MOLECULES
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2019
·Vol. 24
·期 12
·2266
·
IF 3.06
Xueying Liu,Xiaoku Ran,Muhammad Riaz,Haixue Kuang,Deqiang Dou,Decheng Cai
The major objective of this study was to investigate the anti-chronic nonbacterial prostatitis (CNP) mechanism ofT. patulaby metabolomics and network pharmacology. The study demonstrated that the flavonoids and polysaccharides ofT. patulacould alleviate prostatitis by improving the level of DHT, reducing the secretion of PSA and TNF-α. Besides, both could enhance Na+/K+-ATPase activity, decrease the O2consumption, CO2production, heat production, energy expenditure of rats and promote respiratory exchange ratio of rats. Up to 28 potential biomarkers and 8 key metabolic pathways related to the treatment of CNP were elucidated by the metabolomics analysis, including phenylalanine metabolism, taurine and hypotaurine metabolism, tryptophan metabolism etc. Network pharmacology prediction also reflected the potential mechanism was associated with tryptophan metabolism and energy pathway. Generally, the potential anti-CNP mechanism of flavonoids and polysaccharides ofT. patulamight be through reducing the expression of inflammation factors, adjusting the level of hormone and regulating the amino acid metabolism, energy metabolism and glucose and lipid metabolism.Keywords:Tagetes patulaL.;chronic nonbacterial prostatitis;metabolomics;energy metabolism;network pharmacology
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JOURNAL OF SEPARATION SCIENCE
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2019
·Vol. 42
·期 15
·2523-2533
·
IF 2.516
Yuan Yuan,Min Jiang,Hongyang Zhang,Ju Liu,Min Zhang,Ping Hu
We present an ultra high performance liquid chromatography with ultraviolet spectroscopy and quadrupole time-of-flight mass spectrometry method for the simultaneous quantification of ten purines (adenine, hypoxanthine, guanine, xanthine, deoxyadenosine, adenosine, inosine, guanosine, xanthosine, and uric acid) and creatinine in human urine. After chromatographic separation on an ACE Excel 2 AQ column, high abundant creatinine and uric acid and the other low abundant purines were sequentially detected by ultraviolet and quadrupole time-of-flight mass spectrometry within a single run. Method validations including specificity (improved by accurate mass measurement), linearity (correlation coefficients ≥0.9944), limit of quantification (0.002–9.756 µg/mL), intra- and interday precision (relative standard deviations ≤9.1 and 14.0%, respectively), accuracy (relative errors ≤13.1%), extraction recovery (between 90.3 and 109.6%), matrix effect (between 85.3 and 110.5%), and stability (relative errors ≤14.3%) were fully evaluated. This approach was applied to characterize the disordered purine metabolism in acute and chronic gout as an example. Quantitative results (normalized by creatinine) showed that an overproduction of urinary purine precursors might be involved in the gout process. The developed method represents a useful tool to investigate the purine disturbances in gout and other relevant diseases.
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RAPID COMMUNICATIONS IN MASS SPECTROMETRY
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2019
·Vol. 33
·期 22
·1739-1750
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IF 2.045
Yeming Shen,Peilu Zhai,Pengxuan Xi,Chen Chen,Fangjing Mou,Fuxin Li,Jianye Zhang
Rationale Adenosine can induce various physiopathological effects and has been adopted as a drug to treat certain forms of supraventricular tachycardia. Adenosine is predominantly produced via fermentation that may generate many other bioactive compounds with similar structures at trace levels. Thus, it is necessary to identify these trace structurally related impurities. A new method using ultra-high-performance liquid chromatography (UHPLC) coupled with quadrupole time-of-flight tandem mass spectrometry (QTOF-MS/MS) is proposed to separate complex components at trace amounts; to obtain accurate mass measurements providing the elemental composition of unknown compounds; and MS/MS spectra for elucidation of structures. Methods A UHPLC/QTOF-MS method was developed to separate and detect trace related impurities with structures similar to adenosine in formation samples. MS and MS/MS spectra of the impurities detected in real samples were acquired and used to propose their structures. Available reference standards were used to confirm the identification of some of the impurities detected. Results Nine trace impurities of adenosine were separated and characterized. Of these nine, five were confirmed as 5'-adenylic acid, hypoxanthine, inosine, adenine, and 2'-deoxyadenosine by comparison with their available reference standards. The remaining four were proposed to be ADP-ribose, two S-epimers of 5'-deoxy-5'-methylsulfinyl adenosine, and 3'-α-glucosyl adenosine based on their MS and MS/MS spectra, and available literature. Additionally, the MS/MS fingerprints of the monosaccharide glycosyl groups were discovered and discussed. Conclusions A UHPLC/QTOF-MS method was established and used for the separation and characterization of nine trace related impurities of adenosine. Their structures were identified based on the MS and MS/MS spectra and retention times. In addition, the specific MS/MS fingerprints of the monosaccharide glycosyl moieties of the adenosine impurity analogs were summarized.
