RAFT-mediated emulsion polymerization of styrene using a non-ionic surfactant

We report the successful RAFT-mediated emulsion polymerization of styrene using a non-ionic surfactant (Brij98), the highly reactive 1-phenylethyl phenyldithioacetate (PEPDTA) RAFT agent, and water-soluble initiator ammonium persulfate (APS). The molar ratio of RAFT agent to APS was identical in all experiments. Most of the monomer was contained within the micelles, analogous to microemulsion or miniemulsion systems but without the need of shear, sonication, cosurfactant, or a hydrophobe. The number-average molecular weight increased with conversion and the polydispersity index was below 1.2. This ideal 'living' behavior was only found when molecular weights of 9000 and below were targeted. It was postulated that the rapid transportation of RAFT agent from the monomer swollen micelles to the growing particles was fast on the polymerization timescale, and most if not all the RAFT agent is consumed within the first 10% conversion. In addition, it was postulated that the high nucleation rate from the high rate of exit ( of the R radical from the RAFT agent) and high entry rate from water-phase radicals ( high APS concentration) reduced the effects of 'superswelling' and therefore a similar molar ratio of RAFT agent to monomer was maintained in all growing particles. The high polydispersity indexes found when targeting molecular weights greater than 9000 were postulated to be due to the lower nucleation rate from the lower weight fractions of both APS and RAFT agent. In these cases, 'superswelling' played a dominant role leading to a heterogeneous distribution of RAFT to monomer ratios among the particles nucleated at different times.

Reversible active switching of the mechanical properties of a peptide film at a fluid-fluid interface

Designer peptides have recently been developed as building blocks for novel self-assembled materials with stimuli-responsive properties. To date, such materials have been based on self-assembly in bulk aqueous solution or at solid-fluid interfaces. We have designed a 21-residue peptide, AM1, as a stimuli-responsive surfactant that switches molecular architectures at a fluid-fluid interface in response to changes in bulk aqueous solution composition. In the presence of divalent zinc at neutral pH, the peptide forms a mechanically strong 'film state'. In the absence of metal ions or at acid pH, the peptide adsorbs to form a mobile 'detergent state'. The two interfacial states can be actively and reversibly switched. Switching between the two states by a change in pH or the addition of a chelating agent leads to rapid emulsion coalescence or foam collapse. This work introduces a new class of surfactants that offer an environmentally friendly approach to control the stability of interfaces in foams, emulsions and fluid-fluid interfaces more generally.

The survey for ionization in neutral gas galaxies. I. Description and initial results

We introduce the Survey for Ionization in Neutral Gas Galaxies (SINGG), a census of star formation in H I selected galaxies. The survey consists of H alpha and R-band imaging of a sample of 468 galaxies selected from the H I Parkes All Sky Survey (HIPASS). The sample spans three decades in H I mass and is free of many of the biases that affect other star-forming galaxy samples. We present the criteria for sample selection, list the entire sample, discuss our observational techniques, and describe the data reduction and calibration methods. This paper focuses on 93 SINGG targets whose observations have been fully reduced and analyzed to date. The majority of these show a single emission line galaxy (ELG). We see multiple ELGs in 13 fields, with up to four ELGs in a single field. All of the targets in this sample are detected in H alpha, indicating that dormant (non-star-forming) galaxies with M-H I greater than or similar to 3x10(7) M-circle dot are very rare. A database of the measured global properties of the ELGs is presented. The ELG sample spans 4 orders of magnitude in luminosity (H alpha and R band), and H alpha surface brightness, nearly 3 orders of magnitude in R surface brightness and nearly 2 orders of magnitude in H alpha equivalent width (EW). The surface brightness distribution of our sample is broader than that of the Sloan Digital Sky Survey (SDSS) spectroscopic sample, the EW distribution is broader than prism-selected samples, and the morphologies found include all common types of star-forming galaxies (e.g., irregular, spiral, blue compact dwarf, starbursts, merging and colliding systems, and even residual star formation in S0 and Sa spirals). Thus, SINGG presents a superior census of star formation in the local universe suitable for further studies ranging from the analysis of H II regions to determination of the local cosmic star formation rate density.

