Weimin Mo

Ionic liquid-based ultrasonic-assisted extraction of piperine from white pepper

An ionic liquid-based ultrasonic-assisted extraction (ILUAE) method has been developed for the effective extraction of piperine from white pepper powder. A series of 1-alkyl-3-methylimidazolium ionic liquids differing in composition of alkyl chain and anion were evaluated for extraction efficiency. The results indicate that both the characteristics of anions and cations have remarkable effects on the extraction efficiency. In addition, the ILUAE procedure was also optimized on some ultrasonic parameters, such as ultrasonic power, extraction time and solid-liquid ratio. Compared with the conventional heat-reflux extraction (HRE) and regular UAE, the optimized approach gained the highest extraction efficiency (from 1.950% to 3.577%) within the shortest extraction time (from 2 h to 30 min). Furthermore, the developed method was validated by the recovery, correlation coefficient (R(2)), and reproducibility (relative standard deviation (RSD), n=3). Average recoveries of piperine were between 93.5% and 98.7% at spiking levels 0.05, 0.1 and 0.2 mg mL(-1) with RSD lower than 5%. The developed method is linear at concentrations within the tested interval, with R(2) at 0.9994.

Protein A immobilized monolithic capillary column for affinity chromatography

Abstract Monolithic capillary columns for affinity chromatography were prepared by an in situ polymerization procedure using glycidyl methacrylate (GMA) as a monomer and trimethylolpropane trimethacrylate (TRIM) and ethylene dimethacrylate (EDMA) as cross-linkers, respectively. Scanning electron microscopy was applied to characterize the morphology of the end of monolithic capillary and mercury intrusion porosimetry to characterize the polymer rod prepared within the confines of a stainless steel column with 50 mm ×4.6 xa0mm i.d. under the same polymerization condition. Obvious differences in the porous properties between the TRIM- and EDMA-based monoliths could be observed. Moreover, the mechanical stability of these two monolithic capillary columns was compared by testing the reproducibility of the column performance. The rod prepared with GMA and TRIM proved to be mechanically more stable than that prepared with GMA and EDMA. Protein A was immobilized on the monolithic rod for affinity chromatography and the experiments were performed on a capillary electrophoresis instrument, using its pressure system as the driving force. Non-specific adsorption was not observed on the TRIM-based affinity column, as proved with bovine serum albumin (BSA) as a test protein. The affinity column prepared with GMA and TRIM was then applied to determine the hIgG concentration in human serum. The correlative coefficient of the calibration curve reached 0.9942. The amount of adsorbed hIgG was unaffected by the flow rate of the loading buffer, which makes this method suitable for fast determination of biomacromolecules in microliter samples.

Ultrasound-assisted magnetic solid-phase extraction based ionic liquid-coated Fe3O4@graphene for the determination of nitrobenzene compounds in environmental water samples

An ultrasound-assisted magnetic solid-phase extraction procedure with the [C7MIM][PF6] ionic liquid-coated Fe3O4-grafted graphene nanocomposite as the magnetic adsorbent has been developed for the determination of five nitrobenzene compounds (NBs) in environmental water samples, in combination with high performance liquid chromatography-photodiode array detector (HPLC-PDA). Several significant factors that affect the extraction efficiency, such as the types of magnetic nanoparticle and ionic liquid, the volume of ionic liquid and the amount of magnetic nanoparticles, extraction time, ionic strength, and solution pH, were investigated. With the assistance of ultrasound, adsorbing nitrobenzene compounds by ionic liquid and self-aggregating ionic liquid onto the surface of the Fe3O4-grafted graphene proceeded synchronously, which made the extraction achieved the maximum within 20 min using only 144 μL [C7MIM][PF6] and 3xa0mg Fe3O4-grafted graphene. Under the optimized conditions, satisfactory linearities were obtained for all NBs with correlation coefficients larger than 0.9990. The mean recoveries at two spiked levels ranged from 80.35 to 102.77%. Attributed to the convenient magnetic separation, the Fe3O4-grafted graphene could be recycled many times. The proposed method was demonstrated to be feasible, simple, solvent-saving and easy to operate for the trace analysis of NBs in environmental water samples.

