Conformational change of poly(ethylene glycol) near the critical point of isobutyric acid + water.

In solutions of isobutyric acid + water, poly(ethylene glycol) (PEG) can assume a helical conformation. [Alessi, M. L.; Norman, A. I.; Knowlton, S. E.; Ho, D. L.; Greer, S. C. Macromolecules 2005, 35, 9333-9340.] Here we report new measurements of the kinematic viscosity, nu, as a function of temperature for a solution of isobutyric acid + water at the critical composition, to which PEG (number average molecular weight = 1.01 x10(3) g/mol) was added at a concentration of 6.01 mg/mL. The data show that nu decreases near the critical point, with a maximum in nu at about 0.05 degrees C above the critical temperature, Tc. We interpret this change in nu in terms of a change in conformation of the polymer from helix to coil. This interpretation is supported by polarimetry measurements on the same mixture doped with (S)-(+)-1,2-propanediol, which indicates the loss of helicity near Tc and also a second helix-to-coil transition at about 60 degrees C.

Spontaneous formation of vesicles of diblock copolymer EO6BO11 in water: a SANS study.

Small angle neutron scattering (SANS) is used to study the structures formed in water by a diblock copolymer EO6BO11 (having 6 ethylene oxide, EO, and 11 butylene oxide, BO, units). The data show that polymer solutions over a broad concentration range (0.05-20 wt %) contain vesicular structures at room temperature. Interestingly, these vesicles could be formed without any external energy input, such as extrusion, which is commonly required for the formation of other block copolymer or lipid vesicles. The EO6BO11 vesicles are predominantly unilamellar at low polymer concentrations, whereas at higher polymer concentrations or temperatures there is a coexisting population of unilamellar and multilamellar vesicles. At a critical concentration and temperature, the vesicular structures fuse into lyotropic arrays of planar lamellar sheets. The findings from this study are in broad agreement with the work of Harris et al. (Langmuir, 2002, 18, 5337), who used electron microscopy to identify the vesicle phase in the same system.

Microfluidic light scattering as a tool to study the structure of aqueous polymer solutions.

A small-angle light scattering (SALS) apparatus, coupled with a specially designed microfluidic device is shown to monitor the formation and subsequent size distribution of giant multilamellar vesicles of a diblock copolymer in aqueous solution. The closed-face design, fabricated between glass slides using a UV-curable optical adhesive, incorporates multiple inlets, a mixing system, and a viewing window to perform on-line SALS. The mixing of each component is tested using polystyrene latex microspheres. Vesicles of the block copolymer, EO6BO11 in aqueous solution are formed on the SALS chip and the pair distance distribution function determined using an inverse Fourier transformation of the scattered intensity to quantify the population and distribution for a range of vesicle sizes. These experiments provide demonstrations of how SALS on a microfluidic device can be used as a rapid screening tool to optimize processing conditions for a range of polymer solutions.

Phase behavior of block co-poly(ethylene oxide-butylene oxide), E18B9 in water, by small angle neutron scattering.

We present a small angle neutron scattering (SANS) study into the micellar structures of diblock copolymer E18B9 (where E denotes a ethylene oxide unit and B denotes a butylene oxide unit, 18 and 9 being the number of repeat units respectively) in aqueous solution over a range of five different concentrations (0.2, 1.0, 10.0, 20.0, and 40.0% (by mass fraction)) and eight temperatures (10 to 90 degrees C). The NG7 30 m SANS instrument provides a q range of 0.0009 to 0.5548 A(-1), thus probing the structure over a very broad length scale. At low temperature and low concentration, spherical micelles exist, elongating into worm-like structures at higher temperatures. This transition is observed by the scaling of the scattered intensity at low q and confirmed upon fitting to an appropriate model. Upon increasing concentration, the micelles pack into ordered arrays of either hexagonally packed rod-like micelles or lamellar sheets, again dependent on temperature. Both concentration and temperature effects of this block copolymer have been discussed.

Viscosity increase with temperature in cationic surfactant solutions due to the growth of wormlike micelles.

Wormlike micellar solutions based on ionic surfactants typically show an exponential decrease in viscosity upon heating. Here, we report the unusual observation of an increasing viscosity with temperature in certain cationic wormlike micellar solutions. The solutions contain a cationic surfactant with an erucyl (C22, mono-unsaturated) tail and an organic salt, sodium hydroxynaphthalene carboxylate (SHNC). When these solutions are heated, their zero-shear viscosity increases over a range of temperatures. In some cases, the viscosity reaches a peak at a certain temperature and then decreases with further heating. The magnitude of the viscosity increase, the onset of this increase, and the peak temperature can all be tuned by varying the SHNC concentration. Small-angle neutron scattering is used to study the origin of this unusual rheological behavior. The data reveal that the contour length of the micelles increases with temperature, in tandem with the rise in viscosity. A possible explanation for the contour length increase, based on a temperature-dependent counterion binding, is discussed.

The polymerization of actin: structural changes from small-angle neutron scattering.

We present a new analysis of small-angle neutron-scattering data from rabbit muscle actin in the course of the polymerization from G-actin to F-actin as a function of temperature. The data, from Ivkov et al. [J. Chem. Phys. 108, 5599 (1998)], were taken in D2O buffer with Ca2+ as the divalent cation on the G-actin in the presence of ATP and with KCl as the initiating salt. The new analysis of the data using modeling and the method of generalized indirect fourier transform (O. Glatter, GIFT, University of Graz, Austria, http://physchem.kfunigraz.ac.at/sm/) provide shapes and dimensions of the G-actin monomer and of the growing actin oligomer in solution as a function of temperature and salt concentration. This analysis indicates that the G-actin monomer, under the conditions given above, is a sphere 50-54 A in diameter as opposed to the oblate ellipsoid seen by x-ray crystallography. The F-actin dimensions are consistent with x-ray crystal structure determinations.