Wavelength–Ratiometric Probes for the Selective Detection of Fluoride Based on the 6-Aminoquinolinium Nucleus and Boronic Acid Moiety

Herein we report a set of new water-soluble fluorescent probes (N-boronobenzyl-6-aminoquinolinium bromides, BAQBAs) sensitive to aqueous fluoride. These probes shows spectral shifts and intensity changes in the presence of fluoride, in a wavelength ratiometric and colorimetric manner, enabling the detection of fluoride concentrations at visible wavelengths, in the concentration range approximately 1-300 mM. Although the sensing mechanism is different for fluoride as compared to the other halides, we have tested the utility of these probes towards the other halides, and the results reveal that the BAQBAs are in fact potential candidates towards the sensing of the all the halides, but in different concentration ranges. As the probes are based on the boronic acid moiety, which is a well-known fluoride and sugar chelator group, we have investigated the response of sugars (such as glucose and fructose, which are present in biological fluids and foodstuffs) as interferences in fluoride detection using these probes. Interestingly, the BAQBAs show a suppressed sugar response potentially allowing for the predominant fluoride sensitivity. In addition to physiological sugars, we also have assessed the response of aqueous halides as potential interferents, or indeed analytes to be sensed, and show that the new boronic acid containing probes respond well to aqueous fluoride in the presence of a high background of other species, such as in a biological cocktail of 50 mM Glucose, 50 mM aqueous Chloride and 5 mM Fructose.     

The hydration of monosaccharides—an NMR study

At temperatures close to 0°C proton exchange between sugar hydroxyl groups and water is slow, and separate proton resonance peaks can be detected for the hydroxyl protons. All are shifted downfield of the water resonance, the anomeric hydroxyl proton shift being the greatest. Axial anomeric hydroxyl protons are shifted less than corresponding equatorial protons. Proton exchange with water is strongly acid and base catalyzed, but, at least in some cases, there seems to be an additional pH-independent mechanism involved. From the temperature effect on the shifts, and the effect of added dimethyl sulfoxide, we conclude that each hydroxyl group is bonded on average to two water molecules. This estimate of the hydration number for monosaccharides is far greater than those previously deduced from relaxation studies. It is suggested that the source of this difference lies in the residence times of the bound water molecules. Shifts of the hydroxyl proton resonances for sugars in methanol are compared with those for aqueous solutions and are found to be very similar. Hence it is concluded that these shifts do not reveal any special effects due to water structure. There are quite marked differences in the shifts for different sugars, and, in particular, the anomeric hydroxyl proton shifts for ketoses are smaller than those for aldoses.Taken as solvation spectra, Part 56.     

Conversion of N-acetylneuraminic acid glycosyl chloride into dibenzyl glycosyl phosphate: O-glycosylation in the absence of a promoter

Readily accessible N-acetylneuraminic acid (Neu5Ac) glycosyl chloride, which was regarded to be a poor glycosyl donor, was shown to react with dibenzyl phosphoric acid salts in the absence of glycosylation promoters to give the corresponding -Neu5Ac dibenzyl glycosyl phosphate in high yield.     

Tandem mass spectra of ammonium adducts of monosaccharides: differentiation of diastereomers

Tandem mass spectra of ammonium adducts of monosaccharides gave characteristic fragmentation patterns involving elimination of NH3/H2O followed by multiple eliminations of H2O and cross ring cleavages. Tandem mass spectra were examined over a range of collision energies (1-20 eV) on a triple-quadrupole mass spectrometer. The breakdown behavior of the ammonium adducts revealed patterns that could differentiate diastereomers of monosaccharides.     

1-苯基-3-甲基-5-吡唑啉酮衍生中药寡糖的毛细管区带电泳分离

建立了一种可用于中药寡糖分离的毛细管区带电泳(CZE)分析方法。分离条件: 未涂层熔融石英毛细管柱(48 cm×50 μm,有效长度38 cm),紫外检测波长245 nm,采用1-苯基-3-甲基-5-吡唑啉酮(PMP)为寡糖衍生试剂,50 mmol/L磷酸盐溶液(pH 2.5)为运行缓冲液,电压15 kV,重力进样10 cm×2 s。针对中药寡糖实际样品的复杂性,通过添加多种常见单糖进行方法的实用性验证,并且将方法用于板蓝根多糖的控制降解产物的分离。结果表明,板蓝根寡糖组分可按相对分子质量从小到大的顺序分离,分离效果令人满意。该分离方法操作简单、高效,可用于中药寡糖实际样品分析。另外,还对单糖、寡糖PMP衍生物的电泳迁移行为进行了初步的理论探讨。     

植物单糖的高效液相色谱分析

Monosaccharides, including glucose,xylose,galactose,arabinose and mannose,are structure units ofplant cellulose and hemicellulose, Optimal separation of them was achieved by a Bio- Rad Aminex HPX-87Pcolumn at 85℃ eluted with degassed water at 0.6mL/min. Sample pretreatment was perfOrmed with lead ac-etate or lead nitrate, and no sugar Ioss was observed.Quantitative analysis was conducted with n- pentanol asthe internal standard Or with external standard method     

Co-Fermentation of Glucose–Xylose Mixtures from Agroindustrial Residues by Ethanologenic Escherichia coli: A Study on the Lack of Carbon Catabolite Repression in Strain MS04

The production of biofuels, such as bioethanol from lignocellulosic biomass, is an important task within the sustainable energy concept. Understanding the metabolism of ethanologenic microorganisms for the consumption of sugar mixtures contained in lignocellulosic hydrolysates could allow the improvement of the fermentation process. In this study, the ethanologenic strain Escherichia coli MS04 was used to ferment hydrolysates from five different lignocellulosic agroindustrial wastes, which contained different glucose and xylose concentrations. The volumetric rates of glucose and xylose consumption and ethanol production depend on the initial concentration of glucose and xylose, concentrations of inhibitors, and the positive effect of acetate in the fermentation to ethanol. Ethanol yields above 80% and productivities up to 1.85 g_EtOH/Lh were obtained. Furthermore, in all evaluations, a simultaneous co-consumption of glucose and xylose was observed. The effect of deleting the xyIR regulator was studied, concluding that it plays an important role in the metabolism of monosaccharides and in xylose consumption. Moreover, the importance of acetate was confirmed for the ethanologenic strain, showing the positive effect of acetate on the co-consumption rates of glucose and xylose in cultivation media and hydrolysates containing sugar mixtures.     

Highly selective lipophilic diboronic acid that transports fructose as the trisdentate 2,3,6-β-d-fructofuranose ester

The transport of fructose and glucose through supported liquid membranes promoted by a tetrahedral shaped lipophilic monoboronic acid and diboronic acid, both based on a pentaerythritol core, has been studied. The diboronic acid gave a high fructose/glucose selectivity (7.7:1.0). The results of molecular modelling studies and ¹³C NMR experiments with uniformly labelled ¹³C-d-fructose suggest that the enhanced selectivity results from the formation of a trisdentate 2,3,6-β-d-fructofuranose diester within the membrane. Experimental evidence for a previously proposed macrocyclic d-fructopyranose diester formed with an o-phenylene linked diboronic acid has also been found.     

Synthesis of N-aminoglycosides of the alkaloid cytisine

A series of new N-aminoglycosides of the alkaloid cytisine based on industrially available monosaccharides D-glucose, D-galactose, D-xylose, and L-arabinose was synthesized and characterized. The optimal methods for condensing and isolating the products were found. The structures and position of cytisine in the glycosides were proved by PMR spectroscopy. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 596–597, November–December, 2008.