Chemotherapeutic cytotoxic agents such as paclitaxel (PTX) are considered essential for the treatment of various cancers. However, PTX injection is associated with severe systemic side effects and high rates of patient noncompliance. Micelle formulations (MFs) are nano-drug delivery systems that offer a solution to these problems. Herein, we report an advantageous carrier for the transdermal delivery of PTX comprising a new MF that consists of two biocompatible surfactants: cholinium oleate ([Cho][Ole]), which is a surface-active ionic liquid (SAIL), and sorbitan monolaurate (Span-20). A solubility assessment confirmed that PTX was readily solubilized in the SAIL-based micelles via multipoint hydrogen bonding and cation-π and π-π interactions between PTX and SAIL[Cho][Ole]. Dynamic light scattering (DLS) and transmission electron microscopy revealed that in the presence of PTX, the MF formed spherical PTX-loaded micelles that were well-distributed in the range 8.7-25.3 nm. According to DLS, the sizes and size distributions of the micelle droplets did not change significantly over the entire storage period, attesting to their physical stability. In vitro transdermal assessments using a Franz diffusion cell revealed that the MF absorbed PTX 4 times more effectively than a Tween 80-based formulation and 6 times more effectively than an ethanol-based formulation. In vitro and in vivo skin irritation tests revealed that the new carrier had a negligible toxicity profile compared with a conventional ionic liquid-based carrier. Based on these findings, we believe that the SAIL[Cho][Ole]-based MF has potential as a biocompatible nanocarrier for the effective transdermal delivery of poorly soluble chemotherapeutics such as PTX.
In silico and experimental investigations were conducted to explore the effects of substituting hydrophobic residues, Val, Met, Leu, Ile, Trp, and Phe into Gln 114 of T1 lipase. The in silico investigations accurately predicted the enzymatic characteristics of the mutants in the experimental studies and provided rationalization for some of the experimental observations. Substitution with Leu successfully improved the conformational stability and enzymatic characteristics of T1 lipase. However, replacement of Gln114 with Trp negatively affected T1 lipase and resulted in the largest disruption of protein stability, diminished lipase activity and inferior enzymatic characteristics. These results suggested that the substitution of a larger residue in a densely packed area of the protein core can have considerable effects on the structure and function of an enzyme. This is especially true when the residue is next to the catalytic serine as demonstrated with the Phe and Trp mutation.
Research was aimed on microemulsion-based hydrogel for voriconazole. Oleic acid and isopropyl myristate as lipid phases; tween 20: tween 80 as surfactants and PEG600 as cosurfactant were selected to formulate voriconazole microemulsions. The promising microemulsions in terms of zeta potential, pH, viscosity, and drug release were selected and developed into hydrogels using carbopol 934. Resulting microemulsion-based hydrogel (MBH) of voriconazole were evaluated for in vitro diffusion and ex vivo permeation. Antifungal potentials of MBH were assessed against selected fungal strains. Optimal MBH formulations, O6 and O8 had displayed their antifungal potentials with enlarged zone of inhibition against selected fungal strains.
A novel aqueous two-phase system composed of a surfactant and sorbitol was employed for the first time to purify pectinase from Psidium guajava. The influences of different parameters, including the type and concentration of the surfactant and the concentration and composition of the surfactant/sorbitol ratio, on the partitioning behavior and recovery of pectinase were investigated. Moreover, the effects of system pH and the crude load on purification fold and the yield of purified pectinase were studied. The experimental results indicated that the pectinase was partitioned into surfactant-rich top phase, and the impurities were partitioned into the sorbitol-rich bottom phase with the novel method involving an ATPS composed of 26% (w/w) Triton X-100 and 23% (w/w) sorbitol at 54.2% of the TLL crude load of 20% (w/w) at pH 6.0. The enzyme was successfully recovered by this method with a high purification factor of 15.2 and a yield of 98.3%, whereas the phase components were also recovered and recycled at rates above 96%. This study demonstrated that this novel ATPS method can be used as an efficient and economical alternative to the traditional ATPS for the purification and recovery of the valuable enzyme.
