Release of surfactant cargo from interfacially-active halloysite clay nanotubes for oil spill remediation.

Naturally occurring halloysite clay nanotubes are effective in stabilizing oil-in-water emulsions and can serve as interfacially-active vehicles for delivering oil spill treating agents. Halloysite nanotubes adsorb at the oil-water interface and stabilize oil-in-water emulsions that are stable for months. Cryo-scanning electron microscopy (Cryo-SEM) imaging of the oil-in-water emulsions shows that these nanotubes assemble in a side-on orientation at the oil-water interface and form networks on the interface through end-to-end linkages. For application in the treatment of marine oil spills, halloysite nanotubes were successfully loaded with surfactants and utilized as an interfacially-active vehicle for the delivery of surfactant cargo. The adsorption of surfactant molecules at the interface serves to lower the interfacial tension while the adsorption of particles provides a steric barrier to drop coalescence. Pendant drop tensiometry was used to characterize the dynamic reduction in interfacial tension resulting from the release of dioctyl sulfosuccinate sodium salt (DOSS) from halloysite nanotubes. At appropriate surfactant compositions and loadings in halloysite nanotubes, the crude oil-saline water interfacial tension is effectively lowered to levels appropriate for the dispersion of oil. This work indicates a novel concept of integrating particle stabilization of emulsions together with the release of chemical surfactants from the particles for the development of an alternative, cheaper, and environmentally-benign technology for oil spill remediation.

Multicomponent Photocatalytic-Dispersant System for Oil Spill Remediation.

In the present work, the potential application of a fabricated halloysite nanotubes-Ag-TiO2 (HNT-Ag-TiO2) composite loaded with a binary surfactant mixture made up of lecithin and Tween 80 (LT80) in remediating oil spillages was examined. The as-prepared Ag-TiO2 that was used in the fabrication of the HNT-Ag-TiO2-LT80 composite was characterized by X-ray diffraction, Raman spectroscopy, UV-vis and diffuse reflectance spectroscopy, CV analyses, and SEM-EDX. The synthesized composite was also characterized by thermogravimetric analysis, Fourier-transform infrared spectroscopy, and scanning electron microscopy-energy dispersive X-ray spectroscopy. The synthesized composite was active in both the UV and visible light regions of the electromagnetic spectrum. The oil-remediating potential of the as-prepared composite was examined on crude oil, and aromatics and asphaltene fractions of crude oil. The composite was able to reduce the surface tension, form stable emulsions and smaller oil droplet sizes, and achieve a high dispersion effectiveness of 91.5%. A mixture of each of the crude oil and its fractions and HNT-Ag-TiO2-LT80 was subjected to photodegradation under UV light irradiation. The results from the GC-MS and UV-vis analysis of the photodegraded crude oil revealed that the photocatal composite was able to photodegrade the crude oil, aromatics, and asphaltene fractions of crude oil with the formation of intermediate photodegradation products depicting that the HNT-Ag-TiO2-LT80 has a potential as an oil spill remediation material.

Chicken Feather Protein Dispersant for Effective Crude Oil Dispersion in the Marine Environment.

Various studies report that aside from the adverse impact of the crude oil on the marine environment, there is the likelihood that chemical dispersants used on the surface of water as oil-treating agents themselves possess a degree of toxicity, which have additional effects on the environment. To eliminate the subject of toxicity, there exist several materials in nature that have the ability to form good emulsions, and such products include protein molecules. In this study, chicken feathers which are known to contain ≥90% protein were used to formulate a novel dispersant to disperse crude oil in seawater (35 ppt). Protein from chicken feathers was extracted and synthesized into the chicken feather protein (CFP) dispersant using deionized water as a solvent. Emulsions formed from CFP-synthesized dispersants were stable over a considerably long period of time, whereas the droplet sizes of the emulsion formed were on the average very small in diameter, making droplet coalescence very slow. The CFP dispersants exhibited moderate surface and interfacial activity at normal seawater salinity. Using the US EPA's baffled flask test, at 800 and 1000 mg/ml CFP surfactant-to-oil ratios, dispersion effectiveness values of 56.92 and 68.64 vol % were obtained, respectively, which show that CFP has a great potential in crude oil dispersion. Moreover, the acute toxicity test performed on Nile tilapia showed that CFP was practically nontoxic with an LC50 value of more than 100 mg/L after 96 h of exposure. The results obtained showed that the CFP dispersant is environmentally friendly.

Dispersants as an oil spill clean-up technique in the marine environment: A review.

