The synergistic effect of using κ-carrageenan bionanocomposites with the hybridization of cellulose nanocrystals (CNCs) and organically modified montmorillonite (OMMT) reinforcements was studied. The effects of different reinforcements and filler contents were evaluated through mechanical testing, and morphological and water uptake properties. The tensile strength and Young's modulus of both bionanocomposites increased with filler loading and optimized at 4%. OMMT incorporation into the κ-carrageenan/CNCs bionanocomposites resulted in further mechanical property improvement with an optimum ratio of 1:1 (CNCs:OMMT) while maintaining high film transparency. X-ray diffraction and morphological analyses revealed that intercalation occurred between the κ-carrageenan bionanocomposite matrix and OMMT. The water uptake of the κ-carrageenan bionanocomposites was significantly reduced by the addition of both CNCs and OMMT. The enhancements in the mechanical properties and performance of the hybrid bionanocomposite indicate compatibility among the reinforcement, biopolymer, and well-dispersed nanoparticles. This renders the hybrid CNC/OMMT/κ-carrageenan nanocomposites extremely promising for food packaging applications.
Herein, hybrid k-carrageenan bio-nanocomposite films were fabricated by using two types of nanofillers, organically modified montmorillonite (OMMT), and cellulose nanocrystals (CNCs). Hybrid bio-nanocomposite films were made by casting techniques employing 4 wt% of CNCs, OMMT, and hybridized CNCs/OMMT in a 1:1 ratio. The rheological and morphological properties and thermal stability of all composites were investigated using rotational rheometry, thermogravimetry analysis, differential scanning calorimetry, field emission scanning electron microscopy, and transmission electron microscopy (TEM). The results showed that the hybrid CNC/OMMT bio-nanocomposite exhibited significantly improved properties as compared to those for the bio-nanocomposites with single fillers due to the nanosize and homogenous nanofiller dispersion in the matrix. Rheological analysis of the hybrid bio-nanocomposite showed higher dynamic shear storage modulus and complex viscosity values when compared to those for the bio-nanocomposite with individual fillers. The TEM analysis of the hybridized CNC/OMMT bio-nanocomposite revealed that more particles were packed together in the CNC network, which restricted the matrix mobility. The heat resistance and thermal stability bio-nanocomposite k-carrageenan film enhanced rapidly with the addition of hybridized CNCs/OMMT to 275 °C. The hybridized CNCs/OMMT exhibited synergistic effects due to the good affinity through interfacial interactions, resulting in the improvement of the material properties.
Discovery of a novel anticancer drug delivery agent is important to replace conventional cancer therapies which are often accompanied by undesired side effects. This study demonstrated the synthesis of superparamagnetic magnetite nanocomposites (Fe3O4-NCs) using a green method. Montmorillonite (MMT) was used as matrix support, while Fe3O4 nanoparticles (NPs) and carrageenan (CR) were used as filler and stabilizer, respectively. The combination of these materials resulted in a novel nanocomposite (MMT/CR/Fe3O4-NCs). A series of characterization experiments was conducted. The purity of MMT/CR/Fe3O4-NCs was confirmed by X-ray diffraction (XRD) analysis. High resolution transmission electron microscopy (HRTEM) analysis revealed the uniform and spherical shape of Fe3O4 NPs with an average particle size of 9.3 ± 1.2 nm. Vibrating sample magnetometer (VSM) analysis showed an Ms value of 2.16 emu/g with negligible coercivity which confirmed the superparamagnetic properties. Protocatechuic acid (PCA) was loaded onto the MMT/CR/Fe3O4-NCs and a drug release study showed that 15% and 92% of PCA was released at pH 7.4 and 4.8, respectively. Cytotoxicity assays showed that both MMT/CR/Fe3O4-NCs and MMT/CR/Fe3O4-PCA effectively killed HCT116 which is a colorectal cancer cell line. Dose-dependent inhibition was seen and the killing was enhanced two-fold by the PCA-loaded NCs (IC50-0.734 mg/mL) compared to the unloaded NCs (IC50-1.5 mg/mL). This study highlights the potential use of MMT/CR/Fe3O4-NCs as a biologically active pH-responsive drug delivery agent. Further investigations are warranted to delineate the mechanism of cell entry and cancer cell killing as well as to improve the therapeutic potential of MMT/CR/Fe3O4-NCs.