An effective biosurfactant producer and extremophiles bacteria, Bacillus cereus KH1, was isolated from textile effluent and the biosurfactant was produced using molasses as the sole carbon source. Growth parameters such as pH, temperature, salinity and concentration of molasses were optimised for decolourising the textile effluent with 24-h incubation. The biosurfactant property of B. cereus KH1 was evaluated based on haemolytic activity, oil displacement technique, drop-collapsing test and emulsification index. The results of the produced biosurfactant showed a positive reaction in haemolytic activity, oil displacement technique, drop-collapsing test and exhibiting a 67% emulsification index. The cell-free broth was stable in 40 °C pH 7, 7% salinity and 7% molasses. Thin-Layer Chromatography and Fourier Transform Infrared Spectroscopy analysis revealed that the biosurfactant was a lipopeptide with a yield 2.98 g L-1. These findings proved the synergistic action of B. cereus KH1 with lipopeptide biosurfactant may accelerated the decolourisation efficiency to 87%.
In this research we assess the feasibility of using palm oil agricultural refinery waste as a carbon source for the production of rhamnolipid biosurfactant through fermentation. The production and characterization of rhamnolipid produced by Pseudomonas aeruginosa PAO1 grown on palm fatty acid distillate (PFAD) under batch fermentation were investigated. Results show that P. aeruginosa PAO1 can grow and produce 0.43gL(-1) of rhamnolipid using PFAD as the sole carbon source. Identification of the biosurfactant product using mass spectrometry confirmed the presence of monorhamnolipid and dirhamnolipid. The rhamnolipid produced from PFAD were able to reduce surface tension to 29mNm(-1) with a critical micelle concentration (CMC) 420mgL(-1) and emulsify kerosene and sunflower oil, with an emulsion index up to 30%. Results demonstrate that PFAD could be used as a low-cost substrate for rhamnolipid production, utilizing and transforming it into a value added biosurfactant product.
The effects of initial oil concentration and the Corexit 9500 dispersant on the rate of bioremediation of petroleum hydrocarbons were investigated with a series of ex-situ seawater samples. With initial oil concentrations of 100, 500, 1,000 and 2,000 mg/L, removal of total petroleum hydrocarbons (TPHs) with dispersant were 67.3%, 62.5%, 56.5% and 44.7%, respectively, and were 64.2%, 55.7%, 48.8% and 37.6% without dispersant. The results clearly indicate that the presence of dispersant enhanced crude oil biodegradation. Lower concentrations of crude oil demonstrated more efficient hydrocarbon removal. Based on these findings, bioremediation is not recommended for crude oil concentrations of 2,000 mg/L or higher.
A series of surfactants combining carbohydrate and imidazolium head groups were prepared and investigated on their assembly behavior. The presence of the imidazolium group dominated the interactions of the surfactants, leading to high CMCs and large molecular surface areas, reflected in curved rather than lamellar surfactant assemblies. The carbohydrate, on the other hand, stabilized molecular assemblies slightly and reduced the surface tension of surfactant solutions considerably. A comparative emulsion study discourages the use of pure alkyl imidazolium glycosides owing to reduced assembly stabilities compared with APGs. However, the surfactants are believed to have potential as component in carbohydrate based surfactant mixtures.
The cost of chemicals prohibits many technically feasible enhanced oil recovery methods to be applied in oil fields. It is shown that by-products from oil palm processing can be a source of valuable chemicals. Analysis of the pyrolysis oil from oil palm shells, a by-product of the palm oil industry, reveals a complex mixture of mainly phenolic compounds, carboxylic acids, and aldehydes. The phenolic compounds were extracted from the pyrolysis oil by liquid-liquid extraction using alkali and an organic solvent and analyzed, indicating the presence of over 93% phenols and phenolic compounds. Simultaneous sulfonation and alkylation of the pyrolysis oil was carried out to produce surfactants for application in oil fields. The lowest measured surface tension and critical micelle concentration was 30.2 mNm(-1) and 0.22 wt%, respectively. Displacement tests showed that 7-14% of the original oil in place was recovered by using a combination of surfactants and xanthan (polymer) as additives.