Oil is a major source of energy in the industrial world. Exploitation of oil and rigging activities, transportation via sea, and many other mechanical failures lead to oil spills into the marine environment. In view of these, the suitability and effectiveness of oil spill response methods have always been a topical discussion worldwide. It has become necessary, now than ever, for existing spill response methods used to remove oil from the environment to be improved upon and more importantly, develop new response materials that are sustainable and environmentally friendly. There exist surfactants in nature that are non-toxic and biodegradable, which can be explored to produce potential dispersants to help remove oil safely from the surface of marine water. This review comprises of the works and resourceful materials produced by various researchers and agencies in the field of oil spill response, placing emphasis on the use of dispersants in the marine environment.

Curcumin loaded Ag-TiO2-halloysite nanotubes platform for combined chemo-photodynamic therapy treatment of cancer cells.

The use of naturally occurring anticancer materials in combination with doped metal oxide has emerged as one of the most promising ways for improving anticancer treatment efficacy. In this study, the anticancer potential of curcumin-loaded Ag-TiO2-halloysite nanotubes (curcumin-loaded Ag-TiO2-HNTs) was examined. Ag-TiO2-HNTs with different wt% of Ag-TiO2 were synthesized and characterized using XRD, TGA, FT-IR, UV-Vis spectroscopy, and SEM-EDX. The XRD results revealed the presence of crystalline TiO2. However, the presence of Ag was detected through the SEM-EDX analysis. Cyclic voltammetry measurements suggested the enhancement of the release of ROS from TiO2 upon deposition with Ag. FT-IR and TGA analysis confirmed the successful loading of curcumin inside the nanotubes of the halloysite. In vitro drug released studies revealed the release of approximately 80-99% curcumin within 48 hours. Kinetic model studies revealed that the release of curcumin from HNT and Ag-TiO2-HNT followed the first-order and Higuchi models, respectively. The light irradiated curcumin-loaded Ag-TiO2-HNTs samples exhibited considerable anticancer potential as compared to the free curcumin, irradiated Ag-TiO2 NPs samples, and unirradiated curcumin loaded Ag-TiO2-HNTs samples. The obtained results revealed that combined chemo- and photodynamic therapy using curcumin-loaded Ag-TiO2-HNTs nanomaterial has the potential as an effective anticancer treatment method.

Monodispersed AgNPs Synthesized from the Nanofactories of Theobroma cacao (Cocoa) Leaves and Pod Husk and Their Antimicrobial Activity.

Silver nanoparticles (AgNPs) have been synthesized from the more chemically rich and diverse cocoa pod; the synthesis of silver nanoparticles from cocoa leaves, which are less rich and have low diversity in bioactive molecules, is yet to be achieved. In this work, AgNPs produced using the extracts of the cocoa leaf (CL) and cocoa pods (CP) have been investigated and their antimicrobial activity against E. coli was evaluated. UV-visible absorption spectroscopy was used to examine the reduction of silver ions in solution and the surface plasmon resonance of AgNPs. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) were used to further characterize the nanoparticles. The crystalline nature of AgNPs was confirmed by XRD, and the purity and presence of elemental silver were determined by EDX. CL-AgNPs were observed to have a surface plasmon resonance of 425 nm, while CP-AgNPs had a surface plasmon resonance of 440 nm. CL-AgNPs had a significantly higher purity than CP-AgNPs. With a shorter nucleation time, the intensity of the UV-Vis spectrum was always higher in the case of CL-AgNPs, indicating a larger population of bioactive molecules available for CL-AgNPs synthesis. FTIR confirmed the presence of phenolic compounds in the leaf and pod extract, implying that water-soluble polyphenolic and flavonoid chemicals are responsible for nanoparticle reduction, capping, and stability. AgNPs generated from CL and CP extracts are polydispersed, with particle sizes of 10-110 nm and 20-680 nm, respectively, according to DLS. The corresponding zeta potentials measured are -2.7 mV for CL-AgNPs and -0.93 mV for CP-AgNPs. The zeta potential values suggest that the particles have long-term stability. Furthermore, CL-AgNPs outperformed CP-AgNPs in terms of antibacterial activity against Escherichia coli. CL-AgNPs were found to have a maximal inhibitory zone of 21 mm.

Synthesis of TiO2-Ag3PO4 photocatalyst material with high adsorption capacity and photocatalytic activity: application in the removal of dyes and pesticides.

The photocatalytic activity of TiO2 can be enhanced by coupling it with other semiconductors and the semiconductor composites may find useful application in water treatment technologies. TiO2-Ag3PO4 composites were synthesized and characterized with XRD, SEM-EDX and DRS. The synthesized TiO2-Ag3PO4 showed high photocatalytic activity in the presence UV-vis light on rhodamine B, methylene blue and the pesticides imidacloprid, atrazine and pyrimethanil. LC-MS analysis of the photodegraded pyrimethanil led to the identification of hydroxylated and aliphatic derivatives of pyrimethanil. The photocatalytic activity of the coupled semiconductor was higher than that of the bare TiO2 and Ag3PO4 and this was attributed to the unique band matching between TiO2 and Ag3PO4 which resulted in efficient charge separation and subsequent reduction in the electron-hole recombination. In addition, the synthesized TiO2-Ag3PO4 showed strong adsorption for water soluble dyes implying that TiO2-Ag3PO4 can remove pollutants through photocatalysis and adsorption. The results from the study showed the potential application of TiO2-Ag3PO4 composite in water treatment technologies.

