Kinetics of supersaturation decay in the crystallization of lysozyme

The molecular architecture of proteins can be determined by analysing the X-ray diffraction patterns of their crystals. The technology of X-ray crystallography has reached the point, however, where the determination of the structure of a given crystal is controlled by the limited availability of the crystals themselves. Proteins can often be crystallized from pH buffered aqueous solutions of strong electrolytes. When dissolved protein in solution is more stable than crystalline protein, the appearance of crystals can be said to be under thermodynamic control. If, on the other hand, the crystals are more stable than the dissolved protein, and still crystals are slow to appear, the crystallization can be said to be under kinetic control. Using dilatometry, we have followed the rate of decay of the protein supersaturation in crystallizing solutions of chicken egg-white lysozyme under conditions of kinetic control. We have found that the rate of decay of the supersaturation is first order in the supersaturation and that the rate constant is independent of the initial protein concentration, but increases with increasing pH, decreasing temperature, and with increasing concentrations of sodium chloride and buffer salt. We correlate these observed trends in the rate constant with related trends in the solubility and surface charge density of the crystals. We conclude that the rate constant for supersaturation decay is inversely proportional to the protein solubility.     

EELS characterization of radiolytic products in frozen samples

Electron energy loss spectroscopy (EELS) was used to obtain information about the radiation chemistry of frozen aqueous specimens in the electron microscope by observing the hydrogen and oxygen K-edges. Measurements on frozen solutions of 30% hydrogen peroxide revealed the presence of molecular oxygen identified by a distinct 531-eV peak at the O K-edge even for electron doses below 100 e/nm2. The molecular oxygen content of irradiated H?O? solution was determined by least squares fitting of O K-edge reference spectra from water and gas-phase oxygen. It was found that the fraction of molecular oxygen to water oxygen was in the range 0.03-0.05. EELS from pure frozen water showed no features attributable to molecular oxygen or molecular hydrogen (K edge at ~13 eV) even at high electron doses above 10? e/nm2. Spectra from frozen sucrose and protein solutions and their mixtures, however, did show evolution of a molecular hydrogen peak at ~13 eV for doses above 10? e/nm2, consistent with previous measurements and indicative of hydrogen bubble formation. Molecular oxygen was not observed in any of the frozen solutions of organic compounds indicating that oxygen is not a major product of free radical decay, in contrast to molecular hydrogen formation.     

Study of Fluorescence Quenching in Aluminum-Doped Ceria Nanoparticles: Potential Molecular Probe for Dissolved Oxygen

This work investigates a novel usage of aluminum-doped ceria nanoparticles (ADC-NPs), as the molecular probe in optical fluorescence quenching for sensing the dissolved oxygen (DO). Cerium oxide (ceria) nanoparticles can be considered one of the most unique nanomaterials that are being studied today due to the diffusion and reactivity of oxygen vacancies in ceria, which contributes to its high oxygen storage capability. Aluminum can be considered a promising dopant to increase the oxygen ionic conductivity in ceria nanoparticles which can improve the sensitivity of ceria nanoparticles to DO. The fluorescence intensity of ADC-NPs, synthesized via chemical precipitation, is found to have a strong inverse relationship with the DO concentration in aqueous solutions. Stern-Volmer constant of ADC-NPs at room temperature is determined to be 454.6 M^?1, which indicates that ADC-NPs have a promising sensitivity to dissolved oxygen, compared to many presently used fluorophores. In addition, Stern-Volmer constant is found to have a relatively small dependence on temperature between 25 °C to 50 °C, which shows excellent thermal stability of ADC-NPs sensitivity. Our work suggests that ADC-NPs, at 6 nm, are the smallest diameter DO molecular probes between the currently used optical DO sensors composed of different nanostructures. This investigation can improve the performance of fluorescence-quenching DO sensors for industrial and environmental applications.     

Can cosmic-ray catalysed vacuum decay dominate over tunnelling?

We consider the question of whether cosmic-ray catalysed false-vacuum decay can be phenomenologically more important than spontaneous decay via quantum tunnelling. We extend the zero bubble wall width Landau-WKB analysis of catalysed false-vacuum decay to include the leading order effects of finite wall width and derive an expression for the thin-wall bubble action. Using this we calculate the exponential suppression factor for the catalysed decay rate at the critical bubble energy, corresponding to the largest probability of catalysed decay. We show that, in general, cosmic-ray catalysed decay is more important than spontaneous decay for sufficiently thin-walled bubbles (wall thickness less than about 30% of the initial bubble radius), but that spontaneous decay will dominate for the case of thick-walled bubbles. Since any perturbative model with a cosmologically significant false-vacuum decay rate will produce thick-walled bubbles, we can conclude that cosmic-ray catalysed false-vacuum decay will never dominate over tunnelling in imposing phenomenological constraints on perturbative particle physics models.     