The current investigation evaluated the potential of proniosome as a carrier to enhance skin permeation and skin retention of a highly lipophilic compound, α-mangostin. α-Mangostin proniosomes were prepared using the coacervation phase seperation method. Upon hydration, α-mangostin loaded niosomes were characterized for size, polydispersity index (PDI), entrapment efficiency (EE) and ζ-potential. The in vitro permeation experiments with dermis-split Yucatan Micropig (YMP) skin revealed that proniosomes composed of Spans, soya lecithin and cholesterol were able to enhance the skin permeation of α-mangostin with a factor range from 1.8- to 8.0-fold as compared to the control suspension. Furthermore, incorporation of soya lecithin in the proniosomal formulation significantly enhanced the viable epidermis/dermis (VED) concentration of α-mangostin. All the proniosomal formulations (except for S20L) had significantly (p<0.05) enhanced deposition of α-mangostin in the VED layer with a factor range from 2.5- to 2.9-fold as compared to the control suspension. Since addition of Spans and soya lecithin in water improved the solubility of α-mangostin, this would be related to the enhancement of skin permeation and skin concentration of α-mangostin. The choice of non-ionic surfactant in proniosomes is an important factor governing the skin permeation and skin retention of α-mangostin. These results suggested that proniosomes can be utilized as a carrier for highly lipophilic compound like α-mangostin for topical application.
A new synthesis approach towards biantennary lipids of Guerbet glycoside type was developed based on oleic acid as sustainable resource. Functionalization of the double bond provided access to primary alcohols with α-branched C19-skeleton. Formulation studies with corresponding lactosides indicated formation of vesicles with high assembly stability. A relatively narrow bimodal size distribution of the latter, which turns into a narrow unimodal distribution of small vesicles upon addition of an ionic cosurfactant, suggests potential for a vesicular drug delivery system.
Colloidal gas aphron dispersions (CGAs) can be described as a system of microbubbles suspended homogenously in a liquid matrix. This work examines the performance of CGAs in comparison to surfactant solutions for washing low levels of arsenic from an iron rich soil. Sodium Dodecyl Sulfate (SDS) and saponin, a biodegradable surfactant, obtained from Sapindus mukorossi or soapnut fruit were used for generating CGAs and solutions for soil washing. Column washing experiments were performed in down-flow and up flow modes at a soil pH of 5 and 6 using varying concentration of SDS and soapnut solutions as well as CGAs. Soapnut CGAs removed more than 70% arsenic while SDS CGAs removed up to 55% arsenic from the soil columns in the soil pH range of 5-6. CGAs and solutions showed comparable performances in all the cases. CGAs were more economical since it contains 35% of air by volume, thereby requiring less surfactant. Micellar solubilization and low pH of soapnut facilitated arsenic desorption from soil column. FT-IR analysis of effluent suggested that soapnut solution did not interact chemically with arsenic thereby facilitating the recovery of soapnut solution by precipitating the arsenic. Damage to soil was minimal arsenic confirmed by metal dissolution from soil surface and SEM micrograph.
The application of chemical dispersants in marine oil spill remediation is comprehensively reported across the globe. But, the augmented toxicity and poor biodegradability of reported chemical dispersants have created necessity for their replacement with the bio-based green dispersants. Therefore, in the present study, we have synthesized five ionic liquids (ILs) namely 1-butyl-3-methylimidazolium lauroylsarcosinate, 1,1'-(1,4-butanediyl)bis(1-H-pyrrolidinium) dodecylbenzenesulfonate, tetrabutylammonium citrate, tetrabutylammonium polyphosphate and tetrabutylammonium ethoxylate oleyl ether glycolate, and formulated a water based ILs dispersant combining the synthesized ILs at specified compositions. The effectiveness of formulated ILs dispersant was found between 70.75% and 94.71% for the dispersion of various crude oils ranging from light to heavy. Further, the acute toxicity tests against zebra fish and grouper fish have revealed the practically non-toxic behaviour of formulated ILs dispersant with LC50 value greater than 100 ppm after 96 h. In addition, the formulated ILs dispersant has provided excellent biodegradability throughout the test period. Overall, the formulated new ILs dispersant is deemed to facilitate environmentally benign oil spill remediation and could effectively substitute the use of hazardous chemical dispersants in immediate future.