Chitosan-Coated Halloysite Nanotubes As Vehicle for Controlled Drug Delivery to MCF-7 Cancer Cells In Vitro.

The aim of the work is to improve the release properties of curcumin onto human breast cancer cell lines using coated halloysite nanotubes (HNTs) with chitosan as a polycation. A loading efficiency of 70.2% (w/w) was attained for loading 4.9 mg of the drug into 0.204 g bed volume of HNTs using the vacuum suction method. Results acquired from Brunauer-Emmett-Teller (BET), Fourier-transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), scanning electron spectroscopy (SEM), zeta potential, and thermogravimetric analysis (TGA) indicated the presence of the drug and the biopolymer in and around the nanotubes. The release properties of drug-loaded HNTs (DLHNTs) and chitosan-coated drug-loaded HNTs (DLHNTs-CH) were evaluated. The release percentages of DLHNTs and DLHNTs-CH after 6 h were 50.7 and 37%, respectively. Based on the correlation coefficients obtained by fitting the release nature of curcumin from the two samples, the Korsmeyer-Peppas model was found to be the best-fitted model. In vitro cell viability studies were carried out on the human breast cancer cell line MCF-7, using the MTT and trypan blue exclusion assays. Prior to the Trypan blue assay, the IC50 of curcumin was determined to be ~30 µM. After 24 h of incubation, the recorded cell viability values were 94, 68, 57, and 51% for HNTs, DLHNTs-CH, DLHNTs, and curcumin, respectively. In comparison to the release studies, it could be deducted that sustained lethal doses of curcumin were released from the DLHNTs-CH within the same time. It is concluded from this work that the "burst release" of naked drugs could be slowly administered using chitosan-coated HNTs as potential drug carriers.

Microwave- and Formaldehyde-Assisted Synthesis of Ag-Ag3PO4 with Enhanced Photocatalytic Activity for the Degradation of Rhodamine B Dye and Crude Oil Fractions.

The release of crude oil and water-soluble dyes into our marine environment is a major global problem. An efficient semiconductor Ag-Ag3PO4 photocatalyst was synthesized using formaldehyde as a reducing agent to form surface active Ag on Ag3PO4 under microwave radiation for heating, and its potential in destroying environmental pollutants has been examined. The diffuse reflectance spectroscopy of Ag-Ag3PO4 revealed an enhanced absorption in the visible light region. The rate of photocatalytic degradation of rhodamine B by Ag-Ag3PO4 was over 4-fold compared to Ag3PO4. The potential application of Ag-Ag3PO4 in oil spill remediation was also examined through photocatalytic degradation of benzene, n-hexane, and 1:1 v/v benzene/methanol crude oil-soluble fractions. UV-vis and gas chromatography-mass spectrometry analysis of the crude oil components after visible light irradiation showed excellent degradation. The photocatalytic efficiency enhancement of Ag-Ag3PO4 is attributed to the excellent electron trapping of silver nanoparticles deposited on the surface of Ag3PO4. This work will motivate future studies to develop recyclable visible light photocatalysts for many applications.

Characterization and Inhibitory Effects of Magnetic Iron Oxide Nanoparticles Synthesized from Plant Extracts on HeLa Cells.

Magnetic Fe3O4 nanoparticles were synthesized from maize leaves and plantain peels extract mediators. Particles were characterized, and the inhibitory effects were studied on HeLa cells in vitro using cyclic voltammetry (CV). Voltammograms from the CV show that Fe3O4 NPs interaction with HeLa cells affected their electrochemical behavior. The nanoparticles formed with higher Fe3+/Fe2+ molar ratio (2.8 : 1) resulted in smaller crystallite sizes compared to those formed with lower Fe3+/Fe2+ molar ratio (1.4 : 1). The particles with the smallest crystallite size showed higher anodic peak currents, whereas the larger crystallite sizes resulted in lower anodic peak currents. The peak currents relate to cell inhibition and are confirmed by the half-maximum inhibitory concentration (IC50). The findings show that the particles have a different inhibitory mechanism on HeLa cells ion transfer and are promising to be further exploited for cancer treatment.

Ag2CO3-halloysite nanotubes composite with enhanced removal efficiency for water soluble dyes.