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MICROCHIMICA ACTA
·
2018
·Vol. 185
·期 7
·1-6
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IF 5.705
Cheng Ting,Jiao Zhijuan,Liu Xiaoyan,Zhang Haixia
A hybrid material was prepared from graphene oxide and melamine sponge, and modified with phenylboronic acid to obtain a sorbent for the enrichment of the nucleosides cytidine, uridine, inosine, guanosine and adenosine. The loading capacity typically is around 27.8 mg g −1 which is comparable to other sorbents, and highly selectivity for cis-diols is observed even if the concentration of potential interferents is 1500-fold higher. The sorbent was placed in an injector, and the process was operated semiautomatically by using a peristaltic pump. The sorbent is stable and can be re-used six times without decrease in efficiency. It was applied to the selective extraction of the cis -diols (cytidine, uridine, inosine, guanosine, adenosine) from HepG2 cells. It presents good linear between 3 to 5000 μg L −1 and the limits of detection (in HPLC analysis with UV detection) are 1–4 μg L −1 . Good recoveries of 85–101% were obtained with spiked HepG2 cells samples, with relative standard deviation of ≤9.9%.
Schematic for the preparation of boronic acid modified graphene oxide/melamine sponge composite for in-syringe solid-phase extraction of nucleosides.
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JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS
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2018
·
IF 2.831
Mengzhe Guo,Dantong Liu,Qian Sha,Houfa Geng,Jun Liang,Daoquan Tang
The epigenetic modification of DNA or RNA may have relationship with the development of diabetic nephropathy (DN). We designed to develop a liquid chromatography mass spectrometry (LC–MS) coupled with mobile phase additive sensitization method for the analysis of the dissociative epigenetic modified nucleosides in serum of patients from different periods of DN with the health comparison. Serum samples were collected from 43 healthy volunteers and 156 patients, which divided into four groups. A succinic acid enhanced LC–MS/MS strategy was developed for the quantitative analysis of seven nucleosides in serum samples. The signal intensity of seven nucleosides increased three to seven times, respectively. A series of statistical analysis were carried out to demonstrate the dynamic changes of modified nucleosides in four groups. This method showed good specific, accuracy, and stability. The results were calibrated and presented through the formation of m 6 A/C, I/C, 5-mdC/C, 5-mC/C, pseU/U to eliminate the individual and age differences. The m 6 A/C, I/C, and pseU/U were found having the dynamic changes in four groups ( p < 0.05). And these five modified nucleosides can also used as one parameter to distinguish these four groups by ROC and LDA analysis. Additionally, they were found to be connected with several clinical biochemical indexes through multiple linear regression analysis. Our LC–MS/MS method assay successfully quantifies the modified nucleosides in serum. And three modified nucleosides can act as the potential biomarkers to describe the development of DN and help to evaluate the diagnosis, treatment, and prognosis of DN in clinical.
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CHINESE JOURNAL OF ANALYTICAL CHEMISTRY
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2018
·
IF 0.824
Qiang LI,Yuan-Yuan LI,Nan ZHU,Zhu-Xian GAO,Tian-Jun LI,Tong ZHOU,Yu-Long MA
Graphene oxide (GO) was covalently coupled to the surface of amino silica gel by amide bond. β -cyclodextrin ( β -CD) was further chemically bonded with GO to prepare a novel chiral stationary phase. The resulting material was characterized by Fourier transform-infrared (FT-IR) spectra, scanning electron microscopy (SEM), transmission electron microscopy (TEM), elemental analysis and thermogravimetric analysis (TGA). The separation of seven enantiomers was improved in varying degrees. Meanwhile, the stationary phase showed typical characteristics of hydrophilic interaction chromatography (HILIC), and four small nucleoside molecules were separated with the mobile phase of methanol-acetonitrile-water (45:45:10, V/V ) in the HILIC mode. In addition, the separation mechanism of the stationary phase was further explored by studying the effects of mobile phase composition, temperature and pH value on the analyte retention. The low temperature was conducive to the separation of analytes at 20–60 °C. The addition of protonated solvent methanol significantly decreased the retention time of the four analytes. The change of pH affected the degree of protonation of the analyte, the interaction between analytes and the stationary phase, and retention time of analytes. The results showed that GO and β -CD played a synergistic effect in the chiral resolution of the chromatographic stationary phase. The retention of analytes in HILIC was attributed to their mixed-mode retention mechanisms including hydrophilic interaction, electrostatic interaction, hydrogen bonding, π-π stacking and so on.