The survey for ionization in neutral gas galaxies. II. The star formation rate density of the local universe

We derive observed H alpha and R-band luminosity densities of an H I-selected sample of nearby galaxies using the SINGG sample to be l'(H alpha) = (9.4 +/- 1.8) x 10(38) h(70) ergs s(-1) Mpc(-3) for H alpha and l'(R) = (4.4 +/- 9.7) x 10(37) h(70) ergs s(-1) angstrom(-1) Mpc(-3) in the R band. This R-band luminosity density is approximately 70% of that found by the Sloan Digital Sky Survey. This leads to a local star formation rate density of log ((rho)over dot(SFR) [M-circle dot yr(-1) Mpc(-3)]) = -1.80(-0.07)(+0.13)(random) +/- 0.03(systematic) + log (h(70)) after applying a mean internal extinction correction of 0.82 mag. The gas cycling time of this sample is found to be t(gas) = 7.5(-2.1)(+1.3) Gyr, and the volume-averaged equivalent width of the SINGG galaxies is EW(H alpha) = 28.8(-4.7)(+7.2) angstrom (21.2-3.5+4.2 angstrom without internal dust correction). As with similar surveys, these results imply that (rho)over dot(SFR)(z) decreases drastically from z similar to 1.5 to the present. A comparison of the dynamical masses of the SINGG galaxies evaluated at their optical limits with their stellar and H I masses shows significant evidence of downsizing: the most massive galaxies have a larger fraction of their mass locked up in stars compared with H I, while the opposite is true for less massive galaxies. We show that the application of the Kennicutt star formation law to a galaxy having the median orbital time at the optical limit of this sample results in a star formation rate decay with cosmic time similar to that given by the. (rho)over dot(SFR)(z) evolution. This implies that the (rho)over dot(SFR)(z) evolution is primarily due to the secular evolution of galaxies, rather than interactions or mergers. This is consistent with the morphologies predominantly seen in the SINGG sample.

Comparison of surfactant lipids between pleural and pulmonary lining fluids

Saturated phospholipids (PCs), particularly dipalmitoylphosphatidylcholine (DPPC), predominate in surfactant lining the alveoli, although little is known about the relationship between saturated and unsaturated PCs on the outer surface of the lung, the pleura. Seven healthy cats were anesthetized and a bronchoalveolar lavage (BAL) was performed, immediately followed by a pleural lavage (PL). Lipid was extracted from lavage fluid and then analyzed for saturated, primarily dipalmitoylphosphatidylcholine (DPPC), and unsaturated PC species using high-performance liquid chromatography (HPLC) with combined fluorescence and ultraviolet detection. Dilution of epithelial lining fluid (ELF) in lavage fluids was corrected for using the urea method. The concentration of DPPC in BAL fluid (85.3 +/- 15.7 mu g/mL) was significantly higher (P=0.021) than unsaturated PCs (similar to 40 mu g/mL). However, unsaturated PCs (similar to 34 mu g/mL), particularly stearoyl-linoleoyl-phosphatidylcholine (SLPC; 17.4 +/- 6.8), were significantly higher (P = 0.021) than DPPC (4.3 +/- 1.8 mu g/mL) in PL fluid. These results show that unsaturated PCs appear functionally more important in the pleural cavity, which may have implications for surfactant replenishment following pleural disease or thoracic surgery. (c) 2005 Published by Elsevier Ltd.

