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JOURNAL OF ETHNOPHARMACOLOGY · 2018 · IF 3.115

Ethanolic extract of Cordyceps cicadae exerts antitumor effect on human gastric cancer SGC-7901 cells by inducing apoptosis, cell cycle arrest and endoplasmic reticulum stress

Hongqing Xie,Xiaotong Li,Yajie Chen,Mingzi Lang,Zhangfei Shen,Liangen Shi

Ethnopharmacological relevance Cordyceps cicadae (Miq.) Massee is a traditional Chinese medicine that has been used for approximately 1600 years in China. C. cicadae , a member of the Cordyceps genus, exerts a therapeutic effect on many diseases, such as cancer. Objective This study aimed to evaluate the antineoplasmic activity of C. cicadae and to identify its molecular mechanism of cell death. Materials and methods The toxicity of the ethanolic extract of C. cicadae (EEC) against different cancer cell lines was determined through MTT assay. Human gastric cancer SGC-7901 cells were treated with EEC for 48 h. Cell morphology was examined by using an Olympus phase-contrast microscope. The cell apoptosis was quantified through Annexin V-FITC/PI staining. Cells were stained with PI and then subjected to flow cytometry for the investigation of cell cycle status. Cells were subjected to mitochondrial membrane potential (MMP) assay after incubation with JC-1 probes and to intracellular Ca 2+ measurement through flow cytometry after incubation with Fluo-3 AM fluorescent probes . Western blot analysis was conducted to quantify the expression of proteins related to apoptosis, cell cycle and endoplasmic reticulum stress. High-performance liquid chromatography (HPLC) analysis was performed to analyse the biological activity components of EEC. Results EEC suppressed the proliferation of SGC-7901 cells and induced the development of abnormal morphological features in a dose-dependent manner. Flow cytometry results indicated that EEC treatment caused cell apoptosis and arrested the cell cycle in the S phase. In addition, EEC treatment triggered MMP depolarization and Ca 2+ overloading in the cytosol of SGC-7901 cells. Western blot analysis demonstrated that EEC increased Bax, AIF, caspase-8, caspase-6 and caspase-3 activities and decreased Bcl-2 activity. The release of cytochrome c from mitochondria was associated with mitochondrial dysfunction, which was caused by the activation of the cell surface receptor Fas and the cleavage of PARP . EEC-induced S phase arrest was associated with the up-regulation of E2F1, cyclin A2 , cyclin E and p53 expression levels and the down-regulation of CDK2 expression. In addition, EEC increased the expression of endoplasmic reticulum stress-related proteins, such as calpain-1, caspase-12 and caspase-9. HPLC assay results suggested that EEC contained adenine , uridine , adenosine and N6-(2-Hydroxyethyl)-adenosine. Conclusion EEC inhibited the proliferation of SGC-7901 cells by inducing caspase-dependent apoptosis, arresting the cell cycle in the S phase and increasing endoplasmic reticulum stress. This study revealed that C. cicadae is a potential natural source of anticancer drugs .

CAS / MDL: 73-24-5 58-61-7 58-96-8
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MICROCHIMICA ACTA · 2018 ·Vol. 185 ·期 10 ·1-7 · IF 5.705

Colorimetric adenosine aptasensor based on DNA cycling amplification and salt-induced aggregation of gold nanoparticles