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JOURNAL OF CHEMICAL THERMODYNAMICS
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2013
·
IF 2.297
Jun Jing,Zhiyong Li,Yuanchao Pei,Huiyong Wang,Jianji Wang
In this work, a series of novel room temperature ionic liquids (ILs) have been synthesized with cheap, naturally α-amino acid ester as cations and bis(trifluoromethylsulfonyl)imide as anion. The glass transition temperature and thermal decomposition temperature of these ILs, partition coefficients of some coumarins and purine alkaloids between water and the amino acid ester-based ILs at T = 298.15 K, and Gibbs energy, enthalpy and entropy changes for the transfer of caffeine and 6,7-dihydroxycoumarin from water to [LeuC 2 ][Tf 2 N] have been determined. It is shown that these ILs are highly effective materials for the extraction of drug compounds like coumarin, 4-hydroxycoumarin, 7-hydroxycoumarin, 3-aminocoumarin, coumarin-3-carboxylic acid, 6,7-dihydroxycoumarin, 6,7-dihydroxy-4-methylcoumarin, caffeine, theobromine, theophylline, inosine, and 2,6-diaminopurine. The partition process is driven by enthalpy term, and partition coefficients of the drug molecules increase with the increase of hydrophobicity of both the drug molecules and the ILs. Furthermore, the possible partition mechanism has been investigated from 13 C NMR measurements.
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JOURNAL OF CHROMATOGRAPHY A
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2014
·
IF 4.258
Chusheng Liu,Weijia Chen,Guangxin Yuan,Yao Xiao,Jacques Crommen,Shihai Xu,Zhengjin Jiang
In order to investigate the effects of the crosslinker on the separation performance of polar zwitterionic sulfoalkylbetaine-type monolithic columns, three crosslinkers, i.e. 1,4-bis(acryloyl)piperazine (PDA), ethylene dimethacrylate (EDMA) and N , N ′-methylenebisacrylamide (MBA), were copolymerized with the hydrophilic monomer N , N -dimethyl- N -acryloyloxyethyl- N -(3-sulfopropyl)ammonium betaine (SPDA). The chromatographic properties of the three hydrophilic sulfoalkylbetaine-type monolithic columns, including column efficiency, permeability, porosity and separation mechanism, were systematically compared using scanning electron microscopy or micro-HPLC. Good selectivity in micro-HPLC separations was achieved on all three monolithic columns. The results indicate that the polarity of sulfoalkylbetaine-type monolithic columns may be related to the polarity of the crosslinker, which further affects column selectivity and efficiency. A particularly high column efficiency (100,000 plates/m) was obtained on the novel poly(SPDA- co -PDA) monolithic column at a linear velocity of 1 mm/s using thiourea as test analyte. A higher resolution was also observed for nucleobases, nucleosides and hydrophilic organic acids on this novel poly(SPDA- co -PDA) monolithic column compared to the other two columns.
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TALANTA
·
2014
·
IF 3.511
Wei Yin,Huihui Chai,Renhua Liu,Changhu Chu,John A. Palasota,Xiaohui Cai
Iminodiacetic acid (IDA) is dicarboxylic acid amine, which may produce stronger interaction with polar or charged compounds than bidentate α,β-amino acid. In this article, a novel type of tridentate zwitterionic HILIC stationary phase was prepared by covalently bonding N-benzyl IDA on silica gel via copper( I ) catalyzed Huisgen azide-alkyne 1,3-dipolar cycloaddition (CuAAC). The structure of this stationary phase and all related intermediates was confirmed by NMR, FT-IR, MS spectrum and elemental analysis . The new stationary phase showed good HILIC characteristics and high column efficiency (the theoretical plate number is up to 44000 plates m −1 in the case of guanosine) in the application of separation of polar compounds, including organic acids , organic bases, as well as highly polar and hydrophilic compounds, such as cephalosporins and carbapenems . Most of them displayed good peak shape and selectivity.
