed that the use of combined maghemite-titania PVA-alginate beads can have an efficiency of 93.1% better than the use of either maghemite PVA-alginate beads with an efficiency of 91.8% or titania PVA-alginate beads with an efficiency of 90.1%. The experimental data for adsorption of Cs(I) ions from aqueous solution with the initial concentrations of 50, 100 and 200 mg L(-1) on the surface of combined maghemite-titania PVA-alginate beads were well fit by the pseudo-second-order and Langmuir models. The optimal adsorption of Cs(I) ions from aqueous solution by combined maghemite-titania PVA-alginate beads under sunlight occurs at pH 8 with an initial Cs(I) ion concentration of 50 mg L(-1). The combined maghemite-titania PVA-alginate beads can be recycled at least five times with a slight loss of their original properties.
In this study, carbon species were grown on the surface of Ni-impregnated powder activated carbon to form a novel hybrid carbon nanomaterial by chemical vapor deposition. The carbon nanomaterial was obtained by the precipitation of the methane elemental carbon atoms on the surface of the Ni catalyst. The physiochemical properties of the hybrid material were characterized to illustrate the successful growth of carbon species on the carbon substrate. The response surface methodology was used for the evaluation of adsorption parameters effect such as pH, adsorbent dose and contact time on the percentage removal of MB dye from aqueous solution. The optimum conditions were found to be pH = 11, adsorbent dose = 15 mg and contact time of 120 min. The material we prepared showed excellent removal efficiency of 96% for initial MB concentration of 50 mg/L. The adsorption of MB was described accurately by the pseudo-second-order model with R2 of 0.998 and qe of 163.93 (mg/g). The adsorption system showed the best agreement with Langmuir model with R2 of 0.989 and maximum adsorption capacity (Qm) of 250 mg/g.
In this work, a human hair-derived high surface area porous carbon material (HHC) was prepared using potassium hydroxide activation. The morphology and textural properties of the HHC structure, along with its adsorption performance for tetracycline (TC) antibiotics, were evaluated. HHC showed a high surface area of 1505.11m(2)/g and 68.34% microporosity. The effects of most important variables, such as initial concentration (25-355mg/L), solution pH (3-13), and temperatures (30-50°C), on the HHC adsorption performance were investigated. Isotherm data analysis revealed the favorable application of the Langmuir model, with maximum TC uptakes of 128.52, 162.62, and 210.18mg/g at 30, 40, and 50°C, respectively. The experimental data of TC uptakes versus time were analyzed efficiently using a pseudo-first order model. Porous HHC could be an efficient adsorbent for eliminating antibiotic pollutants in wastewater.
Currently, the use of natural gums and mucilage is of increasing importance in pharmaceutical formulations as valuable drug excipient. Natural plant-based materials are economic, free of side effects, biocompatible and biodegradable. Therefore, Ketoprofen matrix tablets were formulated by employing Hibiscus rosa-sinensis leaves mucilage as natural polymer and HPMC (K100M) as a synthetic polymer to sustain the drug release from matrix system. Direct compression method was used to develop sustained released matrix tablets. The formulated matrix tablets were evaluated in terms of physical appearance, weight variation, thickness, diameter, hardness, friability and in vitro drug release. The difference between the natural and synthetic polymers was investigated concurrently. Matrix tablets developed from each formulation passed all standard physical evaluation tests. The dissolution studies of formulated tablets revealed sustained drug release up to 24 h compared to the reference drug Apo Keto® SR tablets. The dissolution data later were fitted into kinetic models such as zero order equation, first order equation, Higuchi equation, Hixson Crowell equation and Korsmeyer-Peppas equation to study the release of drugs from each formulation. The best formulations were selected based on the similarity factor (f2) value of 50% and more. Through the research, it is found that by increasing the polymers concentration, the rate of drug release decreased for both natural and synthetic polymers. The best formulation was found to be F3 which contained 40% Hibiscus rosa-sinensis mucilage polymer and showed comparable dissolution profile to the reference drug with f2 value of 78.03%. The release kinetics of this formulation has shown to follow non-Fickian type which involved both diffusion and erosion mechanism. Additionally, the statistical results indicated that there was no significant difference (p > 0.05) between the F3 and reference drug in terms of MDT and T50% with p-values of 1.00 and 0.995 respectively.
The performance of a modified electrode of nanocomposite films consisting of polypyrrole-chitosan-titanium dioxide (Ppy-CS-TiO₂) has been explored for the developing a non-enzymatic glucose biosensors. The synergy effect of TiO₂ nanoparticles (NPs) and conducting polymer on the current responses of the electrode resulted in greater sensitivity. The incorporation of TiO₂ NPs in the nanocomposite films was confirmed by X-ray photoelectron spectroscopy (XPS) spectra. FE-SEM and HR-TEM provided more evidence for the presence of TiO₂ in the Ppy-CS structure. Glucose biosensing properties were determined by amperommetry and cyclic voltammetry (CV). The interfacial properties of nanocomposite electrodes were studied by electrochemical impedance spectroscopy (EIS). The developed biosensors showed good sensitivity over a linear range of 1-14 mM with a detection limit of 614 μM for glucose. The modified electrode with Ppy-CS nanocomposite also exhibited good selectivity and long-term stability with no interference effect. The Ppy-CS-TiO₂ nanocomposites films presented high electron transfer kinetics. This work shows the role of nanomaterials in electrochemical biosensors and describes the process of their homogeneous distribution in composite films by a one-step electrochemical process, where all components are taken in a single solution in the electrochemical cell.
A novel polyoxometalate-based electrode was developed by incorporating phosphotungstic acid (PWA) in nylon-6,6 nanofiber, followed by carbonization. The developed PWA-carbon nanofiber (PWA-CNF) showed the characteristics of the dual-scale porosity of micro- and mesoporous substrate with surface area of around 684 m2 g-1. The compound exhibited excellent stability in vanadium electrolyte and battery cycling. Evaluation of electrocatalytic properties toward V2+/V3+ and VO2+/VO2+ redox couples indicated promising advantages in electron transfer kinetics and increasing energy efficiency, particularly for the VO2+/VO2+ couple. Moreover, the developed electrode exhibited substantially improved energy efficiency (14% higher than that of pristine carbon felt) in the single cell vanadium redox flow battery. This outstanding performance was attributed to high surface area and abundant oxygen-containing linkages in the developed electrode.