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NEW JOURNAL OF CHEMISTRY · 2020 ·Vol. 44 ·期 27 ·11704-11709 · IF 3.288

The preparation of a core–shell stationary phase by the in situ polymerization of a hydrophilic polymer on the surface of silica and its chromatographic performance

Chao Fan,Hao Tang,Licheng Wang,Yijing Li,Xusheng Wang,Shuai Wang,Xiaojing Liang

Using N-isopropylacrylamide (NIPAM) as a monomer, a core–shell material was successfully prepared via in situ polymerization on the surface of silica microspheres (named NIPAM@Sil), which acts as a hydrophilic interaction chromatography (HILIC) stationary phase. A method for the in situ polymerization of polymer monomers on a silica surface has been developed. It was shown using scanning electron microscopy (SEM) that NIPAM is evenly distributed on the surface of the silica. The synthesized NIPAM@Sil possesses a polar acylamino group arising from the polymerization of NIPAM. As demonstrated by the hydrophilicity, NIPAM@Sil showed excellent HILIC performance for the separation of hydrophilic compounds. This method provides a simple approach for the preparation of a polymer coated silica core–shell stationary phase.

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JOURNAL OF CHROMATOGRAPHY A · 2021 · IF 4.759

N-Vinyl pyrrolidone and undecylenic acid copolymerized on silica surface as mixed-mode stationary phases for reversed-phase and hydrophilic interaction chromatography

Chao Fan,Bei Liu,Hui Li,Kaijun Quan,Jia Chen,Hongdeng Qiu

In this work, three new mixed-mode stationary phases were prepared, based on different ratio of N-vinyl pyrrolidone (NVP) copolymerized together with undecylenic acid (UA) on silica microspheres surface without silanization, which named Sil@NVPUA series. The combination of NVP and UA rendered the Sil@NVPUA suitable for reversed-phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC), and shown excellent methyl, planar, isomers and ion selectivity. Five types of model analytes including eight polycyclic aromatic hydrocarbons, six alkylbenzenes, eight nucleosides and nucleobases, seven ginsenosides and five oxazolidinones can be well separated on this stationary phase. The preparation method of NVP and UA modified silica-based stationary phase is simple, and it also provides a new idea for the design of synthetic polymers to develop mixed-mode chromatography.

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MICROCHIMICA ACTA · 2019 ·Vol. 186 ·期 12 ·1-8 · IF 5.479

Cetyltrimethyl ammonium mediated enhancement of the red emission of carbon dots and an advanced method for fluorometric determination of iron(III)

Li Te,Xie Lianwu,Long Ruiqing,Tong Chaoying,Guo Ying,Tong Xia,Shi Shuyun,Lin Qinlu

Red-emissive carbon dots (CDs) were synthesized by one-step hydrothermal technique using citric acid (CA), and urea in N , N -dimethylformamide (DMF) solution. The CDs has an average diameter of 2.3 nm, excitation/emission maxima at 553/606 nm, and a low photoluminescence quantum yield (4%). Fluorescence is weakly quenched by the ions Fe 3+ , Hg 2+ , Cu 2+ , Co 2+ , Zn 2+ , Ca 2+ , Ni 2+ , and Pb 2+ . After addition of cetyltrimethyl ammonium ion (CTAB), electrostatic interaction between negatively charged CDs and CTAB causes the CDs to self-aggregate. The formation of CD/CTAB increases the average particle diameter to around 13 nm and enhances the quantum yield to 24%. The hydrophobic segments of CTAB twined into a network structure can selectively trap Fe 3+ and then interact with surface groups of the CDs to cause quenching. The CD/CTAB nanoprobe enables fluorometric determination of Fe 3+ with a linear response in the 0.10–10 μM concentration range and a 0.03 μM limit of detection. The probe was utilized for determination of Fe 3+ in human serum samples, and satisfactory results were obtained. Schematic representation of fluorometric analysis of Fe(III) ion by cetyltrimethyl ammonium ion (CTAB) mediated red emission carbon dots (CDs). The hydrophobic segments of CTAB twined into a network structure can selectively trap Fe(III) and then interact with surface groups of the CDs to cause quenching.

