Concentration dependence of excluded volume effects

The concentration dependence of the excluded volume effects in polymer solutions is investigated. Through thermodynamic arguments for the interpenetration of polymer segments and the free energy change, we show that the disappearance of the excluded volume effects should occur at medium concentration. The result is in accord with the recent experimental observations.     

Triacylglycerol/phospholipid molecular species profiling of fatty livers and regenerated non-fatty livers in cystathionine beta-synthase-deficient mice, an animal model for homocysteinemia/homocystinuria

Fatty liver is one of the typical manifestations in homocysteinemia/homocystinuria patients and their genetic animal model, mice lacking cystathionine ??-synthase (Cbs ^?/?). The vast majority of Cbs ^?/? die within 4?weeks after birth via yet unknown mechanisms, whereas a small portion survive to adulthood, escaping fatty degeneration of the liver during lactation periods, through regeneration. To investigate the molecular basis of such fatty changes, we analyzed lipid components in fatty livers of 2-week-old Cbs ^?/? and regenerated non-fatty livers of 8-week-old Cbs ^?/? survivors using a chip-based nanoESI (electrospray ionization)-MS system, which allows quantitative detection of triacylglycerol/phospholipid molecular species. Hepatic levels of all major triacylglycerol species were much higher in Cbs ^?/? than in wild-type mice at 2?weeks, although not at 8?weeks. Levels of some phospholipid species were either up- or downregulated in 2-week-old Cbs ^?/?; e.g. saturated (16:0 and 18:0) or mono-unsaturated (16:1 and 18:1) fatty acids-containing phosphatidylcholine/phosphatidylethanolamine species were upregulated, while poly-unsaturated fatty acids-containing phosphatidylcholine (18:2?C18:2 and 18:2?C20:5), phosphatidylethanolamine (18:1?C20:4), and phosphatidylinositol (18:0?C20:4) were downregulated. Capillary electrophoresis-MS analysis identified high-level accumulation of S-adenosylmethionine and S-adenosylhomocysteine in fatty livers of 2-week-old Cbs ^?/? but much less in non-fatty livers of 8-week-old Cbs ^?/?. Although hepatic S-adenosylmethionine/S-adenosylhomocysteine ratios were comparable between 2-week-old Cbs ^?/? and wild-type, global protein arginine methylation was disturbed in fatty livers of Cbs ^?/?. Our results suggest that cellular signaling mediated by altered phospholipid contents might be involved in pathogenesis of fatty liver in Cbs ^?/?C.     

Synthesis and oxidative polymerization of dialkyl fluorene-9,9-dicarboxylates

Novel long-chain dialkyl fluorene-9,9-dicarboxylates were synthesized by treating fluorene with lithium diisopropylamide followed by alkyl chloroformates. The fluorene derivatives were readily electro-oxidized to form electroactive films on the surface of a glassy carbon electrode. From the viewpoint of suitable potential window (from −2.5 to 1.5 V vs Ag/Ag⁺), cyclic voltammograms of the films indicated the electroactive properties of the fluorene derivatives that make them good candidates for electrochemical capacitor materials.     

Periodic Oscillatory Motion of a Self-Propelled Motor Driven by Decomposition of H2O2 by Catalase

A self-propelled motor driven by the enzymatic reaction of catalase adsorbed onto a filter paper floating on an aqueous solution of H₂O₂ was used to study nonlinear behavior in the motor's motion. An increase in the concentration of H₂O₂ resulted in a change from no motion to irregular oscillatory motion, periodic oscillatory motion, and continuous motion. The mechanisms underlying oscillation and mode bifurcation are discussed based on experimental results on O₂ bubble formation and growth on the underside of the motor.     

