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ANALYTICA CHIMICA ACTA · 2021 · IF 6.558

Successive liquid-phase microextraction of acidic and basic analytes

Ruiqin Zhu,Hang Mei,Huajing Liu,Changbao Hong,Xiantao Shen,Chuixiu Huang

Practical biological and environmental samples always contain both acidic and basic substances, and the samples are always precious. Thus, separation of analytes with different nature from the same sample was of great significance. Successive liquid phase microextraction (sLPME) of acidic and basic analytes under optimal extraction conditions was therefore proposed for the first time. The concept of sLPME was proved by using three acidic analytes (naproxen, flurbiprofen and diclofenac) and three basic analytes (haloperidol, fluoxetine and sertraline) as model analytes, and using polypropylene glycol with an average molecular weight of 4000 (PPG4000) as SLM . The recoveries of all target analytes by sLPME were similar to that by individual LPME due to good affinity of PPG4000 to both acidic and basic analytes. Under optimal extraction conditions, the recoveries for all analytes by sLPME from urine samples were in the range of 62%–95%. Moreover, combined with LC-MS/MS, such sLPME approach was also evaluated with urine samples. The matrix effect of sLPME-LC-MS/MS at different levels for all analytes ranged from −14.1%–13.2%. The linear ranges with R 2  > 0.996 were 5–1000 ng mL −1 for basic analytes, and 20–1000 ng mL −1 for acidic analytes except diclofenac (1–1000 ng mL −1 ). The repeatability and accuracy at four levels were in the range of 3%–10% and 86%–120%, respectively. The limit of detection (LOD, S/N = 3) and limit of quantification (LOQ, S/N = 10) were found to be 0.07–0.49 ng mL −1 and 0.25–1.63 ng mL −1 , respectively. Finally, the strategy for constructing a sLPME system was further confirmed with urine, plasma and saliva using another two versatile SLM solvents possessing high affinity to both acidic and basic analytes. Successive LPME enabled separation of acidic and basic analytes from the same sample under optimum extraction conditions for all target analytes. Thus, we believe that the sLPME system will become a potent platform for forensic toxicology analysis, food science, environmental analysis and epidemiology study.

研究领域: 分析化学 · 环境科学 · 法医学毒理学
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Biomaterials Science · 2023 ·Vol. 11 ·期 10 ·3737-3749 · IF 6.6

A 3D-printed microneedle extraction system integrated with patterned electrodes for minimally invasive transdermal detection

Changyuan Zhan,Fanmao Liu,Zhiran Shen,Xinshuo Huang,Shuang Huang,Xiangling Li,Jing Liu,Jiang Yang,Jiefeng Xu,Xi Xie,Hui-Jiuan Chen

Point-of-Care-Testing (POCT) is a convenient and timely clinical analysis method, leading the development trend of advanced biosensors. The development of POCT equipment that can achieve minimally invasive percutaneous monitoring can avoid the pain felt by the subjects and achieve in vivo and efficient measurement. Here, we reported the development of a microneedle (MN) extraction system based on patterned electrodes, which could provide convenient and minimally invasive detection of bio-analytes (including glucose, pH, and H2O2). The 3D-printed hollow MN array was used as a painless transdermal tool, while the interstitial fluid was extracted under negative-pressure conditions. The patterned electrodes could improve the electrochemical performance of the sensor, with the synergistic effect of the micropillar structure to increase the enzyme coating surface area and the nanomaterial electron layer. The patterned electrodes were placed on the back of the MN arrays for electrochemical detection. In vitro and in vivo studies showed that the MN-extraction system could detect the corresponding bio-analytes in a minimally invasive manner and it did not cause significant tissue damage. The system developed in this work will provide promising technology to expand the application of POCT for minimal tests on interstitial fluids.

