水溶性芴与噻吩共聚物的合成及蛋白质对其荧光猝灭的影响

采用Suzuki偶合方法合成了含羧酸基团的新型阴离子型水溶性绿光的9,9’-二丙酸钠芴(DPF)和噻吩(TH)共聚物,聚合物分子量约为9000左右,具有较好的水溶性(5 mg/mL).研究了共聚物在不同pH水溶液中的荧光性质,结果表明当pH ＜4时,羧基以COOH形式存在,造成共聚物溶解度降低并产生聚集,荧光减弱;当p...     

Fragmentation studies of pentacoordinated bisaminoacylspirophosphoranes by negative electrospray ionization mass spectrometry

Fragmentation pathways of a series of pentacoordinated bisaminoacylspirophosphoranes were elucidated by electrospray ionization multistage mass spectrometry (ESI-MS(n)) in negative mode. The deprotonated ions of pentacoordinated bisaminoacylspirophosphoranes tend to eliminate a corresponding amino acid to form base peak. The hydrogen/deuterium exchange experiment, the high-resolution mass spectrometry, (13)C stable isotope labeling experiment and theoretical calculations were used to rationalize the proposed fragmentation pathways and to verify the differences between the fragmentation pathways. The results indicate that the negative molecular ions of pentacoordinated bisaminoacylspirophosphoranes dissociate through its open-chain tricoordinated tautomers. The relative Gibbs free energies (ΔG) of the product ions and proposed fragmentation pathways were estimated using the B3LYP/6-31 + + G(d, p) model. The results have some potential applications in the identification structures of similar spirophosphorane compounds by ESI-MS(n).     

Intracellular transport and localization of microsomal cytochrome P450

The cytochrome P450 (P450) enzymes are mainly localized to the endoplasmic reticulum (ER), where they function within catalytic complexes metabolizing xenobiotics and some endogenous substrates. However, certain members of families 1–3 were also found in other subcellular compartments, such as mitochondria, plasma membrane, and lysosomes. The physiological function of these enzymes in non-ER locations is not known, although plasma-membrane-associated P450s have been described to be catalytically active and to participate in immune-mediated reactions with autoantibody formation that can trigger drug-induced hepatitis. Several retention/retrieval mechanisms are active in the ER retention of the P450s and inverse integration of the translated P450 into the ER membrane appears to be responsible for transport to the plasma membrane. Furthermore, hydrophilic motifs in the NH₂-terminal part have been suggested to be important for mitochondrial import. Phosphorylation of P450s has been described to be important for increased rate of degradation as well as for targeting into mitochondria. It was also suggested that the mitochondria-targeted P450s from families 1–3 could be active in drug metabolism using an alternative electron transport chain. In this review we present an update of the field emphasizing studies concerning localization, posttranslational modification, such as phosphorylation, and intracellular transport of microsomal P450s.     

Protein surface recognition of the novel tetra-carboxylphenyl calix[4]arene to cytochrome c

The interaction of the novel tetra-carboxylphenyl calix[4]arene （TCPC） with the bovine heart cytochrome c （Cc） was first investigated by fluorescence spectroscopy and molecular modeling methods. The formation of a stable 1：1 complex was monitored by fluorescence titration, and its binding constant is 1.916 ×10^7 L mol^-1. Molecular modeling reveals the recognition mechanism of TCPC to the Cc surface, that is, the electrostatic interaction drives TCPC to the Cc surface, and the van der Waals interaction orientates TCPC parallel to the cleft of Cc.     

基于逐步回归法的近红外光谱信息提取及模型的研究

基于多元线性回归的逐步分析算法 ,依据小麦粉的近红外吸收特性机理 ,对小麦粉的近红外光谱(10 0 0～ 2 5 0 0nm)划分三波段 (Ⅰ :10 0 0～ 14 0 0nm ;Ⅱ :14 0 0～ 186 0nm ;Ⅲ :186 0～ 2 5 0 0nm) ,并进行了各波段的光谱信息提取 ,确定了回归特征波长 ,对不同波段建立的回归模型进行了比较 ,给出了各段回归的最佳数学模型。通过对小麦粉近红外谱的信息提取及蛋白质成分的定量分析 ,比较和讨论了不同波段所建模型对小麦粉蛋白质含量的近红外分析结果 ,在应用中有一定的参考价值。     

Affinity Labelling at the 4-Hydroxyl Group of N-Acetylglucosamine and N-Acetylgalactosamine

Derivatives of N-acetylgalactosamine and N-acetylglucosamine in which the 4-OH group could be selectively labelled have been prepared from a common precursor.     

Expression and Characterization of an Active Chimeric Protein of Human Extracellular Superoxide Dismutase and hCuZnSOD in Pichiapastoris

Mammalian cells express two isoforms of Cu-and Zn-containing superoxide dismutases(SODs),CuZnSOD and extracellular SOD(EC-SOD),involved in the defense system against reactive oxygen species(ROS).The two SODs have structurally homologous centre domain with distinct N-and C-terminuses,resulting in the different characteristics of the structure and function of the two molecules.We generated a hybrid SOD molecule(namely hySOD) via replacing the N-and C-terminuses of hCuZnSOD with the counterparts of hEC-SOD.The...     

Computational investigations of folded self-avoiding walks related to protein folding

Various subsets of self-avoiding walks naturally appear when investigating existing methods designed to predict the 3D conformation of a protein of interest. Two such subsets, namely the folded and the unfoldable self-avoiding walks, are studied computationally in this article. We show that these two sets are equal and correspond to the whole n-step self-avoiding walks for n ≤ 14, but that they are different for numerous n ≥ 108, which are common protein lengths. Concrete counterexamples are provided and the computational methods used to discover them are completely detailed. A tool for studying these subsets of walks related to both pivot moves and protein conformations is finally presented.     

Neural activity-induced modulation of BOLD poststimulus undershoot independent of the positive signal

Despite intense research on the blood oxygenation level-dependent (BOLD) signal underlying functional magnetic resonance imaging, our understanding of its physiological basis is far from complete. In this study, it was investigated whether the so-called poststimulus BOLD signal undershoot is solely a passive vascular effect or actively induced by neural responses. Prolonged static and flickering black-white checkerboard stimulation with isoluminant grey screen as baseline condition were employed on eight human subjects. Within the same region of interest, the positive BOLD time courses for static and flickering stimuli were identical over the entire stimulus duration. In contrast, the static stimuli exhibited no poststimulus BOLD signal undershoot, whereas the flickering stimuli caused a strong BOLD poststimulus undershoot. To ease the interpretation, we performed an additional study measuring both BOLD signal and cerebral blood flow (CBF) using arterial spin labeling. Also for CBF, a difference in the poststimulus period was found for the two stimuli. Thus, a passive blood volume effect as the only contributor to the poststimulus undershoot comes short in explaining the BOLD poststimulus undershoot phenomenon for this particular experiment. Rather, an additional active neuronal activation or deactivation can strongly modulate the BOLD poststimulus behavior. In summary, the poststimulus time course of BOLD signal could potentially be used to differentiate neuronal activity patterns that are otherwise indistinguishable using the positive evoked response.