Effects of pretreatments and modifiers on electrochemical properties of carbon paste electrodes

The electrochemical properties of carbon paste electrodes (CPEs), including unmodified and modified with protein and polycations, were investigated by impedance spectroscopy (IS) using ferricyanide and ferrocene monocarboxylic acid (FcMA) as redox probes. Various electrochemical pretreatments were applied to the unmodified CPE. The heterogeneous charge transfer rate constant of ferro/ferricyanide couple is enhanced by 2 to 10 times compared with that obtained at untreated electrodes. It was found that for ferricyanide the more suitable pretreatments are successive cyclic voltammetric scans, cathodization and a square wave-like stepping rather than high-potential anodization. However, the pretreatment only exhibits a slight effect on the kinetics of FcMA. At the CPEs containing modifier, the electron transfer rate of the redox couple depends more on the pH of electrolyte solution if ferro/ferricyanide is used. The results can be explained by the differently charged states of the CPEs that were caused by the protonation or deprotonation of the modifiers in various pH solutions and demonstrate the importance of the electrostatic interaction on the kinetics of the highly polar species such as ferricyanide. The different adsorptive behavior of ferricyanide and FcMA is also discussed.     

Acridinium ester chemiluminescence: pH dependent hydrolysis of reagents and flow injection analysis of hydrogen peroxide and glutamate

An automated analysis system is described for the measurement of hydrogen peroxide based on a chemiluminescence reaction with phenyl 10-methylacridinium-9-carboxylate (PMAC). A reversed FIA experimental arrangement is used to establish the operating conditions for the measurement of submicromolar levels of hydrogen peroxide. The carrier stream consists of hydrogen peroxide standards prepared in a pH 9.0, boric acid buffer and the flow rate for this carrier/sample stream is 4 ml/min. Twenty microliters of a 10 mM PMAC solution, prepared in a pH 3 phosphate buffer, are injected into the carrier/sample stream. Hydrogen peroxide mixes with the PMAC reagent in an incubation coil that is constructed by wrapping 107 cm of polyethylene tubing around a 1 cm o.d. plastic rod. The chemiluminescence reaction is then initiated by adding base just before the sample passes in front of a photomultiplier tube (PMT) detector. The calculated limit of detection (S/N = 3) for hydrogen peroxide is 0.25 M. In addition, the pH dependent hydrolysis of the PMAC reagent is characterized by an HPLC method which has been specifically developed for the separation and detection of the hydrolysis products of PMAC. Results indicate that a pH of 3.0 is required for long term stability of the PMAC reagent. Finally, this system has been successfully extended to the measurement of glutamate by coupling a bioreactor column of glutamate oxidase with the hydrogen peroxide detection scheme. A detection limit (S/N = 3) of 0.5 M has been established for glutamate with a throughput of 200 samples per hour.     

Laquinimod Modulates Human Astrocyte Function and Dampens Astrocyte-Induced Neurotoxicity during Inflammation

Astrocytes greatly participate to inflammatory and neurotoxic reactions occurring in neurodegenerative diseases and are valuable pharmacological targets to support neuroprotection. Here we used human astrocytes generated from reprogrammed fibroblasts as a cellular model to study the effect of the compound Laquinimod and its active metabolite de-Laquinimod on astrocyte functions and the astrocyte–neuron interaction. We show that human iAstrocytes expressed the receptor for the inflammatory mediator IL1 and responded to it via nuclear translocation of NFκB, an event that did not occur if cells were treated with Laquinimod, indicating a direct anti-inflammatory activity of the drug on the human astrocyte. Similarly, while exposure to IL1 downregulated glial glutamate transporters GLAST and GLT1, treatment with Laquinimod supported maintenance of physiological levels of these proteins despite the inflammatory milieu. Laquinimod also induced nuclear translocation of the aryl hydrocarbon receptor (AHR), suggesting that drug action was mediated by activation of the AHR pathway. However, the drug was effective despite AHR inhibition via CH223191, indicating that AHR signaling in the astrocyte is dispensable for drug responses. Finally, in vitro experiments with rat spinal neurons showed that laquinimod did not exert neuroprotection directly on the neuron but dampened astrocyte-induced neurodegeneration. Our findings indicate that fibroblast-derived human astrocytes represent a suitable model to study astrocyte–neuron crosstalk and demonstrate indirect, partial neuroprotective efficacy for laquinimod.     

Thermal behavior of glutamic acid and its sodium,lithium and ammonium salts

Glutamic acid (H2_glu) and its lithium, sodium and ammonium monosalts were submitted to thermal analysis using thermogravimetry (TG) and differential thermal analysis (DTA). The main goal of these studies was to compare the relative thermal stability and to evaluate the effect of the counter ion in the thermal decomposition pathways. Salts were obtained by direct neutralization of the purified acid with LiOH, NaOH or NH₄OH and were characterized by elemental analysis (C, H and N) and IR spectroscopy. Decomposition occurred after conversion to the pyroglutamic acid or the respective pyroglutamates and ammonium salt loosing NH₃ being converted to H₂glu before decomposition.     