Ultrasound‐assisted magnetic SPE based on Fe3O4‐grafted graphene for the determination of polychlorinated biphenyls in water samples

An ultrasound-assisted magnetic SPE procedure with an Fe3 O4 -grafted graphene nanocomposite as the magnetic adsorbent has been developed to determine seven polychlorinated biphenyls (PCBs; PCB28, PCB52, PCB101, PCB118, PCB138, PCB153, and PCB180) simultaneously in 200 mL environmental water samples, in combination with GC-MS/MS. Several factors related to magnetic SPE efficiencies, such as the superparamagnetic intensity and amount of adsorbent, extraction time, sample pH, and desorption conditions were investigated. With the assistance of ultrasound, the extraction achieved the maximum within only 20 s, attributed to the powerful adsorptive ability of the magnetic adsorbent toward the PCBs. Under the optimized conditions, an excellent linearity was observed in the range of 0.1-100 ng/L for PCB28, 0.2-100 ng/L for PCB52, and 0.5-100 ng/L for the other five PCBs with the correlation coefficients ranging from 0.9988 to 0.9996. The mean recoveries at spiked levels of 5.0 and 10.0 ng/L were 84.9-108.5%, the coefficients of variations were <6.5%. With convenient magnetic separation, the synthesized magnetic adsorbent could be recycled more than ten times. The proposed method was demonstrated to be feasible, simple, rapid, and easy to operate for the trace analysis of the PCBs in environmental water samples.

Screening of glycoside isomers in P. scrophulariiflora using ionic liquid-based ultrasonic-assisted extraction and ultra-performance liquid chromatography/electrospray ionization quadrupole time-of-flight tandem mass spectrometry

A powerful ionic liquid-based ultrasonic-assisted extraction (ILUAE) method combined with ultra-performance liquid chromatography coupled to electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UPLC/ESI-QTOFMS(n) ) was employed in the rapid simultaneous screening of iridoid glycosides, phenylethanoid glycosides, and cucurbitacin glycosides from P. scrophulariiflora. The ILUAE procedure was optimized over several ultrasonic parameters, including the ultrasonic power, concentration of the ionic liquid, and solid-liquid ratio. A comparison with conventional heat-reflux extraction and regular UAE demonstrated that the optimized approach yielded a high extraction efficiency (Picroside I, 2.84%; Picroside II, 3.57%; 6-O-E-feruloyl catalpol, 2.20%) within a short extraction time of 30u2009min. Negative ion mode ESI-QTOFMS(2) analysis of the fragmentation reactions of the [M-H](-) ions was conducted to characterize the diagnostic ions related to the glycosyl moieties, aglycone units, and the type and substituted position of the ester groups. Interestingly, the positional isomers of the iridoid glycosides could be easily discriminated based on the characteristic ions. A total of 15 glycosides, including three groups of iridoid glycoside isomers and two groups of phenylethanoid glycoside isomers, were conveniently identified within 13.5u2009min. Moreover, 6-O-vanilloyl catalpol was identified in P. scrophulariiflora for the first time. The method developed here was further validated by measuring the recovery, correlation coefficient (R(2) ), and reproducibility (RSD, nu2009=u20095) of three iridoid glycosides: 89.60%-109.02%, 0.9991-0.9998, and 0.93%-1.44%, respectively. This study demonstrated the capabilities of ILUAE combined with UPLC/ESI-QTOFMS(n) for the rapid screening of glycosides in P. scrophulariiflora. This method offers an approach to similar studies on other natural plants.