Chemical dispersants are extensively used for marine oil spill remediation. However, the increased toxicity and low biodegradability of these dispersants restrict their employment in the marine environment. Hence, in this work, we have developed an eco-friendly formulation composed of an ionic liquid,1-butyl-3-methylimidazolium lauroyl sarcosinate [BMIM][Lausar] and sorbitan monooleate (Span) 80. Micellar and interfacial parameters, dispersion effectiveness, as well as the toxicity and biodegradability of the developed formulation were investigated. Micellar properties confirmed a high degree of synergism among the surfactant molecules and the formation of stable micelle. The dispersion effectiveness, at dispersant-to-oil ratio (DOR) of 1:25 (v/v), against three crude oils (Arab, Ratawi, and Doba) was assessed. We achieved a dispersion effectiveness of 68.49%, 74.05%, and 83.43% for Ratawi, Doba, and Arab crude oil, respectively, using a 70:30 (w/w) ratio of Span 80 to [BMIM][Lausar]. Furthermore, the results obtained from optical microscopy and particle size analysis (PSA) indicated that the oil droplet size decreased with higher DOR. Additionally, acute toxicity experiments were conducted on zebrafish (Danio rerio) using the developed formulation, confirming its non-toxic behavior, with LC50 values of 800 mg/L after 96 h. The formulation also exhibited high biodegradability, with only 25.01% of the original quantity remaining after 28 days. Hence, these results suggest that the new formulation has the potential to be a highly effective and environmentally friendly dispersant for oil spill remediation.
A series of sugar-based surfactants, involving a single hydrophobic chain (C12) and two side-by-side arranged head groups, was prepared form simple glucose precursors. All surfactants were highly water soluble and exhibited exclusively micellar assemblies. This behavior makes them interesting candidates for oil in water emulsifiers.
A series of glucose based surfactants varying in chain length and anomeric configuration were synthesized and investigated on their surfactant properties. The synthesis applied glycosylation of propargyl alcohol followed by cycloaddition with alkyl azides in CLICK chemistry fashion. This approach enables a homogeneous coupling of hydrophilic unprotected sugars and hydrophobic paraffin components in low molecular weight alcohols without solvent side reactions, as commonly found for APGs. The combination of alcohols as inert medium with practically quantitative coupling of the surfactant domains avoids particularly hydrophobic contaminations of the surfactant, thus providing access to pure surfactants. ATGs with chain lengths up to 12 carbons exhibit Krafft points below room temperature and no cloud points were detected. The values for the CMC of ATGs with 12 carbon alkyl chains and above were in good agreement with those of corresponding alkyl glucosides. However, lower homologues exhibited significantly smaller CMCs, and the trend of the CMC upon the chain length did not match common surfactant behavior. This deviation may be related to the triazole that links the two surfactant domains.
Quaternary ammonium compounds (QACs) are commonly used as disinfectant in medical care, food industry, detergents and glue industries. This is due to a small concentration of QACs is sufficient to inhibit the growth of various bacteria strains. In this work, the inhibitive power of cationic surfactants, alkyltrimethylammonium bromide (C(n)TAB) in the presence of anionic surfactants, sodium alkyl methyl ester α-sulfonate (C(n)MES) was studied. The growth inhibition test with gram-positive (Staphylococcus aureus) and gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria were used to determine the toxicity of single and mixed surfactants. Results from this work showed that certain mixed surfactants have lower minimum inhibition concentration (MIC) as compared to the single C(n)TAB surfactants. Besides that, it was also found that alkyl chain length and the mixing ratios of the surfactants play a significant role in determining the mixture inhibitive power.