CAS / MDL: 9001-37-0 81-88-9
研究领域: 医学工程 · 生物传感 · 临床诊断
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The Innovation · 2025 · IF 25.7

Self-calibrating multiplexed microneedle electrode array for continuous mapping of subcutaneous multi-analytes in diabetes

Xiangling Li,Shantao Zheng,Mengyi He,Xinshuo Huang,Cheng Yang,Jingshan Mo,Jingbo Yang,Chengduan Yang,Huijiuan Chen,Xi Xie

Monitoring multiplexed biochemical markers is beneficial for the comprehensive evaluation of diabetes-associated complications. Techniques for multiplexed analyses in interstitial fluids have often been restricted by the difficulties of electrode materials in accurately detecting chemicals in complex subcutaneous spaces. In particular, the signal stability of enzyme-based sensing electrodes often inevitably decreases due to enzyme degradation or interference in vivo . In this study, we developed a self-calibrating multiplexed microneedle (MN) electrode array (SC-MMNEA) capable of continuous, real-time monitoring of multiple types of bioanalytes (glucose, cholesterol, uric acid, lactate, reactive oxygen species [ROSs], Na + , K + , Ca 2+ , and pH) in the subcutaneous space. Each type of analyte was detected by a discrete MN electrode assembled in an integrated array with single-MN resolution. Moreover, this device utilized an MN-delivery-mediated self-calibration technique to address the inherent problem of decreased accuracy of implantable electrodes caused by long-term tissue variation and enzyme degradation, and this technique might increase the reliability of the MN sensors. Our results indicated that SC-MMNEA could provide real-time monitoring of multiplexed analyte concentrations in a rat model with good accuracy, especially after self-calibration. SC-MMNEA has the advantages of in situ and minimally invasive monitoring of physiological states and the potential to promote wearable devices for long-term monitoring of chemical species in vivo .

研究领域: 医学工程 · 生物传感器 · 糖尿病研究
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Journal of Materials Chemistry B · 2021 ·Vol. 9 ·期 27 ·5503-5513 · IF 6.331

In situ synthesis of fluorescent polydopamine polymer dots based on Fenton reaction for a multi-sensing platform

Quan Li,Taoyi Zhang,Jing Chen,Wenxi Ji,Yun Wei

The development of fluorescent nanosensors has attracted extensive research interest owing to their superior optoelectronic properties. However, current fluorescent nanoprobes generally involve complicated synthesis processes, background signal disturbance, and limited analyte detection. In this work, a facile and time-saving synthetic strategy for the preparation of green emitting polydopamine polymer dots (PDA–PDs) from dopamine via Fenton reaction at room temperature was proposed for the first time. The obtained PDA–PDs possessed excellent luminescence properties, with a long-wavelength emission of 522 nm, a large Stokes shift of 142 nm, and good photostability against ionic strength and UV irradiation. The formation mechanism of fluorescent PDA–PDs is as follows: in the presence of Fe2+ and H2O2, dopamine could rapidly undergo oxidation to its quinone derivatives and further polymerize to synthesize the fluorescent PDA–PDs with the acceleration of hydroxyl radicals produced from the Fenton reaction. Thus, a versatile turn-on fluorescence sensing method was developed for the detection of multi-analytes (including Fe2+, dopamine, H2O2, and glucose) based on monitoring the intrinsic fluorescence signal of the in situ formation of PDA–PDs. This sensing method could be efficiently applied for the detection of Fe2+, dopamine, and glucose in real human serum samples. Moreover, a three-input AND molecular logic gate based on this sensing platform was designed with the fluorescence signal of PDA–PDs as the gate. Finally, the proposed PDA–PDs could have immense broad prospects in nanomaterials and biosensors.

研究领域: 材料科学 · 生物传感 · 化学
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Polymers · 2019 ·Vol. 11 ·期 7 ·1139 · IF 3.164

Highly Selective Fluorescence Sensing and Imaging of ATP Using a Boronic Acid Groups-Bearing Polythiophene Derivate

Lihua Liu,Linlin Zhao,Dandan Cheng,Xinyi Yao,Yan Lu

A boronic acid groups-bearing polythiophene derivate (L) was designed and synthesized for highly sensitive fluorescence detection of ATP based on a multisite-binding coupled with analyte-induced aggregation strategy.Lhas a polythiophene backbone as fluorophores and two functional side groups, i.e., quaternary ammonium group and boronic acid group, as multibinding sites for ATP. When various structural analogues such as ADP, AMP, and various inorganic phosphates were added into the aqueous solution ofL, only ATP caused a remarkable fluorescence quenching of about 60-fold accompanied by obvious color changes of solution from yellow to purple. The detection limit is estimated to be 2 nM based on 3σ/slope. With the advantage of good water solubility, low toxicity, and highly selective response to ATP,Lwas successfully utilized as a probe to real-time assay activity of adenylate kinase (ADK) and map fluorescent imaging of ATP in living cells.Keywords:ATP detection;fluorescent probe;polythiophene;multisite binding;analyte-induced aggregation