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MOLECULES · 2019 ·Vol. 24 ·期 22 ·4119 · IF 3.06

A Nucleoside/Nucleobase-Rich Extract from Cordyceps Sinensis Inhibits the Epithelial–Mesenchymal Transition and Protects against Renal Fibrosis in Diabetic Nephropathy

Zhonghua Dong,Yueyue Sun,Guangwei Wei,Siying Li,Zhongxi Zhao

Cordyceps Sinensis, a traditional Chinese medicine and a healthy food, has been used for the treatment of kidney disease for a long time. The aim of present study was to isolate a nucleoside/nucleobase-rich extract fromCordyceps Sinensis(CS-N), determine the contents of nucleosides and nucleobases, and explore its anti-diabetic nephropathy activity. CS-N was isolated and purified by using microporous resin and glucan columns and the unknown compounds were identified by using HPLC-DAD and LC-MS. The effects of CS-N on the epithelial–mesenchymal transition (EMT), extracellular matrix (ECM) depositions, and the MAPK signaling pathway were evaluated in streptozotocin (STZ)-induced diabetic mice and high glucose (HG)-exposed HK-2 cells. CS-N significantly attenuated the abnormity of renal functional parameters, ameliorated histopathological changes, and inhibited EMT and ECM accumulation by regulating p38/ERK signaling pathways. Our findings indicate that CS-N exerts a therapeutic effect on experimental diabetic renal fibrosis by mitigating the EMT and the subsequent ECM deposition with inhibition of p38 and ERK signaling pathways.Keywords:nucleosides and nucleobases;diabetic nephropathy;HK-2 cells;extracellular matrix;epithelial–mesenchymal transition

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ANALYTICA CHIMICA ACTA · 2019 · IF 5.256

Fabrication and application of zwitterionic phosphorylcholine functionalized monoliths with different hydrophilic crosslinkers in hydrophilic interaction chromatography

Qiqin Wang,Qiaoxuan Zhang,Hao Huang,Pengwei Zhao,Lingjue Sun,Kun Peng,Xiao Liu,Meng Ruan,Huikai Shao,Jacques Crommen,Pei Yu,Zhengjin Jiang

In this study, a series of zwitterionic phosphorylcholine functionalized monolithic columns were fabricated via the thermally initiated co-polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) and different hydrophilic crosslinkers, including 1,4-bis(acryloyl)piperazine (PDA), N,N′-methylenebisacrylamide (MBA) and 2-(methacryloyloxy)ethyl-[N-(2-methacryloyloxy)ethyl]phosphorylcholine (MMPC). The physicochemical and chromatographic properties of these MPC functionalized monoliths, including column morphology, pore size distribution , permeability, column efficiency, retention mechanism and ζ-potential analysis, were systematically compared. Furthermore, the influence of the crosslinker on the chromatographic performance of these MPC functionalized monoliths was evaluated. The chromatographic results indicate that the polarity of MPC functionalized monoliths may be related to the polarity of the crosslinker, which further affects the column selectivity and efficiency. A particularly high column efficiency (88,000 plates/m) was obtained on the novel poly(MPC- co -MMPC) monolith at optimum linear velocity using thiourea as test analyte. Compared to the poly(MPC- co -MBA) and poly(MPC- co -PDA) monoliths, the poly(MPC- co -MMPC) monolith exhibited higher separation selectivity for polar analytes, including nucleobases , nucleosides and benzoic acid derivatives. Moreover, 24  N -glycopeptides could be detected after enrichment with the poly(MPC- co -MMPC) versus 19 and 10  N -glycopeptides with the poly(MPC- co -MBA) and poly(MPC- co -PDA) monoliths, and no N -glycopeptide without enrichment. Therefore, MMPC has a great potential as a new and alternative hydrophilic crosslinker for the development of zwitterionic polymeric monoliths.

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ANALYTICA CHIMICA ACTA · 2019 · IF 5.256

Reshaping of pipette tip: A facile and practical strategy for sorbent packing-free solid phase extraction

Shuangshou Wang,Zhendong He,Wenzhi Li,Jiayi Zhao,Tong Chen,Shimin Shao,Hongmei Chen

Pipette tip-based solid phase extraction (PT-SPE) has been proved to be an effective and user-friendly separation technique due to its miniaturized procedure and practical convenience. However, the vast majority of existing PT-SPE devices consist of a filter-sorbents-filter sandwich structure, which may suffer the unforeseen risk of sorbents leakage caused by the looseness of filters. More importantly, many high-capacity nanosorbents with particle size smaller than pore size of filters are unavailable. Thus, sorbent packing-free and sample low-consumption PT-SPE could be a more robust strategy for separation and detection, but such a possibility has not been explored yet. Herein we report a tubing reshaping strategy for facile fabrication of sorbent packing-free PT-SPE devices. Three types of reshaped PTs, namely stretched tube-like, self-crimping and filter in-built PTs, were fabricated via simple heating and stretching operations. The reshaped PTs exhibited flexible surface chemical post-modification. The SPE process was directly performed in reshaped PTs with an obviously enhanced extraction efficiency compared to once-shaping PTs while no need of packing sorbents. Extraction of nucleosides from human urine by boronic acid-functionalized reshaped PTs was demonstrated. Our findings technically renovate the structural composition of PT-SPE devices. As PTs are inexpensive and high-plasticity, the sorbent packing-free SPE scheme presented herein could find more promising applications and provides a new perspective for design and fabrication of novel sorbent packing-free SPE devices.

