Morphology development of 10‐μm scale polymer particles prepared by SPG emulsification and suspension polymerization

Classicalparticle morphologies, core‐shell, hemisphere, sandwich, and so on, were all reproducible by starting from ca. 10‐μm uniform droplets composed of monomers, initiator, solvents, and polymer, and polymerizing them by subsequent suspension polymerization. SPG (Shirasu porous glass) membrane was employed to form uniform size droplets having the coefficient of variation (CV) around 10%. Styrene (ST) and acrylic monomers were used as monomers, and their polymers were dissolved in the droplets to investigate the development of phase separation. When hydrophilic methyl methacrylate (MMA) was polymerized in the droplets with a mixed solvent consisting of hydrophilic hexanol (HA) and hydrophobic benzene and hexadecane (HD), the resulting morphology shifted from hemisphere to sandwich and eventually to PMMA/solvent core‐shell with increasing hydrophilicity of the mixed solvent. The sandwich was converted to the core‐shell after several weeks elapsed. As styrene was added to MMA, the morphology shifted from hemisphere core/solvent shell to raspberry core/solvent shell as the fraction of ST increased. The domain of the mixed solvent in the raspberry core was reduced with increasing the hydrophilicity of the mixed solvent. All these morphologies were eventually converted to the copolymer core/solvent shell. When a mixed monomer of styrene and MMA dissolving polystyrene (PS) was polymerized, the resulting morphology shifted from salami to core‐shell with increasing the MMA fraction in the comonomer. The salami particles were then swollen with toluene, and after the swelling, toluene was removed under the different temperature and pressure. The final particle morphology converted to the core‐shell with a milder rate of toluene removal which was predicted from the thermodynamic model. When styrene and cyclohexyl acrylate (CHA), a pair with widely different reactivity ratios, were copolymerized, salami morphologies, with tiny CHA‐rich domains dispersed in the matrix, were obtained even at a higher fraction of CHA in comonomer. Effects of glass transition temperature of the polymers, molecular weight, and the composition of copolymers were taken in consideration whenever the final morphologies were discussed. By these experiments, the authors tried to demonstrate an advantage of using large uniform spheres for the particle morphology studies. SPG emulsification technique was a potential tool because of its free formulation of the droplets, and the subsequent polymerization could undergo without the breakup or coalescence of the droplets. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2200–2220, 2001     

α-Amylase immobilization capacities of mesoporous silicas with different morphologies and surface properties

α-Amylase was encapsulated in several mesoporous materials (folded sheet mesoporous silica (FSM), cubic mesoporous silica (KIT-6), and two-dimensional hexagonal mesoporous silica (SBA-15)) that differed morphologically in terms of particle shape, pore size, and pore structure. The encapsulation capacity and thermal stability of encapsulated α-amylase were examined. The amount of α-amylase encapsulated increased with increasing pore size in the following order: SBA-15 < KIT-6 < FSM. Nitrogen adsorption experiments were performed before and after α-amylase encapsulation in mesoporous silicas with pore sizes larger than the size of α-amylase, confirming that α-amylase was encapsulated in the pores. Among mesoporous silicas with similar pore sizes, FSM was found to have the highest capacity for α-amylase encapsulation both per weight and per surface area of silica. Furthermore, α-amylase encapsulated in FSM demonstrated high thermal stability at 90 °C relative to the thermal stability of free α-amylase or free α-amylase encapsulated in other mesoporous silicas. Zeta potential measurements showed that the FSM surface had an isoelectric point that was lower than that of other mesoporous silicas, and hydrophilicity measurements showed that its surface was more hydrophilic. The surface properties of FSM contributed to the high thermal stability of the α-amylase encapsulated within the pores.     

Role of zinc compounds on the formation, morphology, and adsorption characteristics of β-FeOOH rusts

To simulate the corrosion of galvanized steel in marine zone, β-FeOOH was prepared by aging the FeCl₃ solutions containing ZnCl₂ and zinc rusts such as ZnO and zinc hydroxychloride (Zn₅(OH)₈Cl₂·H₂O:ZHC). Adding ZnCl₂, ZnO, and ZHC inhibited the crystallization and particle growth of β-FeOOH and the inhibitory effect was in order of ZHC ≈ ZnO > ZnCl₂. The adsorption of H₂O and CO₂ was suppressed by adding ZnCl₂, ZnO, and ZHC. These results imply that the rust formed on galvanized steel in marine environment is more compact, amorphous, and hydrophobic in nature which may lead to improve the corrosion resistance.     

