Tautomerization in gas-phase ion chemistry of isomeric C-8 deoxyguanosine adducts from phenol-induced DNA damage

Collision-induced dissociation (CID) of 8-(4'-hydroxyphenyl)-2'-deoxyguanosine and 8-(2'-hydroxyphenyl)-2'-deoxyguanosine was investigated using sequential tandem mass spectrometry. These adducts represent biomarkers of DNA damage linked to phenolic radicals and were investigated to gain insight into the effects of chemical structure of a C-8 modification on fragmentation pathways of modified 2'-deoxyguanosine (dG). CID in MS(2) of the deprotonated molecules of both the isomers generated the same product ion having the same m/z values. CID in MS(3) of the product ion at m/z 242 and CID in MS(4) experiments carried out on the selected product ions at m/z 225 and m/z 218 afford distinct fragmentation patterns. The conformational properties of isomeric product ions from CID showed that the ortho-isomers possess the unique ability to tautomerize through an intramolecular proton transfer between the phenolic OH group and the imine nitrogen (N7). Tautomerization of ortho-isomers to their keto-tautomers led to differences in their system of conjugated double bonds compared with either their enol-tautomer or the para-isomer. The charge redistribution through the N-7 site on the imidazole ring is a critical step in guanosine adduct fragmentation which is disrupted by the formation of the keto-tautomer. For this reason, different reaction pathways are observed for 8-(4'-hydroxyphenyl)-2'-deoxyguanosine and 8-(2'-hydroxyphenyl)-2'-deoxyguanosine. We present herein the dissociation and the gas-phase ion-molecule reactions for highly conjugated ions involved in the CID ion chemistry of the investigated adducts. These will be useful for those using tandem mass spectrometry for structural elucidation of C-8 modified dG adducts. This study demonstrates that the modification at the C-8 site of dG has the potential to significantly alter the reactivity of adducts. We also show the ability of tandem mass spectrometry to completely differentiate between the isomeric dG adducts investigated.     

规定安全间隔的CNS性能环境研究

对平行航路下规定安全间隔的CNS性能环境评估问题进行了研究.首先分析了CNS性能环境对飞机碰撞风险的影响,并结合Reich模型和概率论方法建立了CNS性能环境下飞机纵向、侧向和垂直方向上的碰撞风险模型;其次对碰撞风险模型进行分析转化得到了规定的安全间隔和安全目标水平下CNS性能环境的评估计算方法.最后对平行航路的CNS性能环境进行了评估计算,得到符合航路安全目标水平1.5×10~(-8)的CNS性能环境为RNP10、RCP400、RSP20.     

Adaptive panel representation for oblique collision of two vortex rings

In this article, we use a hierarchical panel method for representing vortex sheet surface motion in 3D flow to investigate the oblique collision of two vortex rings. The particles representing the sheet are advected by a regularized Biot-Savart integral with smoothed Rosenhead-Moore kernel. The particle velocities are evaluated by an adaptive treecode algorithm based on Taylor expansions in Cartesian coordinates. The method allowed us to consider late stages of a vortex rings collision, producing a funnel region. Vorticity iso-surfaces evolution is also investigated.     

Collision efficiency of two nanoparticles with different diameters in Brownian coagulation

The collision efficiency of two nanoparticles with different diameters in the Brownian coagulation is investigated. The collision equations are solved to obtain the collision efficiency for the dioctyl phthalate nanoparticle with the diameter changing from 100 nm to 750 nm in the presence of the van der Waals force and the elastic deformation force. It is found that the collision efficiency decreases as a whole with the increase of both the particle diameter and the radius ratio of two particles. There exists an abrupt increase in the collision efficiency when the particle diameter is equal to 550 nm. Finally, a new expression is presented for the collision efficiency of two nanoparticles with different diameters.     

基于能量原理确定系泊碰撞载荷的有限元法

准确地确定出船舶系泊时的撞击载荷, 对船舶及海洋平台的强度研究都是极其重要的. 提出了通过能量原理和有限元分析确定系泊撞击载荷的方法. 碰撞时, 动能和变形能满足能量守恒, 动能是包括附连水质量在内的船体总动能, 此动能在撞击时转化为变形能, 根据变形能与载荷的关系, 求出碰撞载荷. 通过具有碰撞载荷理论解的梁的验证, 表明该方法是完全可行的. 为实际工程提供了确定护舷撞击力的理论依据和计算方法.     

Stochastic sensitivity of attractors for a piecewise smooth neuron model

ABSTRACT

We consider a one-dimensional model of neural activity, given by a piecewise smooth discontinuous map. Fold bifurcations as well as border collision bifurcations are described in detail. Using the method of stochastic sensitivity functions, noise-induced phenomena, such as transitions within attractor and between attractors, and spike generation, are described. Statistical characteristics of interspike intervals depending on noise intensity are studied.     

Down/up crossing properties of weighted Markov collision processes

This paper concentrates on considering the down/up crossing property of weighted Markov collision processes. The joint probability generating function of down crossing and up crossing numbers of weighted Markov collision processes until its extinction are obtained by constructing and studying a related multi-dimensional Markov chain. Hence, the joint probability distribution of down crossing and up crossing numbers and the mean numbers are obtained.     

He原子与O2分子相互作用势及碰撞微分截面的研究

本文用量子力学从头算方法深入研究了He原子与O2分子的相互作用势,选定CCSD(T)/6-311++G(3df,2pd)方法和基组,同时采用了Boys和Bernardi提出的Full Couterpoise方法消除了计算中的基组重叠误差(BSSE),得出了该体系的各向异性相互作用势的单点能数据,通过拟合得到了较为准确的He-O2体系相互作用势的解析表达式.采用精确度较高的密耦(Close-Coupling)近似方法,计算了He-O2碰撞体系的碰撞激发微分截面,计算得到的微分截面数据与实验值符合较好,并得出了不同碰撞能量时He原子与O2分子的碰撞的微分截面的规律.     

A new two-dimensional approach to quantitative prediction for collision cross-section of more than 110 singly protonated peptides by a novel moecular electronegativity-interaction vector through quantitative structure-spectrometry relationship studies

Based on two-dimensional topological characters, a novel method called molecular electronegativity-interaction vector (MEIV) is proposed to parameterize molecular structures. Applying MEIV into quantitative structure-spectrometry relationship studies on ion mobility spectrometry collision cross-sections of 113 singly protonated peptides, three models were strictly obtained, with correlative coefficient r and leave-one-out cross-validation q of 0.983, 0.979, 0.981, 0.979 and 0.980, 0.978, respectively. Thus, the MEIV is confirmed to be potent to structural characterizations and property predictions for organic and biologic molecules. Translated from Chinese Journal of Analytical Chemistry, 2006, 34(6) (in Chinese)     

核－核碰撞的独立源模型及中心快度区末态产生粒子横能量分布

将强子－核碰撞的独立源模型推广到核－核碰撞，给出了核－核碰撞末态产生粒子横能量分布方程，将其与ＣＥＲＮ的ＮＡ３５合作组得到的实验数据相比较，模型较好地解释了实验结果．