生物体系中电子转移机理的研究Ⅱ: 分子间电子转移及 电子供、受体间不同基 团的影响

利用自编程序MOPAC-ET中AM1方法,及KT(Koopman'sTheorem)法,研究了二苯负离子体系的分子间电子转移现象,计算了其电子供、受体在不同距离下的V~A~B及它们之间的相关性,另外,还对两苯环间不同介入基团对电子转移的影响做了初步研究,发现不同的介入基团存在着较大的差异。     

KTB iron mineralogy at iridium deficient layers revealed by Mössbauer spectroscopy

Mössbauer spectroscopic studies of two sedimentary layers from Petriccio section in Gubbio formation are presented. It is found that these layers have almost the same iron phases nanophase hematite and phyllosilicate and with the same compositions as those in the Cretaceous-Tertiary Boundary (KTB) in Petriccio. The two layers also show enhancement in the siderophile elements such as Cr, Ni, Fe, Ca etc. to that found in the KTB layer. The two layers are well separated from the KTB layer, 128 and 149 cm below this layer, and show no enhancement of iridium. From the data it is suggested that the two layers also represent some kind of impact by extraterrestrial (ET) bolides.     

Melting of mesoscopic lattices of magnetic fluid thin film subjected to perpendicular fields

Applying a magnetic field on the magnetic fluid thin film perpendicularly, leads a phase separation that is concentrated in particles separating from a dilute phase. The concentrated phase forms cylindrical columns that construct two-dimensional lattices. This kind of artificial lattice is a novel mesoscopic system and has been explored with optical microscope, CCD, and digital imaging analysis. We explore the ordering evolution of the two-dimensional extraordinary lattice by varying the applied field. The ordering of these lattices is analyzed in terms of translational and bond-orientation correlation functions to address the two-dimensional melting.     

高温超导体中磁场诱导的能量耗散行为的转变

高温超导体在强电方面应用的关键问题是如何克服磁通运动所造成的能量损耗。由于存在极强的各向异性,短的相干长度和小的磁通钉扎势,因此与磁通运动紧密相关的混合态相图变得很复杂,文章综述了根据一系列灵敏的电磁测量所观察到的磁场诱导的能量耗散行为的转变。     

Critical properties of XY model on two-layer Villain－ferromagnetic lattice

We investigate phase transitions of the XY model on a two-layer square lattice which consists of a Villain plane (J) and a ferromagnetic plane (I), using Monte Carlo simulations and a histogram method. Depending on the values of interaction parameters (I,J), the system presents three phases: namely, a Kosterlitz－Thouless (KT) phase in which the two planes are critical for I predominant over J, a chiral phase in which the two planes have a chiral order for J predominant over I and a new phase in which only the Villain plane has a chiral order and the ferromagnetic plane is paramagnetic with a small value of chirality. We clarify the nature of phase transitions by using a finite size scaling method. We find three different kinds of transitions according to the values of (I,J): the KT transition, the Ising transition and an XY-Ising transition with ν=0.849(3). It turns out that the Ising or XY-Ising transition is associated with the disappearance of the chiral order in the Villain plane.     

Asymptotical good behavior on inequalities with completely approximate K-T concept

We characterize a wide class of regular convex functionals that are asymptotically well behaved on a convex set given by (infinite) inequalities, namely, those restricted functions whose stationary sequences (bounded or not) are minimizing ones. After showing the equivalence with the Kuhn-Tucker type stationarity, we prove that the class of such functions remains unchanged when the Kuhn-Tucker system is completely relaxed. This allows us to proceed for enlarging the scope of convergence of certain penalty (exterior as well as interior) methods including a new exterior penalization for infinite inequalities.     

GIAO‐DFT calculation of 15N NMR chemical shifts of Schiff bases: Accuracy factors and protonation effects

¹⁵N NMR chemical shifts in the representative series of Schiff bases together with their protonated forms have been calculated at the density functional theory level in comparison with available experiment. A number of functionals and basis sets have been tested in terms of a better agreement with experiment. Complimentary to gas phase results, 2 solvation models, namely, a classical Tomasi's polarizable continuum model (PCM) and that in combination with an explicit inclusion of one molecule of solvent into calculation space to form supermolecule 1:1 (SM + PCM), were examined. Best results are achieved with PCM and SM + PCM models resulting in mean absolute errors of calculated ¹⁵N NMR chemical shifts in the whole series of neutral and protonated Schiff bases of accordingly 5.2 and 5.8 ppm as compared with 15.2 ppm in gas phase for the range of about 200 ppm. Noticeable protonation effects (exceeding 100 ppm) in protonated Schiff bases are rationalized in terms of a general natural bond orbital approach.     

Theoretical and experimental study of 15N NMR protonation shifts

A combined theoretical and experimental study revealed that the nature of the upfield (shielding) protonation effect in ¹⁵N NMR originates in the change of the contribution of the sp²‐hybridized nitrogen lone pair on protonation resulting in a marked shielding of nitrogen of about 100 ppm. On the contrary, for amine‐type nitrogen, protonation of the nitrogen lone pair results in the deshielding protonation effect of about 25 ppm, so that the total deshielding protonation effect of about 10 ppm is due to the interplay of the contributions of adjacent natural bond orbitals. A versatile computational scheme for the calculation of ¹⁵N NMR chemical shifts of protonated nitrogen species and their neutral precursors is proposed at the density functional theory level taking into account solvent effects within the supermolecule solvation model. Copyright © 2015 John Wiley & Sons, Ltd.