Headgroup effect on drag reduction and rheological properties of micellar solutions of quaternary ammonium surfactants

Two sets of cationic surfactants each with essentially the same alkyl chains but different headgroup structures were studied to investigate the effects of surfactant headgroup structure on micelle microstructures, drag reduction (DR) and rheological properties at certain counterion and surfactant concentrations. Cetyldimethylethylammonium bromide (CDMEAB) was compared with alkyltrimethyl ammonium bromide (CnTAB) and benzyldimethyl(hydrogenated tallow)ammonium chloride (DMHTB) was compared with alkyltrimethylammonium chloride (CmTAC), respectively. Surfactants with larger headgroups showed lower high temperature limits for DR. CDMEAB systems have better DR abilities than CnTAB below room temperature but the opposite is true at higher temperatures. DMHTB has stronger counterion binding ability than CmTAC, giving better DR properties than CmTAC at low counterion concentration, but has a lower upper temperature limit for DR. These results provide further understanding of the self-assembly nature of threadlike micelles of cationic surfactants and guidance for design of effective surfactant structures to meet particular DR requirements.     

Modulation of fragmental charge transfer via hydrogen bonds. Direct measurement of electronic contributions

Hydrogen bonds play an important role in an overwhelming variety of fields from biology to surface and supramolecular chemistry. The term "hydrogen bond" refers to a wide range of interactions with various covalent and polar contributions. In particular, hydrogen bonds have an important role in the folding and packing of peptides and nucleic acids. Recent studies also point to the importance of hydrogen bonding in the context of second-shell interactions, in metal binding and selectivity in metalloproteins, and in controlling the dynamics of membrane proteins. In this study, we demonstrate and quantify the modulation of fragmental charge transfer from hydrogen-bonded ligands to a metal center, by employing our recently introduced molecular potentiometer. The molecular details that affect this type of fragmental charge transfer are presented and a path for transferring chemical information is demonstrated. We found that H-bond interactions in the extended positions of axial ligands provide an effective means of modulating the amount of fragmental charge transfer to a metal center, thereby dramatically influencing the electronic properties of the ligand, the binding affinity, and the binding of additional ligands. The magnitude of fragmental charge-transfer modulation induced by a single ligand-solvent H-bond interaction is comparable to those induced by covalent substitution, although H-bond enthalpy is only on the order of several kilojoules per mole. Importantly, we find a significant change in the ligand electronic properties, even for weak C-H...O=C H-bond formation, where the bond enthalpy is substantially lower than for conventional H-bond interactions. The excess fragmental charge transferred to the metal center, deduced from the spectroscopic measurements, correlates well with the computationally determined values. Our findings underscore the importance of second-shell interactions in the active sites of enzymes, beyond the structural and electrostatic importance that is widely recognized today.     

Photocontrolled variations in the wetting capability of photochromic polymers enhanced by surface nanostructuring

The wetting characteristics of surfaces of polymers doped with photochromic spiropyran molecules can be tuned when irradiated with laser beams of properly chosen photon energy. The hydrophilicity is enhanced upon UV laser irradiation since the embedded nonpolar spiropyran molecules convert to their polar merocyanine isomers. The process is reversed upon green laser irradiation. Structuring of the photochromic polymeric surfaces with soft lithography enhances significantly the hydrophobicity of the system, indicating that the water droplets on the patterned features interact with air that is trapped in the microcavities, thus creating superhydrophobic air-water contact areas. Furthermore, the light-induced wettability variations of the structured surfaces are enhanced by a factor of 3 compared to those on the flat surfaces. This significant enhancement is attributed to the photoinduced reversible volume changes to the imprinted gratings, which additionally contribute to the wettability changes due to the light-induced photochromic interconversions.     

Protein-A-mediated Targeting of Bacteriochlorophyll-IgG to Staphylococcus aureus: A Model for Enhanced Site-Specific Photocytotoxicity

Abstract— A model for studying the efficiency of photodynamic action with a photosensitizer placed exclusively on the bacterial cell wall has been used. Bacteriochlorophyllide molecules, conjugated to rabbit immunoglobulin G (IgG), were synthesized. The conjugated pigment bacteriochlo-rophyll (Bchl)-IgG bound with high specificity to protein-A residues naturally exposed on the cell wall of the bacterium Staphylococcus aureus Cowan I. In bacterial suspensions the phototoxicity of the targeted conjugates (0.5-2.5 pigment per IgG molecule) was dose dependent (LD₅₀= 1.7 μ M ) in the presence of light (Λ > 550 nm) and inhibited by native IgG but not by ovalbumin, suggesting selective interaction with protein-A on the bacterial cell wall. No dark toxicity was noticed even with the highest conjugate concentration tested. In contrast, the photocytotoxicity of bacteriochlorophyll-serine (Bchl-Ser, LD₅₀= 0.07 μ M ) used as a nontargeted control was not inhibited by IgG. In spite of its lower apparent potency, Bchl-IgG was found to be 30 times more efficacious than Bchl-Ser: At LD₅₀, only 66000 Bchl-IgG molecules were bound per bacterium compared to 1900 000 molecules of Bchl-Ser. The higher efficacy of Bchl-IgG is explained by its exclusive position on the bacterial cell wall. Consequently, photogeneration of oxidative species is confined to the cell wall and its vicinity, a seemingly highly susceptible domain for photodynamic action. In considering the design of cell-specific sensitizers for bacterial and cancer therapies, it would be beneficial to identify the more discretely sensitive subcellular domains as targets.     