Kong Caiyun,Gao Linna,Chen Zhengbo

An aptamer based assay is described for the colorimetric detection of adenosine. The presence of adenosine triggers the deformation of hairpin DNA oligonucleotide (HP1) containing adenosine aptamer and then hybridizes another unlabeled hairpin DNA oligonucleotide (HP2). This leads to the formation of a double strand with a blunt 3′ terminal. After exonuclease III (Exo III)-assisted degradation, the guanine-rich strand (GRS) is released from HP2. Hence, the adenosine-HP1 complex is released to the solution where it can hybridize another HP2 and initiate many cycles of the digestion reaction with the assistance of Exo III. This leads to the generation of a large number of GRS strands after multiple cycles. The GRS stabilize the red AuNPs against aggregation in the presence of potassium ions. If, however, GRS forms a G-quadruplex, it loses its ability to protect gold nanoparticles (AuNPs) from salt-induced AuNP aggregation. Therefore, the color of the solution changes from red to blue which can be visually observed. This colorimetric assay has a 0.13 nM detection limit and a wide linear range that extends from 5 nM to 1 μM. Schematic presentation of a colorimetric aptamer biosensor for adenosine detection based on DNA cycling amplification and salt-induced aggregation of gold nanoparticles.

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JOURNAL OF CHROMATOGRAPHY A · 2018 · IF 3.716

Monolithic column with polymeric deep eutectic solvent as stationary phase for capillary electrochromatography

Rong Wang,Zhenkun Mao,Zilin Chen

A novel monolithic column based on the copolymerization of ethylene dimethacrylate and a deep eutectic solvent (DES), which composed of chlorocholine chloride and itaconic acid, was developed for capillary electrochromatography (CEC). The structure and morphology of the obtained monolithic column was characterized by Fourier transform infrared spectra and scanning electron microscopy, which showed a porous monolithic structure with good permeability. The influence of pH value and acetonitrile content on electroosmotic flow (EOF) of DES-based monolithic column was investigated. The DES-based monolithic column was used as the separation column of CEC and exhibited excellent performance for the separation of neutral compounds, phenols, toluidines, nucleosides, nucleotide bases and alkaloids. The retention mechanism might be attributed to synergistic effect of hydrophobic interaction, hydrogen bond interaction and electronic interaction. The DES-based monolithic column showed good repeatability with relative standard deviations of migration time less than 0.80%, 2.15%, 4.26% and 3.08% for intra-day, inter-day, column-to-column and batch-to-batch, respectively. Thus, organic polymer monolithic columns with DESs as functional monomers are a promising option in chromatographic separation.

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ANALYTICA CHIMICA ACTA · 2018 · IF 5.123

Tuning selectivity via electronic interaction: Preparation and systematic evaluation of serial polar-embedded aryl stationary phases bearing large polycyclic aromatic hydrocarbons

Yujie Zhang,Qiaoqi Li,Hui Zhong,Shouyong Zhou,Yijiang Zhao,Mingliang Zhang,Haifeng Han,Hongdeng Qiu

Aromatic stationary phases showing complementary selectivity to their alkyl counterparts are extremely useful for certain challenging separation tasks. Herein, a series of polar-embedded aryl stationary phases were synthesized from reactive derivatives of large polycyclic aromatic hydrocarbons (PAHs), including anthracene (three-ring, catacondensed), pyrene (four-ring, pericondensed) and triphenylene (four-ring, fully-benzenoid). These PAHs were functionalized with hydroxymethyl group (PAH-CH 2 OH), then catalytically converted to carbamates (PAH-CH 2 OC(=O)NH-R) using isocyanate , and finally covalently grafted onto silica to produce corresponding carbamate-embedded PAH stationary phases. To gain insight into the connection and difference among the attached species, the chromatographic behaviors of these new adsorbents were systematically evaluated in terms of surface coverage, hydrophobic and aromatic features, shape selectivity and charge-transfer property, using different classes of analytes, such as alkylbenzenes , PAH congeners and isomeric multi-substituted benzenes, and the results were further compared with conventional octadecyl ones (C18). The relationships between the shape selectivity and the surface chemistry revealed unique behavioral patterns of theses immobilized conjugated ligands, as well as marked differences amongst them, which formed sharp contrast to the case of C18. The effects of temperature and mobile phase compositions on the shape selectivity were further studied. The charge-transfer characteristics demonstrated the great potential of such polar-embedded PAH materials for highly selective separation of electron-deficient compounds through electron donor-acceptor complexation.

