2-(4-β-D-吡喃阿洛糖苷-苯基)-5-取代芳基-1,3,4-噁二唑的合成及镇静活性研究

以豆腐果苷为原料, 与取代苯甲酰肼反应生成中间体4-β-D-吡喃阿洛糖苷-苯甲醛取代苯甲酰腙(2a～2g), 在溴作催化剂的条件下发生关环反应, 合成了一系列豆腐果苷类似物3a～3g. 所有化合物结构经IR, ¹H NMR以及MS谱得以证实. 初步药理实验结果表明, 化合物3a, 3c, 3f与豆腐果苷相比有更好的镇静活性.     

无溶剂合成1,3,5-三芳基-2-芳酰基环己醇衍生物和晶体结构

在NaOH存在下室温研磨查尔酮与丙二腈,可以有效地得到1,3,5-三芳基-2-芳酰基环己醇衍生物,本合成方法反应时间短、操作简单、产率高,符合绿色化学特点.产物结构经过红外、核磁、元素分析和高分辨质谱确证,并对3b做了单晶衍射测定.     

Improving confidence in detection and characterization of protein N-glycosylation sites and microheterogeneity

Protein glycosylation is one of the most common post-translational modifications, estimated to occur in over 50% of human proteins. Mass spectrometry (MS)-based approaches involving different fragmentation mechanisms have been frequently used to detect and characterize protein N-linked glycosylations. In addition to the popular Collision-Induced Dissociation (CID), high-energy C-trap dissociation (HCD) fragmentation, which is a feature of a linear ion trap orbitrap hybrid mass spectrometer (LTQ Orbitrap), has been recently used for the fragmentation of tryptic N-linked glycopeptides in glycoprotein analysis. The oxonium ions observed with high mass accuracy in the HCD spectrum of glycopeptides can be combined with characteristic fragmentation patterns in the CID spectrum resulting from consecutive glycosidic bond cleavages, to improve the detection and characterization of N-linked glycopeptides. As a means of automating this process, we describe here GlypID 2.0, a software tool that implements several algorithmic approaches to utilize MS information including accurate precursor mass and spectral patterns from both HCD and CID spectra, thus allowing for an unequivocal and accurate characterization of N-linked glycosylation sites of proteins.     

催化动力学光度法测定青霉素G及其机理研究

研究了在青霉素G存在下双氧水氧化苋菜红的褪色反应,建立了催化动力学光度法测定微量青霉素G的方法.方法线性范围为0.20～4.00μg/mL,回归方程y=-0.015p(μg/mL)+0.311,r=0.9998;方法线性范围为4.00～50.0μg/mL,回归方程y=0.001p(μg/mL)+0.280,r=0.99...     

A multistage pathway for human prion protein aggregation in vitro: from multimeric seeds to β-oligomers and nonfibrillar structures

Aberrant protein aggregation causes numerous neurological diseases including Creutzfeldt-Jakob disease (CJD), but the aggregation mechanisms remain poorly understood. Here, we report AFM results on the formation pathways of β-oligomers and nonfibrillar aggregates from wild-type full-length recombinant human prion protein (WT) and an insertion mutant (10OR) with five additional octapeptide repeats linked to familial CJD. Upon partial denaturing, seeds consisting of 3-4 monomers quickly appeared. Oligomers of ~11-22 monomers then formed through direct interaction of seeds, rather than by subsequent monomer attachment. All larger aggregates formed through association of these β-oligomers. Although both WT and 10OR exhibited identical aggregation mechanisms, the latter oligomerized faster due to lower solubility and, hence, thermodynamic stability. This novel aggregation pathway has implications for prion diseases as well as others caused by protein aggregation.     

