Determination of UV filters in river water samples by in‐line SPE‐CE‐MS

The use of SPE coupled in‐line to CE using electrospray MS detection (in‐line SPE‐CE‐ESI‐MS) was investigated for the preconcentration and separation of four UV filters: benzophenone‐3, 2,2‐dihydroxy‐4‐methoxybenzophenone, 2,4‐dihydroxybenzophenone and 2‐phenylbenzimidazole‐5‐sulphonic acid. First, a CE‐ESI‐MS method was developed and validated using standard samples, obtaining LODs between 0.06 μg/mL and 0.40 μg/mL. For the in‐line SPE‐CE‐ESI‐MS method, three different sorbents were evaluated and compared: Oasis HLB, Oasis MCX, and Oasis MAX. For each sorbent, the main parameters affecting the preconcentration performance, such as sample pH, volume, and composition of the elution plug, and sample injection time were studied. The Oasis MCX sorbent showed the best performance and was used to validate the in‐line SPE‐CE‐ESI‐MS methodology. The LODs reached for standard samples were in the range between 0.01 and 0.05 ng/mL with good reproducibility and the developed strategy provided sensitivity enhancement factors between 3400‐fold and 34 000‐fold. The applicability of the developed methodology was demonstrated by the analysis of UV filters in river water samples.     

Water PMF for predicting the properties of water molecules in protein binding site

Water is an important component in living systems and deserves better understanding in chemistry and biology. However, due to the difficulty of investigating the water functions in protein structures, it is usually ignored in computational modeling, especially in the field of computer‐aided drug design. Here, using the potential of mean forces (PMFs) approach, we constructed a water PMF (wPMF) based on 3946 non‐redundant high resolution crystal structures. The extracted wPMF potential was first used to investigate the structure pattern of water and analyze the residue hydrophilicity. Then, the relationship between wPMF score and the B factor value of crystal waters was studied. It was found that wPMF agrees well with some previously reported experimental observations. In addition, the wPMF score was also tested in parallel with 3D‐RISM to measure the ability of retrieving experimentally observed waters, and showed comparable performance but with much less computational cost. In the end, we proposed a grid‐based clustering scheme together with a distance weighted wPMF score to further extend wPMF to predict the potential hydration sites of protein structure. From the test, this approach can predict the hydration site at the accuracy about 80% when the calculated score lower than ?4.0. It also allows the assessment of whether or not a given water molecule should be targeted for displacement in ligand design. Overall, the wPMF presented here provides an optional solution to many water related computational modeling problems, some of which can be highly valuable as part of a rational drug design strategy. © 2012 Wiley Periodicals, Inc.     

MICELLE FORMATION BY ANIONIC AND CATIONIC SURFACTANTS IN AQUEOUS 18-CROWN-6 ETHER,P-CYCLODEXTRIN,AND 1,10-PHENANTHROLINE SOLUTIONS AT DIFFERENT TEMPERATURES

The conductances of sodium perfluorooctanoate (SPFO), sodium dodecylsulphate (SDS), dodecyltrimethylammonium bromide (DTAB), and tetradecyltrimethylammonium bromide (TTAB) in 18-crown-6 ether + water (CR+W), p-cyclodextrin + water (CY+W), and 1,10-phenanthroIine + water (Phen+W) mixtures with fixed 4 mM of each additive were determined over the temperature range of 5-55 °C. The conductivity plots for all the surfactants showed single break from which the critical micellization concentration (cmc) and degree of micelle ionization (x) were computed. From the pre and the post micellar slopes of the conductivity curves, the equivalent conductivities of the monomeric (Aass) and the micellar states (Amjc), respectively, were calculated and discussed with respect to the surfactant-additive complexation. It was observed that the micelle formation of all the ionic surfactants irrespective of the nature of their head groups were delayed in CYC+W in comparison to that in CR+W and Phen+W systems over the temperature range studied. The micelle formation of SPFO and SDS in CR+W and Phen+W systems showed stabilization of the respective micelles due to the adsorption of Na⁺-CR and Na+-Phen complexes at the micelle solution interface in comparison to that of DTAB and TTAB.     