Superparamagnetic magnetite nanocomposites (Fe3O4-NCs) were successfully synthesized, which comprised of montmorillonite (MMT) as matrix support, Kappaphycus alvarezii (SW) as bio-stabilizer and Fe3O4 as filler in the composites to form MMT/SW/Fe3O4-NCs. Nanocomposite with 0.5 g Fe3O4 (MMT/SW/0.5Fe3O4) was selected for anticancer activity study because it revealed high crystallinity, particle size of 7.2 ± 1.7 nm with majority of spherical shape, and Ms = 5.85 emu/g with negligible coercivity. Drug loading and release studies were carried out using protocatechuic acid (PCA) as the model for anticancer drug, which showed 19% and 87% of PCA release in pH 7.4 and 4.8, respectively. Monolayer anticancer assay showed that PCA-loaded MMT/SW/Fe3O4 (MMT/SW/Fe3O4-PCA) had selectivity towards HCT116 (colorectal cancer cell line). Although MMT/SW/Fe3O4-PCA (0.64 mg/mL) showed higher IC50 than PCA (0.148 mg/mL) and MMT/SW/Fe3O4 (0.306 mg/mL, MMT/SW/Fe3O4-PCA showed more effective killing towards tumour spheroid model generated from HCT116. The IC50 for MMT/SW/Fe3O4-PCA, MMT/SW/Fe3O4 and PCA were 0.132, 0.23 and 0.55 mg/mL, respectively. This suggests the improved penetration efficiency and drug release of MMT/SW/Fe3O4-PCA towards HCT116 spheroids. Moreover, concentration that lower than 2 mg/mL MMT/SW/Fe3O4-PCA did not result any hemolysis in human blood, which suggests them to be ideal for intravenous injection. This study highlights the potential of MMT/SW/Fe3O4-NCs as drug delivery agent.
Organomontmorillonites were synthesized by grafting cationic surfactants i.e quaternary ammonium compounds into the interlayer space and were characterized using XRD, FTIR and N2 adsorption/ desorption analysis. The organomontmorillonites were applied as catalyst for the esterification of glycerol (GL) with lauric acid (LA). The catalyst which had symmetrical onium salts (tetrabuthylammoniumbromide, TBAB) gave higher activity than that of unsymmetrical onium salts (cetyltrimethylammoniumbromide, CTAB). Over the TBAB-montmorillonite catalyst, glycerol monolaurate was obtained with a selectivity of about 80%, a lauric acid conversion of about 71% and a glycerol monolaurate yield of about 57%.
A thermoplastic elastomer (TPE) based nanocomposite with the same weight ratio of hybrid nanofillers composed of carbon nanotubes (CNTs) and montmorillonite nanoclay (DK4) was prepared using a melt blending technique with an internal mixer. The TPE composite was blended from polylactic acid (PLA), liquid natural rubber (LNR) as a compatibilizer and natural rubber (NR) in a volume ratio of 70:10:20, respectively. The weight ratio of CNTs and DK4 was 2.5 wt%. The prepared samples were exposed to gamma radiation at range of 0-250 kGy. After exposure to gamma radiation, the mechanical, thermo-mechanical, thermal and electrical conductivity properties of the composites were significantly higher than unirradiated TPE composites as the irradiation doses increased up to 150 kGy. Transmission electron microscopy (TEM) micrographs revealed the good distribution and interaction between the nano-fillers and the matrix in the prepared TPE hybrid nanocomposites. In summary, the findings from this work definite that gamma irradiation might be a viable treatment to improve the properties of TPE nanocomposite for electronic packaging applications.