研究领域: 生物化学 · 分析化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF CHROMATOGRAPHY A · 2022 · IF 4.601

Accuracy improvement of determination of seven minor tobacco alkaloids in mainstream cigarette smoke using analyte protectants by gas chromatography-mass spectrometry

Qiong Guo,Yaqiong Qin,Lining Pan,Fuwei Xie,Shaofeng Liu,Xuehui Sun,Xiaoyu Wang,Junlan Cai,Xiaodong Zhao,Huimin Liu

A bstract Tobacco alkaloids are important precursors of carcinogenic tobacco-specific nitrosamines . Therefore, accurate quantification of tobacco alkaloids is highly important. This study investigates the compensation effects of novel analyte protectants (APs) for matrix effects (MEs) to determine seven minor tobacco alkaloids (nornicotine, myosmine , anabasine , anatabine , nicotyrine , 2,3′-bipyridine, and cotinine) in mainstream cigarette smoke with high accuracy and robustness. By comparing the heights and shapes of the chromatographic peaks before and after the addition of APs to standard solutions prepared in dichloromethane and cigarette smoke solutions, the compensation effects of 12 APs and their combinations on the MEs of seven minor tobacco alkaloids were evaluated, and the best combination of 2-pyridylethylamine (2 mg/mL)+1,2-decanediol (1 mg/mL) was identified. This AP combination could effectively improve the shapes and increase the heights (by 7–371%) of chromatographic peaks for standard solutions prepared in dichloromethane and cigarette smoke solutions. Before the addition of this AP combination, the slope ratios of the calibration curves for two types of standard solutions of the seven target chemicals were 71.4–159.8%, while they were 87.4–105.6% after the addition, indicating that this AP combination reduced the matrix difference between pure solvent and cigarette smoke solution. After adding the AP combination, the standard curves of solutions prepared in dichloromethane showed good linearity ( r 2 ≥ 0.999), the spiked recoveries were between 80.9% and 119.6%, and the inter- and intraday precisions were between 1.5–9.5% and 3.1–8.5%, respectively. Three commercial cigarette samples and one mixed standard solution were also tested under four different instrument working conditions to verify the long-term accuracy and ruggedness of the approach in routine real-world analysis of the method. The results showed that the RSD values were higher (3.5–25.4%) without the AP combination than that (<6.7%) with the AP combination. Because of its high accuracy, precision, and robustness, this method has good practical prospects.

研究领域: 化学 · 毒理学
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DYES AND PIGMENTS · 2020 · IF 4.613

Controllable excitation-dependent fluorescence triggered by the increasing graphitic nitrogen in carbon dots and its application in multi-analyte detection

Changqing Ye,Lei Xu,Shuoran Chen,Caihong Wang,Meng Su,Guoliang Dai,Xiaomei Wang,Fengyu Li,Yanlin Song

Carbon dots ( CD s) with controllable excitation-dependent fluorescence ( EDFL ) were elaborately prepared for the application of multiplex metal ion discrimination. A serial of CD samples were synthesized through a simple solvothermal reaction in which extra nitrogen sources with enhancing chemical reducibility were added into a specific nitrogen-contained precursor. Both experimental characterizations and theoretical calculations based on density functional theory have proved that the functional group of graphitic nitrogen ( GN ) is the key factor to achieve EDFL , and the content of GN was determined by the reducibility strength of extra nitrogen sources in the synthesis. In that case, sensing channels with different response behaviours to multiplex analytes can be formed due to the controllable EDFL of CD s. As a result, seventeen types of metal ions can be detected and recognized through the as-prepared CD probes. This work provides a novel angle to understand and engineer the EDFL property of CD s, as well as a facile strategy to appropriately construct high effective sensing channels for multi-analyte detection.