Atom probe tomography of nanoscale microstructures within precipitate free zones in Al–Zn–Mg(–Ag) alloys

Solute distributions in the vicinity of grain boundaries in Al–Zn–Mg(–Ag) alloys were studied using a three-dimensional atom probe, in order to elucidate the mechanism of formation of precipitate free zones (PFZs) and the fundamental role of Ag in controlling PFZ width. It is shown that nanoscale clusters are formed within the PFZ in Al–Zn–Mg, despite the solute concentration remaining at the levels in the as-quenched state. Such observations have not previously been possible, and show unambiguously that vacancy depletion is the dominant mechanism of formation of PFZs in this alloy. In the Ag-containing alloy, a narrower PFZ is observed, with a reduced solute level, showing that here the dominant mechanism of PFZ formation is solute depletion. The role of Ag in this change of mechanism appears to be due to its favorable interactions not only with Mg and Zn atoms but also with vacancies.     

Numerical analysis of a reactive extrusion process. Part II: Simulations and verifications for the twin screw extrusion

A newly designed extruder reactor for grafting vinyl monomers onto polyolefins was studied experimentally and theoretically. The process was made up of a self‐wiping co‐rotating twin screw extruder with a separated reaction zone and two vent zones. The reactive extrusion was performed using a linear low density polyethylene, vinyltrimethoxysilane and di‐t‐butylperoxide under different operation conditions. For the purpose of process analysis, we built a computer simulation based on the reaction kinetics and rheological models studied in the preceding paper. The flow field in the extruder was calculated by the flow analysis network (FAN) method with non‐isothermal non‐Newtonian flow conditions. The iterative procedure was organized to predict local pressure, filling factor, cumulative residence time and temperature along the extruder. Furthermore, we succeeded in representing the profiles of reaction conversion and shear viscosity. Calculated results showed good agreements with the experimental data.     

Identification of Ustilago cynodontis as a new producer of glycolipid biosurfactants, mannosylerythritol lipids, based on ribosomal DNA sequences

Mannosylerythritol lipids (MELs) are one of the most promising glycolipid biosurfactants known because of their multifunctionality and biocompatibility. The search for novel producers of MELs was undertaken based on the analysis of ribosomal DNA sequences on basidiomycetous yeasts. The bermuda grass smut fungus Ustilago cynodontis NBRC 7530, which taxonomically relates to Pseudozyma shanxiensis known as a MEL-C producer, was found to accumulate glycolipids in the cultured medium. Under a shake flask culture with soybean oil, the amount of the glycolipids was 1.4 g/L for 7 days at 25 degrees C. As a result of the structural characterization, the main glycolipids was identified as 4-O-[(4'-O-acetyl-3'-O-alka(e)noyl-2'-O-butanoyl)-beta-D-mannopyranosyl]-D-erythritol, and the major fatty acids were C(14) and C(16) ones. The glycolipid was highly hydrophilic MEL-C, and very similar to those produced by P. shanxiensis. The fungi of the genus Ustilago are thus likely to be potential producers of MELs as well as the yeasts of the genus Pseudozyma.     

Packing density of glycolipid biosurfactant monolayers give a significant effect on their binding affinity toward immunoglobulin G

Mannosylerythritol lipid-A (MEL-A) is one of the most promising glycolipid biosurfactants, and abundantly produced by Pseudozyma yeasts. MEL-A gives not only excellent self-assembling properties but also a high binding affinity toward human immunoglobulin G (HIgG). In this study, three kinds of MEL-A were prepared from methyl myristate [MEL-A (m)], olive oil [MEL-A (o)], and soybean oil [MEL-A (s)], and the effect of interfacial properties of each MEL-A monolayer on the binding affinity toward HIgG was investigated using surface plasmon resonance (SPR) and the measurement of surface pressure (pi)-area (A) isotherms. Based on GC-MS analysis, the main fatty acids were C(8) and C(10) acids in all MEL-A, and the content of unsaturated fatty acids was 0% for MEL-A (m), 9.1% for MEL-A (o), 46.3% for MEL-A (s), respectively. Interestingly, the acid content significantly influenced on their binding affinity, and the monolayer of MEL-A (o) gave a higher binding affinity than that of MEL-A (m) and MEL-A (s). Moreover, the mixed MEL-A (o)/ MEL-A (s) monolayer prepared from 1/1 molar ratio, which comprised of 27.8% of unsaturated fatty acids, indicated the highest binding affinity. At the air/water interface, MEL-A (o) monolayer exhibited a phase transition at 13 degrees C from a liquid condensed monolayer to a liquid expanded monolayer, and the area per molecule significantly expanded above 13 degrees C, while the amount of HIgG bound to the liquid expanded monolayer was much higher than that bound to liquid condensed monolayer. The binding affinity of MEL-A toward HIgG is thus likely to closely relate to the monolayer packing density, and may be partly controlled by temperature.     