This study evaluated the use of alginate-immobilized bentonite to remove Cu(II) as an alternative to mitigate clogging problems. The adsorption efficacy (under the influence of time, pH and initial Cu(II) concentration) and reusability of immobilized-bentonite (1% w/v bentonite) was tested against plain alginate beads. Results revealed that immobilized bentonite demonstrated significantly higher sorption efficacy compared to plain alginate beads with 114.70 and 94.04 mg Cu(II) adsorbed g(-1) adsorbent, respectively. Both sorbents were comparable in other aspects where sorption equilibrium was achieved within 6 h, with optimum pH between pH 4 and 5 for adsorption, displayed maximum adsorption capacity at initial Cu(II) concentrations of 400 mg l(-1), and demonstrated excellent reusability potential with desorption greater than 90% throughout three consecutive adsorption-desorption cycles. Both sorbents also conformed to Langmuir isotherm and pseudo-second order kinetic model. Immobilized bentonite is therefore recommended for use in water treatments to remove Cu(II) without clogging the system.
Acid waste bentonite is a byproduct from vegetable oil bleaching that is acidic (pH < 3.0) and hydrophobic. These materials are currently disposed of in landfills and could potentially have a negative impact on the effective function of microbes that are intolerant of acidic conditions. A study was undertaken using three different sources of acid waste bentonites, namely soybean oil bentonite (SB), palm oil bentonite (PB), and rice bran oil bentonite (RB). These materials were co-composted with rice husk, rice husk ash, and chicken litter to eliminate their acid reactivity and hydrophobic nature. The organic carbon (OC) content, pH, exchangeable cations, and cation exchange capacity (CEC) of the acid-activated bentonites increased significantly after the co-composting phase. In addition, the hydrophobic nature of these materials as measured using the water drop penetration time (WDPT) decreased from >10 800 s to 16 to 80 s after composting. Furthermore, these composted materials showed positive impacts on soil physical attributes including specific surface area, bulk density, and available water content for crop growth. Highly significant increases in maize biomass (Zea mays L.) production over two consecutive cropping cycles was observed in treatments receiving co-composted bentonite. The study clearly demonstrates the potential for converting an environmentally hazardous material into a high-quality soil conditioner using readily available agricultural byproducts. It is envisaged that the application of these composted acid waste bentonites to degraded soils will increase productivity and on-farm income, thus contributing toward food security and poverty alleviation.
One of the factors on which the incidence of leptospirosis is dependent is the survival time of shed leptospires in surface water or soil water, and this time is in turn affected by the acidity or alkalinity of the water. The authors have therefore studied the survival of four leptospiral serotypes in buffered distilled water at pH's ranging from 5.3 to 8.0. All survived longer in alkaline than in acid water, and significant differences between the serotypes were found in response to pH. Survival at pH's under 7.0 ranged from 10 to 117 days and at pH's over 7.0 from 21 to 152 days. Survival was also studied in aqueous extracts of soil samples from different areas in Malaya; no correlation was found between pH and survival time.It was also noted that in a group of Malayan ricefields a low incidence of leptospirosis in man was accompanied by a high infection rate among rodents, and when it was found that this phenomenon could not be explained by pH or salinity, attention was turned to the soil. Bentonite clay, similar to the montmorrillonite clay of the ricefields, was found to adsorb about half the leptospires in suspension. The authors recommend that field study of this laboratory observation be undertaken.
Silver nanoparticles (AgNPs) of a small size were successfully synthesized using the wet chemical reduction method into the lamellar space layer of montmorillonite/chitosan (MMT/Cts) as an organomodified mineral solid support in the absence of any heat treatment. AgNO3, MMT, Cts, and NaBH4 were used as the silver precursor, the solid support, the natural polymeric stabilizer, and the chemical reduction agent, respectively. MMT was suspended in aqueous AgNO3/Cts solution. The interlamellar space limits were changed (d-spacing = 1.24-1.54 nm); therefore, AgNPs formed on the interlayer and external surface of MMT/Cts with d-average = 6.28-9.84 nm diameter. Characterizations were done using different methods, ie, ultraviolet-visible spectroscopy, powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray fluorescence spectrometry, and Fourier transform infrared spectroscopy. Silver/montmorillonite/chitosan bionanocomposite (Ag/MMT/Cts BNC) systems were examined. The antibacterial activity of AgNPs in MMT/Cts was investigated against Gram-positive bacteria, ie, Staphylococcus aureus and methicillin-resistant S. aureus and Gram-negative bacteria, ie, Escherichia coli, E. coli O157:H7, and Pseudomonas aeruginosa by the disc diffusion method using Mueller Hinton agar at different sizes of AgNPs. All of the synthesized Ag/MMT/Cts BNCs were found to have high antibacterial activity. These results show that Ag/MMT/Cts BNCs can be useful in different biological research and biomedical applications, including surgical devices and drug delivery vehicles.