研究领域: 材料科学 · 分析化学
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TALANTA · 2025 · IF 6.1

Systematic investigation into matrix effect compensation in the GC-MS analysis of flavor components using analyte protectants

Ruihong Liu,Lining Pan,Yaqiong Qin,Fuwei Xie,Cong Nie,Xiaoyu Wang,Xiaobing Zhang,Mantang Chen,Bing Wang,Peijian Sun,Jizhao Guo,Huapeng Cui

Accurate quantitative analysis of flavor components is critical to eusuring product quality and safety. Matrix effects (MEs) in gas chromatography (GC) analysis frequently leads to a low sensitivity and inaccurate quantitation. This study first analyzed the MEs of 32 representative flavor components that cover the volatility range of GC-amenable analytes. The results revealed that flavor components with high boiling points, polar groups, or at low concentrations were particularly susceptible to MEs. The compensatory effects of 23 potential APs on MEs were evaluated, and the impacts of retention time ( t R ), hydrogen bonding capability, and concentration of APs on their compensatory effects were explored. The results indicated that a broader t R coverage rate and stronger hydrogen bonding capability led to better enhancement, while increasing AP concentration improved analyte peak intensity. However, similar t R , strong hydrogen bond capability or high AP concentration could also introduce negative effects, such as interference, insolubility, t R shift or peak distortion. Based on a comprehensive assessment of both positive and negative effects, a suitable AP combination of malic acid +1,2-tetradecanediol (both at 1 mg/mL) was developed to compensate the MEs across more analytes. After adding the combination, significant improvements were observed in the linearity, limit of quantitation (5.0–96.0 ng/mL), and recovery rate (89.3–120.5 %) of the method. This study comprehensively considered factors including the solubility, interference, protective effect of the agents, providing an efficient strategy for developing potential APs. This strategy holds broad application prospects in various fields, such as foods, beverages, cosmetics and more.

研究领域: 食品科学 · 分析化学 · 香料研究
✓ 已验证 DOI PubMed 高影响因子
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JOURNAL OF SEPARATION SCIENCE · 2012 ·Vol. 36 ·期 2 ·262-269 · IF 2.733

Preparation and application of novel zwitterionic monolithic column for hydrophilic interaction chromatography

Zhenghua Liu,Yongbo Peng,Tingting Wang,Guangxin Yuan,Qiaoxuan Zhang,Jialiang Guo,Zhengjin Jiang

A novel zwitterionic hydrophilic porous monolithic stationary phase was prepared based on the thermal-initiated copolymerization of N , N -dimethyl- N -(3-methacryl-amidopropyl)- N -(3-(sulfopropyl)ammonium betaine and ethylene glycol dimethacrylate. A typical hydrophilic separation mechanism was observed at a highly organic mobile phase (ACN >60%) on this optimized zwitterionic hydrophilic interaction chromatography (HILIC) monolithic stationary phase. Good permeability, stability, and column efficiency were observed on the final monolithic column. Additionally, a weak electrostatic interaction for charged analytes was confirmed in analysis of six benzoic acids by studying the influence of mobile phase pH and salt concentration on their retention behaviors on the obtained zwitterionic HILIC monolithic column. The optimized zwitterionic HILIC monolith exhibited good selectivity for a range of polar test analytes.

研究领域: 分析化学 · 色谱技术
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2021 · IF 4.464

A versatile sensing platform based on FeOOH nanorod/expanded graphite for electrochemical quantification of bioanalytes

Kewei Meng,Xiaomin Hu,Yuanyuan Zhang,Ting Zeng,Qijin Wan,Guosong Lai,Xinyue Chen,Nianjun Yang

Quantitative analysis of biologically important compounds plays extraordinary roles in diagnostic studies of human health. In this study, a versatile electrochemical sensing platform is proposed for selective quantification of ascorbic acid (AA), dopamine (DA), uric acid (UA), acetaminophen (AC) and l -tryptophan (Trp). Such a platform is based on a nanocomposite of FeOOH nanorod and expanded graphite (FeOOH nanorod/EG), prepared through a hydrothermal process. The characterization of its morphology and electrochemical properties by means of microscopic methods and electrochemical techniques reveals that this nanocomposite exhibits outstanding electrocatalytic activity and sensing performance toward these bioanalytes. A combined action between EG and FeOOH is confirmed, where the former provides a huge electroactive surface area as well as a fast electron transfer rate, while the latter features strong electrical catalytic ability. This platform exhibits high sensitivity toward voltammetric quantitation of AA, DA, UA, AC and Trp, and their detection limits are 3.28, 0.22, 0.02, 0.0014 and 0.03 μM (S/N = 3), respectively. Beyond that, the proposed FeOOH nanorod/EG electrochemical sensing platform shows good selectivity, high reproducibility and stability in the quantitative analysis of these bioanalytes. The established sensing platform has been also successfully adopted in analyzing these bioanalytes in real biological serum and urine samples or commercial drugs. Consequently, the fabricated FeOOH nanorod/EG nanocomposite is a promising electrode material in the applications of sensing different bioanalytes.

