Effects of glucose and mannose on the flocculation behavior of Saccharomyces cerevisiae at different life stages

The temporal flocculation behavior of Saccharomyces cerevisiae at different life stages is investigated using glucose and mannose as the different carbon sources, and the temporal variations of cell size, zeta potential and stability ratio of cell suspension are measured. It is found that the largest cell size and the lowest stability ratio of cell suspension occurred at the middle period of the exponential growth phase independent of carbon sources. The colloidal aspect was analyzed by using the DLVO theory, and indicated that the gravitational force plays a major role in determining the flocculation behavior of yeast cells.     

Access to the syntheses of sydnonyl-substituted α,β-unsaturated ketones and 1,3-dihydro-indol-2-ones by modified Knoevenagel reaction

A convenient method for the preparation of sydnonyl-substituted α, β-unsaturated ketones, based on Knoevenagel condensation, is presented. Although well known, this reaction has never been utilized in the condensation involving sydnone derivatives. Thus, 3-aryl-4-formylsydnones (1) are reacted with active methylene compounds such as acetylacetone (2a), ethyl acetoacetate (2b), diethyl malonate (2c), malononitrile (4a), ethyl cyanoacetate (4b) and cyanoacetamide (4c) by modified Knoevenagel condensation to afford multifunctional derivatives. Also, sydnonyl-substituted 1,3-dihydro-indol-2-one derivatives 10 were synthesized successfully by condensing 3-aryl-4-formylsydnones (1) with oxindoles 9.     

Enhancing stability and oxidation activity of cytochrome C by immobilization in the nanochannels of mesoporous aluminosilicates

Hydrothermally stable and structrurally ordered mesoporous and microporous aluminosilicates with different pore sizes have been synthesized to immobilize cytochrome c (cyt c): MAS-9 (pore size 90 A), MCM-48-S (27 A), MCM-41-S (25 A), and Y zeolites (7.4 A). The amount of cyt c adsorption could be increased by the introduction of aluminum into the framework of pure silica materials. Among these mesoprous silicas (MPS), MAS-9 showed the highest loading capacity due to its large pore size. However, cyt c immobilized in MAS-9 could undergo facile unfolding during hydrothermal treatments. MCM-41-S and MCM-48-S have the pore sizes that match well the size of cyt c (25 x 25 x 37 A). Hence the adsorbed cyt c in these two medium pore size MPS have the highest hydrothermal stability and overall catalytic activity. On the other hand, the pore size of NaY zeolite is so small that cyt c is mostly adsorbed only on the outer surface and loses its enzymatic activity rapidly. The improved stability and high catalytic activity of cyt c immobilized in MPS are attributed to the electrostatic attraction between the pore surface and cyt c and the confinement provided by nanochannels. We further observed that cyt c immobilized in MPS exists in both high and low spin states, as inferred from the ESR and UV-vis studies. This is different from the native cyt c, which shows primarily the low spin state. The high spin state arises from the replacement of Met-80 ligands of heme Fe (III) by water or silanol group on silica surface, which could open up the heme groove for easy access of oxidants and substrates to iron center and facilitate the catalytic activity. In the catalytic study, MAS-9-cyt c showed the highest specific activity toward the oxidation of polycyclic aromatic hydrocarbons (PAHs), which arises from the fast mass transfer rate of reaction substrate due to its large pore size. For pinacyanol (a hydrophilic substrate), MCM-41-S-cyt c and MCM-48-S-cyt c showed higher specific activity than NaY-cyt c and MAS-9-cyt c. The result indicated that cyt c embedded in the channels of MCM-41-S and MCM-48-S was protected against unfolding and loss of activity. By increasing the concentration of the spin trapping agent, 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in ESR experiments, we showed that cyt c catalyzes a homolytic cleavage of the O-O bond of hydroperoxide and generates a protein cation radical (g = 2.00). Possible mechanisms for MPS-cyt c catalytic oxidation of hydroperoxides and PAHs are proposed based on the spectroscopic characterizations of the systems.     

