Kinetic-Fluorimetric Determination of Choline and Acetylcholine by Oxidation with Ce(IV)

Abstract

A kinetic fluorimetric method for the determination of choline and acetylcholine based on the oxidation of these analytes by Ce(IV) in a sulfuric acid medium yielding fluorescent Ce(III) is proposed. The calibration graph of each analyte is linear over the range 1.7x10^?5 ? 1×10^?3 M and the relative standard deviation is about 2% in both cases. The rate of appearance of Ce(III) fluorescence was found to be influenced by various processes in addition to the oxidation reaction and experiments were carried out in order to elucidate them.     

Analysis of Choline in Milk Powder Using Electrogenerated Chemiluminescence Including a Mechanism Study

A novel and simple method for detection of choline in milk powder using electrogenerated chemiluminescence (ECL) without prior separation was developed and its mechanism was studied thoroughly. Choline could not strengthen ECL signals of tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy)3²⁺) to be detected. Heated to its melting point, choline decomposed into two new compounds, trimethylamine and N,N-dimethyl-2-aminoethanol. Both of them were tertiary amines and could act as ECL co-reactants to strengthen the ECL signals of Ru(bpy)3²⁺ sharply. The detection method overcame the defects of the commonly used method based on enzyme procedures and liquid chromatography-mass spectrometric technique.     

Fabrication of a Nanobiocomposite Film Containing Heme Proteins and Carbon Nanotubes on a Choline Modified Glassy Carbon Electrode: Direct Electrochemistry and Electrochemical Catalysis

A nanocomposite electrochemical sensing film is assembled on choline (Ch) modified glassy carbon electrode (GCE), which contains multiwalled carbon nanotubes (MWNTs), Nafion cation exchanger, and myoglobin (Mb) or hemoglobin (Hb). The MWNTs provide a 3D porous and conductive network for the enzyme immobilization and Nafion acts as polymeric binder to give cast thin films. Both MWNTs and Nafion provide negative functionalities to bind to the positively charged redox proteins and to attach at the positively charged Ch modified layer, and drive the formation of homogeneous and stable nanocomposite film, the MWNT‐Nafion‐Mb. The nanocomposite film was characterized by field emission scanning electron microscope (FE‐SEM). The Mb in the nanocomposite film showed a pair of well‐defined and nearly reversible cyclic voltammetric peaks at about ?0.32 V vs. SCE at pH 7.0 solution for the heme Fe(III)/Fe(II) redox couple. The immobilized heme proteins can display the features of peroxidase in electrocatalytic reductions of oxygen, hydrogen peroxide, nitric oxide, trichloroacetic acid (TCA), and bromate.     

Simultaneous determination of allantoin, choline and L-arginine in Rhizoma Dioscoreae by capillary electrophoresis

A rapid, easy and reproducible capillary electrophoresis (CE) method for the simultaneous determination of allantoin, choline and arginine in Rhizoma Dioscoreae was developed first time. Under the optimum condition, the three analytes could be well separated within 5 min in a 70 cm (60 cm effective length) x 75 microm i.d. capillary. The relative standard deviations for both migration time and peak height were less than 3.20%. The linear response range was 5.0-150, 0.9-100 and 1.0-200 microg/ml for arginine, choline and allantoin, respectively. The detection limit of three components was 2.0, 0.4 and 0.5 microg/ml for arginine, choline and allantoin, respectively. Contents of arginine, choline and allantoin in the crude drug of Rhizoma Dioscoreae could be easily determined by the proposed method with satisfactory results.     

基于胆碱修饰层为基底的纳米金固定过氧化物酶修饰电极的研究

玻碳电极上共价修饰上单分子层胆碱(Ch)可以显著提高电极的活性。本研究利用该电极上胆碱层带有的正电荷,牢固吸附带负电荷的纳米金溶胶,继而利用纳米金颗粒良好固载辣根过氧化物酶(HRP),制备出了基于HRP酶直接电化学的H2O2传感器。以阻抗谱、循环伏安等方法表征了修饰电极的性质。结果显示,该电化学传感器具有良好的催化活性,电活性HRP的表面浓度(Γ*)为1.2×10-9mol/cm2,米氏常数KMapp=1.55±0.11 mmol/L。该修饰电极在H2O2浓度1.2×10-6~3.2×10-3mol/L范围内有线性响应,检出限(S/N=3)为4.0×10-7mol/L。本修饰电极制备简单,选择性高,稳定性好,可以作为进一步构筑生物传感器的基础。     

1H magnetic resonance spectroscopy of the normal testis: preliminary findings

PURPOSE: The purpose of this study was to determine the pre- and postpubertal 1H magnetic resonance spectroscopic characteristics of the normal testis to establish baseline values for further clinical studies. MATERIALS AND METHODS: The subjects consisted of male volunteers, of whom 19 were prepubertal with ages between 7 and 13 years and 24 were postpubertal with ages between 19 and 39 years. Their testes were evaluated at 1.5 T with magnetic resonance spectroscopy; in addition, testis volumes were measured. Major metabolite peaks were identified and their ratios were calculated. Metabolite differences of testis between pre- and postpubertal age were analyzed. RESULTS: Major constituents of spectra were 3.21 ppm choline and 0.9-1.3 ppm lipid peaks. At the echo time (TE) spectrum of 31 ms, choline/lipid ratios ranged from 0.35 to 8.30 (mean=1.87) in postpubertal males and from 0.06 to 5.45 (mean=0.88) in prepubertal males (P<.013). At the TE spectrum of 136 ms, choline/lipid ratios ranged from 0.66 to 15.42 (mean=4.09) in postpubertal males and from 0.05 to 4.91 (mean=0.9) in prepubertal males (P<.016). CONCLUSIONS: Choline/lipid ratio was higher in the postpubertal period. The existence of higher choline peak in that age group should be due to the initiation of spermatogenesis. The decrease in the lipid peak may represent the effect of testosterone on testicular tissue or may be due to histochemical changes initiated by puberty. The significant decrease in choline/lipid ratio noted after puberty could represent the presence of spermatogenesis. This hypothesis should be evaluated by further studies on postpubertal subjects with impaired spermatogenesis.     