Physicochemical Studies on an All-Purpose Pesticide Spray Adjuvant-(APSA-80)

APSA-80, an useful pesticide spray adjuvant is a mixture of 2-[2-(4-nonylphenoxy) ethoxy] ethanol, 1-butanol and tall oil fatty acids. It is strongly surface active and can decrease the surface tension of water to ～20 mNm^?1 at its critical micelle concentration (CMC) of 0.006 g%. APSA-80 itself and its binary mixtures, (APSA-80 + water) and (APSA-80 + isopropylmyristate [IPM]) and ternary mixtures (APSA-80 + water +IPM) can undergo a number of physical changes with rise in temperature; the main changes are in color, turbidity and phases. The ternary mixtures of APSA-80/water/IPM with changing compositions can form mono-, bi-, and triphasic solutions as well as gels and viscous solutions. The gel and viscous phases show characteristic rheological properties of both shear thinning and thickening types. They also show permeation of hydrophilic and oleophilic dyes through them. SEM and optical microscopic measurements have shown interesting surface morphologies of the gels and their vertical projections in three-dimensional pictorial mode. Salts like LiCl, NaCl, KCl, CsCl, MgSO₄, and Al₂(SO₄)₃ can have both minor and major effects on the gel consistencies. The alkanols like ethanol, propanol, and isopropanol are also mild to fairly large gel influencing co solvents. The antibacterial properties of APSA-80 have been studied with two Gram positive bacteria and a yeast; the activities found were moderate.     

Emulsions of Heavy Crude Oils. II. Viscous Responses and Their Influence on Emulsion Stability Measurements

The stability of 30 heavy crude oil emulsions was studied in a parallel-plate laboratory coalescer (DC field). Particularly, viscous responses and their influence on the emulsion stability measurements were investigated. In addition to highlighting previous results from the same experimental setup and discussing these based on recent experience, new results at different temperatures and volume fractions of water were presented. A new semi-empirical model for the characteristic time of the destabilization process was presented. The electrical forces were modelled with a point-dipole approximation and the hydrodynamic resistance to droplet transport was modelled with an empirical term including the logarithmic viscosity of the oil phase. The new model clearly performed much better than the previous model, particularly for very viscous crude oils. Studies of the performance of industrial electrocoalescers have showed that simple electrostatic theory can potentially explain complex separation phenomena when the resistance to the coalescence step is reduced by an efficient demulsifier. The ultimate goal is to build a model for both the laboratory setup and the industrial coalescer so that laboratory experiments can be used to predict the behavior of the industrial process.     

Relationship Between the Polymer Structures and Destabilization of Polymer‐Containing Water‐in‐Oil Emulsions

The viscous properties, scanning electronic microscopy (SEM), and water/oil interfacial tension (IFT) of partially hydrolyzed polyacryamide (HPAM) and hydrophobically associating hydrolyzed polyacryamides modified with N‐dodecylacrylamide were studied with the objective of investigating the influence on destabilization of emulsions. As expected, the copolymers exhibit significant viscosity enhancing capacity and three‐dimensional network structures due to intermolecular hydrophobic associations, and also present high interfacial activities as the IFT decrease with increasing polymer concentration. As a result, the existences of copolymers increased both the viscosity of emulsions and the intensity of interfacial film, in which case slow down the diffusion of demulsifier molecules and enhance the stability of emulsions, finally, the separation of water from oil becomes more difficult.     

Water‐in‐Crude Oil Emulsions in the Burgan Oilfield: Effects of Oil Aromaticity,Resins to Asphaltenes Content (R/(R+A)), and Water pH

Asphaltenes and resins separated from emulsion samples collected from Burgan oil field were used with heptane‐toluene mixtures as model oil to study the effect of oil aromaticity, resin content, and pH of the aqueous phase on the stability of water in model emulsions. It was confirmed that, as long as the asphaltenes are completely solubilized, increasing aromaticity leads to less stable emulsions. A consistent correlation between emulsion stability and relative resin mass content (R/(R+A)) was observed for all three of the field samples. There was a sharp decrease in stability when the R/(R+A) value exceeded 0.75. Emulsion stability was enhanced at high pH and possibly at very low pH (<2).     

