Shengda Qi

Solid-phase synthesis of highly fluorescent nitrogen-doped carbon dots for sensitive and selective probing ferric ions in living cells.

Carbon quantum dots (C-Dots) have drawn extensive attention in recent years due to their stable physicochemical and photochemical properties. However, the development of nitrogen-doped carbon quantum dots (N-doped C-Dots) is still on its early stage. In this paper, a facile and high-output solid-phase synthesis approach was proposed for the fabrication of N-doped, highly fluorescent carbon quantum dots. The obtained N-doped C-Dots exhibited a strong blue emission with an absolute quantum yield (QY) of up to 31%, owing to fluorescence enhancement effect of introduced N atoms into carbon dots. The strong coordination of oxygen-rich groups on N-doped C-Dots to Fe(3+) caused fluorescence quenching via nonradiative electron-transfer, leading to the quantitative detection of Fe(3+). The probe exhibited a wide linear response concentration range (0.01-500 μM) to Fe(3+) with a detection limit of 2.5 nM. Significantly, the N-doped C-Dots possess negligible cytotoxicity, excellent biocompatibility, and high photostability. All these features are favorable for label-free monitoring of Fe(3+) in complex biological samples. It was then successfully applied for the fluorescence imaging of intracellular Fe(3+). As an efficient chemosensor, the N-doped C-Dots hold great promise to broaden applications in biological systems.

In situ synthesis of MIL-100(Fe) in the capillary column for capillary electrochromatographic separation of small organic molecules.

Because of the unusual properties of the structure, the metal organic frameworks (MOFs) have received great interest in separation science. However, the most existing methods for the applications of MOFs in separation science require an off-line procedure to prepare the materials. Here, we report an in situ, layer-by-layer self-assembly approach to fabricate MIL-100(Fe) coated open tubular (OT) capillary columns for capillary electrochromatography. By a controllable manner, the OT capillary columns with a tailored MIL-100(Fe) coating have been successfully synthesized. The results of SEM, XRD, FT-IR, and ICP-AES indicated that MIL-100(Fe) was successfully grafted on the inner wall of the capillary. Some neutral, acidic and basic analytes were used to evaluate the performance of the MIL-100(Fe) coating OT capillary column. Because of the size selectivity of lattice aperture and hydrophobicity of the organic ligands, three types of analytes were well separated with this novel MIL-100(Fe) coating OT capillary column. For three consecutive runs, the intraday relative standard deviations (RSDs) of migration time and peak areas were 0.4-4.6% and 1.2-6.6%, respectively. The interday RSDs of migration time and peak areas were 0.6-8.0% and 2.2-9.5%, respectively. The column-to-column reproducibility of retention time was in range of 0.6-9.2%. Additionally, the 10 cycles OT capillary column (10-LC) could be used for more than 150 runs with no observable changes on the separation efficiency.

Sample stacking and sweeping in microemulsion electrokinetic chromatography under pH-suppressed electroosmotic flow

Two on-line sample concentration techniques, sample stacking and sweeping under pH-suppressed electroosmotic flow, were evaluated in microemulsion electrokinetic chromatography. The concept of stacking with anion selective electrokinetic injection and a water plug in a reverse-migrating microemulsion (SASIW-RMME) was brought forward in this article. Six flavonoids were concentrated using a microemulsion consisting of 80 mM sodium dodecyl sulfate, 1.2% (v/v) ethyl acetate, 0.6% (v/v) 1-butanol, 10% acetonitrile (v/v) and 50 mM phosphoric acid (pH* 1.8). Significant detector response improvements were achieved. The limits of detection were in the low ng/ml level. Finally, the sample of Fructus aurantii Immaturus was analyzed using sweeping technique.