Silver nanoparticles (Ag NPs) were synthesized by the chemical reducing method in the external and interlamellar space of montmorillonite (MMT) as a solid support at room temperature. AgNO(3) and NaBH(4) were used as a silver precursor and reducing agent, respectively. The most favorable experimental conditions for synthesizing Ag NPs in the MMT are described in terms of the initial concentration of AgNO(3). The interlamellar space limits changed little (d-spacing = 1.24-1.47 nm); therefore, Ag NPs formed on the MMT suspension with d-average = 4.19-8.53 nm diameter. The Ag/MMT nanocomposites (NCs), formed from AgNO(3)/MMT suspension, were characterizations with different instruments, for example UV-visible, PXRD, TEM, SEM, EDXRF, FT-IR, and ICP-OES analyzer. The antibacterial activity of different sizes of Ag NPs in MMT were investigated against Gram-positive, ie, Staphylococcus aureus and methicillin-resistant S. aureus (MRSA) and Gram-negative bacteria, ie, Escherichia coli, Escherichia coli O157:H7, and Klebsiella pneumoniae, by the disk diffusion method using Mueller-Hinton agar (MHA). The smaller Ag NPs were found to have significantly higher antibacterial activity. These results showed that Ag NPs can be used as effective growth inhibitors in different biological systems, making them applicable to medical applications.
Silver nanoparticles (Ag-NPs) were synthesized into the interlamellar space of montmorillonite (MMT) by using the γ-irradiation technique in the absence of any reducing agent or heat treatment. Silver nitrate and γ-irradiation were used as the silver precursor and physical reducing agent in MMT as a solid support. The MMT was suspended in the aqueous AgNO(3) solution, and after the absorption of silver ions, Ag(+) was reduced using the γ-irradiation technique. The properties of Ag/MMT nanocomposites and the diameters of Ag-NPs were studied as a function of γ-irradiation doses. The interlamellar space limited particle growth (d-spacing [d(s)] = 1.24-1.42 nm); powder X-ray diffraction and transmission electron microscopy (TEM) measurements showed the production of face-centered cubic Ag-NPs with a mean diameter of about 21.57-30.63 nm. Scanning electron microscopy images indicated that there were structure changes between the initial MMT and Ag/MMT nanocomposites under the increased doses of γ-irradiation. Furthermore, energy dispersive X-ray fluorescence spectra for the MMT and Ag/ MMT nanocomposites confirmed the presence of elemental compounds in MMT and Ag-NPs. The results from ultraviolet-visible spectroscopy and TEM demonstrated that increasing the γ-irradiation dose enhanced the concentration of Ag-NPs. In addition, the particle size of the Ag-NPs gradually increased from 1 to 20 kGy. When the γ-irradiation dose increased from 20 to 40 kGy, the particle diameters decreased suddenly as a result of the induced fragmentation of Ag-NPs. Thus, Fourier transform infrared spectroscopy suggested that the interactions between Ag-NPs with the surface of MMT were weak due to the presence of van der Waals interactions. The synthesized Ag/MMT suspension was found to be stable over a long period of time (ie, more than 3 months) without any sign of precipitation.
In this work, the optimum filler loading to prepare epoxy/organoclay nanocomposites by the in-situ polymerization method was studied. Bi-functionalized montmorillonite at different filler loading (0.5, 1.0, 2.0, 4.0 wt %) was dispersed in epoxy resin by using a high shear speed homogenizer. The effect on morphology, thermal, dynamic mechanical, and tensile properties of the epoxy/organoclay nanocomposites were studied in this work. Wide-angle X-ray scattering (WAXS) and field emission scanning electron microscope (FESEM) studies revealed that possible intercalated structures were obtained in epoxy/organoclay nanocomposites. Thermogravimetric analysis (TGA) shows that epoxy/organoclay nanocomposites exhibit higher thermal stability at the maximum and final decomposition temperature, as well as higher char content, compared to pristine epoxy. The dynamic mechanical analysis (DMA) indicate that storage modulus (E'), loss modulus (E″), cross-link density and glass transition temperature (Tg) of the nanocomposites were improved with organoclay loading up to 1 wt %. Beyond this loading limit, the deterioration of properties was observed. A similar trend was also observed on tensile strength and modulus. We concluded from this study that organoclay loading up to 1 wt % is suitable for further study to fabricate hybrid nanocomposites for various applications.
