Quantitative MALDI-MS<Superscript><Emphasis Type="Italic">n</Emphasis></Superscript> analysis of cocaine in the autopsied brain of a human cocaine user employing a wide isolation window and internal standards

Detection of drugs in tissue typically requires extensive sample preparation in which the tissue is first homogenized, followed by drug extraction, before the extracts are finally analyzed by LC/MS. Directly analyzing drugs in intact tissue would eliminate any complications introduced by sample pretreatment. A matrix-assisted laser desorption/ionization tandem mass spectrometry (MALDI-MS ⁿ ) method as been developed for the quantification of cocaine present in postmortem brain tissue of a chronic human cocaine user. It is shown that tandem mass spectrometry (MS² and MS³) increase selectivity, which is critical for differentiating analyte ions from background ions such as matrix clusters and endogenous compounds found in brain tissue. It is also shown that the use of internal standards corrects for signal variability during quantitative MALDI, which can be caused by inhomogeneous crystal formation, inconsistent sample preparation, and laser shot-to-shot variability. The MALDI-MS ⁿ method developed allows for a single MS³ experiment that uses a wide isolation window to isolate both analyte and internal standard target ions. This method is shown to provide improved precision [∼10–20 times reduction in percent relative standard deviation (%RSD)] for quantitative analysis compared to using two alternating MS³ experiments that separately isolate the target analyte and internal standard ions.     

Development of a strategy for the asymmetric synthesis of polycyclic polyprenylated acylphloroglucinols via N-amino cyclic carbamate hydrazones: application to the total synthesis of (+)-clusianone

A broadly applicable asymmetric synthetic strategy utilizing N-amino cyclic carbamate alkylation that provides access to the various stereochemical permutations of a common structural motif found in many polycyclic polyprenylated acylphloroglucinols is described. The utility of this methodology is demonstrated through the first asymmetric total synthesis of the antiviral agent (+)-clusianone.     

Envelope solitons in acoustically dispersive vitreous silica

Acoustic radiation-induced static strains, displacements, and stresses are manifested as rectified or 'dc' waveforms linked to the energy density of an acoustic wave or vibrational mode via the mode nonlinearity parameter of the material. An analytical model is developed for acoustically dispersive media that predicts the evolution of the energy density of an initial waveform into a series of energy solitons that generates a corresponding series of radiation-induced static strains (envelope solitons). The evolutionary characteristics of the envelope solitons are confirmed experimentally in Suprasil W1 vitreous silica. The value (- 11.9 ± 1.43) for the nonlinearity parameter, determined from displacement measurements of the envelope solitons via a capacitive transducer, is in good agreement with the value (- 11.6 ± 1.16) obtained independently from acoustic harmonic generation measurements. The agreement provides strong, quantitative evidence for the validity of the model.     

相对论重离子碰撞的温度涨落与热容

使用LUCIAE3.0模型模拟了SPS能区Pb+Pb和C+C在不同能量(E_lab=20—200A GeV)和不同中心度下的重离子碰撞.并通过逐个事件的粒子温度涨落提取出了相应粒子的热容,发现对于同一碰撞系统,单位发射粒子的热容随碰撞能量的升高而下降直至饱和,随着碰撞参数b的增大而减小,而且发现单位发射粒子的热容具有随粒子质量的变大而变大的关系.同时还发现不同碰撞系统中同一种粒子具有相同的单位发射粒子热容,并给出了相应的解释.     

Applications of Inverse Limits to Extensions of Operators and Approximation of Lipschitz Functions

We consider extensions of linear operators from finite dimensional subspaces. As a corollary of Steenrod's theorem about inverse limits of topological spaces, we obtain new results concerning approximation in tensor product spaces and the stability of the Cauchy functional equation.     

158A GeV的相对论重离子碰撞的强子快度分布及温度拟合

针对最近NA49在158A GeV的实验(C+C,Si+Si,Pb+Pb)数据,应用LUCIAE3.0模型进行模拟,得到了强子的快度分布和横向动量分布,并与实验数据进行比较,发现基本与实验数据相吻合。并对横向动量分布进行温度拟合,给出了和实验数据吻合很好的结果,但是对于重系统或重强子LUCIAE3.0给出的结果与实验符合相对较差.     

高能重离子碰撞中正负荷电粒子比单事例起伏研究

用强子和弦级联模型,JPCIAE及相应的Monte Carlo事例产生器,研究相对论性核–核碰撞中有限快度区间内正负荷电粒子比单事例起伏与能量、中心度、共振态衰变及快度间隔的关系.JPCIAE模型能够较好地符合CERN/SPS能区Pb+Pb碰撞的实验结果.本文还用此模型预言了RHIC能区Au+Au碰撞和ALICE能区Pb+Pb碰撞中的正负荷电粒子比单事例起伏.可以看出碰撞能量、中心度、共振态衰变及快度间隔对正负荷电粒子比单事例起伏的影响都不大.     

Theoretical Study of Hydrated Cd~（2＋） Interactions with Guanine

Theoretical study was performed to investigate how the hydration of cadmium ca-tion influences the structure and properties of guanine.The aqueous environment was simulated by both explicit solvent(1-5 water molecules) model and implicit solvent model.For complexes in which Cd2+ attached to the N(7) and O(6) sites of guanine,energy analysis together with the Natural Bonding Orbital(NBO) analysis were performed to elucidate the bonding characteristics in detail.The most stable structures are penta-coordinate complexes without aqua ligand located at the guanine site.Higher number of water ligands corresponds to higher stabilization energies.Average bonding energies of G-Cd increase with the number of water molecules.Bonding energies of water ligands depend on its position in the complexes.The charge distribution of guanine changed with increasing the number of water ligands,which may also influence the base-pairing pattern of guanine.There is positive charge transfer from guanine to aqua ligand as the number of the hydration waters increases.IEFPCM optimization has results comparable to the [CdG(H2O)5]2+ structure 5a.     

Quantum Interference Line Shifts of Broad Dipole‐Allowed Transitions

High‐resolution laser spectroscopy serves the purpose of determining the energy difference between states of atoms and molecules with the best possible accuracy. Therefore, one may face the problem of finding the center of a symmetric line within a small fraction of the line width, or one needs to extract the energy difference from an asymmetric line without a uniquely defined center. Multiplets of atomic resonance lines are subject to mutual line pullings and give rise to asymmetric line distortions due to quantum interference. This paper reviews the treatment of these distortions for dipole‐allowed one‐photon transitions. Specific examples are given for hydrogen and helium spectroscopy.     

Preparation and Storage of Silver Nanoparticles in Aqueons Polymers

以水溶性聚合物为保护剂,采用化学还原法制备了银纳米粒子,分别利用透射电子显微镜、紫外可见光谱、同步光散射光谱等手段对其进行了表征,并探索了制备银纳米粒子的最佳实验条件。通过将银纳米粒子-聚合物溶液进行脱水,得到含有银纳米粒子的固态聚合物膜。将固态聚合物膜重新溶解于水,其水溶液的紫外可见光谱与脱水前的溶液进行了比较,发现两者性质并无明显差异。因此,将银纳米粒子分散固定在聚合物膜中是一种崭新而有效的银纳米粒子制备和存储方法。