Interfacial Phenomena of Natural Dispersants for Crude Oil Spills.

A natural surfactant was studied to simulate the dispersion process of crude oil in water. The interfacial phenomena of this natural dispersant was compared with a commercially available chemical dispersant, COREXIT EC9500A. This functional surfactant was extracted from the mucilage of the Opuntia ficus-indica cactus species. The evaluation to determine the efficacy to disperse crude oil of the cactus-based mucilage extract (nongelling extract, NE) was based on characterizing surface and interfacial tension, dispersion efficiency, mixing effects, salinity effects, stability, and droplets size distributions. We found that surface tension values follow a linear relationship with respect to the natural logarithm of the concentrations of NE. The application of NE in the water phase led to decreasing oil/water interfacial tensions. Surface tension tests were also used to quantify the effect of oil-in-water (O/W) emulsion ratios once either natural or commercialized dispersants were added. A key finding of our work is that the surface tension between typical 6% and 3% v/v O/W emulsions was significantly reduced with the addition of discrete amounts of NE. This result indicated that the dynamic balance between O/W and water-in-oil (W/O) emulsions was thermodynamically more stable toward O/W emulsion states with NE. We also found that O/W emulsions with higher dispersion effectiveness were formed for both 10 and 35 practical salinity units, as the dispersant to oil ratios increased, with a significant correlation to the mixing energy. We observed that the O/W emulsions with natural dispersants had a significantly smaller weighted average diameter compared to those with COREXIT EC9500A. Such a phenomenon can be explained by understanding intermolecular interactions due to the structure and type of dispersant. In conclusion, cactus-based mucilage extracts could be used as environmentally benign dispersants and, therefore, reduce negative social perceptions of the application of dispersants to clean up spilled oil.

Responsive coatings from naturally occurring pectin polysaccharides.

Pectin polysaccharides have significant potential as all-natural, non-toxic "green" coatings that exhibit thermally-cued swelling behavior. Herein, ultra-thin coatings of highly-esterified pectin polysaccharides were cross-linked with calcium chloride (CaCl2) and their swelling in water was investigated with ellipsometry. At low temperatures, the coatings swell to 2-3 times their dry layer thickness. As the temperature is increased, the coatings show a pronounced decrease in swollen thickness, reminiscent of the hydrophilic-hydrophobic transition observed in lower critical solution temperature (LCST) polymers. Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy establishes that this transition is driven by dehydration of the esterified galacturonic acid residues along the pectin backbone. By adjusting both the CaCl2 concentration used to crosslink the pectin coatings as well as pH of swelling medium, the pectin coatings could be judiciously tuned for a desired swelling response as a function of temperature. Due to their non-toxic and responsive nature, it was further demonstrated that such coatings could be used in applications to control cell adhesion.

Combining Ferric Salt and Cactus Mucilage for Arsenic Removal from Water.

New methods to remediate arsenic-contaminated water continue to be studied, particularly to fill the need for accessible methods that can significantly impact developing communities. A combination of cactus mucilage and ferric (Fe(III)) salt was investigated as a flocculation-coagulation system to remove arsenic (As) from water. As(V) solutions, ferric nitrate, and mucilage suspensions were mixed and left to stand for various periods of time. Visual and SEM observations confirmed the flocculation action of the mucilage as visible flocs formed and settled to the bottom of the tubes within 3 min. The colloidal suspensions without mucilage were stable for up to 1 week. Sample aliquots were tested for dissolved and total arsenic by ICP-MS and HGAFS. Mucilage treatment improved As removal (over Fe(III)-only treatment); the system removed 75-96% As in 30 min. At neutral pH, removal was dependent on Fe(III) and mucilage concentration and the age of the Fe(III) solution. The process is fast, achieving maximum removal in 30 min, with the majority of As removed in 10-15 min. Standard jar tests with 1000 µg/L As(III) showed that arsenic removal and settling rates were pH-dependent; As removal was between 52% (high pH) and 66% (low pH).

Inhibition of heparin precipitation, bacterial growth, and fungal growth with a combined isopropanol-ethanol locking solution for vascular access devices.

BACKGROUND: Clinical reports of ethanol-lock use for the prevention of catheter-related bloodstream infections have been marked by the occurrence of serious catheter occlusions, particularly among children with mediports. We hypothesized that precipitate forms when ethanol mixes with heparin at the concentrations relevant for vascular access devices, but that the use of a combination of two alcohols, ethanol and isopropanol, would diminish heparin-related precipitation, while retaining anti-bacterial and anti-fungal effects. METHODS: Heparin (0-100units/mL) was incubated in ethanol-water solutions (30%-70% vol/vol) or in an aqueous solution containing equal parts (35% and 35% vol/vol) of isopropanol and ethanol. Precipitation at temperatures from 4 to 40°C was measured in nephelometric turbidity units using a benchtop turbidimeter. Growth of Escherichia coli, Staphylococcus aureus, and Candida albicans colonies were measured following exposure to solutions of ethanol or isopropanol-ethanol. Groupwise comparisons were performed using analysis of variance with Bonferroni-corrected, post-hoc T-testing. RESULTS: Seventy percent ethanol and heparin exhibit dose-dependent precipitation that is pronounced and significant at the concentrations typically used in mediports (p<0.05). Precipitate is significantly reduced by use of a combined 35% isopropanol-35% ethanol solution rather than 70% ethanol (p<0.05), while maintaining the solution's anti-bacterial and anti-fungal properties. On the other hand, although ethanol solutions under 70% form less precipitate with heparin, such concentrations are also less effective at bacterial colony inhibition than solutions of either 70% ethanol or 35% isopropanol-35% ethanol (p<0.05). CONCLUSIONS: A combined 35% isopropanol-35% ethanol locking solution inhibits bacterial and fungal growth similarly to 70% ethanol, but results in less precipitate than 70% ethanol when exposed to heparin. Further study of a combined isopropanol-ethanol locking solution for the prevention of catheter-related bloodstream infections should focus on the determination as to whether such a locking solution may reduce the rate of precipitation-related catheter occlusion, and whether it may be administered with low systemic toxicity.

