The solvation and hydrophobic interaction of non-polar molecules in water in the approximation of interatomic potentials: The Monte Carlo method

The problem of calculating thermodynamic functions of solvation and hydrophobic interaction of non-polar molecules in water is considered, and the functions of ‘switched off’ interaction which allow one to compare calculated and experimental data are introduced and discussed. Expressions for the free energies, entropies and internal energies of solvation and hydrophobic interaction are deduced by statistical mechanics, and the possibility of computing these quantities from information about interatomic potential functions is considered. An application of the Monte Carlo method with the Boltzmann transition probabilities between the states of a Markov chain has allowed us to evaluate configuration integrals and thermodynamic functions of solvation and hydrophobic interaction. For solvation, the calculated values are in good agreement with the experimental data if the periodic boundary conditions are observed, and in moderate agreement should these be neglected. For hydrophobic interaction, the plot of F _HI(R ₁₂) is built and the potentials of average force for two methane molecules, as well as two hard spheres, is evaluated.     

计入固液界面作用的润滑热力学模型与分析

摩擦与润滑过程是典型的能量耗散过程, 在机理上与非平衡热力学中的熵增、耗散结构等理论颇有相似之处. 通过热力学分析可以对一些典型的摩擦磨损过程做出合理的机理揭示与推测. 本文利用热力学理论对典型的润滑过程进行了建模分析. 采用分离压模型表征和计入了微尺度下的固液界面作用, 揭示分析了润滑热力学模型与润滑状态Stribeck曲线的联系. 从分析计算结果来看, 润滑Stribeck曲线的摩擦系数最低点与系统热力学上的熵增率最低点具有相当好的对应关系, 而润滑状态从弹流润滑向薄膜润滑的转变过程, 可以用耗散结构理论加以机理解释. 文中的热力学模型和方法能够有效地体现出润滑过程中多物理要素跨尺度非线性耦合的作用, 对实际工程与实验有着重要的指导作用.     

荧光光谱法研究黄豆黄素与牛血清白蛋白的相互作用

用荧光光谱法在pH 7.4的PBS中研究了黄豆黄素(Glycitein,GL)与牛血清白蛋白(Bovine serum albumin,BSA)分子之间的相互作用方式及机理.结果表明GL可静态猝灭BSA的内源荧光.310K和315K的结合位点数与表观结合常数分别为1.30,8.09×104L·mol-1和1.73,5....     

Nonequilibrium phase transitions associated with DNA replication

Thermodynamics governing the synthesis of DNA and RNA strands under a template is considered analytically and applied to the population dynamics of competing replicators. We find a nonequilibrium phase transition for high values of polymerase fidelity in a single replicator, where the two phases correspond to stationary states with higher elongation velocity and lower error rate than the other. At the critical point, the susceptibility linking velocity to thermodynamic force diverges. The overall behavior closely resembles the liquid-vapor phase transition in equilibrium. For a population of self-replicating macromolecules, Eigen's error catastrophe transition precedes this thermodynamic phase transition during starvation. For a given thermodynamic force, the fitness of replicators increases with increasing polymerase fidelity above a threshold.     

温库边界对布朗热机性能的影响

研究了单势垒锯齿势中,布朗粒子在外力和空间周期温度场作用下构成的布朗热机的热力学性能.考虑布朗粒子动能变化以及高、低温库之间热漏引起的热流.用Smoluchowski方程描述粒子在黏性介质中的动力学特性,推导出高、低温库的热流以及热机功率和效率的解析表达式.通过数值计算分析势垒高度、外力和温库边界对热机性能的影响.研究表明:由于动能变化和热漏引起的不可逆热流的存在,布朗热机为不可逆热机,热机的功率效率特性为一闭合的关系曲线;势垒边界与温库边界重合时,热机的功率达到最大值;通过改变温库边界的位置,可以在一定范围内提高热机的效率,但同时减小了热机的输出功率.     

Fluxes and the elimination of fast-relaxing variables

The behavior of fluxes under elimination of fast-relaxing variables from linear dynamical evolution equations is investigated. It is found that the fluxes corresponding to evolution equations which result from eliminations do not in general yield an adequate representation of the fluxes corresponding to the evolution equations from which the variables have been eliminated. In all examples considered, a discrepancy occurs when the eliminations reduce a cycle with nonzero thermodynamic force to a single state. The entropy production corresponding to the evolution equations resulting from the eliminations lacks terms corresponding to such cycles.     