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CHEMICAL ENGINEERING SCIENCE · 2019 · IF 3.372

On the kinetics of catalytic hydrogenation over Pd nanoparticles regulated by various nucleosides

Tengda Wang,Jianxing Shan,Li Wang,Xiangwen Zhang,Guozhu Li

Aqueous-phase hydrogenation of 4-nitrophenol (4-NIP) by H 2 has been investigated in the presence of Pd nanoparticles (NPs) regulated by small biological molecules. Nucleosides and their derivatives were employed as capping agents of Pd NPs, and their effect on Pd activity was evaluated. All four kinds of nucleosides exhibited obvious promoting effect on the activity of Pd NPs in comparison to that without any capping agent. The general promoting effect sequence of nucleosides and their derivatives on the activity of Pd NPs was nucleoside ≥ nucleotide > deoxynucleoside > base > deoxynucleotide. The quantitative correlation between the activity promoting effect and the structure of nucleosides and their derivatives were also studied using the method based on poly-parameter linear free energy relationships. Moreover, the kinetic behaviors of 4-NIP hydrogenation over Pd NPs regulated by different nucleosides (adenosine, guanosine, cytidine, and β-thymidine) were studied systematically and different kinetic models were developed to fit the data. The obtained kinetic data fitted well to the Langmuir-Hinshelwood (L-H) model, where the surface reaction is the rate-controlling step. The apparent activation energy, adsorption enthalpy of 4-NIP, and dissociated adsorption enthalpy of hydrogen were calculated and compared for a better understanding of the mechanism. Pd NPs regulated by cytidine showed the lowest apparent activation energy of 43.66 kJ mol −1 .

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JOURNAL OF CHROMATOGRAPHY A · 2019 · IF 3.858

Polyethyleneimine-functionalized carbon dots and their precursor co-immobilized on silica for hydrophilic interaction chromatography

Tianpei Cai,Haijuan Zhang,Jia Chen,Zhan Li,Hongdeng Qiu

A new strategy based on synergistic effect of the carbon dots and their precursor was proposed to enhance the selectivity of hydrophilic interaction liquid chromatography (HILIC). In this work, polyethyleneimine (PEI) and PEI-functionalized carbon dots (PEICDs) mix-grafted silica packing material was prepared to act as a novel HILIC stationary phase. Both inner and outer surface of the porous silica are decorated with the mixture of PEI and carbon dots. This stationary phase, namely Sil-PEI/CDs, demonstrate enhanced retention ability and selectivity toward polar analytes, with which 11 nucleosides and nucleobases and 9 ginsenosides can be nicely separated. The Sil-PEI/CDs (RSD 0.12% – 0.54%) exhibited even better stability than the traditional PEI modified stationary phase (RSD 0.39% – 0.87%) within 40 h of continuously elution. And excellent column efficiency was observed from Sil-PEI/CDs (∼65,000 plates/m for cytidine). The strategy of mixed stabilization revealed a new method to prepare good performanced carbon dots based chromatographic column.

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Nature Communications · 2019 ·Vol. 10 ·期 1 ·1-14 · IF 11.878

ABHD5 blunts the sensitivity of colorectal cancer to fluorouracil via promoting autophagic uracil yield

Ou Juanjuan,Peng Yuan,Yang Weiwen,Zhang Yue,Hao Jie,Li Fu,Chen Yanrong,Zhao Yang,Xie Xiong,Wu Shuang,Zha Lin,Luo Xi,Xie Ganfeng,Wang Liting,Sun Wei,Zhou Qi,Li Jianjun,Liang Houjie

The efficacy of Fluorouracil (FU) in the treatment of colorectal cancer (CRC) is greatly limited by drug resistance. Autophagy has been implicated in chemoresistance, but the role of selective autophagic degradation in regulating chemoresistance remains unknown. In this study, we revealed a critical role of ABHD5 in charging CRC sensitivity to FU via regulating autophagic uracil yield. We demonstrated that ABHD5 localizes to lysosome and interacts with PDIA5 to prevent PDIA5 from interacting with RNASET2 and inactivating RNASET2. ABHD5 deficiency releases PDIA5 to directly interact with RNASET2 and leave RNASET2 in an inactivate state, which impairs RNASET2-mediated autophagic uracil yield and promotes CRC cells to uptake FU as an exogenous uracil, thus increasing their sensitivity to FU. Our findings for the first time reveal a novel role of ABHD5 in regulating lysosome function, highlighting the significance of ABHD5 as a compelling biomarker predicting the sensitivity of CRCs to FU-based chemotherapy.