Adsorption Mechanism of Comb Polymer Dispersants at the Cement/Water Interface

Comb polymers are commonly used as dispersants to stabilize highly concentrated cement suspensions. The effectiveness of such polymeric additives to stabilize these suspensions is determined to a large extent by the amount adsorbed. In this study we investigated the adsorption characteristics of various comb dispersant containing different graft densities on surfaces of cement particle. The effect of inorganic salts on their adsorption was also examined in order to elucidate their adsorption mechanism. The results show that the adsorption of comb polymer dispersants on cement surface conforms approximately to Langmuir's adsorption isotherm and the characteristic plateau A _s and adsorption free energy ΔG_ads are largely dependent on the anionic group content of the comb polymers. The A _s and ΔG_ads increase with increasing anionic group content. This information suggests that the adsorption of comb polymers on cement surfaces is dominated by electrostatic interaction between COO-groups on the comb polymers and the positive surface of the cement. This conclusion is supported by effects of inorganics such as calcium and sulfate ions, and diffuse reflectance FTIR spectroscopy. The implication of results for tuning polymers for the required performance in cement manufacture should be noted.     

Micellization of Sodium Dodecyl Sulfate in Glycerol Aqueous Mixtures

The effect of glycerol on both micellar formation and the structural evolution of the sodium dodecyl sulfate (SDS) aggregates in the context of the action mechanism of the cosolvent has been studied. The critical micelle concentration and the degree of counterion dissociation of the surfactant over a temperature range from 20°C to 40°C were obtained by the conductance method. The thermodynamic parameters of micellization were estimated by using the equilibrium model of micelle formation. The analysis of these parameters indicated that the lower aggregation of the surfactant is mainly due to a minor cohesive energy of the mixed solvent system in relation to the pure water. The effect of glycerol on the mean aggregation number of the micelles of SDS was analyzed by the static quenching method. It was found that the aggregation number decreased with the glycerol content. This reduction in the micellar size seems to be controlled by an increase in the surface area per headgroup, which was ascribed to a participation of glycerol in the micellar solvation layer. Studies on the micropolarity of the aggregates, as sensed by the probe pyrene, indicated that this microenvironmental parameter is almost unaffected by the presence of glycerol in the mixture. However, an increase in the micellar microviscosity at the surface region was observed from the photophysical behavior of two different probes, rhodamine B and auramine O. These results suggest a certain interaction of the cosolvent in the micellar solvation of SDS micelles.     

Rapid Removal of Organics and Oil Spills from Waters Using Silicone Rubber “Sponges”

We have developed a simple, robust, and efficient technology utilizing cheap and recoverable materials based on commercially available silicone elastomer networks for removing organic solvents and crude oil from waters. Hydrophobic and oleophilic properties of silicone elastomers endow poly(dimethyl siloxane) (PDMS) with the capacity to absorb a large variety of organics, including benzene (B), toluene (T), ethylbenzene (E), and xylene (X), commonly referred to as BTEX, and also crude oils, while at the same time enabling the organic “sponges” to float on waters, which facilitates straightforward handling. We developed a method for generating PDMS particles with variable sizes (ranging from hundreds nanometers to few millimeters) by drop-wise depositing siloxane/cross-linker mixtures into warm water, a process which leads to the cross-linking of the PDMS components. We have tested the capability of the PDMS particles to remove toluene and benzene from water. We also performed similar experiments by utilizing PDMS sheets. In both instances we observed a rapid sorption of the organic phase into PDMS; the amount of absorbed organic solvent depended on the concentration in water and the total mass (volume) of PDMS and did not depend on the geometry of the PDMS “sponge.” In addition, we have examined the uptake of toluene and benzene from toluene/benzene (T/B) mixtures dissolved in water. Our results indicate that the amount of benzene absorbed from the T/B mixtures into PDMS increases relative to the uptake from pure benzene/water solutions. This behavior is associated with toluene acting as a “surfactant” that effectively replaces the more unfavorable PDMS/B contacts with less costly T/B ones. Finally, a simple experiment demonstrates qualitatively that PDMS is also capable of removing crude oils from oil-contaminated waters.