圆管层流脉冲流动对流换热数值分析

对等热流和等壁温边界条件下圆管内层流脉冲流动对流换热问题进行了数值模拟。在等热流边界条件下的数值计算结果与理论解吻合很好。计算结果表明:在等热流和等壁温边界下脉冲流动可引起速度、温度以及努塞尔数随时间波动,振幅越大,脉冲频率越小,波动越大。但它们的时均值均等于在相同雷诺数下稳态流动的值,脉冲流动不能强化换热。     

一般边界条件下球形压力容器钢壁中氚和氦-3的浓度变化规律研究

为了认识储氚高压容器壁材料的力学性能变化及其导致的容器承载能力变化, 必须研究储氚期间, 容器壁中氚和氦-3浓度的空间分布和随时间的变化. 针对容器外表面为一般传质边界条件和容器内部氚为范德瓦尔斯气体的情况, 同时考虑容器腔内和容器壁中氚的衰变和扩散, 建立求解储氚高压容器壁中氚和氦-3浓度的解析理论模型, 导出了氚和氦-3浓度的理论公式. 通过解析计算给出了器壁中氚和氦-3浓度随外表面传质系数的变化曲线和浓度的时空变化曲线, 提出了氦-3浓度的2β ₁ + β ₂ / 2倍定律, 即处于开放空间的储氚球形高压容器, 器壁中氦-3的浓度呈内高外低的分布, 时间越长, 浓度沿径向的梯度越大, 在时间足够长时, 各处浓度逼近时间无限长时的最终值, 也就是各处的最大值, 内表面处的最大值是该处氚初始时刻浓度的2β ₁ + β ₂ / 2倍, 这里β ₁ 和β ₂ 为与氚的范德瓦尔斯常数相关的参数. 研究结果为储氚高压容器的强度安全性评估提供了前提.     

A new method for the determination of oxygen solubilities by EPR

Free radicals dissolved in oxygen-containing solutions give rise to EPR spectra characterized by very broad lines due to Heisenberg spin exchange. In the method herein proposed oxygen is consumed at a constant rate, within the cavity of an EPR spectrometer, by alkyl radicals generatedin situ by thermal decomposition of an aliphatic azo compound in the presence of a nitroxide probe. The effect of decreasing the oxygen concentration is to reduce the width, and therefore to increase the height of the spectral lines of the nitroxide, which reach a maximum when oxygen has been completely consumed. From the knowledge of the rate of generation of the alkyl radicals, the oxygen solubility in a given solvent can be easily determined.     

非定常可压等熵流非线性方程显式解析解的推导

本文对作者以前凭试凑、灵感、运气与经验得出的一系列非定常可压流动显式解析解,寻找线索,总结出其可能的推导途径,并以非定常可压等熵一维流为例,具体给出了四种新的求解方法。这些方法会对今后寻找工程热物理领域的非线性主控方程的解析解有所帮助。本文同时还给出了两个新的解析解。     

Stability of asymmetric spike solutions to the Gierer-Meinhardt system

In this paper, we study the spectra of asymmetric spike solutions to the Gierer-Meinhardt system. It has previously been shown that the spectra of such solutions may be determined by finding the generalized eigenvalues of matrices, which are determined by the positions of the spikes and various parameters from the system. We will examine the spectra of asymmetric solutions near the point at which they bifurcate off of a symmetric branch. We will confirm that all such solutions are unstable in a neighborhood of the bifurcation point and we derive an explicit expression for the leading order terms of the critical eigenvalues.     

Effect of dopant polarizability on oxygen sublattice order in phase-stabilized cubic bismuth oxides

Bismuth oxide doped with isovalent rare earth cations retains the high temperature defective fluorite structure upon cooling down to room temperature. However, these doped materials undergo an order-disorder transition of the oxygen sublattice at about 600 °C. When annealed at temperatures less than the transition temperature the oxygen sublattice continues to order, and consequently oxygen ion conductivity undergoes a decay. Modeling of ordered structures based on TEM diffraction patterns indicates a 〈111〉 vacancy ordering in the anion sublattice. Neutron diffraction studies show additional structural changes in the oxygen sublattice due to ordering. These studies indicate that the ionic conductivity is dependent on the distribution of oxygen ions between the regular 8c sites and the interstitial 32f sites in the fluorite structure. Earlier neutron diffraction studies indicate that short range ordering of the anion sublattice is related to the polarizability of the cations. In this study we relate the stability of the disordered structure and the formation of long range order to the polarizability of the dopant cations, in terms of the time constant for conductivity decay and the dielectric constant. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Molecular multivalent electrolytes: microstructure and screening lengths