力与耦合系统的交互作用和随机能量共振

外界对系统作功的过程就是系统状态发生变化的过程.根据Langevin方程的随机动力学特性,采用微观动力学和宏观热力学方法,建立了基于单一随机轨线的耦合双稳系统的热力学关系.通过力与耦合系统的功交互作用定量地刻画了能量的传递和转换关系,揭示了耦合系统中存在着的随机能量共振现象.从作功与能量的关系进行分析,进一步揭示了随机共振产生的物理本质. 关键词： 耦合双稳系统 随机热力学 随机能量共振 功     

A Curie-Weiss Model with Dissipation

We consider stochastic dynamics for a spin system with mean field interaction, in which the interaction potential is subject to noisy and dissipative stochastic evolution. We show that, in the thermodynamic limit and at sufficiently low temperature, the magnetization of the system has a time periodic behavior, despite of the fact that no periodic force is applied.     

铁磁纳米阵列膜温度稳定性的损伤扩散研究

利用损伤扩散方法研究了三角点阵量子磁盘的温度稳定性问题.为建立实际体系的伊辛模型,我们作了三方面考虑：1)计入自旋间的长程相互作用;2)考虑纳米线阵列中纳米线长度的不一致性,3)推导出矫顽力与自旋交换常数间的关系并利用矫顽力定量估算出自旋交换常数的数值.模拟结果表明,自旋间的作用范围越长,损伤扩散越难,即稳定性越好;而纳米线的长度混乱度越大,温度稳定性越差. 关键词： 量子磁盘 温度稳定性 损伤扩散方法     

光谱法研究抗癌药物槲皮素和人血清白蛋白的相互作用

研究槲皮素与人血清白蛋白(HSA)的相互作用,以阐明槲皮素在体内的运输过程。利用荧光光谱和紫外吸收光谱进行实验,采用Stern-Volmer方程,Lineweaver-Burk双倒数方程和双对数回归曲线模型处理实验数据,求出了不同温度下槲皮素与HSA的结合常数、结合位点数和相关热力学参数。随槲皮素浓度的增大,HSA在210nm和280nm处的紫外吸收峰增强,HSA的内源荧光强度被猝灭。槲皮素和HSA作用后形成了新的复合物,静态猝灭是槲皮素对HSA荧光猝灭的主要原因。不同模型得到的结合常数和热力学参数有所不同,都表明槲皮素和HSA二者之间具有较强的作用力,其相互作用是自发进行的。抗癌药物槲皮素是可以被HSA所储存和运输的。     

荧光光度法研究金莲橙G与牛血清白蛋白的作用

利用荧光光度法研究了金莲橙G与牛血清白蛋白(BSA)的相互作用。金莲橙G对牛血清白蛋白的内源荧光有显著的猝灭作用,是形成超分子复合物的静态猝灭过程。测定了金莲橙G与BSA结合常数以及其相互作用的热力学参数,并根据Ross理论,和作用过程的热力学参数确定了金莲橙G与牛血清白蛋白之间主要结合力是静电引力。由Foerster非辐射能量转移理论,推导出能量供体金莲橙G与受体BSA间的结合距离。     

Particle clustering and Mott transitions in nuclear matter at finite temperature: (I). Method and general aspects

The thermodynamic state of nuclear matter as regards dependence on density and temperature is considered. Expressions for the association degree are derived describing the ratio of nuclear matter which is clustered to bound states. The problem of two nucleons imbedded in the surrounding nuclear matter is considered with the help of the Bethe-Goldstone equation for thermodynamic Green functions. The two-particle energy shift due to the effective nuclear matter hamiltonian is considered in a Hartree-Fock approximation, and a Mott density is obtained so that for densities of nuclear matter higher than the Mott density bound states cannot exist. With a simplified effective two-nucleon interaction the association degree is calculated as a function of the nucleon density and the temperature.     