The release of water soluble dyes into the environment is an utmost concern in many countries. This paper presents the effects of Ag2CO3-halloysite composites on the efficient removal of water soluble dyes. In this study, NaHCO3 solution was added dropwisely to halloysite nanotubes (HNTs) dispersed in aqueous AgNO3 to form Ag2CO3-HNTs composite. The synthesized Ag2CO3-HNTs composite was characterized with Diffused Reflectance Spectroscopy (DRS), X-ray Diffraction (XRD), Thermogravimetric analysis (TGA), Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDX) and Fourier Transform Infra-Red (FT-IR) spectroscopy. The photocatalytic activity and the adsorption capacity of Ag2CO3-HNTs on methylene blue and rhodamine b dyes were dependent on pH and the amount of HNTs used in the synthesis. The photodegradation efficiency of Ag2CO3 was lower when compared with that of the composite material. This observation is due to the reduction in the electron-hole recombination with the HNTs acting as electron trapping site and the enhanced aqueous dispersity of Ag2CO3-HNTs. The enhanced adsorption of water soluble dyes by the Ag2CO3-HNTs resulted from the electrostatic attraction of cationic dyes to the surface of the HNTs (negatively charged). The Ag2CO3-HNTs therefore removed dye pollutants through a combination of photocatalytic and adsorption processes. The results obtained during the study confirmed the potential application of Ag2CO3-HNTs composite in water treatment technologies.

Modified halloysite nanoclay as a vehicle for sustained drug delivery.

This paper presents the effect of modified halloysite nanotubes on the sustained drug release mechanisms of sodium salicylate. Acid treatment and composite polymer-halloysite modification techniques were adopted in this study. After each modification, sodium salicylate drug was loaded, and in vitro release properties were evaluated and compared with the raw unmodified halloysite nanotubes. The results obtained from SEM, TEM and FTIR analyses indicate that both acid treatment and composite formation have no effect on the tubular structure and morphology of halloysite. However, modification of the halloysite nanotubes did influence the drug release rate. In the acid treatment modification, there was an improved loading of sodium salicylate drug which resulted in the sustain release of large amount of the sodium salicylate. In the polymer/halloysite composite formation, a consistent layer of polymer was formed around the halloysite during the composite formation and thus delayed release providing sustained release of sodium salicylate drug over a longer period of time as compared to the acid treated and unmodified halloysite. The results from the invitro release were best fitted with the Higuchi and the Koresymer-Peppas models.

The effect of titanium dioxide synthesis technique and its photocatalytic degradation of organic dye pollutants.

Nanostructured mesoporous titanium dioxide (TiO2) particles with high specific surface area and average crystallite domain sizes within 2 nm and 30 nm have been prepared via the sol-gel and hydrothermal procedures. The characteristics of produced nanoparticles have been tested using X-Ray Diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area analysis, Scanning Electron Microscopy (SEM), Fourier Transform Infra-Red (FTIR), and Raman Spectroscopy as a function of temperature for their microstructural, porosity, morphological, structural and absorption properties. The as-synthesized TiO2 nanostructures were attempted as catalysts in Rhodamine B and Sudan III dyes' photocatalytic decomposition in a batch reactor with the assistance of Ultra Violet (UV) light. The results show that for catalysts calcined at 300 °C, ∼100 % decomposition of Sudan III dye was observed when Hydrothermal based catalyst was used whiles ∼94 % decomposition of Rhodamine B dye was observed using the sol-gel based catalysts. These synthesized TiO2 nanoparticles have promising potential applications in the light aided decomposition of a wide range of dye pollutants.

Interfacial adsorption and surfactant release characteristics of magnetically functionalized halloysite nanotubes for responsive emulsions.

Magnetically responsive oil-in-water emulsions are effectively stabilized by a halloysite nanotube supported superparamagnetic iron oxide nanoparticle system. The attachment of the magnetically functionalized halloysite nanotubes at the oil-water interface imparts magnetic responsiveness to the emulsion and provides a steric barrier to droplet coalescence leading to emulsions that are stabilized for extended periods. Interfacial structure characterization by cryogenic scanning electron microscopy reveals that the nanotubes attach at the oil-water interface in a side on-orientation. The tubular structure of the nanotubes is exploited for the encapsulation and release of surfactant species that are typical of oil spill dispersants such as dioctyl sulfosuccinate sodium salt and polyoxyethylene (20) sorbitan monooleate. The magnetically responsive halloysite nanotubes anchor to the oil-water interface stabilizing the interface and releasing the surfactants resulting in reduction in the oil-water interfacial tension. The synergistic adsorption of the nanotubes and the released surfactants at the oil-water interface results in oil emulsification into very small droplets (less than 20µm). The synergy of the unique nanotubular morphology and interfacial activity of halloysite with the magnetic properties of iron oxide nanoparticles has potential applications in oil spill dispersion, magnetic mobilization and detection using magnetic fields.