We study small rod-like molecular electrolytes solutions with their corresponding atomic counterions. The asymptotic length scales (decay length and wavelength) of the structural correlations are analyzed using the formalism of the dressed interaction site theory (DIST). The correlation functions are determined using the reference interaction site model equation complemented with a mixed approach in which the hypernetted-chain closure is used for the repulsive interactions, and the mean spherical approximation is used for the attractive interactions. The results from this scheme are in good agreement with the Monte Carlo computer simulations reported here. The asymptotic properties of the correlation functions of this molecular system are compared against those corresponding to two related simple (atomic) electrolyte models. The main conclusion is that the molecular structure of the ions lowers by two orders of magnitude the concentration at which the transition from monotonic to oscillatory decay occurs.     

Is X(3872) really a molecular state?

After taking into account both the pion and sigma meson exchange potential, we have performed a dynamical calculation of the D⁰D̄^*0 system. The σ meson exchange potential is repulsive from heavy quark symmetry and numerically important for a loosely bound system. Our analysis disfavors the interpretation of X(3872) as a loosely bound molecular state if we use the experimental D^*Dπ coupling constant g=0.59 and a reasonable cutoff around 1 GeV, which is the typical hadronic scale. Bound state solutions with negative eigenvalues for the DD̄^* system exist only with either a very large coupling constant (twice the experimental value) or a large cutoff (Λ ∼ 6 GeV or β ∼ 6 GeV²). In contrast, there probably exists a loosely bound S-wave BB̄^* molecular state. Once produced, such a molecular state would be rather stable, since its dominant decay mode is the radiative decay through B^*→Bγ. Experimental search of these states will be very interesting. PACS  12.39.Pn; 12.40.Yx; 13.75.Lb     

Decay of solitons in an isotropic collisionless quasineutral plasma with isothermal pressure

Soliton-type solutions of the complete unreduced system of transport equations describing the plane-parallel motions of an isotropic collisionless quasineutral plasma in a magnetic field with constant ion and electron temperatures are studied. The regions of the physical parameters for fast and slow magnetosonic branches, where solitons and generalized solitary waves—nonlocal soliton structures in the form of a soliton “core” with asymptotic behavior at infinity in the form of a periodic low-amplitude wave—exist, are determined. In the range of parameters where solitons are replaced by generalized solitary waves, soliton-like disturbances are subjected to decay whose mechanisms are qualitatively different for slow and fast magnetosonic waves. A specific feature of the decay of such disturbances for fast magnetosonic waves is that the energy of the disturbance decreases primarily as a result of the quasistationary emission of a resonant periodic wave of the same nature. Similar disturbances in the form of a soliton core of a slow magnetosonic generalized solitary wave essentially do not emit resonant modes on the Alfvén branch but they lose energy quite rapidly because of continuous emission of a slow magnetosonic wave. Possible types of shocks which are formed by two types of existing soliton solutions (solitons and generalized solitary waves) are examined in the context of such solutions.     

Prompt isothermal decay of thermoluminescence in MgB4O7:Dy,Na and LiB4O7:Cu,In dosimeters

According to standard delocalized kinetic models of thermoluminescence (TL), when an irradiated sample is held at a high temperature T, the isothermal TL signal will decay with a characteristic thermal decay constant λ which depends strongly on the temperature T. This prediction of standard delocalized kinetic theory is investigated in this paper by studying two TL dosimeters, MgB₄O₇:Dy, Na and LiB₄O₇:Cu, In (hereafter MBO and LBO correspondingly). In the case of LBO it was found that the thermal decay constant λ of the main dosimetric TL peak follows exactly the predictions of standard delocalized kinetic theory. Furthermore, the thermal activation energy of the main peak evaluated by the isothermal decay method is in full agreement with values obtained from initial rise and glow curve fitting methods. However, in the case of MBO it was found that the thermal decay constant λ varies little with the isothermal decay temperature T. In order to explain these unusual results for MBO, the TL glow curves and isothermal decay curves were analyzed using analytical expressions derived recently from a radiative tunneling recombination model. Based on the different behavior of the two TL dosimeters, it is suggested that the isothermal decay of TL at high temperatures can be used to discriminate between radiative delocalized recombination and radiative localized recombination processes.     

