Evidence for an additional coupling of the innermost shells in very heavy quasi-molecular ion-atom collisions

Due to the tremendous spin-orbit splitting of quasi-molecular levels in superheavy collision systems (Z = Z_1 + Z_2 {\ge\approx} 137) bombarding energy 0.5-6 MeV N{^-1}, unusual couplings may occur around Z \simeq 165. Experimental evidence for such a theoretically predicted coupling is discussed.

Theoretical evidence for quasi-molecular structure at small internuclear distances in elastic ion-atom scattering

The potential energy curve of the system Ne-Ne is calculated for small internuclear distances from 0.005 to 3.0 au using a newly developed relativistic molecular Dirac-Fock-Slater code. A significant structure in the potential energy curve is found which leads to a nearly complete agreement with experimental differential elastic scattering cross sections. This demonstrates the presence of quasi-molecular effects in elastic ion-atom collisions at keV energies.

Bayesian alignment of continuous molecular shapes using random fields

Statistical methodology is proposed for comparing molecular shapes. In order to account for the continuous nature of molecules, classical shape analysis methods are combined with techniques used for predicting random fields in spatial statistics. Applying a modification of Procrustes analysis, Bayesian inference is carried out using Markov chain Monte Carlo methods for the pairwise alignment of the resulting molecular fields. Superimposing entire fields rather than the configuration matrices of nuclear positions thereby solves the problem that there is usually no clear one--to--one correspondence between the atoms of the two molecules under consideration. Using a similar concept, we also propose an adaptation of the generalised Procrustes analysis algorithm for the simultaneous alignment of multiple molecular fields. The methodology is applied to a dataset of 31 steroid molecules.

Branching Ratios of alpha Decay for Nuclei near Deformed Shell Closures

The generalized liquid drop model (GLDM) is extended to the region around deformed shell closure (270)Hs by taking into account the excitation energy EI+ of the residual daughter nucleus and the centrifugal potential energy V-cen(r). The branching ratios of alpha decays from the ground state of a parent nucleus to the ground state 0(+) of its deformed daughter nucleus and to the first excited state 2(+) are calculated in the framework of the GLDM. The results support the proposal that a measurement of alpha spectroscopy is a feasible method to extract information on nuclear deformation of superheavy nuclei around the deformed nucleus (270)Hs.

Analytic expressions for alpha particle preformation in heavy nuclei

Experimental alpha decay energies and half-lives are investigated systematically to extract alpha particle preformation in heavy nuclei. Formulas for the preformation factors are proposed that can be used to guide microscopic studies on preformation factors and perform accurate calculations of the alpha decay half-lives. There is little evidence for the existence of an island of long stability of superheavy nuclei.

Half-Lives of Superheavy Nuclei in Z=113 Alpha Decay Chain

The generalized liquid drop model (GLDM), including the proximity effects and centrifugal potential, and the cluster model with Cosh potential are used to study the half-lives of some Z=113 isotopes and their alpha-decay products.The experimental half-lives of (284)113, (283)113, (282)113and their alpha-decay products are well reproduced by the two models when zero angular momenta transfer is assumed. For (278)113 and its alpha-decay products, both the GLDM andthe cluster model could provide satisfactory results if we assume the alpha particle carry five units of angular momenta, which indicates that possible non zero angular momenta transfer and need further experimental measurements with high precision. Finally, we show that half-lives of alpha-decay are quite sensitive to the angular momentum transfers, and a formula could be used to describe the correlation between alpha-decay half-life and angular momentum transfer successfully.

alpha decay half-lives of new superheavy nuclei within a generalized liquid drop model

The alpha decay half-lives of the recently produced isotopes of the 112, 114, 116 and 118 nuclei and decay products have been calculated in the quasi-molecular shape path using the experimental Q(alpha) value and a Generalized Liquid Drop Model including the proximity effects between nucleons in the neck or the gap between the nascent fragments. Reasonable estimates are obtained for the observed alpha decay half-lives. The results are compared with calculations using the Density-Dependent M3Y effective interaction and the Viola-Seaborg-Sobiczewski formulae. Generalized Liquid Drop Model predictions are provided for the alpha decay half-lives of other superheavy nuclei using the Finite Range Droplet Model Q(alpha) and compared with the values derived from the VSS formulae.