Fluorinated heterocyclic compounds. 2. 2,4-difluoro and 4-amino-2-fluoropyrimidines,nucleoside base analogs

Nucleoside base analogs in which fluoro substituents replace the enolic hydroxy groups of uracil, thymine and cytosine have been prepared. Improved methods for the preparation and isolation of the known 2,4-di-fluoropyrimidine, 2,4-difluoro-6-methylpyrimidine and the new 2,4-difluoro-5-methylpyrimidine, 2-fluoro-4-aminopyrimidine, 4-fluoro-2-aminopyrimidine, and other alkylaminofluoropyrimidines are described.     

Drag reduction using surfactants in a rotating cylinder geometry

Turbulent Couette flow between two circular cylinders has been used for drag reduction experiments using surfactants. In the experiments presented here, only the outer cylinder rotates, the inner cylinder remains at rest and accurate measurements of the torque at the inner cylinder are measured. Water is used as a reference fluid. A drag reducing surfactant called Arquad S-50 (Akzo Nobel Surface Chemistry LLC, Chicago, Ill., USA) (5 mM)+NaSal (12.5 mM) was used as the drag reduction agent. This surfactant can reduce the drag up to 70% (a Reynolds number of about 70,000–150,000) as measured by pressure drop in a pipe flow. Experiments in Couette flow also show drag reduction in the turbulent range. Two arrangements were used, (1) one small trip-wire on the inner cylinder, and (2) four larger trip-wires on the outer cylinder. These trips reduce the critical Reynolds number for transition from laminar to turbulent flow. In case (1), we obtained 18% drag reduction at 5,000<Re<15,000 and in case (2), we obtained an average reduction of about 20% at 2,000<Re<10,000, increasing up to 30% at Re=15,000. The paper also discusses two important problems. First, the shear rate is not constant in the radial gap in circular Couette flow. For non-Newtonian fluids, where the molecular viscosity is a function of the shear rate, this effect must be considered. Second, which viscosity should be used in the Reynolds number? For pipe flow measurements, most authors use the viscosity of the solvent (generally water and Newtonian). For measurements in the Couette flow, we use a different approach, which is described in this paper. We conclude that Couette flow is a useful method for drag reduction investigations. Its advantage is the much smaller geometry in comparison to those of conventional test facilities such as wind tunnels, water, or oil channels or in tubes.     

WST11, a novel water-soluble bacteriochlorophyll derivative; cellular uptake, pharmacokinetics, biodistribution and vascular-targeted photodynamic activity using melanoma tumors as a model

WST11 is a novel negatively charged water-soluble palladium-bacteriochlorophyll derivative that was developed for vascular-targeted photodynamic therapy (VTP) in our laboratory. The in vitro results suggest that WST11 cellular uptake, clearance and phototoxicity are mediated by serum albumin trafficking. In vivo, WST11 was found to clear rapidly from the circulation (t1/2=1.65 min) after intravenous bolus injection in the mouse, whereas a longer clearance time (t1/2=7.5 min) was noted in rats after 20 min of infusion. The biodistribution of WST11 in mouse tissues indicates hepatic clearance (t1/2=20 min), with minor (kidney, lung and spleen) or no intermediary accumulation in other tissues. As soon as 1 h after injection, WST11 had nearly cleared from the body of the mouse, except for a temporal accumulation in the lungs from which it cleared within 40 min. On the basis of these results, we set the VTP protocol for a short illumination period (5 min), delivered immediately after WST11 injection. On subjecting M2R melanoma xenografts to WST11-VTP, we achieved 100% tumor flattening at all doses and a 70% cure with 9 mg/kg and a light exposure dose of 100 mW/cm2. These results provide direct evidence that WST11 is an effective agent for VTP and provide guidelines for further development of new candidates.     

Generalized correlations for molecular weight and concentration dependence of zero-shear viscosity of high polymer solutions

Data are presented to show that two correlations of viscosity–concentration data are useful representations for data over wide ranges of molecular weight and up to at least moderately high concentrations for both good and fair solvents. Low molecular weight polymer solutions (below the critical entanglement molecular weight M_c) generally have higher viscosities than predicted by the correlations. One correlation is η_sp/c[η] versus k′[η], where η_sp is specific viscosity, c is polymer concentration, [η] is intrinsic viscosity, and k′ is the Huggins constant. A standard curve for good solvent systems has been defined up to k′[η]c ≈? 3. It can also be used for fair solvents up to k′[η]c ≈? 1.25· low estimates are obtained at higher values. A simpler and more useful correlation is η_R versus c[η], where η_R is relative viscosity. Fair solvent viscosities can be predicted from the good solvent curve up to c[η] ≈? 3, above which estimates are low. Poor solvent data can also be correlated as η_R versus c[η] for molecular weights below 1 to 2 × 10⁵.