From stability to permeability of adhesive emulsion bilayers

Water drops dispersed in chloroform and stabilized with phospholipids become adhesive if a bad solvent for lipids, such as silicone oil, is added to the continuous phase. In this way, two sticking drops are separated by a bilayer of phospholipids. By using microfluidic technologies, we probe the stability and properties of such membranes likewise encountered in foams or vesicles. We first establish the stability diagram of adhering drop pairs as a function of the continuous phase composition. We found two regimes of destabilization of the bilayer. The first one concerns a competition between the dynamics of adhesion and the transport of surfactants toward the interfaces that leads to a dilute surfactant coverage. The second one corresponds to a dense surface coverage where the lifetime distribution of the bilayer exponentially decreases as a signature of a nucleation process. In the stable regime, we observe the propagation of adhesion among a concentrated collection of drops. This is another remarkable illustration of the suction consequence when two close deformable objects are pulled apart. Moreover, the present experimental strategy offers a novel way to study the phase diagrams of bilayers from a single phospholipid to a mixture of phospholipids. Indeed, we detect phase transitions at a liquid-liquid interface that are ruled by the amount of bad solvent. Finally, we probe the transport of water molecules through the bilayer and show that its permeability is linked to the adhesion energy that reflects its fluidity.     

The Surge of Metal–Organic-Framework (MOFs)-Based Electrodes as Key Elements in Electrochemically Driven Processes for the Environment

Metal–organic-frameworks (MOFs) are emerging materials used in the environmental electrochemistry community for Faradaic and non-Faradaic water remediation technologies. It has been concluded that MOF-based materials show improvement in performance compared to traditional (non-)faradaic materials. In particular, this review outlines MOF synthesis and their application in the fields of electron- and photoelectron-Fenton degradation reactions, photoelectrocatalytic degradations, and capacitive deionization physical separations. This work overviews the main electrode materials used for the different environmental remediation processes, discusses the main performance enhancements achieved via the utilization of MOFs compared to traditional materials, and provides perspective and insights for the further development of the utilization of MOF-derived materials in electrified water treatment.     

Predicting the solubility of xenon in n-hexane and n-perfluorohexane: a simulation and theoretical study

The solubility of xenon in n-hexane and n-perfluorohexane has been studied using both molecular simulation and a version of the SAFT approach (SAFT-VR). The calculations were performed close to the saturation line of each solvent, between 200 K and 450 K, which exceeds the smaller temperature range where experimental data are available in the literature. Molecular dynamics simulations, associated with Widom's test particle insertion method, were used to calculate the residual chemical potential of xenon in n-hexane and n-perfluorohexane and the corresponding Henry's law coefficients. The simulation results overestimate the solubility of xenon in both solvents when simple geometric combining rules are used, but are in good agreement if a binary interaction parameter is included. With the SAFT-VR approach we are able to reproduce the experimental solubility for xenon in n-hexane, using simple Lorentz-Berthelot rules to describe the unlike interaction. In the case of n-perfluorohexane as a solvent, a binary interaction parameter was introduced, taken from previous work on (xe + C₂F₆) mixtures. Overall, good agreement is obtained between the simulation, theoretical and experimental data.     

Dictums for problem solving and approximation in mathematical acoustics: examples involving low-frequency vibration and radiation

A sequence of dictums for mathematical acoustics is given representing opinions intended to be regarded as authoritative, but not necessarily universally agreed upon. The dictums are presented in the context of the detailed solution for a class of problems involving the forced vibration of a long cylinder protruding half-way into a half-space bounded by a compliant surface (impedance boundary) characterized by a spring constant. One limiting case corresponds to a cylinder vibrating within an infinite rigid baffle, and another limiting case corresponds to a vibrating cylinder on the compliant surface of an incompressible fluid. The second limiting case is identified as analogous to that of a floating half-submerged cylinder whose vibrations cause water waves to propagate over the surface. Attention is focused on vibrations at very low frequencies. Difficulties with insuring a causal solution are pointed out and dictums are given as to how one overcomes such difficulties. Various approximation techniques are described. The derivations involve application of the theory of complex variables and the method of matched asymptotic expansions, and the results include the apparent entrained mass in the near field of the cylinder and the radiation resistance per unit length experienced by the vibrating cylinder.     