低共熔溶剂的热稳定性研究

近年来,低共熔溶剂(DESs)引起了人们的广泛关注,在诸多领域得到应用。DESs一般由氢键供体(HBDs)和氢键受体(HBAs)通过氢键作用形成,其热稳定性研究对于其高温应用具有重要意义。本文利用热重分析法(TG)对40种DESs的热稳定性进行了系统研究,并得到了所研究DESs的开始分解温度(T_onset)。值得注意的是,DESs受热后的变化情况与离子液体不同,呈现出分阶段失重的现象。通常形成DESs的氢键在升温后首先被破坏,从而导致DESs分解成组成其的HBDs和HBAs。然后热稳定性较差(或者沸点较低)的HBDs首先分解(或挥发),而HBAs则在更高温度下分解(或挥发)。例如常见的HBA氯化胆碱(ChCl)在250 ℃附近开始分解。氢键强度对DESs受热后的表现起着重要的作用,DESs中的氢键会阻碍分子“逃脱”,使得T_onset向高温方向移动。此外,我们考察了阴离子、氢键供体、摩尔比对DESs热稳定性的影响,发现HBDs自身的挥发或分解对DESs的热稳定性起着决定性作用。由于用T_onset值会高估DESs的热稳定性,长期热稳定性的考察对其工业应用具有重要价值。本研究能帮助人们理解DESs的热分解行为,为制备具有适当热稳定性的DESs提供依据。     

An Efficient Protocol for the Synthesis of N‐Alkyl‐ and N‐Arylimides Using the Lewis Acidic Ionic Liquid Choline Chloride·2ZnCl2

Lewis acidic ionic liquid choline chloride·2ZnCl₂ is shown to be for the first time an excellent medium and efficient catalyst for the synthesis of N‐alkyl‐ and N‐arylimides in good yields under mild conditions.     

A colloidal suspension of nanostructured poly(N-butyl benzimidazole)-graphene sheets with high oxidase yield for analytical glucose and choline detections

A colloidal suspension of nanostructured poly(N-butyl benzimidazole)-graphene sheets (PBBIns-Gs) was used to modify a gold electrode to form a three-dimensional PBBIns-Gs/Au electrode that was sensitive to hydrogen peroxide (H₂O₂) in the presence of acetic acid (AcOH). The positively charged nanostructured poly(N-butyl benzimidazole) (PBBIns) separated the graphene sheets (Gs) and kept them suspended in an aqueous solution. Additionally, graphene sheets (Gs) formed “diaphragms” that intercalated Gs, which separated PBBIns to prevent tight packing and enhanced the surface area. The PBBIns-Gs/Au electrode exhibited superior sensitivity toward H₂O₂ relative to the PBBIns-modified Au (PBBIns/Au) electrode. Furthermore, a high yield of glucose oxidase (GOD) on the PBBIns-Gs of 52.3 mg GOD per 1 mg PBBIns-Gs was obtained from the electrostatic attraction between the positively charged PBBIns-Gs and negatively charged GOD. The non-destructive immobilization of GOD on the surface of the PBBIns-Gs (GOD-PBBIns-Gs) retained 91.5% and 39.2% of bioactivity, respectively, relative to free GOD for the colloidal suspension of the GOD-PBBIns-Gs and its modified Au (GOD-PBBIns-Gs/Au) electrode. Based on advantages including a negative working potential, high sensitivity toward H₂O₂, and non-destructive immobilization, the proposed glucose biosensor based on an GOD-PBBIns-Gs/Au electrode exhibited a fast response time (5.6 s), broad detection range (10 μM to 10 mM), high sensitivity (143.5 μA mM⁻¹ cm⁻²) and selectivity, and excellent stability. Finally, a choline biosensor was developed by dipping a PBBIns-Gs/Au electrode into a choline oxidase (ChOx) solution for enzyme loading. The choline biosensor had a linear range of 0.1 μM to 0.83 mM, sensitivity of 494.9 μA mM⁻¹ cm⁻², and detection limit of 0.02 μM. The results of glucose and choline measurement indicate that the PBBIns-Gs/Au electrode provides a useful platform for the development of oxidase-based biosensors.     

Solubilities of carbon dioxide in the eutectic mixture of levulinic acid (or furfuryl alcohol) and choline chloride

The solubilities of carbon dioxide (CO₂) in the renewable deep eutectic solvents (DESs) containing levulinic acid (or furfuryl alcohol) and choline chloride were determined at temperatures (303.15, 313.15, 323.15, and 333.15) K and pressures up to 600.0 kPa using an isochoric saturation method. The mole ratios of levulinic acid (or furfuryl alcohol) to choline chloride were fixed at 3:1, 4:1 and 5:1. Standard Gibbs free energy, dissolution enthalpy and dissolution entropy were calculated from Henry’s law constant of CO₂ in the DESs. Results indicated that levulinic acid based DESs are more effective to capture CO₂ than furfuryl alcohol based ones. The solubility of CO₂ in the DESs increased with increasing mole ratio of levulinic acid (or furfuryl alcohol) to choline chloride as well as pressure and decreased with increasing temperature.