The interaction between poly(N-isopropylacrylamide) and salts in aqueous media: The “salting-out” phenomenon as studied by attenuated total reflection/fourier transform infrared spectroscopy

The effect of two strong salting-out salts (Na₂SO₄ and K₂SO₄) on the temperature-induced phase-separation process in aqueous solutions of poly(N-isopropylacrylamide) (PNIPA) was examined by attenuated total reflectance/Fourier transform infrared spectroscopy, differential scanning calorimetry, and viscosity measurements. On the basis of these measurements, a detailed scenario of the phase-separation process was deduced. The phase-separation scenario of solutions containing PNIPA and water was altered in the presence of sulfate ions. Here, the sulfate ions induced partial intrachain collapse, manifested by a relatively compact structure well below the lower critical solution temperature. This led to a more gradual, smooth phase transition, with temperature-resolved intrachain collapse and interchain aggregation and a lesser extent of hysteresis. Although at the macrolevel one may not be able to differentiate among various scenarios altering the solvent into a poor solvent, the aforementioned microlevel measurements provided a way to expose the difference between raising the temperature and adding cosolutes. Follow-up studies on the effect of salting-in salts will be presented. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 33–46, 2004     

Solid Phase Synthesis of 2-Substituted 1,3-Oxazin-6-ones Using Resin-bound Cyclic Malonic Acid Ester

A facile solid phase synthesis of 2-substituted 1,3-oxazin-6-ones using polymer-supported Meldrum‘s acid has been reported. Reaction of the resin-bound cyclic malonic acid ester with triethyl orthoformate and subsequent double substitution with amide, afforded the corresponding polymer-supported acylaminomethylene cyclic malonic acid ester, which upon thermal treatment led to 1, 3-oxazin-6-ones in good yields and with high purity.     

Stable nonequilibrium probability densities and phase transitions for meanfield models in the thermodynamic limit

A nonlinear Fokker-Planck equation is derived to describe the cooperative behavior of general stochastic systems interacting via mean-field couplings, in the limit of an infinite number of such systems. Disordered systems are also considered. In the weak-noise limit; a general result yields the possibility of having bifurcations from stationary solutions of the nonlinear Fokker-Planck equation into stable time-dependent solutions. The latter are interpreted as non-equilibrium probability distributions (states), and the bifurcations to them as nonequilibrium phase transitions. In the thermodynamic limit, results for three models are given for illustrative purposes. A model of self-synchronization of nonlinear oscillators presents a Hopf bifurcation to a time-periodic probability density, which can be analyzed for any value of the noise. The effects of disorder are illustrated by a simplified version of the Sompolinsky-Zippelius model of spin-glasses. Finally, results for the Fukuyama-Lee-Fisher model of charge-density waves are given. A singular perturbation analysis shows that the depinning transition is a bifurcation problem modified by the disorder noise due to impurities. Far from the bifurcation point, the CDW is either pinned or free, obeying (to leading order) the Grüner-Zawadowki-Chaikin equation. Near the bifurcation, the disorder noise drastically modifies the pattern, giving a quenched average of the CDW current which is constant. Critical exponents are found to depend on the noise, and they are larger than Fisher's values for the two probability distributions considered.     

随机化交通灯的二维元胞自动机交通模型

元胞自动机交通模型以简单的规则反映交通系统中的多种因素，可以分析各种交通现象，且可在计算机上方便、高效地运作·Ｂｉｈａｍ－Ｍｉｄｄｌｅｔｏｎ－Ｌｅｖｉｎｅ模型（ＢＭＬ模型）实现了二维交通问题的元胞自动机模型的模拟研究·本文对ＢＭＬ模型作了改进，解除了该模型中关于交通灯同步变化的限制·在新模型中，每个路口的交通灯可以自由选定起始工作时间和变化节奏，于是可以更全面、准确地反映交通灯对交通系统性能的影响·本文还对新模型中出现的若干新效应作了解释·     

Modules over Operator Algebras and Its Module Maps

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A Note on Topological Entropy of Maps

For a given collection of subsets of a compact metric space X which cover X,the entropies,hm(f)and hi(f),are introduced for a continuous map f of X to itseif. Also the concept of shadowing property with same end point (SPSEP for short) is introduced. The main results are,(1)H(f)≤hi(f)+hm(f)and,(2)h(f)=hm(f)whenever f has SPSEP,where h(f) is the topological entropy of f. Moreover,several corollaries are obtained.     

A highly selective solid phase extraction sorbent for pre-concentration of sameridine made by molecular imprinting

Summary A novel approach to solid phase extraction, based on the use of a highly selective molecularly imprinted polymer, is presented. The versatility of this type of sorbent for solid phase extraction was demonstrated in a model batch-wise pre-concentration of sameridine prior to gas chromatography. Problems associated with leakage of remaining imprint molecules during the desorption phase could be eliminated by the use of a close structural analogue of sameridine as the imprint species. It was found that a major benefit of the imprinted polymer was its specificity, which lead to distinctly cleaner chromatographic traces and ability to improve sensitivity by extracting sameridine from larger sample volumes.     

Solid phase synthesis of azapeptides using an automatic synthesizer

Peptides containing azaglycine located terminally or within the backbone have been prepared in the solid phase by means of an automatic synthesizer.     

Time-resolved synchrotron X-ray study of crystalline phase transition in poly(aryl ether ketone ketone) containing alternated terephthalic/isophthalic moieties

Unique crystallization and melting behavior in poly(aryl ether ketone ketone) containing alternated terephthalic and isophthalic moieties were studied by time-resolved synchrotron x-ray methods. Recently, this material has been shown to exhibit three polymorphs (forms I, II, and III). In this work, we further investigated their distinctive thermal properties and found that form I is the dominating and the most thermally stable phase while form II is favored by fast nucleation conditions and is the least stable phase. On the other hand, form III represents a minor intermediate phase that usually coexists with form I and can be transferred from form II and to form I. Structural and morphological changes in form I have been followed by simultaneous wide-angle x-ray diffraction (WAXD)/small-angle x-ray scattering (SAXS) measurements during cold- or melt-crystallization and subsequent melting. In all cases, a larger dimensional change was found in the crystallographic a-axis than the b-axis during heating and cooling. This may be due to the greater lateral stress variation with respect to temperature along the a direction of the primary lamellae which is induced by either the formation of secondary lamellae or the preferential chain-folding direction in poly(aryl ether ketone ketone)s. During the phase transitions of form II ← III in the cold-crystallized specimen and form III ← I in the melt-crystallized samples, lamellar variables (long period, lamellar thickness, and invariant) obtained from SAXS remain almost constant. This indicates that the density distribution in the long spacing is independent of the melting in form II or III. For melt-crystallization, the corresponding changes in unit-cell dimensions and lamellar morphology during the annealing-induced low endotherm are most consistent with the argument that these changes are due to the melting of thin lamellar population. © 1995 John Wiley & Sons, Inc.     

Chemiluminescence upon isomerization of dimethyldioxirane in the gas phase and on a sorbent surface

Chemiluminescence (CL) was found upon the isomerization of dimethyldioxirane in the gas phase under argon atmosphere. The intensity of CL increases as temperature increases and decreases with time at constant temperature. If Silipor is placed in a cell containing the dimethyldioxirane vapor in argon, the intensity of CL sharply increases (more than 10 times) and then decreases following the exponential law. In all cases tripletly excited methyl acetate is the emitter of chemiluminescence.[/ p]Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2582–2583, October 1996.