Calculation of affinities of peptides for proteins

Several methodologies were employed to calculate the Gibbs standard free energy of binding for a collection of protein-ligand complexes, where the ligand is a peptide and the protein is representative for various protein families. Almost 40 protein-ligand complexes were employed for a continuum approach, which considers the protein and the peptide at the atomic level, but includes solvent as a polarizable continuum. Five protein-ligand complexes were employed for an all-atom approach that relies on a combination of the double decoupling method with thermodynamic integration and molecular dynamics. These affinities were also computed by means of the linear interaction energy method. Although it generally proved rather difficult to predict the absolute free energies correctly, for some protein families the experimental ranking order was correctly reproduced by the continuum and all-atom approach. Considerable attention has also been given to correctly analyze the affinities of charged peptides, where it is required to judge the effect of one or more ions that are being decoupled in an all-atom approach to preserve electroneutrality. The various methods are further judged upon their merits.     

Potential of zero total charge of platinum single crystals: A local approach to stepped surfaces vicinal to Pt(111)

The electrochemical behavior of platinum single-crystal electrodes is revisited, with special emphasis on the determination of the potential of zero charge. We show that the measure of the charge displaced during CO adsorption allows the determination of the potential of zero total charge (PZTC). The estimation of the potential of zero free charge (PZFC) is discussed, with different degrees of approximation. The application of this methodology to the study of the PZTC of platinum stepped surfaces vicinal to Pt(111) reveals a marked decrease of the PZTC due to the introduction of surface steps. This effect is interpreted as the result of the existence of markedly smaller surface potentials localized on step sites. The importance of considering local aspects of the interface is emphasized with the use of N₂O reduction as a sensitive probe to the local structure of the surface. It is proposed that the different local maxima observed in the absolute value of the reduction current correspond to the local values of PZTC. It is shown that there is, in general, good agreement between the overall PZTC, obtained from the CO displacement, and that calculated from the local values inferred from the N₂O reduction. Further insight is obtained with the application of the laser-induced temperature jump method. This technique is useful to calculate the potential of maximum entropy of the double-layer formation. The resulting value of this potential for Pt(111) is discussed in the light of the PZFC value obtained from different approaches. For stepped surfaces vicinal to Pt(111), two local maxima in the entropy of the double layer are observed that are close to the local PZTC values estimated from the N₂O reduction. This result suggests the existence of cooperative effects in the organization of the water dipoles close to the electrode surface. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 11, pp. 1275–1292. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

A computational study of the LiH dimer

A theoretical study of the properties of the linear LiH dimer was undertaken. In this dimer, an unusual type of hydrogen bonding (termed "inverse" hydrogen bonding by some authors), which involves the hydrogen bonded molecule acting as an electron donor (rather than as a proton donor), is exhibited. The optimized geometry, dipole moment, interaction energy, atomic charges, harmonic vibrational frequencies, and frequency shifts for the dimer are computed at the SCF, MP2, and QCISD levels of theory using mainly a 6-31++G(d,p) basis set. We also examined the relative stability of the mono-deuterated isotopomers of linear (LiH)(2), i.e., Li-H...Li-D and Li-D...Li-H. Analysis of the normal vibrational modes, changes in the partial atomic charges, and changes in the vibrational frequencies of LiH on complexation were used to gain insight into the bonding and properties of the linear LiH dimer and its isotopomers.     

ELECTRON PARAMAGNETIC RESONANCE STUDIES OF SINGLE CRYSTAL SODIUM HEXAMOLYBDOCHROMATE (Ⅲ)Cr~(3+)/Na_3(AlMo_6O_(24)H_6)·8H_2O

An X-band EPR study on a Na_3(CrMo_6O_(24)H_6)·8H_2O single crystal diluted by its isomor-phic compound Na_3(AlMo_6O_(24)H_6)·8H_2O at room temperature is reported. Using the least squares-fitting method to simulate the EPR data for principal planes, the Hamiltonian parameterswere obtained. The principal values of the g tensors are g_(ZZ) = 1.904, g_(XX)= 1.973, g_(YY)=1.933. The zero field splitting tensor parameters are D = 0.275 cm~(-1), E = 0.05 cm~(-1). The fielddependence of Cr~(3+) energy levels with field at different angles from the principal axes whenthe field is along the principal planes is calculated based on these experimental parameters.The isofrequency plots of calculated field vs. angle are also shown. They agree well with theexperimental results.     