Alpha-decay for heavy nuclei in the ground and isomeric states

The alpha-decay half-lives of nuclei in the ground states and Isomeric states have been calculated within the WKB approximation and Royer's formulas. The barrier in the quasimolecular shape path is determined within a generalized liquid drop model (GLDM). in which the centrifugal potential energy has been introduced to study the unfavored a-decay The agreement between the calculated results and experimental data indicates the reliability of studying alpha-decay of isomeric states with the generalized liquid drop model We find that their is no significant difference of preformation probability between Isomeric states and the corresponding ground states generally in favored alpha-decay Additionally. we extended Royer's formulas by taking account of the role of centrifugal harrier to study the unfavored alpha-decay, and some predicts oil the a decay half-lives of Isomers are made Finally. the effects of angular momontum transfer and Q(alpha) on alpha-decay half-life have been discussed Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved

Concise methods for proton radioactivity

Concise methods are proposed to study proton radioactivity. The spectroscopic factor is obtained from relativistic mean field (RMF) theory combined with the BCS method (RMF+BCS). The assault frequency is estimated by a quantum mechanical method considering the structure of the parent nucleus. The penetrability is calculated by the WKB approximation. No additional parameters are introduced. The extracted experimental spectroscopic factors are compared with those from the calculations by the RMF+BCS, and the agreement is good, implying that the present methods work quite well for proton radioactivity. Predictions are provided for some most possible proton emissions, which may be useful for future experiments.

Improvement of a Fission-Like Model for Nuclear alpha Decay

The alpha decay constant is the product of the penetrability P and assault frequency nu(0) in the fission-like model. An effective assault frequency P-nu replacing the previous assault frequency nu(0) is introduced for improvement of a fission-like model named the generalized liquid drop model (GLDM) to describe the nuclear alpha decay process more accurately. Two analytical formulae are proposed for the effective assault frequency due to experimental data within the GLDM. The improved model can be used to give accurate calculations for alpha decay half-lives.

On the generalized continuum model of dipolar solvation dynamics

The continuum model of dipolar solvation dynamics is reviewed. The effects of non-spherical molecular shapes, of non-Debye dielectric relaxation of the polar solvent and of dielectric inhomogeneity of the solvent around the solute dipole are investigated. Several new theoretical results are presented. It is found that our generalized continuum model, which takes into account the dielectric inhomogeneity of the surrounding solvent, provides a description of solvation dynamics consistent with recent experimental results.

Diffusion ordered spectroscopy for resolution of double bonded cis, trans-isomers

NMR spectroscopic separation of double bonded cis- and trans-isomers, that have different molecular shapes but identical mass have been carried out using Diffusion Ordered Spectroscopy (DOSY). The mixtures of fumaric acid and maleic acid, that have similar hydrodynamic radii, have resolved been on the basis of their diffusion coefficients arising due to their different tendencies to associate with micelles or reverse micelles. Sodium dodecyl sulfate (SDS) and Dioctyl sulfosuccinate sodium salt (AOT) have been used as the media to mimic the chromatographic conditions, modify the average mobility and to achieve differential diffusion rates. The best separation of the components has been achieved by Dioctyl sulfosuccinate sodium salt (AOT) in D2O solution. (C) 2012 Elsevier B.V. All rights reserved.

Spectral Migration of Fluorescence in Graphene Oxide Aqueous Dispersions: Evidence for Excited-State Proton Transfer

Aqueous dispersions of graphene oxide (GO) exhibit strong pH-dependent fluorescence in the visible that originates, in part, from the oxygenated functionalities present. Here we examine the spectral migration on nanosecond time-scales of the pH dependent features in the fluorescence spectra. We show, from time-resolved emission spectra (TRES) constructed from the wavelength dependent fluorescence decay curves, that the migration is associated with excited state proton transfer. Both `intramolecular' and `intermolecular' transfer involving the quasi-molecular oxygenated aromatic fragments are observed. As a prerequisite to the time-resolved measurements, we have correlated the changes in the steady state fluorescence spectra with the sequence of dissociation events that occur in GO dispersions at different values of pH.