Two novel glycolipids have been synthesized and their phase behaviour studied. They have been characterized using FT-IR, FAB and 13C NMR and 1H NMR to ensure the purity of novel glycolipids. The two glycolipids are distinguished based on the head group of glycolipids (monosaccharide/glucose and disaccharide/maltose). These two novel glycolipids have been used as surfactant to perform two phase diagrams. Phase behaviours that have been investigated are 2-hexyldecyl-beta-D-glucopyranoside (2-HDG)/n-octane/water ternary system and 2-hexyldecyl-beta-D-maltoside (2-HDM)/n-octane/water ternary system. SAXS and polarizing optical microscope have been used to study the phase behaviours of these two surfactants in ternary phase diagram. Study of effect of the head group on branched-alkyl chain surfactants in ternary system is a strategy to derive the structure-property relationship. For comparison, 2-HDM and 2-HDG have been used as surfactant in the same ternary system. The phase diagram of 2-hexyldecyl-beta-D-maltoside/n-octane/water ternary system exhibited a Lalpha phase at a higher concentration regime, followed with two phases and a micellar solution region in a lower concentration regime. The phase diagram of 2-HDG/water/n-octane ternary system shows hexagonal phase, cubic phase, rectangular ribbon phase, lamellar phase, cubic phase as the surfactant concentration increase.
Previous work (M. Sagisaka, et al. Langmuir 31 (2015) 7479-7487), showed the most effective fluorocarbon (FC) and hydrocarbon (HC) chain lengths in the hybrid surfactants FCm-HCn (sodium 1-oxo-1-[4-(perfluoroalkyl)phenyl]alkane-2-sulfonates, where m = FC length and n = HC length) were m and n = 6 and 4 for water solubilization, whereas m 6 and n 6, or m 6 and n 5, were optimal chain lengths for reversed micelle elongation in supercritical CO2. To clarify why this difference of only a few methylene chain units is so effective at tuning the solubilizing power and reversed micelle morphology, nanostructures of water-in-CO2 (W/CO2) microemulsions were investigated by high-pressure small-angle neutron scattering (SANS) measurements at different water-to-surfactant molar ratios (W0) and surfactant concentrations. By modelling SANS profiles with cylindrical and ellipsoidal form factors, the FC6-HCn/W/CO2 microemulsions were found to increase in size with increasing W0 and surfactant concentration. Ellipsoidal cross-sectional radii of the FC6-HC4/W/CO2 microemulsion droplets increased linearly with W0, and finally reached ∼39 Å and ∼78 Å at W0 = 85 (close to the upper limit of solubilizing power). These systems appear to be the largest W/CO2 microemulsion droplets ever reported. The aqueous domains of FC6-HC6 rod-like reversed micelles increased in size by 3.5 times on increasing surfactant concentration from 35 mM to 50 mM: at 35 mM, FC6-HC5 formed rod-like reversed micelles 5.3 times larger than FC6-HC6. Interestingly, these results suggest that hybrid HC-chains partition into the microemulsion aqueous cores with the sulfonate headgroups, or at the W/CO2 interfaces, and so play important roles for tuning the W/CO2 interfacial curvature. The super-efficient W/CO2-type solubilizer FC6-HC4, and the rod-like reversed micelle forming surfactant FC6-HC5, represent the most successful cases of low fluorine content additives. These surfactants facilitate VOC-free, effective and energy-saving CO2 solvent systems for applications such as extraction, dyeing, dry cleaning, metal-plating, enhanced oil recovery and organic/inorganic or nanomaterial synthesis.
Colloidal gas aphrons (CGAs) are highly stable, spherical, micrometer-sized bubbles encapsulated by surfactant multilayers. They have several intriguing properties, including: high stability, large interfacial area, and the ability to maintain the same charge as their parent molecules. The physical properties of CGAs make them ideal for biotechnological applications such as the recovery of a variety of: biomolecules, particularly proteins, yeast, enzymes, and microalgae. In this review, the bio-application of CGAs for the recovery of natural components is presented, as well as: experimental results, technical challenges, and critical research directions for the future. Experimental results from the literature showed that the recovery of biomolecules was mainly determined by electrostatic or hydrophobic interactions between polyphenols and proteins (lysozyme, β-casein, β-lactoglobulin, etc.), yeast, biological molecules (gallic acid and norbixin), and microalgae with CGAs. Knowledge transfer is essential for commercializing CGA-based bio-product recovery, which will be recognized as a viable technology in the future.