CAS / MDL: 58-61-7 723-46-6
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CHINESE JOURNAL OF ANALYTICAL CHEMISTRY · 2018 · IF 0.824

Preparation of Cyclodextrin Type Stationary Phase Based on Graphene Oxide and Its Application in Enantioseparation and Hydrophilic Interaction Chromatography

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 CHROMATOGRAPHY A · 2014 · IF 4.258

Influence of the crosslinker type on the chromatographic properties of hydrophilic sulfoalkylbetaine-type monolithic columns

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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RSC Advances · 2015 ·Vol. 5 ·期 110 ·90457-90465 · IF 3.84

High performance SERS active substrates fabricated by directly growing graphene on Ag nanoparticles

Shicai Xu,Jihua Wang,Yan Zou,Hanping Liu,Guiying Wang,Xiumei Zhang,Shouzhen Jiang,Zhen Li,Dongyan Cao,Rongxia Tang

An efficient surface enhanced Raman scattering (SERS) substrate of graphene-isolated Ag nanoparticle (G/AgNP) has been developed by using excimer laser to ablate the ordered pyrolytic graphite in high vacuum onto Ag nanoparticles. By combining the electromagnetic activity of AgNPs and unique physical/chemical properties of graphene, the G/AgNP substrates shows high performance in terms of sensitivity, signal-to-noise ratio and reproducibility. The average enhancement factor obtained from the G/AgNP substrates for rhodamine 6G probe molecules is over 108. The maximum deviations of SERS intensities from 20 positions of a same SERS substrate are in the range of 4.20% to 6.75% and from 20 different substrates in various batches are in the range of 4.43% to 7.71%, depending on different vibration modes. As a practical application of this SERS system, we detect the adenosine concentration in human serum. The detection results show a good linear correlation between SERS intensity and adenosine concentration within the range of 2 to 200 nM. This work may open up new opportunities in developing the applications of SERS in biomedical diagnostics, biological sensing and other biotechnology.

CAS / MDL: 58-61-7 989-38-8
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TALANTA · 2014 · IF 3.511

Click N-benzyl iminodiacetic acid: Novel silica-based tridentate zwitterionic stationary phase for hydrophilic interaction liquid chromatography

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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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2015 ·Vol. 407 ·期 12 ·3525-3529 · IF 3.436

Synthesis of boronic-acid-functionalized magnetic attapulgite for selective enrichment of nucleosides

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

Ultrasensitive and universal fluorescent aptasensor for the detection of biomolecules (ATP, adenosine and thrombin) based on DNA/Ag nanoclusters fluorescence light-up system

Ying Zhu,Xiao-chun Hu,Shuo Shi,Ru-ru Gao,Hai-liang Huang,Yan-yan Zhu,Xiao-yan Lv,Tian-ming Yao

We report here an ultrasensitive strategy based on the recognition-induced conformational alteration of aptamer and fluorescence turn-on abilities of guanine-rich (G-rich) DNA sequence in proximity to silver nanoclusters for adenosine triphosphate (ATP), adenosine (A) and thrombin (TB) detection. Herein, we designed two tailored DNA sequences noted as complementary DNA (abbreviated as c-DNA) and signal probe DNA (abbreviated as s-DNA), respectively. c-DNA is designed as a special structure consisting of a sequence complementary to aptamer at the 3′-end and a guanine-rich DNA sequence at the 5′-end; s-DNA contains a cytosine-rich sequence responsible for Ag NCs templated synthesis at the 3′-end and a link sequence (part of aptamer) complementary to partial of the c-DNA at the 5′-end. In the presence of target, the aptamer associated with the target, resulting in the formation of duplex DNA (dsDNA), the DNA–Ag NCs thereafter could close to the guanine-rich sequence, leading to enhanced fluorescence signal readout. The widespread application of the sensing system is achieved success in the detection of three biomolecules . ATP, adenosine and thrombin in the range of 0.5-8.0   μM, 0.5-7.0   μM and 50-900   nM could be linearly detected with the detection limits of 91.6   nM, 103.4   nM and 8.4   nM, respectively. This label-free and turn-on fluorescent sensing system employing the mechanism proposed here turns out to be sensitive, selective, and convenient for the detection of biomolecules without washing and separation steps.