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MICROCHIMICA ACTA
·
2014
·Vol. 182
·期 3
·547-555
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IF 3.719
Liu Jinshui,Liu Guoning,Zang Lingjie,Liu Wenxiu
Calcein was first covalently grafted onto the surface of magnetic silica nanoparticles to obtain a novel fluorescent nanoprobe for sensitive and selective determination of Cu(II) ion. The nanoparticles were synthesized in a two-step reaction under mild conditions and characterized using small-angle X-ray scattering, Fourier transform infrared spectroscopy, transmission electron microscopy, and thermogravimetric analysis. The nanoprobe also displays good selectivity over other metal ions and is highly stable under conditions of high ionic strength. The response to Cu(II) ranges from 80 nM to 1.25 μM. The detection limit (LOD) is 43 nM which is lower than previously reported LODs. The probe can be regenerated by adding the complexing agent EDTA and also can be separated from a sample mixture by applying a magnetic field. We conclude that this method represents a new and convenient approach to the development of magnetic and reusable optical probes.
Calcein was first covalently grafted onto the surface of magnetic silica nanoparticles to obtain a novel fluorescent nanoprobe for sensitive and selective determination of Cu(II) ion. The nanoprobe displays good selectivity over other metal ions and is highly stable under conditions of high ionic strength.
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY
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2015
·Vol. 407
·期 12
·3525-3529
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IF 3.436
Cheng Ting,Li Huihui,Ma Ying,Liu Xiaoyan,Zhang Haixia
2,4-Difluoro-3-formyl-phenylboronic acid (DFFPBA)-modified magnetic attapulgite (ATP-Fe 3 O 4 -NH 2 -DFFPBA) was synthesized and employed to capture and enrich cis -diol-containing biomolecules. The resulting material exhibited a high saturation magnetization value of 20.71 emu/g, allowing the absorbent to be conveniently magnetically separated. Combining the Fe 3 O 4 nanoparticles with the high specific surface area of attapulgite yielded a material with a high capture capacity (13.78 mg/g) for adenosine. Furthermore, ATP-Fe 3 O 4 -NH 2 -DFFPBA was found to possess remarkable selectivity for adenosine at a low molar ratio of adenosine/2-deoxyadenosine (1:500). The potential applications of this material were explored by using it to extract five nucleosides from urine samples, and the results demonstrate that it can decrease matrix interference and selectively enrich analytes.
Boronic-acid-functionalized magnetic attapulgite could selectively enrich the nucleosides in urine samples with the help of an external magnet
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BIOSENSORS & BIOELECTRONICS
·
2015
·
IF 6.409
Xiao-Jing Xing,Wan-Lu Xiao,Xue-Guo Liu,Ying Zhou,Dai-Wen Pang,Hong-Wu Tang
We developed a fluorescent aptasensor based on the making use of double-stranded DNA (dsDNA)/graphene oxide (GO) as the signal probe and the activities of exonuclease I (Exo I). This method takes advantage of the stronger affinity of the aptamer to its target rather than to its complementary sequence (competitor), and the different interaction intensity of dsDNA, mononucleotides with GO. Specifically, in the absence of target, the competitor hybridizes with the aptamer, preventing the digestion of the competitor by Exo I, and thus the formed dsDNA is adsorbed on GO surface, allowing fluorescence quenching . When the target is introduced, the aptamer preferentially binds with its target. Thereby, the corresponding nuclease reaction takes place, and slight fluorescence change is obtained after the introduction of GO due to the weak affinity of the generated mononucleotides to GO. Adenosine (AD) was chosen as a model system and tested in detail. Under the optimized conditions, smaller dissociation constant ( K d , 311.0 µM) and lower detection limit (LOD, 3.1 µM) were obtained in contrast with traditional dye-labeled aptamer/GO based platform ( K d =688.8 µM, LOD=21.2 µM). Satisfying results were still obtained in the evaluation of the specificity and the detection of AD in human serum, making it a promising tool for the diagnosis of AD-relevant diseases. Moreover, we demonstrated the effect of the competitor on the LOD, and the results reveal that the sensitivity could be enhanced by using the rational competitor. The present design not only constructs a label-free aptamer based platform but also extends the application of dsDNA/GO complex in biochemical and biomedical studies.
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