Copper- and base-free Sonogashira-type cross-coupling reaction of triarylantimony dicarboxylates with terminal alkynes under an aerobic condition

A simple copper- and base-free palladium-catalyzed Sonogashira-type cross-coupling by the use of triarylantimony dicarboxylates is described. Reaction of triarylantimony diacetates with terminal alkynes in the presence of 1 mol % of PdCl₂(PPh₃)₂ catalyst led to the formation of cross-coupling products in good to excellent yields. The reaction proceeded effectively under an aerobic condition, in that two of the three aryl groups on antimony could be transferred to the coupling products, whereas only one of them was involved in the reaction in an argon atmosphere. The reaction is sensitive to the electronic nature of the diacetates, and those bearing an electron-withdrawing group on the aromatic ring showed higher reactivity than those having an electron-donating group.     

The reaction of mono-aryl substituted methylenecyclobutanes with diphenyl diselenide in the presence of iodosobenzene diacetate and H2O

The mono-aryl substituted methylenecyclobutanes undergo an interesting reaction with diphenyl diselenide in the presence of iodosobenzene diacetate and H₂O at 40 °C in 1,2-dichloroethane to give the corresponding aryl-(1-phenylselanylcyclobutyl)methanones in moderate to good yields within 30 h. A plausible reaction mechanism has been discussed on the basis of the control and ¹⁸O-labeling experiments.     

Optical probes for detection and quantification of neutrophils’ oxidative burst. A review

Neutrophils, also known as polymorphonuclear leukocytes (PMN), are the most common type of white blood cells, comprising about 50-70% of all white blood cells. In the event of inflammatory processes, neutrophils display increased mobility, tissue influx ability, prolonged life span, and an increased phagocytic capacity, constituting the initial participants in the cellular defense of the organism. One of the most important defense systems of neutrophils corresponds to their ability to mediate a strong oxidative burst through the formation of reactive oxygen species (ROS) and reactive nitrogen species (RNS). While oxidative burst is important for the elimination of invading microorganisms, the overproduction of ROS and RNS or the impairment of endogenous antioxidant defenses may result to detrimental effects to the host. The nature and the extent of ROS and RNS production by neutrophils in response to different stimuli is, consequently, a matter of extensive research, with scientific reports showing an enormous variability on the detection methodologies employed. This review attempts to provide a critical assessment of the most common approaches to identify and quantify reactive species formed during the neutrophils’ oxidative burst. The detection mechanisms and performance, as well as advantages and limitations of the different methodologies, are scrutinized, focusing on the use of fluorimetric, chemiluminometric and colorimetric probes.     

Fluorescein thiocarbamyl amino acids as internal standards for migration time correction in capillary sieving electrophoresis

A number of algorithms have been developed to correct for migration time drift in capillary electrophoresis. Those algorithms require identification of common components in each run. However, not all components may be present or resolved in separations of complex samples, which can confound attempts for alignment. This paper reports the use of fluorescein thiocarbamyl derivatives of amino acids as internal standards for alignment of 3-(2-furoyl)quinoline-2-carboxaldehyde (FQ)-labeled proteins in capillary sieving electrophoresis. The fluorescein thiocarbamyl derivative of aspartic acid migrates before FQ-labeled proteins and the fluorescein thiocarbamyl derivative of arginine migrates after the FQ-labeled proteins. These compounds were used as internal standards to correct for variations in migration time over a two-week period in the separation of a cellular homogenate. The experimental conditions were deliberately manipulated by varying electric field and sample preparation conditions. Three components of the homogenate were used to evaluate the alignment efficiency. Before alignment, the average relative standard deviation in migration time for these components was 13.3%. After alignment, the average relative standard deviation in migration time for these components was reduced to 0.5%.     

激光光散射研究二醋酸纤维素在丙酮中的聚集

采用激光光散射研究了二醋酸纤维素的溶液性质. 发现在丙酮中二醋酸纤维素除了以单链形式存在外,还形成了胶束以及胶束簇集体. 随着浓度的增加,平均流体力学半径线性增加,而均方根回旋半径与平均流体力学半径的比值线性减小,表明由于二醋酸纤维素分子间的相互作用,胶束之间发生聚集,并形成胶束簇集体.     