A sensitive colorimetric method for the determination of nitrite in water supplies, meat and dairy products using ionic liquid-modified methyl red as a colour reagent

This paper describes a colorimetric approach to determine trace amounts of nitrite in water supplies, meat and dairy products using 1-butyl-3-methylimidazolium-modified methyl red ([BMIM]MR) as a colour reagent. The technique capitalises on the catalytic effect of nitrite on the oxidative degradation of [BMIM]MR by potassium bromate in acidic media. The absorbances were proportional to nitrite concentrations in the range of 8.70×10(-2) to 4.17 μM with a detection limit of 1.64×10(-2) μM. Compared with the method using methyl red as a colour reagent, 60 times improvement of sensitivity was obtained. Activation energy and the apparent rate constant for the catalytic reaction are 61.11 kJ mol(-1) and 1.18×10(4) s(-1), respectively. The proposed method was successfully applied for the analysis of nitrite in Yellow River water, chicken, and milk with recoveries ranging from 96% to 105%.

Metallic nanoparticles immobilized in magnetic metal–organic frameworks: preparation and application as highly active, magnetically isolable and reusable catalysts

Separation and recycling of catalysts after catalytic reactions are critically required to reduce the cost of catalysts as well as to avoid the generation of waste in industrial applications. In this paper, ultrafine noble metallic nanoparticles are incorporated into cauliflower-like porous magnetic metal–organic frameworks (MOFs). With the restriction effects of the pore/surface structure in the MOFs, “surfactant-free” metallic nanoparticles are successfully obtained on a 2–3 nm scale. In addition, both the thickness of MOFs shell and the content of noble metallic NPs are tunable on the MOFs coating. Moreover, the microspheres exhibit excellent performance for the catalytic reduction of p-nitrophenol with a turnover frequency of 3094 h−1. The uniform cavities in the MOFs shell provide docking sites for p-nitrophenol and act as confinement nanoreactors, which greatly improves the catalytic performance. Most importantly, the magnetically responsive microspheres can be easily recovered by a magnetic field and show excellent reusability. The as-prepared catalyst also shows good activity for the reduction of other nitrobenzenes. Consequently, this work provides a highly active, magnetically isolable, and recyclable catalyst, which can be used for various catalytic industrial processes. The fundamental model can be further employed in a variety of biomedical fields including drug delivery and biological molecules separation.

Extremely Large Volume Electrokinetic Stacking of Cationic Molecules in MEKC by EOF Modulation with Strong Acids in Sample Solutions

In this report, a novel facile way of online preconcentration of trace levels of analytes in capillary electrophoresis is presented. The proposed strategy is based on the combination of strong acidic phosphate as sample buffers with borate separation buffer containing sodium dodecyl sulfate. When injection voltage is applied, the continuous introduction of low pH sample causes the apparent bulk flow inside the capillary gradually slows down. Finally at a certain point, it reaches the same magnitude as that of the oppositely migrating anionic micelles, thus the frontier of the micelle zone becomes stagnant. This steady state can be maintained for a very long time so that essentially extremely large volume of sample solutions can be injected into the capillary, and the cationic analytes may be efficiently stacked at the neutralized micelle zone. A theoretical model was proposed and preconcentration conditions of two model analytes, matrine and oxymatrine, were optimized with the aid of the model. Under optimized conditions, more than 1000-fold increase in sensitivity was obtained as compared with the normal hydrodynamic injection without sample stacking. The limits of detection for oxymatrine and matrine were 0.81 and 0.18 ng/mL, respectively, using photodiode array UV detection at wavelength 211 nm.

Separation and determination of the anthraquinones in Xanthophytum attopvensis pierre by nonaqueous capillary electrophoresis

A nonaqueous capillary electrophoresis (NACE) method with direct on-column UV detection has been developed for the separation of the pharmaceutically important anthraquinones from the total grass of Xanthophytum attopvensis pierre extract. The separation of three main anthraquinones (1-hydroxy-2-methoxy-3-hydroxymethyl-9, 10-anthraquinone-1-O-beta-d-glucoside (1), rubiadin- 1-methylether (2) and 1-methoxy-2-formyl-3-hydroxy-9, 10-anthraquinone (3)) was optimized with respect to concentration of sodium cholate (SC) and acetic acid, addition of acetonitrile (ACN), and applied voltage. Baseline separation was obtained for the three analytes within 5min using a running buffer containing 50mM sodium cholate (SC), 1.0% acetic acid and 40% ACN in methanol. The method of NACE for the separation and determination of bioactive ingredient in traditional Chinese medicines was discussed.