Identification of Pseudozyma graminicola CBS 10092 as a producer of glycolipid biosurfactants, mannosylerythritol lipids

A basidiomycetous yeast, Pseudozyma graminicola CBS 10092, was found to accumulate a large amount of glycolipids in the cultured medium when grown on soybean oil as the sole carbon source. Based on thin layer chromatography, the extracellular glycolipids gave spots corresponding to those of mannosylerythritol lipids (MELs), which are highly functional and promising biosurfactants. From the structural characterization by 1H and 13C NMR, the main product was identified as 4-O-[(4'-mono-O-acetyl-2', 3'-di-O-alka(e)noyl)-beta-D-mannopyranosyl]-D-erythritol, which is a highly hydrophilic derivative of MELs known as MEL-C. According to high-performance liquid chromatography analysis, the main product, MEL-C, comprised approximately 85% of all the MELs, and the total amount reached approximately 10 g/L for 7 days. The fatty acids of the present MEL-C consisted of mainly C6, C8 and C14 acids, considerably different from those of MEL-C produced by other Pseudozyma strains such as P. antarctica and P. shanxiensis. The observed critical micelle concentration (CMC) and the surface-tension at CMC of the MEL-C were 4.0 x 10(-6) M and 24.2 mN/m, respectively, while those of MEL-A, the most intensively studied MEL, were 2.7 x 10(-6) M and 28.4 mN/m, respectively. This implied that the MEL-C has higher hydrophilicity than conventional MELs hitherto reported. In addition, on a water-penetration scan, the MEL-C efficiently formed the lamella phase (Lalpha) at a wide range of concentrations, indicating its excellent self-assembling properties. From these results, the newly identified MELs produced by P. graminicola are likely to have great potential for use in oil-in-water type emulsifiers and/or washing detergents, and would thus facilitate a broad range of applications for the promising yeast biosurfactants.     

Characterization of the ybdT gene product of Bacillus subtilis: Novel fatty acid β-hydroxylating cytochrome P450

We have characterized the gene encoding fatty acid α-hydroxylase, a cytochrome P450 (P450) enzyme, from Sphingomonas paucimobilis. A database homology search indicated that the deduced amino acid sequence of this gene product was 44% identical to that of the ybdT gene product that is a 48 kDa protein of unknown function from Bacillus subtilis. In this study, we cloned the ybdT gene and characterized this gene product using a recombinant enzyme to clarify function of the ybdT gene product. The carbon monoxide difference spectrum of the recombinant enzyme showed the characteristic one of P450. In the presence of H₂O₂, the recombinant ybdT gene product hydroxylated myristic acid to produce β-hydroxyristic acid and α-hydroxymyristic acid which were determined by high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry. The amount of these products increased with increasing reaction period and amount of H₂O₂ in the reaction mixture. The amount of β-hydroxyl product was slightly higher than that of α-hydroxyl product at all times during the reaction. However, no reaction products were detected at any time or at any concentration of H₂O₂ when heat-inactivated enzyme was used. HPLC analysis with a chiral column showed that the β-hydroxyl product was nearly enantiomerically pure R-form. These results suggest that this P450 enzyme is involved in a novel biosynthesis of β-hydroxy fatty acid.     

Characterization of carbonaceous films deposited on metal substrates by liquid-phase electrodeposition in methanol

In this study, we report the characterization of carbonaceous films deposited on metal substrates by liquid-phase electrodeposition in methanol. The characterization of carbonaceous films by electrodeposition was examined by means of Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), electron energy loss spectroscopy (EELS), secondary ion mass spectrometry (SIMS), atom probe (AP) and high resolution-elastic recoil detection analysis (HR-ERDA). From these results, it was found that the films deposited on the metal substrates were composed of the sp² and sp³ carbon contents, of which the ratio was about 7:3. Furthermore, the films by electrodeposition contained much hydrogen. The hydrogen contents in the surface were about 60 at.% and those in the subsurface were a few 10 at.%.