研究领域: 分析化学 · 生物医学工程 · 材料科学
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MICROCHEMICAL JOURNAL · 2021 · IF 4.821

Combined use of analyte protectants and precolumn backflushing for a robust, high-throughput quantitative determination of aroma compounds in cigarette mainstream smoke by gas chromatography-tandem mass spectrometry

Qiong Guo,Lining Pan,Yaqiong Qin,Fuwei Xie,Xiaoyu Wang,Xiaodong Zhao,Li Chen,Bing Wang,Junlan Cai,Huimin Liu

Trace analysis of multi-targets in complex matrices such as cigarette smoke has always been a great challenge for analysts. In this paper, a high-throughput qualitative and quantitative method was developed and validated to determine 559 aroma compounds in mainstream smoke using gas chromatography-tandem mass spectrometry. Among four commonly used extraction solvents, dichloromethane showed obvious advantages in extracting the target aroma compounds with different polarity. An analyte protectant mixture consisting of 3-methoxy-1,2-propanediol, 1,2-octandiol, 1,2-nonanediol, and 1,2-tetradecanediol was first presented to compensate for the matrix effect, which was suitable for solvents of a wide polarity range such as hexane, dichloromethane, acetone, acetonitrile, and methanol. Moreover, the introduction of precolumn backflushing markedly improved the instrument robustness in analyzing complex cigarette smoke. The results showed that the system retained good stability after 30 days of injection. The proposed method performed well in terms of key validation parameters: accuracy (70.3–118.8% for 552 compounds), inter/intraday precision (0.1–10.7% and 0.2–18.2%), and sensitivity (limit of detection 0.12–102.54 ng/mL). Finally, this method was successfully applied to analyze 12 different commercial cigarette brands. The proposed method has good application prospects based on its robustness and may be used as a potential tool to transfer the cigarette design from an experience-dependent mode to a digital design mode. This method also shows potential in assaying aroma compounds in essentials, food or plant-based substrates.

研究领域: 分析化学 · 烟草科学
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ELECTROCHIMICA ACTA · 2019 · IF 5.383

Dual-analyte electrochemical sensor for fructose and alizarin red S specifically sensitive detection based on indicator displacement assay

Fen Liu,Xianwen Kan

In this work, a novel dual-analyte electrochemical sensor was developed based on the combination of boronate affinity and indicator displacement assay (IDA) strategy. Reduced graphene oxidation (RGO) and poly(3-aminophenylboronic acid) (pAPBA) were modified on glassy carbon electrode (GCE), which further bound dopamine (DA) via a reversible covalent interaction between the APBA and DA. Due to the higher affinity of pAPBA to the analytes, the bound DA can be displaced by fructose (Fru) or Alizarin Red S (ARS). As an indicator, the decrease of DA current caused by the displacement was used to monitor the concentration of the analyte. For non electro-active molecule, the decrease of DA current was directly proportional to the logarithm of Fru concentration in a range from 7.0 × 10 −8 to 1.0 × 10 −4  mol/L. For electro-active molecule, the current of DA decreased along with the increase of ARS current owing to the displacement, which were combined as a dual-signl for ARS sensitive detection with a linear range of 9.0 × 10 −8 - 1.0 × 10 −5  mol/L. The results of determining analytes with their interferences demonstrated the good specific affinity of the sensor toward the analytes. The dual-analyte electrochemical sensor based on IDA strategy probably provides a potential guidance for multi-analyte facile, sensitive, and specific detection.

研究领域: 生物化学 · 分析化学
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