Theory of ring formation in a reversible system: general solutions

The enumeration theory is extended in this work into a more general theory, taking back-reactions into consideration. The solutions may faithfully reproduce real processes from arbitrary starting points to a steady-state. Therefore, the presented theory includes the equilibrium theory by Jacobson-Stockmayer, the numerical solution by Gordon-Temple, and the irreversible theory by the present authors. The solutions are described first in general forms of transition probabilities {P}, and then explicitly with the aid of rate equations; simple proofs are given. The presented theory was applied to an experimental data: the distribution of cyclic species in poly(ethylene terephthalate). We shall show that agreement between theory and experiment is nearly perfect.AB model N ₀ Total number of units - V System volume - C ₀=N ₀/N _A ·V Initial concentration (N _A : Avogadro's number) - L _x AB type chain x-mer; (AB)_x - N _x Number of AB type x-mers - R _x Ring x-mer - N _Rx Number of ring x-mers - E Small molecule eliminated by bond-formation - N _E Number of small molecules eliminated by bond-formation - h _k Number of reacted functional units (f.u.) in statek - _k Number of reacted functional units (f.u.) in chains in statek - _k Total number of units in chains in statek - D=h _k /N ₀ Extent of reaction in statek - D ^*= _k / _k Extent of reaction in chains in statek - k _L Chain-propagation rate constant - k _Rx Cyclization rate constant of chain x-mers - k _B Bond breakage rate constant of chains - k _B,Rx Bond breakage rate constant of cyclic x-mers - <k _Rx > _k Mean cyclization rate constant in statek - g(x)=k _B,Rx /k _B Ring-opening factor of cyclic x-mers - P _Lx,k Probability that a chain x-mer will be formed in statek - {P} Set of transition probabilities per single jump in forward direction or reverse direction (see the text on individual transition probabilities) AB model M _A Total AA monomer unit number - M _B Total BB monomer unit number - M ₀=M _A +M _B Total particle number - _A,i =2M _A –h _i Unreacted A functional unit (f.u.) number in statei - _B,i =2M _B –h _i Unreacted B f.u. number in statei - _Ax Unreacted A f.u. number on x-mers - h _i Number of reacted A (or B) f.u. in statei - _i Number of reacted A (or B) f.u. in chains in statei - _A,i =2M _A –h _i + _i A f.u. number in chains in statei - _B,i =2M _B –h _i + _i B f.u. number in chains in statei - _i =2(M ₀–h _i + _i ) Total f.u. number in chains in statei - D=h _i /M ₀ Extent of reaction in statei - D _A ^* = _i / _A,i Extent of reaction of A f.u. in chains in statei - D _B ^* = _i / _B,i Extent of reaction of B f.u. in chains in statei - D ^*=2 _i / _i Extent of reaction in chains in statei - L _x (AA-BB)_x-1-AA type chain x-mer;x=1,2,3,... - L _x BB-(AA-BB)_x type chain x-mer;x=0,1,2,... - L _x (AA-BB)_x type chain x-mer;x=1,2,3,... - N _x Number of type x-mers - N _x Number of type x-mers - N _x Number of type x-mers     

Cyclotron resonance in lead —I: Tipping effect of magnetic field

The cyclotron resonances in lead in field tipped geometry have been observed for large tipping angles up to 40° from the sample surfaces of the (111) and (100) planes. In addition to the resonance of the orbit ζ on a cylindrical arm of the electron Fermi surface, two new series of resonances, ζ^A and ζ^B have been found, of which the clotron masses are very close to that of ζ but which differ slightly in tipping angle dependence. The mass of ζ^A is dependent on microwave frequency, so that ζ^A is attributed to the Doppler-shifted cyclotron resonance of a non-stationary orbit near, ζ, whose location is discussed in relation to the Fermi surface model of Van Dyke. In field geometry normal to the (100) surface, two series of resonances have been observed, which are characterized as the extinction of even numbered harmonic resonances. This effect arises from the skipping orbit which has a trajectory topologically similar to a baseball seam in real space. One of these series is attributed to the orbit v around the junction of four electron arms.