Crown Ether As The Phase-Transfer Catalyst for Free Radical Polymerization of Hydrophobic Vinyl Monomers

Various crown ethers were used as phase-transfer catalysts for free radical polymerizations of some water-insoluble vinyl monomers such as acrylonitrile, methylmethacrylate and styrene with persulfate as initiator. The catalytic abilities of these crown ethers for free radical polymerization of acrylonitrile with S₂O₈^2?ion as an initiator were in the order: 18-crown-6 > 15-crown-4 > 12-crown-4 > benzo-15-crown-5 > dibenzo-18-crown-6. Among various persulfates such as Na₂S₂O₈ K₂S₂O₈ and (NH₄)₂S₂O₈, ammonium persulfate was the optimum initiator for the polymerization of acrylonitrile catalyzed by 18-crown-6 or 15-crown-5. Among the organic solvents used, chloroform seems to be the best solvent for the catalytic polymerization of acrylonitrile. An apparent activation energy of 72.9 kJ mol^?1 was observed for the polymerization of acrylonitrile. The catalytic reaction rates of free radical polymerization for these hydrophobic vinyl monomers were in the order: acrylonitrile > methylmethacrylate > styrene > isoprene. Effects of concentrations of crown ether, initiator, and nitrogen on the polymerization of these vinyl monomers were investigated.     

Characterization,crystallization kinetics,and melting behavior of poly(ethylene succinate) copolyester containing 10 mol % butylene succinate

Copolyester was synthesized and characterized as having 89.9 mol % ethylene succinate units and 10.1 mol % butylene succinate units in a random sequence, as revealed by NMR. Isothermal crystallization kinetics was studied in the temperature range (T_c) from 30 to 73 °C using differential scanning calorimetry (DSC). The melting behavior after isothermal crystallization was investigated using DSC by varying the T_c, the heating rate and the crystallization time. DSC curves showed triple melting peaks. The melting behavior indicates that the upper melting peaks are associated primarily with the melting of lamellar crystals with various stabilities. As the T_c increases, the contribution of recrystallization slowly decreases and finally disappears. A Hoffman‐Weeks linear plot gives an equilibrium melting temperature of 107.0 °C. The spherulite growth of this copolyester from 80 to 20 °C at a cooling rate of 2 or 4 °C/min was monitored and recorded using an optical microscope equipped with a CCD camera. Continuous growth rates between melting and glass transition temperatures can be obtained after curve‐fitting procedures. These data fit well with those data points measured in the isothermal experiments. These data were analyzed with the Hoffman and Lauritzen theory. A regime II → III transition was detected at around 52 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2431–2442, 2008     

Syntheses and characterizations of aniline/butylthioaniline copolymers: Comparisons of copolymers prepared by the new concurrent reduction and substitution route and the conventional oxidative copolymerization method

New highly solution‐processable aniline/butylthioaniline copolymers were prepared via oxidative copolymerization (OCP) and by concurrent reduction and substitution (CRS). Butylthio‐substituted polyaniline obtained via the CRS route (Pan‐SBu), being in line with the expected property changes after the addition of an electron‐donating substituent to an aromatic ring, displayed a lowered redox potential (E⁰) and a redshifted maximum wavelength (λ_max; ultraviolet–visible) in comparison with its parent unsubstituted polyaniline (Pan). However, copolymers CP1–CP4 (obtained via the OCP method) displayed opposite behaviors, showing higher E⁰ values and blueshifts in λ_max than the unsubstituted Pan. The results suggested that CP1–CP4 had shorter conjugation lengths than the unsubstituted Pan, possibly because of their chain conjugation defects (e.g., 1,3‐ring linkage structures), as evidenced by IR studies. The results of ¹H NMR studies also indicated that Pan‐SBu had much higher structural homogeneity than copolymer CP4. Because the CRS synthetic route involved no backbone alternations, the resultant copolymer (Pan‐SBu) should have maintained the same backbone structure and hence the high conductivity of the parent unsubstituted Pan. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1767–1777, 2005