广义等温等压系综-分子动力学模拟全原子水的气液共存形貌

探测相变过程中瞬时共存相的形貌等特征对理解其微观机制十分重要.本文应用广义等温等压系综-分子动力学模拟方法,研究全原子水模型的气液两相平衡及相变的中间过程.研究发现,此广义系综方法能够通过持续降温,连续地历经从气态、气液共存到液态的整个相变过程,通过持续升温历经其相反过程,而不会发生标准正则系综中的过饱和热滞现象.该方法不需要使用副本交换等增强抽样方法,因此可以用于较大体系的研究,多个独立的模拟即能获得整个气态液态区的平衡性质及共存相特征.本文还提出了计算气液共存界面面积的新方法,给出了水的气液共存界面形状随温度、压强的变化规律.结果表明,低压时水的气液共存界面因其较大的表面张力而接近球面,符合经典成核理论的描述,但随着压强升高接近其临界压强时,气态和液态的差别减小,界面的表面张力变小,界面形状变为无规则的枝杈结构,表现为二阶相变特征.     

Lamellar phase coexistence induced by electrostatic interactions

Membranes containing highly charged biomolecules can have a minimal free-energy state at small separations that originates in the strongly correlated electrostatic interactions mediated by counterions. This phenomenon can lead to a condensed, lamellar phase of charged membranes that coexists in thermodynamic equilibrium with a very dilute membrane phase. Although the dilute phase is mostly water, entropy dictates that this phase must contain some membranes and counterions. Thus, electrostatics alone can give rise to the coexistence of a condensed and an unbound lamellar phase. We use numerical simulations to predict the nature of this coexistence when the charge density of the membrane is large, for the case of multivalent counterions and for a membrane charge that is characteristic of biomolecules. We also investigate the effects of counterion size and salt on the two coexisting phases. With increasing salt concentration, we predict that electrostatic screening by salt can destroy the phase separation.     

Strong-coupling electrostatics in the presence of dielectric inhomogeneities

We study the strong-coupling (SC) interaction between two like-charged membranes of finite thickness embedded in a medium of higher dielectric constant. A generalized SC theory is applied along with extensive Monte Carlo simulations to study the image charge effects induced by multiple dielectric discontinuities in this system. These effects lead to strong counterion crowding in the central region of the intersurface space upon increasing the solvent-membrane dielectric mismatch and change the membrane interactions from attractive to repulsive at small separations. These features agree quantitatively with the SC theory at elevated couplings or dielectric mismatch where the correlation hole around counterions is larger than the thickness of the central counterion layer.     

Structural characterization and gas‐transport properties of brominated matrimid polyimide

The commercial polyimide Matrimid was modified by bromination for the purpose of improving its membrane‐transport properties as a gas‐separation material and providing functional group reactivity for further modifications. The unmodified and brominated polymers were characterized by elemental analysis and one‐dimensional and two‐dimensional NMR, which revealed that one bromine atom per repeat unit was incorporated regioselectively onto the indane aromatic ring. The thermal and physical properties of the polymers before and after bromination were also investigated. The gas‐transport properties of the unmodified and brominated polymers were compared. © 2002 Government of Canada. Exclusive worldwide publication rights in the article have been transferred to Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4193–4204, 2002     

Negative feedback regulation of Wnt signaling by G�¦�-mediated reduction of Dishevelled

Wnt signaling is known to be important for diverse embryonic and post-natal cellular events and be regulated by the proteins Dishevelled and Axin. Although Dishevelled is activated by Wnt and involved in signal transduction, it is not clear how Dishevelled-mediated signaling is turned off. We report that guanine nucleotide binding protein beta 2 (Gnb2; Gβ₂) bound to Axin and Gβ₂ inhibited Wnt mediated reporter activity. The inhibition involved reduction of the level of Dishevelled, and the Gβ₂γ₂ mediated reduction of Dishevelled was countered by increased expression of Axin. Consistent with these effects in HEK293T cells, injection of Gβ₂γ₂ into Xenopus embryos inhibited the formation of secondary axes induced either by XWnt8 or Dishevelled, but not by β-catenin. The DEP domain of Dishevelled is necessary for both interaction with Gβ_2γ2 and subsequent degradation of Dishevelled via the lysosomal pathway. Signaling induced by Gβ_2γ2 is required because a mutant of Gβ₂, Gβ₂ (W332A) with lower signaling activity, had reduced ability to downregulate the level of Dishevelled. Activation of Wnt signaling by either of two methods, increased Frizzled signaling or transient transfection of Wnt, also led to increased degradation of Dishevelled and the induced Dishevelled loss is dependent on Gβ₁ and Gβ₂. Other studies with agents that interfere with PLC action and calcium signaling suggested that loss of Dishevelled is mediated through the following pathway: Wnt/Frizzled→Gβγ→PLC→Ca⁺²/PKC signaling. Together the evidence suggests a novel negative feedback mechanism in which Gβ₂γ₂ inhibits Wnt signaling by degradation of Dishevelled.     