Solid-phase extraction based on chloromethylated polystyrene magnetic nanospheres followed by gas chromatography with mass spectrometry to determine phthalate esters in beverages

An ultrasound-assisted magnetic solid-phase extraction procedure with chloromethylated polystyrene-coated Fe3 O4 nanospheres as magnetic adsorbents has been developed to determine eight phthalate esters (bis(4-methyl-2-pentyl) phthalate, dipentyl phthalate, dihexyl phthalate, benzyl butyl phthalate, bis(2-butoxyethyl) phthalate, dicyclohexyl phthalate, di-n-octyl phthalate, and dinonyl phthalate) simultaneously in beverage samples, in combination with gas chromatography coupled to tandem mass spectrometry for the first time. Several factors related to magnetic solid-phase extraction efficiencies, such as amount of adsorbent, extracting time, ionic strength, and desorption conditions were investigated. The enrichment factors of the method for the eight analytes were over 2482. A good linearity was observed in the range of 10-500 ng/L for bis(2-butoxyethyl) phthalate and 2-500 ng/L for the other phthalate esters with correlation coefficients ranging from 0.9980 to 0.9998. The limits of detection and quantification for the eight phthalate esters were in the range of 0.20-2.90 and 0.67-9.67 ng/L, respectively. The mean recoveries at three spiked levels were 75.8-117.7%, the coefficients of variations were <11.6%. The proposed method was demonstrated to be a simple and efficient technique for the trace analysis of the phthalate esters in beverage samples.

Single electron redox via an ion‐neutral complex in the fragmentation of protonated benzoylferrocenes

RATIONALEnFerrocene derivatives have become very popular molecules for biological applications. Although considerable experimental and theoretical calculation studies have demonstrated that ferrocene derivatives are easily oxidized during electrospray ionization (ESI), the details of the single electron redox reaction for protonated benzoylferrocenes in collision-induced dissociation (CID) mass spectrometry (MS) has not been obtained. Characterizing this mechanism is useful for further understanding the properties of ferrocene-containing biomaterials.nnnMETHODSnAll CID MS experiments were carried out using ESI ion trap mass spectrometry in positive ion mode. In addition, the accurate mass of fragments was measured on a ESI quadrupole time-of-flight (QTOF) mass spectrometer in positive ion mode. Theoretical calculations were carried out by the density functional theory (DFT) method with a hybrid basis set consisting of 6-31G (d) and ECP LanL2DZ in the Gaussian 03 program.nnnRESULTSnIn the fragmentation of protonated benzoylferrocenes, the characterized ferrocinium cation was observed, which was proposed from the cleavage of the bond between the ipso-carbon atom and the carbonyl carbon followed by a single electron redox in [substituted benzoyl/ferrocene] complexes. Moreover, when the complex contained an oxidant (substituted benzoyl cation) with higher electron affinity, the single electron redox reaction was more efficient. A correlation was established between the intensities of the two competitive product ions and the electron affinities of substituted benzoyl cations.nnnCONCLUSIONSnThe single electron redox reaction by the [substituted benzoyl/ferrocene] complexes was proposed by CID MS and theoretical calculations, which provided potential evidence to further understand the reversible reduction characteristics of ferrocene-containing biomaterials.

Identifying the proton transfer reaction mechanism via a proton-bound dimeric intermediate for esomeprazoles by a kinetic method combined with density functional theory calculations