Ratiometric Detection of Intracellular Lysine and pH with One-Pot Synthesized Dual Emissive Carbon Dots

Recently, the development of new fluorescent probes for the ratiometric detection of target objects inside living cells has received great attention. Normally, the preparation, modification as well as conjugation procedures of these probes are complicated. On this basis, great efforts have been paid to establish convenient method for the preparation of dual emissive nanosensor. In this work, a functional dual emissive carbon dots (dCDs) was prepared by a one-pot hydrothermal carbonization method. The dCDs exhibits two distinctive fluorescence emission peaks at 440 and 624 nm with the excitation at 380 nm. Different from the commonly reported dCDs, this probe exhibited an interesting wavelength dependent dual responsive functionality toward lysine (440 nm) and pH (624 nm), enabling the ratiometric detection of these two targets. The quantitative analysis displayed that a linear range of 0.5-260 μM with a detection limit of 94 nM toward lysine and the differentiation of pH variation from 1.5 to 5.0 could be readily realized in a ratiometric strategy, which was not reported before with other carbon dots (CDs) as the probe. Furthermore, because of the low cytotoxicity, good optical and colloidal stability, and excellent wavelength dependent sensitivity and selectivity toward lysine and pH, this probe was successfully applied to monitor the dynamic variation of lysine and pH in cellular systems, demonstrating the promising applicability for biosensing in the future.

Off-line hyphenation of molecularly imprinted magnetic nanoparticle-based extraction with large volume sample stacking capillary electrophoresis for high-sensitivity detection of trace chloro-phenols

The present work developed a sensitive and selective method for the determination of 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP) in an environmental water sample by molecularly imprinted magnetic nanoparticle (Fe3O4@MIP) based extraction coupled with capillary electrophoresis (CE). The highly selective, fast and effective sample pretreatment method with Fe3O4@MIPs can overcome the low sensitivity of the highly efficient capillary electrophoresis-ultraviolet detection method (CE-UV). In order to further improve the detection sensitivity, the analytes eluted from the Fe3O4@MIPs were analyzed by the on-line sample preconcentration large volume sample stacking (LVSS) technique with MEKC. Under optimal concentration conditions, signal enhancements of 781, 3276 and 8916-fold were achieved for 4-CP, 2,4-DCP and 2,4,6-TCP, respectively. The average recoveries of the three analytes in spiked water samples were 99.33–104.5% with a relative standard deviation (RSD) below 6.8%. The detection limits for 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol were 1.1 × 10−3, 2.13 × 10−4 and 6.68 × 10−5 μg mL−1, respectively.

Ionic Liquids as Modifiers to Improve the Separation Efficiency of Nonaqueous Capillary Electrophoresis with High Electric Field Strengths

A method of nonaqueous capillary electrophoresis based on ionic liquids was developed with a high electric field (800 V/cm). The ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate was used as modifier to improve the separation efficiency; trishydroxymethylaminomethane and sodium cholate were used as background electrolytes in methanol and acetonitrile. The ionic liquids used in this paper have the ability to assist in the separation of hydrophobic mixtures while maintaining adequate background current. They can also improve the efficiency of heat diffusion in the capillary because they demonstrate high thermal conductivity. The developed method was used to analyze kaempferol-3-O-glucoside, 7-hydroxy-8-methoxycoumarin and 8-hydroxycoumarin-7-O-glucoside in samples of Sinacalia tangutica. The obtained quantities of the three analytes in the flower of Sinacalia tangutica were 0.27, 0.18 and 0.57%, respectively. The recovery was determined with standard addition and the results were 85.1-100.4%.