Microwave-Assisted Preparation of a β-Cyclodextrin-Based Stationary Phase for Open Tubular Capillary Electrochromatography

Fluorescein isothiocyanate was used as a label to show that a 3-aminopropylmethyldimethoxysilane (KH 550)-modified capillary column was prepared by microwave irradiation. A bromoacetate-substituted β-cyclodextrin (Br-β-CD) was successfully bound to the KH 550-modified column as a chiral stationary phase for open tubular capillary electrochromatography. Compared with conventional synthesis, the microwave-assisted process significantly decreased the preparation time of the stationary phase from 16 h to 40 min. Baseline chiral separation of 1-phenyl-1,2-ethanediol was achieved using the Br-β-CD modified column.     

Analysis of alpha-1-acid glycoprotein isoforms using CE-LIF with fluorescent thiol derivatization

The analysis of glycoprotein isoforms is of high interest in the biomedical field and clinical chemistry. Many studies have demonstrated that some glycoprotein isoforms could serve as biomarkers for several major diseases, such as cancers and vascular diseases, among others. Capillary zone electrophoresis (CZE) is a well-established technique to separate glycoprotein isoforms, however, it suffers from limited sensitivity when UV-Vis detection is used. On the other hand, with laser-induced fluorescence (LIF) detection, derivatization reaction to render the proteins fluorescent can destroy the resolution of the isoforms. In this work, a derivatization procedure through the thiol groups of glycoproteins using either 5-(iodoacetamide) fluorescein (5-IAF) or BODIPY iodoacetamide is presented with the model protein of alpha-1-acid glycoprotein (AGP). The derivatization process presented enabled high-resolution analysis of AGP isoforms by CZE-LIF. The derivatization procedure was successfully applied to label AGP from samples of serum and secretome of artery tissue, enabling the separation of the AGP isoforms by CE-LIF in natural samples at different concentration levels.     

荧光光度法测定食用酒精中氰化物含量的研究

基于无色荧光素在铜离子和氰化物存在下,能够被氧化生成荧光素的原理,拟定了一个高灵敏度的氰化物的荧光测定法。方法不仅精密度高、准确度好,而且操作简单快速,检出下限为6.8×10-3ng·m1-1,运用于食用酒精中氰化物含量的测定,结果满意。     

Liposome destruction by hydrodynamic cavitation in comparison to chemical,physical and mechanical treatments

Liposomes are widely applied in research, diagnostics, medicine and in industry. In this study we show for the first time the effect of hydrodynamic cavitation on liposome stability and compare it to the effect of well described chemical, physical and mechanical treatments. Fluorescein loaded giant 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) lipid vesicles were treated with hydrodynamic cavitation as promising method in inactivation of biological samples. Hydrodynamic treatment was compared to various chemical, physical and mechanical stressors such as ionic strength and osmolarity agents (glucose, Na⁺, Ca²⁺, and Fe³⁺), free radicals, shear stresses (pipetting, vortex mixing, rotational shear stress), high pressure, electroporation, centrifugation, surface active agents (Triton X-100, ethanol), microwave irradiation, heating, freezing-thawing, ultrasound (ultrasonic bath, sonotrode). The fluorescence intensity of individual fluorescein loaded lipid vesicles was measured with confocal laser microscopy. The distribution of lipid vesicle size, vesicle fluorescence intensity, and the number of fluorescein loaded vesicles was determined before and after treatment with different stressors. The different environmental stressors were ranked in order of their relative effect on liposome fluorescein release. Of all tested chemical, physical and mechanical treatments for stability of lipid vesicles, the most detrimental effect on vesicles stability had hydrodynamic cavitation, vortex mixing with glass beads and ultrasound. Here we showed, for the first time that hydrodynamic cavitation was among the most effective physico-chemical treatments in destroying lipid vesicles. This work provides a benchmark for lipid vesicle robustness to a variety of different physico-chemical and mechanical parameters important in lipid vesicle preparation and application.     

A direct route to isoflavan quinones. The synthesis of colutequinones A and B

The first syntheses of colutequinone A and colutequinone B were achieved. Radical generation via phenyliodoso diacetate was superior to radical generation via ammonium persulfate.