HPLC法测定鸡精中谷氨酸钠的含量

以邻苯二甲醛与谷氨酸钠中的氨基进行柱前在线衍生化反应,采用C18色谱柱分离、荧光检测器（激发340nm,发射450nm）进行测定,建立了柱前衍生反相高效液相色谱测定鸡精中谷氨酸钠含量的方法。该方法相对标准偏差为0．69％,加标回收率为99．1％～101％,在0．10~50．0mg／L范围内,谷氨酸钠的峰面积和浓度之间的相关系数为0．9999,保留时间和峰面积的相对标准偏差分别为1．22％和0．71％,鸡精中谷氨酸钠定量下限为0．2μg／g。     

Efficient synthesis of optically active α-substituted glutamate analogs possessing α-hydroxymethyl and α-alkoxymethyl groups

Highly enantioselective synthesis of (2R)-α-(hydroxymethyl)glutamate (1), a selective agonist of mGluR2 and 3, was achieved in short steps using an asymmetric version of the Strecker synthesis. This was converted into its α-methoxymethyl- and α-benzyloxymethyl derivatives 2 and 3, possible ligands as tools to investigate glutamate receptors, via protection of the sterically hindered amino group by means of phase transfer catalyst.     

具有刚性液晶元侧基的嵌段共聚物PHEMAChol-b-PBLG的合成及自组装研究

以胆固醇和谷氨酸苄酯为主要出发原料,采用可逆加成-断裂链转移(RAFT)自由基聚合、氨基酸环内酸酐(NCA)开环聚合(ROP)以及"点击化学"(click chemistry)组合方法,设计、合成了系列具有刚性液晶元侧基的聚甲基丙烯酸羟乙酯胆固醇碳酸酯-嵌段-聚谷氨酸苄酯(PHEMAChol-b-PBLG),并通过核磁共振(NMR)、红外光谱(FTIR)、凝胶渗透色谱(GPC)和静态光散射(SLS)对其化学结构进行了表征.运用热重分析仪(TGA)、热台偏光显微镜(POM)和示差扫描量热仪(DSC)研究了系列共聚物的热稳定性、液晶相结构及相转变行为,并通过固体红外、13C固体核磁共振(13C CP/MAS)和X射线衍射仪(XRD)研究了PBLG均聚物及系列嵌段共聚物中聚氨基酸多肽链段的二级结构.研究结果表明,系列嵌段共聚物均具有良好的热稳定性,表现为近似向列相的液晶织构,PBLG链段趋于呈刚直棒状的α-螺旋构型,且其多肽链段越长,二级结构越规整.进一步采用圆二色谱(CD)和透射电镜(TEM)对系列嵌段共聚物在四氢呋喃溶液中的二级结构及自组装行为进行了研究,制备得到纺锤形自组装聚集体和大复合胶束,并通过变性酸三氟乙酸的引入实现对嵌段共聚物中PBLG的二级结构及相应自组装聚集体形貌的有效调控.     

Astrocyte and ions metabolism during epileptogenesis:A review for modeling studies

As a large group of cells in a central nervous system, astrocytes have a great influence on ion and energy metabolism in a nervous system. Disorders of neuronal ion and energy metabolism caused by impaired astrocytes play a key role in the pathogenesis of epilepsy. This paper reviews the existing computational models of epileptogenesis resulting from impaired astrocytes and presents several open perspectives with regard to ion and energy metabolism-induced epileptogenesis in a neuron-astrocyte-capillary coupled model.     

Monitoring of metabolic profiling and water status of Hayward kiwifruits by nuclear magnetic resonance

The metabolic profiling of kiwifruit (Actinidia deliciosa, Hayward cultivar) aqueous extracts and the water status of entire kiwifruits were monitored over the season (June-December) using nuclear magnetic resonance (NMR) methodologies. The metabolic profiling of aqueous kiwifruit extracts was investigated by means of high field NMR spectroscopy. A large number of water-soluble metabolites were assigned by means of 1D and 2D NMR experiments. The change in the metabolic profiles monitored over the season allowed the kiwifruit development to be investigated. Specific temporal trends of aminoacids, sugars, organic acids and other metabolites were observed.The water status of kiwifruits was monitored directly on the intact fruit measuring the T₂ spin-spin relaxation time by means of a portable unilateral NMR instrument, fully non-invasive. Again, clear trends of the relaxation time were observed during the monitoring period.The results show that the monitoring of the metabolic profiling and the monitoring of the water status are two complementary means suitable to have a complete view of the investigated fruit.