RATIONALEnEsomeprazole analogs are a class of important proton pump inhibitors for the treatment of gastro-esophageal reflux diseases. Understanding the fragmentation reaction mechanism of the protonated esomeprazole analogs will facilitate the characterization of their complex metabolic fate in humans. In this paper, the kinetic method and theoretical calculations were applied to evaluate the fragmentation of protonated esomeprazole analogs.nnnMETHODSnAll collision-induced dissociation (CID) mass spectrometry experiments were carried out using electrospray ionization (ESI) ion trap mass spectrometry in positive ion mode. Also the accurate masses of fragments were measured on by ESI quadrupole time-of-flight (QTOF) MS in positive ion mode. Theoretical calculations were carried out by the density functional theory (DFT) method with the 6-31G(d) basis set in the Gaussian 03 program.nnnRESULTSnIn the fragmentation of the protonated esomeprazole analogs, C-S bond breakage is observed, which gives rise to protonated 2-(sulfinylmethylene)pyridines and protonated benzimidazoles. DFT calculations demonstrate that the nitrogen atom of the pyridine part is the thermodynamically most favorable protonation site, and the C-S bond cleavage is triggered by the transfer of this ionizing proton from the nitrogen atom of the pyridine part to the carbon atom of the benzimidazole part to which the sulfinyl is attached. Moreover, with the kinetic plot, the intensity ratios of two protonated product ions yield a linear relationship with the differences in proton affinities of the corresponding neutral molecules, which provides strong experimental evidence that the reaction proceeds via proton-bound 2-(sulfinylmethylene)pyridine/benzimidazole complex intermediates.nnnCONCLUSIONSnThe kinetic method combined with theoretical calculations was successfully applied to probe the proton transfer reaction by proton-bound 2-(sulfinylmethylene)pyridine/benzimidazole complexes in the fragmentation of protonated esomeprazole analogs by ESI CID MS, which is a strong evidence that the kinetic method can be applied in identifying a proton-bound dimeric intermediate in the fragmentation of protonated ions.

Friedel‐Crafts dealkylation reaction mediated by a stereoselective proton transfer in the fragmentation of protonated cyclic indolyl α‐amino esters

RATIONALEnChiral cyclic indolyl α-amino esters are valuable substructures of peptides and peptidomimetics. Systematically exploring the fragmentation behavior of the protonated cyclic indolyl α-amino esters by a combination of high-resolution high-energy collisional dissociation mass spectrometry, hydrogen-deuterium exchange experiments and density functional theory (DFT) calculations is useful for further understanding their intrinsic properties and the fragmentation mechanisms of peptidomimetics constructed with them.nnnMETHODSnAll high-resolution high-energy collisional dissociation tandem mass spectrometry experiments were carried out using electrospray ionization hybrid Quadrupole-Orbitrap mass spectrometry in positive ion mode. Only the labile hydrogens were exchanged with deuterium in hydrogen-deuterium exchange experiments. Theoretical calculations were carried out by the DFT method at the B3LYP level with the 6-311G(d,p) basis set in the Gaussian 03 package of programs.nnnRESULTSnIn the fragmentation of protonated cyclic indolyl α-amino esters, when the two labile hydrogens on the N(8) position are successively transferred to the C(3) and C(4) positions, a Friedel-Crafts dealkylation reaction takes place spontaneously, with concomitant formation of an ion-neutral complex of [cyclic N-sulfonyl ketimino esters/protonated indoles]. Direct separation of this complex formed the protonated indoles, while a stereoselective proton transfer between the two components in the complex gave rise to protonated cyclic N-sulfonyl ketimino esters, which coincided with the hydrogen-deuterium experiments.nnnCONCLUSIONSnUsing H/D exchange experiments combined with theoretical calculations, a Friedel-Crafts dealkylation reaction mediated by a stereoselective proton transfer in the [cyclic N-sulfonyl ketimino esters/protonated indoles] complex was proposed for the fragmentation of protonated cyclic indolyl α-amino esters in high-energy collisional dissociation tandem mass spectrometry for the first time. Copyright

Investigating acidic ionic liquid-based ultrasonic-assisted extraction of leonurine from Herba Leonuri

ABSTRACT An ultrasonic-assisted extraction (UAE) method based on the acidic ionic liquid (IL) of 1-methyl-3-H-imidazolium hydrogen sulfate ([HMIM][HSO4]) has been successfully developed to extract leonurine from Herba Leonuri. The results indicate that the acidity of the IL has remarkable effect on the extraction efficiency. In addition, several parameters affecting the extraction efficiency, such as ultrasonic power and time, concentration of IL and solid-liquid ratio, were also optimized. Using the proposed approach, the extraction efficiency of leonurine from Herba Leonuri powder reached 0.136‰ within 30 min using only 20 mL of 1 mol·L−1 [HMIM][HSO4] aqueous solution.