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RSC Advances · 2015 ·Vol. 5 ·期 128 ·106161-106170 · IF 3.84

Fabrication of a dendrimer-modified boronate affinity material for online selective enrichment of cis-diol-containing compounds and its application in determination of nucleosides in urine

Li Gao,Jin Du,Chaozhan Wang,Yinmao Wei

Boronate adsorbents have been widely used in the extraction of cis-diol-containing molecules, but most do not have efficient capacity due to limited binding sites on their surface. In this work, a high binding capacity dendrimer-modified boronate affinity material (SiO2@dBA) was synthesized via introducing tris(2-aminoethyl)amine as branching points and using poly(amidoamine) as the main dendrimeric scaffold before modification by boronate groups. The high density of amino groups on the dendrimer supplied a large number of binding sites for modifying boronate groups. Thus the adsorption capacity (676.8 μmol g−1 for catechol, 771.3 μmol g−1 for dopamine, 770.0 μmol g−1 for adrenaline) of SiO2@dBA was greatly improved. Moreover, when coupled with large-volume injection and online column-switching solid phase extraction, SiO2@dBA was able to capture cis-diols from 10 000-fold interference and enrichment factors reached up to 497–514, which was 26- to 51-fold higher than those of analogous non-dendrimer materials. Especially, the proposed method exhibited a striking low limit of detection, 0.24 ng mL−1 for cytidine, 0.52 ng mL−1 for uridine, 0.37 ng mL−1 for guanosine, 0.67 ng mL−1 for adenosine. Finally, the method was successfully applied to online determination of trace nucleosides in healthy human urine. In conclusion, the prepared adsorbent has potential to effectively enrich a large range of trace cis-diol substances in real samples.

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ANALYTICA CHIMICA ACTA · 2015 · IF 4.513

The preparation of high-capacity boronate affinity adsorbents by surface initiated reversible addition fragmentation chain transfer polymerization for the enrichment of ribonucleosides in serum

Chaozhan Wang,Huanhuan Xu,Yinmao Wei

Boronate affinity adsorption is uniquely selective for cis-diol-containing molecules. The preparation and application of boronate affinity materials has attracted much attention in recent years. In this work, a high-capacity boronate affinity adsorbent was prepared by surface-initiated reversible addition–fragmentation chain transfer polymerization (SI-RAFT). Commercial aminated poly(glycidyl methacrylate) (PGMA) microspheres were modified with the chain transfer agent (CTA) S-1-dodecyl-S-(α,α-dimethyl-α-acetic acid)trithiocarbonate (DDATC). Boronate-affinity adsorbents were then prepared via SI-RAFT polymerization employing 3-acrylamidophenylboronic acid (AAPBA) as the monomer . The Fourier transform infrared spectroscopy (FT-IR), nitrogen adsorption and desorption measurements have proven the successful grafting of AAPBA on PGMA microspheres surface. The boronate affinity adsorbents thus prepared possess much higher adsorption capacity (99.2 µmol/g of adenosine) and both faster adsorption and desorption speed towards ribonucleosides , the adsorption and desorption could be completed in 2 min. The high selectivity of the adsorbents to ribonucleosides was verified in the presence of a large excess of deoxynucleosides. The boronate affinity adsorbents were then employed for sample pretreatment before HPLC analysis of ribonucleosides in serum. The ribonucleosides were effectively enriched by boronate affinity dispersive solid-phase extraction (BA-DSPE), with high mass recoveries and good precision. The simultaneous determination of uridine and guanosine in calf serum was achieved by utilizing the standard addition method, their contents were determined to be 170 ± 11.6 ng/mL and 39.6 ± 4.4 ng/mL respectively. The results proved that the prepared boronate affinity materials could be applied for sample pretreatment of cis-diol containing molecules in biological samples.

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