基于Bootstrap的厚尾相依序列持久性变点检验

基于修正方差比率函数给出一种检验厚尾序列持久性变点的统计量.在无变点的假设下得到了统计量的渐近分布.为避免检验渐近分布中的厚尾指数,构造Bootstrap抽样方法来确定渐近分布的经验临界值.数值模拟研究结果说明修正方差比率统计量及Bootstrap抽样方法的有效性.     

丝氨酸异构体的电子-分子形状共振态及其解离动力学理论研究

Shape resonances of electron-molecule system formed in the low-energy electron attachment to four low-lying conformers of serine (serine 1, serine 2, serine 3, and serine 4) in gas phase are investigated using the quantum scattering method with the non-empirical model potentials in single-center expansion. In the attachment energy range of 0-10 eV, three shape resonances for serine 1, serine 2, and serine 4 and four shape resonances for serine 3 are predicted. The one-dimensional potential energy curves of the temporary negative ions of electron-serine are calculated to explore the correlations between the shape resonance and the bond cleavage. The bond-cleavage selectivity of the different resonant states for a certain conformer is demonstrated, and the recent experimental results about the dissociative electron attachment to serine are interpreted on the basis of present calculations.     

Base dependent pyrrolidine ring pucker in aep-PNA monomers: NMR and PSEUROT analysis

The aep-PNA is a chiral and cyclic PNA analogue, which has a stronger and base dependent binding affinity with complementary DNA. To understand the base dependent properties at monomer level, the structural studies of aep-PNA-(T/C/A) monomers have been carried out focussing on the conformational analysis of pyrrolidine ring pucker in aep-PNA by ¹H NMR and the coupling constant data fitted into PSEUROT software. The results indicate that the type of pyrrolidine pucker depends on the electronic nature of substituent, implying the effect of pyrimidine or purine substituents in determining the ring pucker in monomers. This may consequently influence the aep-PNA oligomer conformation. Since pyrrolidine nucleic acids have emerged as an important class of PNA analogues, present results may have importance for their future development.     

Contours of constant Δ and Ψ in the 2–4 plane for the ellipsometric functions

Contour graphs of ₂ vs ₄ for different film thicknesses and a range of angles of incidence have been plotted for the ellipsometric functions Δ and Ψ in both the reflection and transmission modes. In the case of reflection ellipsometry, when the plots for Δ_R and Ψ_R are superimposed, the two sets of contours cross nearly at right angles over a large part of the field, this being indicative of the high accuracy obtainable in using this technique to determine ₄ and ₂ and hence the optical constants, n and k, for the film material. The reflection ellipsometric technique is accurate over angles of incidence between 30° and 75° and for a range of film thicknesses between λ/30 and 5λ. Transmission ellipsometry is less useful, due to anomalies in both X_s and X_p where sudden phase changes of ±π occur in regions of interest. There is also the possibility of multiple solutions, although the use of a multiangle technique would enable the “correct” values to be more easily determined.     

Effect of spermine and DNase on DNA release from bacteriophage T5

Bacterial viruses (bacteriophages) consist of nucleic acid protected by a protein envelope called capsid. At the start of infection, the phage genome is translocated into the bacterial cytoplasm. In vitro (and also in vivo), this DNA release can be triggered by binding a specific receptor protein to the phage tail. The force responsible for the release arises from energy stored in the capsid due to strong confinement of the DNA. We show that this force can be modified by adding molecules like spermine that affect DNA conformation. The tetravalent cation spermine can reduce the pressure inside the capsid and induce condensation of the released DNA. We examine the effect of spermine on DNA ejection from phage T5 by using light scattering and gel electrophoresis to measure the amount of DNA remaining in the capsid at the end of ejection. We discuss the results in terms of free energy minimization and we demonstrate that the presence of a DNA condensate outside the phage generates an additional force pulling passively on the DNA remaining inside the capsid.     

Does a Reinforced Kinetic Macrocyclic Effect Exist? The Demetallation in Strong Acid of Copper(II) Complexes with Open and Cyclic Tetramines Containing a Piperazine Fragment

The demetallation in acidic solution of the Cu(II) complexes with open-chain and cyclic tetramines containing a piperazine unit (2 and 3) has been investigated in terms of its kinetic aspects and compared with the behaviour of unsubstituted counterparts (tetramines 1 and 4). The presence of the piperazine fragment slows demetallation of the open-chain-ligand complex owing to the activation barrier associated with the conformational change from boat-to-half-boat; however, it does not affect the demetallation of the macrocyclic complex, which involves the spontaneous boat-to-twist conformational change. Thus, lateral reinforcement of a cyclam-like ligand does not add any further contribution to the typical inertness in demetallation of macrocyclic complexes.     

Characterizing abrupt changes in the stock prices using a wavelet decomposition method

Abrupt changes in the stock prices, either upwards or downwards, are usually preceded by an oscillatory behavior with frequencies that tend to increase as the moment of transition becomes closer. The wavelet decomposition methods may be useful for analysis of this oscillations with varying frequencies, because they provide simultaneous information on the frequency (scale) and localization in time (translation). However, in order to use the wavelet decomposition, certain requirements have to be satisfied, so that the linear and cyclic trends are eliminated by standard least squares techniques. The coefficients obtained by the wavelet decomposition can be represented in a graphical form. A threshold can then be established to characterize the likelihood of a short-time abrupt change in the stock prices. Actual data from the São Paulo Stock Exchange (Bolsa de Valores de São Paulo) were used in this work to illustrate the proposed method.     

A geometrical measure for entropy changes

The geometrical approach to statistical mechanics is used to discuss changes in entropy upon sequential displacements of the state of the system. An interpretation of the angle between two states in terms of entropy differences is thereby provided. A particular result of note is that any state can be resolved into a state of maximal entropy (both states having the same expectation values for the constraints) and an orthogonal component. A cosine law for the general case is also derived.     

CHEMICAL STRUCTURE DEPENDENCE OF THE INTERNAL ENERGY CONTRIBUTION IN RUBBER ELASTICITY

Conformational elasticity theory recently developed has been used to explore the internal energy contribution tothe elastic force f_e/f as a function of strain for poly(cis-1,4-isoprene) and poly(trans-1, 4-isoprene). Calculated f_e/f values arein good agreement with those obtained experimentally. Results show that behavior of f_e/f is mainly contributed by chemicalstructure, or intramolecular interaction, supporting the experimental observations, and that the internal energy contribution isstrain dependent.