荧光光谱法研究咖啡因与肌红蛋白的相互作用

采用荧光光谱法在生理pH 7.4条件下研究了药物咖啡因与肌红蛋白分子间的相互作用,表明这种相互作用能使肌红蛋白的内源荧光猝灭。通过猝灭常数,结合常数和结合位点数的计算,证明此猝灭为静态猝灭机制。咖啡因和肌红蛋白形成1∶1稳定配合物,形成常数(18 ℃)K_A=1.82×104 L·mol-1;根据热力学参数确定了它们之间的主要作用力为疏水力和静电力。利用同步荧光光谱法研究了咖啡因对肌红蛋白构象的影响。咖啡因能使肌红蛋白的构象发生改变,导致蛋白质分子中色氨酸和酪氨酸残基所处微环境由原来的疏水环境不同程度地向亲水环境转变。     

Perturbation theory for non-axial molecular fluids

The thermodynamic perturbation theory in which all angle-dependent interactions are considered as a perturbation of the central potential is applied to study the equilibrium properties of a fluid composed of non-axial molecules. The influence of a large number of anisotropic pair and three-body non-additive interactions have been taken into account. Using the same set of force parameters the calculation is made for gaseous pressure second and third virial coefficients and liquid phase thermodynamic properties (Helmholtz free-energy, configurational energy, pressure and entropy). It is shown that the non-axial approximation is an improvement over the axial one. Excellent agreement between theory and experiment is obtained for ethylene.     

Interaction of colloidal molecules adsorbed on soft solid films

Colloidal molecules adsorbed on soft solid films interact indirectly via elastic substrate deformations. For this substrate mediated attraction force an effective pair potential can be evaluated by using the elasticity theory for solids. The range of the indirect force increases with increasing film thickness. For very soft substrates the interaction is found to be strong enough to influence the structure and the thermodynamic properties of the adsorbate, e.g. enforce aggregation or crystallization.     

对磺酸基杯芳烃与胃蛋白酶相互作用的光谱研究

模拟人体生理条件,利用荧光光谱和UV-Vis吸收光谱研究对磺酸基杯芳烃与胃蛋白酶的作用机理。由Stern-Volmer方程及UV-Vis吸收光谱得其荧光猝灭类型为静态猝灭,求出结合常数。由热力学参数判断其作用力主要为静电作用。同时根据能量转移理论得出荧光给体和受体间的距离r。并由同步荧光光谱研究得出对磺酸基杯芳烃存在下胃蛋白酶的构象发生了变化。     

荧光光谱法研究2,4-滴丙酸及其手性对映体与牛血清白蛋白的相互作用

用荧光光谱法研究了手性除草剂2,4-滴丙酸及其两种手性异构体分别与牛血清白蛋白（BSA）的相互作用。结果表明：2,4-滴丙酸对BSA的荧光有较强的猝灭作用,且属于静态猝灭。实验获得了不同温度下2,4-滴丙酸及其对映体与牛血清白蛋白作用的结合常数,发现相同温度下S型2,4-滴丙酸比R型更易与BSA结合,其外消旋体的结合能力居于两者之间。通过计算反应热力学参数,推测它们之间的主要作用力为疏水作用力。同步荧光光谱法研究2,4-滴丙酸对BSA构象的影响,表明2,4-滴丙酸与BSA的结合位点位于色氨酸残基附近。     

Experiment and theory in the Casimir effect

Casimir effect is the attractive force which acts between two plane parallel, closely spaced, uncharged, metallic plates in vacuum. This phenomenon was predicted theoretically in 1948 and reliably investigated experimentally only in recent years. In fact, the Casimir force is similar to the familiar van der Waals force in the case of relatively large separations when the relativistic effects come into play. We review the most important experiments on measuring the Casimir force by means of torsion pendulum, atomic force microscope and micromechanical torsional oscillator. Special attention is paid to the puzzle of the thermal Casimir force, i.e. to the apparent violation of the third law of thermodynamics when the Lifshitz theory of dispersion forces is applied to real metals. Thereafter we discuss the role of the Casimir force in nanosystems including the stiction phenomenon, actuators, and interaction of hydrogen atoms with carbon nanotubes. The applications of the Casimir effect for constraining predictions of extra-dimensional unification schemes and other physics beyond the standard model are also considered.