Multi-component nanohybrids comprising of organo-modified montmorillonite (MMT) and immiscible biopolymer blends of poly(3-hydroxybutyrate) (PHB) and epoxidized natural rubber (ENR-50) were prepared by solvent casting technique. The one and three dimensional morphology of PHB/ENR-50/MMT systems were studied using Polarizing Optical Microscopy (POM) and Scanning Electron Microscopy (SEM). Differential scanning calorimetry (DSC) technique was used to evaluate the thermal properties of the nanohybrids. The melting temperature (Tm) and enthalpy of melting (ΔHm) of PHB decrease with respect to the increase in ENR-50 as well as MMT content. The non-isothermal decomposition of the nanohybrids was studied using thermogravimetric (TG-DTG) analysis. FTIR-ATR spectra supported ring opening of the epoxide group via reaction with carboxyl group of PHB and amines of organic modifier. The reaction mechanism towards the formation of the nanohybrids is proposed.
Ostrich oil has been used extensively in the cosmetic and pharmaceutical industries. However, rancidity causes undesirable chemical changes in flavour, colour, odour and nutritional value. Bleaching is an important process in refining ostrich oil. Bleaching refers to the removal of certain minor constituents (colour pigments, free fatty acid, peroxides, odour and non-fatty materials) from crude fats and oils to yield purified glycerides. There is a need to optimize the bleaching process of crude ostrich oil prior to its use for therapeutic purposes. The objective of our study was to establish an effective method to bleach ostrich oil using peroxide value as an indicator of refinement. In our study, we showed that natural earth clay was better than bentonite and acid-activated clay to bleach ostrich oil. It was also found that 1 hour incubation at a 150 °C was suitable to lower peroxide value by 90%. In addition, the nitrogen trap technique in the bleaching process was as effective as the continuous nitrogen flow technique and as such would be the recommended technique due to its cost effectiveness.
Paracetamol (PCM)-loaded composite nanoparticles (NPs) composed of a biodegradable poly(d,l-lactide) (PLA) polymer matrix filled with organically modified montmorillonite (MMT) nanoparticles were fabricated by antisolvent nanoprecipitation in a microfluidic co-flow glass capillary device. The incorporation of MMT in the polymer improved both the drug encapsulation efficiency and the drug loading, and extended the rate of drug release in simulated intestinal fluid (pH 7.4). The particle size increased on increasing both the drug loading and the concentration of MMT in the polymer matrix, and decreased on increasing the aqueous to organic flow rate ratio. The drug encapsulation efficiency in the NPs was higher at higher aqueous to organic flow rate ratio due to faster formation of the NPs. The PCM-loaded PLA NPs containing 2 wt% MMT in PLA prepared at an aqueous to organic flow rate ratio of 10 with an orifice size of 200 μm exhibited a spherical shape with a mean size of 296 nm, a drug encapsulation efficiency of 38.5% and a drug loading of 5.4%. The encapsulation of MMT and PCM in the NPs was confirmed by transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis and attenuated total reflection-Fourier transform infrared spectroscopy.