两种银莲花属植物的化学成分研究

本学位论文由5 章组成。第1 章报道了两头尖中三萜皂苷类化合物的全扫描电喷雾多级质谱分析及银莲花素A 的电喷雾质谱裂解规律；第2 和3 章报道了两种银莲花属药用植物化学成分的研究结果；第4 章报道了银莲花素A 的化学结构修饰及其对一种蛋白酪氨酸磷酸酯酶（PTP-1B）的抑制活性；第5 章综述了电喷雾质谱在皂苷类化合物结构鉴定中的应用进展。 第1 章报道了运用全扫描电喷雾多级质谱对两头尖中三萜皂苷类化合物的快速定性检测，共检测出18 个准分子离子峰，根据多级质谱数据并结合文献报道，对其中的15 个准分子离子峰进行了归属，并区分了一些同分异构体；更有意思的是，发现了3 个未见文献报道的三萜皂苷类化合物。根据它们的多级质谱数据，对其结构分别进行了初步解析。本章同时对银莲花素A 特殊的质谱裂解途径通过衍生物制备及其质谱分析进行了确认。 第2 和3 章，分别报道了两头尖和打破碗花花中水溶性多糖苷的分离纯化和结构鉴定。采用D101 大孔树脂和反复硅胶柱层析等分离手段，从两头尖水溶性部分分离得到8 个三萜皂苷类化合物，通过红外、电喷雾质谱和核磁共振等现代谱学方法，并结合传统的化学手段鉴定了它们的结构，其中4 个化合物为新化合物，分别命名为多被银莲花皂苷19、多被银莲花皂苷20、多被银莲花皂苷21和多被银莲花皂苷22。从打破碗花花水溶性部位分离得到6 个三萜皂苷类化合物，通过现代谱学手段，并结合传统的化学方法对它们进行了鉴定，其中1 个为新化合物，命名为打破碗花花苷H。 第4 章报道了以银莲花素A 及其同系物为先导化合物，进行化学结构修饰并对修饰产物进行广泛的生物活性筛选，发现在银莲花素A 及其同系物的结构中引入一些酸性基团后，其生物活性发生了变化，一些修饰产物显示出很强的PTP-1B 抑制作用，提示这些化合物有可能用于治疗II 型糖尿病。 第5 章综述了电喷雾多级质谱用于皂苷类化合物结构鉴定的研究进展。 This dissertation composes of five chapters. The first chapter elaborates the detection and qualification of the triterpenoidal saponins in Anemone raddeana by positive and negative full scan ESI-MSn. This part also reports the special fragmentation pathway of Raddeanin A by ESI-MS/MS. The second and third chapters present the phytochemical investigation of two medicinal plants from Anemone. The fourth part dwells on the structure modification of Raddeanin A and their inhibitory activity against PTP-1B. The last part is a review on the progress in the application of ESI-MSn in the structure identification of saponins. The first chapter reports the application of full scan ESI-MSn for fast analysis of triterpenoid saponins in Anemone raddeana. Eighteen quasi- molecular ion peaks were detected in the positive full scan ESI-MS and fifteen of them were identified by analysis of their tandem mass spectral data in the negative ion mode. Several isomers were differentiated. More interesting, three unreported triterpenoid saponins in this medicinal plant were detected and their structures were deduced according to the dissociation pathway of the known triterpenoidal saponins. This chapter also confirms the special fragmentation pathway of Raddeanin A by its derivative and the mass spectral analysis. The second and third chapters expatiate on the isolation and identification of the chemical constituents from A. raddeana and A. hupehensis. Eight compounds were isolated from the roots and stems of A. raddeana by methanol extraction and repeated column chromatography (including D101 and silica gel), and their structures were determined on the basis of IR, ESI-MS, NMR and chemical methods (including acid hydrolysis and alkaline saponification). Among them, four are new triterpenoid saponins and named as Raddeanoside R19, Raddeanoside R20, Raddeanoside R21 and Raddeanoside R22. Six compounds were isolated from the whole plants of A. hupehensis by the same methods as above, and their structures were also determined with the same way. One of them was confirmed to be new triterpenoid saponins and named as hupehensis saponin H. In the fourth chapter, in order to look for new active compounds, the structure of Raddeanin A and its analogs were modified. It was found that the modified products exhibited obvious inhibitory activity against PTP-1B when several acid groups were introduced. The fifth chapter summarizes the progress on the application of ESI-MSn in the structure identification of saponins.

Alpha decay half-lives of heavy nuclei within a generalized liquid drop model

Theoretical alpha-decay half-lives of the heaviest nuclei are calculated using the experimental Q value. The barriers in the quasi-molecular shape path is determined within a Generalized Liquid Drop Model (GLDM) and the WKB approximation is used. The results are compared with calculations using the Density-Dependent, M3Y (DDM3Y) effective interaction and the Viola-Seaborg-Sobiczewski (VSS) formulae. The calculations provide consistent estimates for the half-lives of the a decay chains of these superheavy elements. The experimental data stand between the GLDM calculations and VSS ones in the most time.