Removing heavy metals in water: the interaction of cactus mucilage and arsenate (As (V)).

High concentrations of arsenic in groundwater continue to present health threats to millions of consumers worldwide. Particularly, affected communities in the developing world need accessible technologies for arsenic removal from drinking water. We explore the application of cactus mucilage, pectic polysaccharide extracts from Opuntia ficus-indica for arsenic removal. Synthetic arsenate (As (V)) solutions were treated with two extracts, a gelling extract (GE) and a nongelling extract (NE) in batch trials. The arsenic concentration at the air-water interface was measured after equilibration. The GE and NE treated solutions showed on average 14% and 9% increases in arsenic concentration at the air-water interface respectively indicating that the mucilage bonded and transported the arsenic to the air-water interface. FTIR studies showed that the -CO groups (carboxyl and carbonyl groups) and -OH (hydroxyl) functional groups of the mucilage were involved in the interaction with the arsenate. Mucilage activity was greater in weakly basic (pH 9) and weakly acidic (pH 5.5) pH. This interaction can be optimized and harnessed for the removal of arsenic from drinking water. This work breaks the ground for the application of natural pectic materials to the removal of anionic metallic species from water.

Removal of sediment and bacteria from water using green chemistry.

Although nearly all newly derived water purification methods have improved the water quality in developing countries, few have been accepted and maintained for long-term use. Field studies indicate that the most beneficial methods use indigenous resources, as they are both accessible and accepted by communities they help. In an effort to implement a material that will meet community needs, two fractions of mucilage gum were extracted from the Opuntia ficus-indica cactus and tested as flocculation agents against sediment and bacterial contamination. As diatomic ions are known to affect both mucilage and promote cell aggregation, CaCl(2) was studied in conjunction and compared with mucilage as a bacteria removal method. To evaluate performance, ion-rich waters that mimic natural water bodies were prepared. Column tests containing suspensions of the sediment kaolin exhibited particle flocculation and settling rates up to 13.2 cm/min with mucilage versus control settling rates of 0.5 cm/min. Bacillus cereus tests displayed flocculation and improved settling times with mucilage concentrations lower than 5 ppm and removal rates between 97 and 98% were observed for high bacteria concentration tests (>10(8) cells/ml). This natural material not only displays water purification abilities, but it is also affordable, renewable and readily available.

Alpha,omega-bis(thioacetyl)oligophenylenevinylene chromophores from thioanisol precursors.

The selective cleavage of arylmethyl thioethers provides a convenient protocol for the synthesis of all-E isomers of alpha, omega-bis(thioacetyl)oligophenyenevinylene molecules (OPVs). The S-methyl group is tolerant of Wittig-type and Heck-type reactions for forming OPV structures and can be converted to the S-acetyl group by treatment with sodium thiomethoxide and acetyl chloride. The thermal conditions of the deprotection/reprotection step concurrently isomerize the conjugated chromophore to the all-E isomer, regardless of the stereochemistry of the starting olefins. This approach is demonstrated for a variety of linear and [2.2]paracyclophane containing OPVs, which have been characterized by electrochemical and spectroscopic techniques. Additionally, these S-acetyl-terminated OPVs self-assemble on gold surfaces. Monolayers containing these molecules were characterized by water contact angle measurements, ellipsometry, and X-ray photoelectron spectroscopy.

Preparing contamination-free mica substrates for surface characterization, force measurements, and imaging.

Due to its perfect cleavage that provides large areas of molecularly smooth, chemically inert surfaces, mica is the most commonly used natural substrate in measurements with the surface forces apparatus (SFA), in atomic force microscopy (AFM), and in many adsorption studies. However, preparing mica surfaces that are truly clean is not easy since mica is a high-energy surface that readily adsorbs water, organic contaminants, and gases from the atmosphere. Mica can also become charged on cleaving, which makes it prone to picking up oppositely charged particles or mica flakes from the surroundings. High refractive index particles, such as metals, will adhere to mica through van der Waals forces. Recent articles have demonstrated that particle contamination is obtained when inappropriate cutting and handling procedures for the mica are used. In this paper, we show that both particle and other critical contamination is easy to detect and provide proper steps to take during the sample preparation process.