Dehydration at the lens surface:surface energy and surfactant persistence

Purpose: Most published surface wettability data are based on hydrated materials and are dominated by the air-water interface. Water soluble species with hydrophobic domains (such as surfactants) interact directly with the hydrophobic domains in the lens polymer. Characterisation of relative polar and non-polar fractions of the dehydrated material provides an additional approach to surface analysis. Method: Probe liquids (water and diiodomethane) were used to characterise polar and dispersive components of surface energies of dehydrated lenses using the method of Owens and Wendt. A range of conventional and silicone hydrogel soft lenses was studied. The polar fraction (i.e. polar/total) of surface energy was used as a basis for the study of the structural effects that influence surfactant persistence on the lens surface. Results: When plotted against water content of the hydrated lens, polar fraction of surface energy (PFSE) values of the dehydrated lenses fell into two rectilinear bands. One of these bands covered PFSE values ranging from 0.4 to 0.8 and contained only conventional hydrogels, with two notable additions: the plasma coated silicone hydrogels lotrafilcon A and B. The second band covered PFSE values ranging from 0.04 to 0.28 and contained only silicone hydrogels. Significantly, the silicone hydrogel lenses with lowest PFSE values (p<0.15) are found to be prone to lipid deposition duringwear. Additionally, more hydrophobic surfactants were found to be more persistent on lenses with lower PFSE values. Conclusions: Measurement of polar fraction of surface energy provides an importantmechanistic insight into surface interactions of silicone hydrogels.

Subunit vaccines distearoylphosphatidylcholine-based liposomes entrapping antigen offer a neutral alternative to dimethyldioctadecylammonium-based cationic liposomes as an adjuvant delivery system

The adjuvanticity of liposomes can be directed through formulation to develop a safe yet potent vaccine candidate. With the addition of the cationic lipid dimethyldioctadecylammonium bromide (DDA) to stable neutral distearoylphosphatidylcholine (DSPC):cholesterol (Chol) liposomes, vesicle size reduces while protein entrapment increases. The addition of the immunomodulator, trehalose 6,6-dibehenate (TDB) to either the neutral or cationic liposomes did not affect the physiochemical characteristics of these liposome vesicles. However, the protective immune response, as indicated by the amount of IFN-? production, increases considerably when TDB is present. High levels of IFN-? were observed for cationic liposomes; however, there was a marked reduction in IFN-? release over time. Conversely, for neutral liposomes containing TDB, although the initial amount of IFN-? was slightly lower than the cationic equivalent, the overall protective immune responses of these neutral liposomes were effectively maintained over time, generating good levels of protection. To that end, although the addition of DSPC and Chol reduced the protective immunity of DDA:TDB liposomes, relatively high protection was observed for the neutral counterpart, DSPC:Chol:TDB, which may offer an effective neutral alternative to the DDA:TDB cationic system, especially for the delivery of either zwitterionic (neutral) or cationic molecules or antigens.

Surfactant coated aerosol powders and their properties

The hygroscopic growth of aerosols is an important factor effecting particle size. The consequence of the hygroscopic growth of pharrnaceutical aerosols is a change in their deposition characteristics, such that there is an increase in the total amount deposited in the lung. In this study the hygroscopic growth of disodium fluorescein (DF) aerosol powders was investigated by coating the powders with lauric and capric acids. The coating procedure was carried out in dichloromethane and chloroform, which acted as cosolvents for the fatty acids. An assessment of the extent and the nature of the coating was carried out. The qualitative assessment of the coating was achieved by infra-red spectroscopy, electronscanning chemical analysis and scanning electron microscopy. The quantitative analysis was carried out by differential refractometry, ultra-violet spectroscopy and gas liquid chromatography. These powders were generated under conditions approaching those in the lung, of 97 % relative humidity and 37"C. Coated and uncoated DF aerosol powders were introduced into a controlled temperature and relative humidity apparatus, designed and constructed for the investigation of hygroscopic growth in these studies. A vertical spinning disc device was used to generate the powders. Under conditions of controlled temperature and relative humidity mentioned, the growth ratio of disodium fluorescein alone was 1.45 compared with 1.68, for a nominal coating of DF with lauric acid of 0.12 gg-1, 1.0 for a nominal lauric acid coating of 0.2 gg-1, and 1.02 for a nominal capric acid coating of 0.18 gg-1. The range of control of hygroscopic growth of these aerosols has implications for the deposition of these preparations in the respiratory tract. These implications are discussed in the light of the current knowledge of the effects of hygroscopic growth on the deposition of pharmaceutical and environmental aerosols. A series of experiments in which pulmonary ventilation using a simple radioaerosol generator and delivery system are reported showing that particle size determination may be used to aid the design of diagnostic aerosol generators.