Substituted carborane-appended water-soluble single-wall carbon nanotubes: new approach to boron neutron capture therapy drug delivery

Substituted C(2)B(10) carborane cages have been successfully attached to the side walls of single-wall carbon nanotubes (SWCNTs) via nitrene cycloaddition. The decapitations of these C(2)B(10) carborane cages, with the appended SWCNTs intact, were accomplished by the reaction with sodium hydroxide in refluxing ethanol. During base reflux, the three-membered ring formed by the nitrene and SWCNT was opened to produce water-soluble SWCNTs in which the side walls are functionalized by both substituted nido-C(2)B(9) carborane units and ethoxide moieties. All new compounds are characterized by EA, SEM, TEM, UV, NMR, and IR spectra and chemical analyses. Selected tissue distribution studies on one of these nanotubes, {([Na(+)][1-Me-2-((CH(2))(4)NH-)-1,2-C(2)B(9)H(10)][OEt])(n)(SWCNT)} (Va), show that the boron atoms are concentrated more in tumors cells than in blood and other organs, making it an attractive nanovehicle for the delivery of boron to tumor cells for an effective boron neutron capture therapy in the treatment of cancer.     

Elution behavior of unsaponifiable lipids with various capillary electrochromatographic stationary phases

Capillary electrochromatographic (CEC) separations of unsaponifiable lipids, tocopherols (T), tocotrienols (T3), and plant sterols were studied under various conditions. Investigated stationary phases include pentafluorophenylsilica (PFPS), triacontylsilica (TCS), and octadecylsilica (ODS) phases. A baseline separation of four sterols (ergosterol, lanosterol, sitosterol and stigmasterol) on ODS was achieved and their elution order was found to be dictated by side-chain structures. CEC of the tocol-derived compounds on PFPS in aqueous methanol yielded the most satisfactory results with complete resolution of all components eluting in the order deltaT3>beta3>gammaT3>epsilonP>alphaT3>deltaT>zeta2T>betaT>gammaT>alphaT, while a reversal in elution of the epsilonT-alphaT3 pair was observed in aqueous acetonitrile. CEC with a TCS phase in non-aqueous methanol led to a different elution pattern deltaT3>gammaT3>betaT3>alphaT3epsilonT>deltaT>(zeta2+gamma)T>betaT>alphaT, despite favorable resolution of the (gamma-zeta2)T pair along with the observation of inseparable(beta-gamma)T and (beta-gamma)T3 pairs in non-aqueous dimethylformamide. Non-aqueous acetonitrile mobile phases provided unique selectivity for the (gamma-zeta2)T pair and isomer separations on TCS. Variations in separation and retention factors of relevant antioxidant species with CEC variables were evaluated. Examples of CEC quantification of unsaponifiable fractions of rice bran oils and soybean oils are presented.     

Investigation of the Chemical Differences between Native and Bypass Coronary Artery Plaques from the Same Heart Using Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (CP/MAS-NMR)

The plaque deposits in bypass arteries and native arteries from the same heart have been studied using solid state cross polarization nuclear magnetic resonance (CP/MAS NMR). Both ¹³C and ³¹P signals were observed. The samples are of interest because plaque in native arteries may have deposited during the lifetime of the patient. However, plaque in the bypass occurred since bypass surgery. It has been observed that the mature plaque in native arteries was more calcified than that in bypass arteries, especially if the latter had not matured to become significant in size. Results showed that the concentrations of carboxylate carbons present in cholesterol esters were similar in native and bypass arteries. However, the areas of the ¹³C peaks of the carboxylate compared to the sum of areas of all other ¹³C arteries indicated that the carboxylate was attached to five or six other carbons. From this we can calculate that the carboxylate to other carbon ratio in the remainder must be 1:4 or 1:3. This indicates large quantities of other organic compounds in the deposits. Studies of ³¹P showed that phosphorus existed primarily as hydroxyapatite in the crystalline native plaque. However, a large proportion existed as organic phosphorus in the bypass plaque. In addition, we studied the interactions of calcium with homocysteine and cholesterol. Calcium-homocysteine and cholesterol-homocysteine precipitates were characterized using ¹³C solid state NMR. Results showed that calcium appeared to interact with sulphur in the homocysteine which seemed to form dimers and polymers.