Polymer-clay based nanocomposites are among the attractive materials to be applied for various applications, including biomedical. The incorporation of the nano sized clay (nanoclay) into polymer matrices can result in their remarkable improvement in mechanical, thermal and barrier properties as long as the nanofillers are well exfoliated and dispersed throughout the matrix. In this work, exfoliation strategy through pre-dispersing process of the organically modified montmorillonite (organo-MMT) nanofiller was done to obtain ethyl vinyl acetate (EVA) nanocomposite with improved flexibility, toughness, thermal stability and biostability. Our results indicated that the degree of organo-MMT exfoliation affects its cytotoxicity level and the properties of the resulting EVA nanocomposite. The pre-dispersed organo-MMT by ultrasonication in water possesses higher degree of exfoliation as compared to its origin condition and significantly performed reduced cytotoxicity level. Beneficially, this nanofiller also enhanced the EVA flexibility, thermal stability and biostability upon the in vitro exposure. We postulated that these were due to plasticizing effect and enhanced EVA-nanofiller interactions contributing to more stable chemical bonds in the main copolymer chains. Improvement in copolymer flexibility is beneficial for close contact with human soft tissue, while enhancement in toughness and biostability is crucial to extend its life expectancy as insulation material for implantable device.
Demand for diesel continues to increase due to rapid population growth, which could contribute to fossil fuel exhaustion. Biodiesel has been widely developed as a replacement for conventional diesel to resolve the issue. Biodiesel production from waste cooking oil (WCO) was carried out via the transesterification process using two types of bentonite catalysts, which are raw bentonite and NaOH/bentonite. By using the impregnation method, the NaOH/bentonite catalyst was synthesized at 60°C for 12 hours. The transesterification was conducted with 0.5wt% of catalyst, at 15:1 (methanol- to-oil), for 2 hours at different reaction temperatures. The characterization of both raw bentonite and NaOH/bentonite was done using X-ray Diffraction (XRD) and Brunauer, Emmett, Teller (BET) surface characterization. A high yield of FAMEs (72%) was found to be obtained in continuous stirring at 55ºC for 2 hours and 15:1 methanol/oil molar ratio with 0.5wt.% (0.15g) of NaOH/bentonite catalyst.
The potential of new trimetallic (Ce, Cu, La) loaded montmorillonite clay catalyst for synthesizing biodiesel using novel non-edible Celastrus paniculatus Willd seed oil via two-step transesterification reaction has been reported along with catalyst characterization. Transesterification reaction was optimized and maximum biodiesel yield of 89.42% achieved under optimal operating reaction states like; 1:12 oil to methanol ratio, 3.5% of catalyst amount, 120 °C of reaction temperature for 3 h. The predicted and experimental biodiesel yields under these reaction conditions were 89.42 and 89.40%, which showing less than 0.05% variation. Additionally, optimum biodiesel yield can be predicted by drawing 3D surface plots and 2D contour plots using MINITAB 17 software. For the characterization of the obtained biodiesel, analysis including the GC/MS, FT-IR, 1H NMR and 13C NMR were applied. The fuel properties of obtained biodiesel agrees well with the different European Union (EU-14214), China (GB/T 20828), and American (ASTM-951, 6751) standards.
This study focused on producing high quality and yield of biodiesel from novel non-edible seed oil of abundantly available wild Raphnus raphanistrum L. using an efficient, recyclable and eco-friendly copper modified montmorillonite (MMT) clay catalyst. The maximum biodiesel yield of 83% was obtained by base catalyzed transesterification process under optimum operating conditions of methanol to oil ratio of 15:1, reaction temperature of 150 °C, reaction time of 5 h and catalyst loading of 3.5%. The synthesized catalyst and biodiesel were characterized for their structural features and chemical compositions using various state-of-the-art techniques, including x-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectroscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance (1H, 13C) and gas chromatography-mass spectroscopy. The fuel properties of the biodiesel were estimated including kinematic viscosity (4.36 cSt), density (0.8312 kg/L), flash point (72 °C), acid value (0.172 mgKOH/g) and sulphur content (0.0002 wt.%). These properties were compared and found in good agreement with the International Biodiesel Standards of American (ASTM-951, 6751), European Committee (EN-14214) and China GB/T 20828 (2007). The catalyst was re-used in five consecutive transesterification reactions without losing much catalytic efficiency. Overall, non-edible Raphnus raphanistrum L.. seed oil and Cu doped MMT clay catalyst appeared to be highly active, stable, and cheap contenders for future biofuel industry. However, detailed life cycle assessment (LCA) studies of Raphnus raphanistrum L. seed oil biodiesel are highly recommended to assess the technical, ecological, social and economic challenges.