In situ encapsulation of laccase in nanofibers by electrospinning for development of enzyme biosensors for chlorophenol monitoring

A biosensor based on Trametes versicolor laccase (Lac) was developed for the determination of phenolic compounds. The biosensor was prepared by in situ electrospinning of a mixture of polyvinyl alcohol (PVA), Lac, PEO-PPO-PEO (F108) and gold nanoparticles (Au NPs), where F108 was used as an enzyme stabilizing additive and Au NPs was used to enhance the conductivity of the biosensor. Laser confocal scanning microscopy and electrochemical impedance spectroscopy proved that the enzyme was successfully encapsulated into the electrospun nanofibers. Under the optimal conditions, the lowest detection limit was found to be 0.04 μM (S/N = 3) for 2,4-DCP and the highest detection limit was found to be 12.10 μM for 4-CP. The sensitivity of the biosensor obtained in the linear range for chlorophenols followed the sequence 2,4-dichlorophenol (2,4-DCP) > 2,4,6-trichlorophenol (2,4,6-TCP) > 4-chlorophenol (4-CP). The sensing performance for chlorophenols was attributed to the suitable electrochemical interface of PVA/F108/Au NPs/Lac, resulting from biocompatibility, a high surface area-to-volume ratio (10.42 m(2) g(-1)) and superior mechanical properties of the electrospun nanofibers. The biosensor exhibited good repeatabilities of 7.6%, 2.8% and 9.0% (R.S.D.) and reproducibilities of 14.9%, 10.4% and 13.7% (R.S.D.) for 4-CP, 2,4-DCP and 2,4,6-TCP, respectively. Lac retained 65.8% of its initial activity after a 30-day storage period.     

A systematic study of the synthesis of silver nanoplates: is citrate a "magic" reagent?

In this work we have carried out systematic studies and identified the critical role of hydrogen peroxide instead of the generally believed citrate in the well-known chemical reduction route to silver nanoplates. This improved understanding allows us to develop consistently reproducible processes for the synthesis of nanoplates with high efficiency and yields. By harnessing the oxidative power of H(2)O(2), various silver sources including silver salts and metallic silver can be directly converted to nanoplates with the assistance of an appropriate capping ligand, thus significantly enhancing the reproducibility of the synthesis. Contrary to the previous conclusion that citrate is the key component, we have determined that the group of ligands with selective adhesion to Ag (111) facets can be expanded to many di- and tricarboxylate compounds whose two nearest carboxylate groups are separated by two or three carbon atoms. We have also found that the widely used secondary ligand polyvinylpyrrolidone can be replaced by many hydroxyl group-containing compounds or even removed entirely while still producing nanoplates of excellent uniformity and stability. In addition to the general understanding of NaBH(4) as a reducing agent, it has also been found to act as a capping agent to stabilize the silver nanoparticles, prolong the initiation time required for nanoplate nucleation, and contribute to the control of the thickness as well as the aspect ratio of silver nanoplates. The improved insight into the specific roles of the reaction components and significantly enhanced reproducibility are expected to help elucidate the formation mechanism of this interesting nanostructure.     

Plasmonic gold nanocrosses with multidirectional excitation and strong photothermal effect

We report a facile chemical synthesis of well-defined gold nanocrosses through anisotropic growth along both <110> and <001>, whereas gold nanorods grow only along either <110> or <001>. The multiple branching was achieved by breaking the face-centered-cubic lattice symmetry of gold through copper-induced formation of single or double twins, and the resulting gold nanocrosses exhibited pronounced near-IR absorption with a great extension to the mid-IR region. As studied by discrete dipole approximation (DDA) simulations, the entire nanocross gets excited even when one of the branches is exposed to incident light. The above properties make them useful as octopus antennas for capturing near-IR light for effective photothermal destruction of cells. The cell damage process was analyzed using the Arrhenius model, and its intrinsic thermodynamic characteristics were determined quantitatively. Besides effective photothermal treatment and two-photon luminescence imaging, the near- and mid-IR-absorbing gold nanocrosses may also find applications in IR sensing, thermal imaging, telecommunications, and the like.