介质阻挡放电中微放电的映射方程

利用双水电极介质阻挡放电装置，采用光学方法测量了大气压空气和氩气中介质阻挡放电的微放电时间特性.实验发现微放电通道相邻两次放电时间间隔是长短交替的.根据壁电荷对相邻两次微放电的不同影响，建立了介质阻挡放电时间序列的映射方程.不同放电参量取值情况下的计算结果表明，介质阻挡放电中，壁电荷电场的衰减时间常数远大于100μs量级.由方程所得的结果，解释了相邻两次放电时间间隔长短交替的实验现象，确定了壁电荷衰减时间常数的范围. 关键词： 介质阻挡放电 时间特性 壁电荷 映射方程     

Lie Group of Transformations for a KdV–Boussinesq Equation

We consider a combined Korteweg–deVries and Boussinesq equation governing long surface waves in shallow water. Considering traveling wave solutions, the basic equations will be reduced to a second order ordinary differential equation. Using the Lie group of transformations we reduce it to a first order ordinary differential equation and employ a direct method to derive its periodic solutions in terms of Jacobian elliptic functions and their corresponding solitary wave and explode decay mode solutions.     

Energy accommodation and reactivity of O2 on tungsten

We have determined by direct molecular beam velocity measurements that translational energy accommodation of O₂ molecules scattered from a hot polycrystalline tungsten target is inefficient at high surface temperatures. Translational energy accommodation is inefficient whether the surface is clean or covered with oxygen to a varying extent, even though in the latter case the scattering is diffuse. On a clean tungsten surface the scattering of the O₂ was approximately specular and the reaction probability of O₂ was constant and greater than 90% over the temperature range 1000K to 2800 K. It was shown by simultaneous helium scattering that atomic surface roughness of an oxygen chemilayer, rather than trapping, is a major cause of the observed diffuse scattering of oxygen. At the lowest surface temperature of 1000 K, with an oxygen chemilayer present, the velocity of the most probable number density of the scattered O₂ was lower than in the incoming beam or than that expected for complete equilibration with the surface.     

源强对Rossi-α噪声分析的影响

通过数值模拟手段研究了源强对Rossi-测量的影响。为了定量研究中子源强对Rossi-测量的影响,基于MCNP软件;开发了用于计算Rossi-分布的数值模拟工具。反应堆模型和加速器驱动次临界系统的示意模型的数值模拟结果被用于展示瞬发中子衰减常数与源强之间的关联。数值模拟结果表明,入射源强源中子强度对Rossi-测量结果有显著影响。对于处于次临界状态的反应堆和加速器驱动次临界系统模型,在入射源强较小时,Rossi-方法可以正确给出反应堆中子衰减常数,但当入射源强较大时,测量不能给出正确的中子衰减常数。通过研究源强和测量结果的关系,可以找到能够给出正确测量结果的最大可用源强。通过选择一个可用源强范围内的较强中子源,可以减少测量所需时间。     

Zur Untersuchung von Versetzungen mit Hilfe der magnetischen Kernresonanz

The line width of the nmr signal is obtained for a statistical distribution of distances and orientations of dislocations as a function of the dislocation density. The quadrupolar part of the line width increases proportional to the root of the dislocation density in the case of first order distortion but is proportional to the dislocation density itself in the case of second order distortion. The total line width passes through a maximum within the range of first order distortion and approaches the value of the undistorted central line which arises from magnetic dipole interaction when the dislocation density becomes sufficiently large. The intensity decay of the nmr signal connected with this line width behaviour will also be presented. In the range of second order distortion the total line width is determined by the constant dipole interaction and the quadrupole interaction of the central line which depends on the dislocation density. Under the assumption of a Gaussian distribution for the line shape a simple expression for this width can be obtained. The calculations are checked for the case of first order distortion by measurements on the Na²³ and Cl³⁵ nmr signals of NaCl single crystals and for the case of second order distortion by measurements on the J¹²⁷ signal of KJ single crystals.     

An investigation of the sound field above the audience in large lecture halls with a scale model

Measurements of steady-state sound pressure levels above the audience in large lecture halls show that the classical equation for predicting the sound pressure level is not accurate. The direct field above the seats was measured on a 1:10 scale model and was found to be dependent on the incidence angle and direction of sound propagation across the audience. The reverberant field above the seats in the model was calculated by subtracting the direct field from the measured total field and was found to be dependent on the magnitude and particularly on the placement of absorption. The decrease of sound pressure level versus distance in the total field depends on the angle (controlled by absorption placement) at which the strong reflections are incident upon the audience area. Sound pressure level decreases at a fairly constant rate with distance from the sound source in both the direct and reverberant field, and the decrease rate depends strongly on the absorption placement. The lowest rate of decay occurs when the side walls are absorptive, and both the ceiling and rear wall are reflective. These consequences are discussed with respect to prediction of speech intelligibility.