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MICROCHIMICA ACTA · 2019 ·Vol. 186 ·期 6 ·1-8 · IF 5.479

A versatile fluorometric aptasensing scheme based on the use of a hybrid material composed of polypyrrole nanoparticles and DNA-silver nanoclusters: application to the determination of adenosine, thrombin, or interferon-gamma

Wang Jing,Li Bingzhi,Lu Qiaoyun,Li Xiaoyun,Weng Chenyuan,Yan Xiaoqiang,Hong Junli,Zhou Xuemin

The authors describe a versatile aptasensing scheme based on the use of polypyrrole nanoparticles (PPyNPs) and DNA-silver nanoclusters (DNA-AgNCs) for multiple target detection. The DNA-AgNCs consist of two functional domains, viz. (a) a nucleation domain for attaching the metal core of the nanoclusters, and (b) a recognition domain which consists of a single-stranded aptamer. In the absence of analytes, the single-strand recognition domain will be absorbed onto the surface of the PPyNPs through π stacking and hydrophobic interactions. As a result, the red fluorescence of the DNA-AgNCs (with excitation/emission peaks at 535/625 nm) is quenched by the PPyNPs. On introducing the analytes, the DNA-AgNCs will bind them. This leads to the desorption of DNA-AgNCs and the recovery of the red fluorescence. Based on the above strategy, a versatile, sensitive and selective aptasensor was established for detection of adenosine, thrombin and interferon-gamma. The method was applied to the detection of the above targets in (spiked) serum samples and gave satisfactory results, with detection limit of 0.58 nM for IFN-γ, 0.39 nM for adenosine, and 2.2 nM for thrombin. The use of PPyNPs results in uniquely low non-specific absorption and in improved analytical results in case of real-sample analysis when compared to previously reported methods. Schematic illustration of DNA-silver nanoclusters and polypyrrole nanoparticles in an aptasensor for detection of multiple targets.

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MICROCHIMICA ACTA · 2019 ·Vol. 186 ·期 9 ·1-10 · IF 5.479

An organic polymer monolith modified with an amino acid ionic liquid and graphene oxide for use in capillary electrochromatography: application to the separation of amino acids, β-blockers, and nucleotides

Zhao Shiyuan,Yu Tao,Du Yingxiang,Sun Xiaodong,Feng Zijie,Ma Xiaofei,Ding Wen,Chen Cheng

The preparation of an organic polymer monolithic column modified with an amino acid ionic liquid and graphene oxide (AAIL-GO) and its application to capillary electrochromatography (CEC) was described. The AAIL tetramethylammonium-L-arginine was bonded to a monolithic column that was previously modified with graphene oxide by using an hydrochloride/N-hydroxysuccinimide coupling reaction. The morphology of a poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith was examined by scanning electron microscopy. The incorporation of AAIL and graphene oxide was detected by infrared spectroscopy and elemental analysis. The resulting monolithic column produced a strong and stable electroosmotic flow from the anode to the cathode in the pH range from 3 to 9. Compared with a column modified with AAIL or graphene oxide only, the AAIL-GO-modified column has a better separation ability for amino acids, β-blockers, and nucleotides (the resolution of three amino acids: 2.231 and 2.036, β-blockers: 2.779 and 2.470 and nucleotides: 8.345 and 3.321). Molecular modeling was applied to demonstrate the separation mechanism of small molecules which showed a good support for experimental results. Schematic representation of capillary electrochromatography (CEC) systems with an amino acid ionic liquid-graphene oxide modified organic polymer monolithic column as stationary phases for separation of amino acids, β-blockers, and nucleotides.

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MICROCHIMICA ACTA · 2018 ·Vol. 185 ·期 7 ·1-6 · IF 5.705

Selective, fast and semi-automatic enrichment of nucleosides by using a phenylboronic acid modified hybrid material composed of graphene oxide and melamine sponge

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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