A universal constant for the convergence of Newton's method and an application to the classical homotopy method

We give a new theorem concerning the convergence of Newton's method to compute an approximate zero of a system of equations. In this result, the constanth ₀=0.162434... appears, which plays a fundamental role in the localization of good initial points for the Newton iteration. We apply it to the determination of an appropriate discretization of the time interval in the classical homotopy method.     

面向方向图保形的共口径基站天线去耦技术

为了节省基站天线所占空间资源,降低其运营成本,现代移动通信需要将多个天线阵列紧密地排列在一起,构成多频共口径基站天线。多天线的紧密排列势必造成天线间强烈的耦合,不仅使得天线阻抗失配、隔离度变差,同时也造成辐射方向图的严重变形。因此,近年来多频共口径基站天线的去耦成为工业界和学术界研究的热点,早期的去耦技术主要是面向改善天线的阻抗匹配和隔离度,而对面向方向图保形的去耦技术研究相对较少。文章在简要介绍面向方向图保形的基站天线去耦技术的研究现状的基础上,重点阐述了褚庆昕教授天线射频团队基于感应电流抵消、耦合场抵消和辐射阻断等原理,提出的几种新型的去耦技术。这些技术不仅可以有效地改善基站天线的阻抗匹配和隔离,更重要的是很好地实现了天线方向图保形。仿真和测试结果验证了原理的正确性和设计的可行性。一些技术已被用于5G基站天线产品。     

宽阻带小型化双频带通滤波器

文中提出了一种具有宽阻带的紧凑型双频带通滤波器,它采用了折叠短路枝节负载谐振器、紧凑型微 带单元谐振器(CMRC)和阶跃阻抗谐振器结构。由于多个谐振器产生了五个可控传输零点(TZ),该滤波器实现了两个 通带之间的良好隔离度以及宽阻带特性。制作并测试了尺寸紧凑的双频带通滤波器实验样品,测试结果显示,第一通 带和第二通带的中心频率/ 插入损耗分别为0. 66 GHz/0. 8 dB 和1. 73 GHz/0. 7 dB,阻带频率高达10. 5 GHz,抑制水平 超过15 dB。     

Characterizations of generalized Hermite and sieved ultraspherical polynomials

A new characterization of the generalized Hermite polyno-
mials and of the orthogonal polynomials with respect to the measure
is derived which is based on a ``reversing property" of the coefficients in the corresponding recurrence formulas and does not use the representation in terms of Laguerre and Jacobi polynomials. A similar characterization can be obtained for a generalization of the sieved ultraspherical polynomials of the first and second kind. These results are applied in order to determine the asymptotic limit distribution for the zeros when the degree and the parameters tend to infinity with the same order.

     

The zeros of Faber polynomials generated by an -star

It is shown that the zeros of the Faber polynomials generated by a regular -star are located on the -star. This proves a recent conjecture of J. Bartolomeo and M. He. The proof uses the connection between zeros of Faber polynomials and Chebyshev quadrature formulas.

     

Intrinsic Surface Reaction Constant in 1-pK Model of Mg-Fe Hydrotalcite-like Compounds

The relationship among intrinsic surface reaction constant (K) in 1-pK model, point of zero net charge (PZNC) and structural charge density (σst) for amphoteric solid with structural charges was established in order to investigate the effect of σst on pK. The theoretical analysis based on 1-pK model indicates that the independent PZNC of electrolyte concentration (c) exists for amphoteric solid with structural charges. A common intersection point (CIP) should appear on the acid-base titration curves at different c, and the pH at the CIP is pHPZNC. The pK can be expressed as pK=-pHPZNC log[(1 2αPZNC)/(1-2αPZNC)], where αPZNC≡σst/eNANs, in which e is the elementary charge, NA the Avogadro‘s constant and Ns the total density of surface sites. For solids without structural charges, pK=-pHPZNC. The pK values of hydrotalcite-like compounds (HTlc) with general formula of [Mg1-xFex(OH)2](Cl,OH)x were evaluated. With increasing x, the pK increases, which can be explained based on the affinity of metal cations for H^- or OH^- and the electrostatic interaction between charging surface and H^- or OH^-.