Electron paramagnetic resonance and photoluminescence properties of α-Al2O3:Cr3+ phosphors

The red emitting Cr³⁺ activated α-Al₂O₃ powder phosphor has been prepared by easy combustion reactions from mixed metal nitrate reactants and urea with ignition temperatures of 500 °C. The as-synthesized powder was characterized by X-ray diffraction, scanning electron microscopy, and Fourier-transform infrared techniques. The X-ray diffraction pattern reveals that the phosphor crystallized in the hexagonal α-Al₂O₃ phase directly from the combustion reaction. The EPR spectrum exhibits an intense resonance signal with effective g value at g=3.33 along with a few weak resonance signals with effective g values at g=13.7, 2.34, 1.95, 1.49, and 1.26. The spin concentration (N) and its paramagnetic susceptibility (χ) have been evaluated. The excitation spectrum consists of two broad intense bands at 415 nm and 555 nm and are assigned to ⁴A_2g (F)→⁴T_1g (F) and ⁴A_2g (F)→⁴T_2g (F) transitions, respectively. The intense fluorescence peak around 691 nm is attributed to ²E _g →⁴A_2g transition of Cr³⁺ ion. By correlating EPR and optical data, the crystal field splitting parameter (Dq), Racah inter-electronic repulsion parameter (B) have been evaluated and discussed. The EPR and optical studies reveal that Cr³⁺ ions are occupying in Al³⁺ sites in octahedral coordination.     

Cooperative recombination of a quantized high-density electron-hole plasma in semiconductor quantum wells

We investigate photoluminescence from a high-density electron-hole plasma in semiconductor quantum wells created via intense femtosecond excitation in a strong perpendicular magnetic field, a fully quantized and tunable system. At a critical magnetic field strength and excitation fluence, we observe a clear transition in the band-edge photoluminescence from omnidirectional output to a randomly directed but highly collimated beam. In addition, changes in the linewidth, carrier density, and magnetic field scaling of the photoluminescence spectral features correlate precisely with the onset of random directionality, indicative of cooperative recombination from a high-density population of free carriers in a semiconductor environment.     

Supramolecular Discotic Columnar Liquid Crystals Built through Single Hydrogen Bonding between Carboxylic Acid and Pyridine Moieties

New self-assembled discotic columnar liquid crystals were prepared via single hydrogen bonding between the core molecule of 1,3,5-cyclohexanetricarboxylic acid and the peripheral units of stilbazole derivatives. The hydrogen-bonded liquid crystals exhibited rectangular columnar and hexagonal columnar mesophases depending on the number of alkyl chains in three arms of the discotic mesogen through dipole-dipole interactions between carbonyl groups along the column axis. The intermolecular hydrogen bonding between carboxylic acid and pyridine moieties provides an effortless methodology to prepare the ordered columnar liquid crystals for electronic applications.     

Isolation of Phlorotannins from Eisenia bicyclis and Their Hepatoprotective Effect against Oxidative Stress Induced by tert-Butyl Hyperoxide

Eisenia bicyclis (Kjellman) Setchell is a common brown alga that inhabits the middle Pacific coast around Korea and Japan. In this study, the ethanol extract and its serial solvent fractions were prepared from fresh E. bicyclis, and their hepatoprotective effects were investigated against hepatotoxicity in tert-butyl hyperoxide(t-BHP)-injured HepG2 cells. When these samples were used at a dose of 10-40 μg/mL?1, they significantly protected the t-BHP-induced cell death in HepG2 cells. Among fractions, ethyl acetate fraction (EF) and n-butanol extract (BF) exhibited potent hepatoprotective activities (62.60% for EF and 64.86% for BF) in t-BHP-injured HepG2 cells at a concentration of 10 μg/mL?1. To find the potential factors for this activity, the samples were characterized on total phenolics, chlorophylls, carotenoids, and radical scavenging activity. Among them, EF showed the highest content of total phenolics and the strongest antioxidant activity both in on- and offline assays. Five phlorotannin compounds, oligomers of phloroglucinol, were isolated chromatographically from this fraction and structurally identified by (1)H-NMR and liquid chromatography-electrospray ionization-mass spectrometry analyses as eckol(1), 6,6'-bieckol(2), 8,8'-bieckol(3), dieckol(4), and phlorofucofuroeckol A(5). Compound 5 among five purified compounds showed the strongest protective activity (45.54%) at a concentration of 10 μM. At the high dose (40 μM), the protective activities of three compounds (compound 2, 4, and 5) were higher than that of quercetin treated with 10 μM concentration. Therefore, we can speculate that they can be developed as potential candidates for natural hepatoprotective agents.