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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Directional and on-demand ion transport regulated by pH and voltage in submicrochannel heteromembrane based on conducting polymer

Yuan-Ju Tang,Shu-Jie Zhang,Zi-Tao Zhong,Bin Zhang,Wen-Ming Su,Guo-Ping Wang,Yuan-Di Zhao

The construction of porous ion channels with ion current rectification (ICR) at the submicron scale has great significance for the development of large-area bionic ion channel devices. In this manuscript, one kind of heterogeneous membrane with asymmetric composition, geometry and wettability was prepared by simple drop-coating of the neutral hydrophobic conducting polymer precursor and in-situ thermal polymerization on cylindrical submicron scale anodic aluminum oxide channels (D≈269 nm) at 150 °C. ICR in the submicrochannel heterogeneous membrane was successfully achieved due to the asymmetric charge distribution induced by asymmetric pH gradient. Furthermore, the rectification ratio ( R ic : 1.6 ∼ 42.8) could be effectively regulated by multiple drop-coating, the electrolyte concentration (0.01 mM ∼ 1 M) and pH gradient (3 ∼ 11). Finally, through the permeation experiment of anionic dye and cationic dye, the mechanism of the synergistic effect of surface charge and electrophoresis on the ion selectivity and ICR was discussed, and it was successfully applied to the directional and on-demand transport of anionic and cationic ions under the regulation of pH gradient and voltage driving. It has important potential applications in the treatment of pollutants, the purification of water and energy conversion etc.

研究领域: 生物物理学 · 材料科学 · 仿生学
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TALANTA · 2018 · IF 4.244

The facile approaches to asymmetric modification of glassy biconical microchannel wall with silver, copper or gold

Fengxia Chang,Yang Yang,Xia Xie,Meixian Li,Zhiwei Zhu

The modification of inner surface has significant influence in the properties of the nano or microchannel based on various materials, especially for the ionic current rectification (ICR) that arises from the selective interaction between ions in solution and the inner surface. Herein, we demonstrate a simple strategy to asymmetrically modify the inner wall of a glassy biconical microchannel with silver , copper or gold by means of silver mirror reaction and polydopamine platform, respectively. And the bidirectional ionic current rectification phenomena were observed in all of the modified biconical microchannels. All of the modification methods are simple, facile and low-cost, and can be applied in the modification of other glassy pipettes.

研究领域: 材料科学 · 生物物理
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ANALYTICA CHIMICA ACTA · 2024 · IF 5.7

A bioinspired heterostructured nanochannel based on dendrimer-gold network and aluminum oxide arrays for sensitive detection of miRNA

Wenrui Ma,Lulu Liu,Zhuoya Jiang,Chaoshan Zhao,Zilan Lv,Yuping Yang,Yi Xu,Li Wang,Li Chen,Shunbo Li

Background MicroRNAs, as oncogenes or tumor suppressors, enable to up or down-regulate gene expression during tumorigenesis. The detection of miRNAs with high sensitivity is crucial for the early diagnosis of cancer. Inspired by biological ion channels, artificial nanochannels are considered as an excellent biosensing platform with relatively high sensitivity and stability. The current nanochannel biosensors are mainly based on homogeneous membranes, and their monotonous structure and functionality limit its further development. Therefore, it is necessary to develop a heterostructured nanochannel with high ionic current rectification to achieve highly sensitive miRNA detection. Results In this work, an asymmetric heterostructured nanochannel constructed from dendrimer-gold nanoparticles network and anodic aluminum oxide are designed through an interfacial super-assembly method, which can regulate ion transport and achieve sensitive detection of target miRNA. The symmetry breaking is demonstrated to endow the heterostructured nanochannels with an outstanding ionic current rectification performance. Arising from the change of surface charges in the nanochannels triggered by DNA cascade signal amplification in solution, the proposed heterogeneous nanochannels exhibits excellent DNA-regulated ionic current response. Relying on the nucleic acid's hybridization and configuration transformation, the target miRNA-122 associated with liver cancer can be indirectly quantified with a detection limit of 1 fM and a wide dynamic range from 1 fM to 10 pM. The correlation fitting coefficient R2 of the calibration curve can reach to 0.996. The experimental results show that the method has a good recovery rate (98%–105 %) in synthetic samples. Significance This study reveals how the surface charge density of nanochannels regulate the ionic current response in the heterostructured nanochannels. The designed heterogeneous nanochannels not only possess high ionic current rectification property, but also enable to induce superior transport performance by the variation of surface chemistry. The proposed biosensor is promising for applications in early diagnosis of cancers, life science research, and single-entity electrochemical detection.

研究领域: 生物传感器技术 · 分子生物学 · 纳米科技
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BIOSENSORS & BIOELECTRONICS · 2023 · IF 12.6

Functionalized nanopores based on hybridization chain reaction: Fabrication and microRNA sensing

Xia Qiu,Jingyi Dong,Qingshan Dai,Mimi Huang,Yongxin Li

Enzyme-free hybridization chain reaction (HCR) technology is often used as a signal amplification tool for the detection of different targets. In this study, an ultrasensitive and label-free method for detecting miRNA-21 was developed using the nanopore ionic current rectification (ICR) technology coupled with HCR technology. The probe oligonucleotide (DNA1) was combined with the gold-coated nanopore through the Au–S bond to form a DNA1-functionalized gold-coated nanopore (DNA1-Au-coated nanopore). Since miRNA-21 is partially complementary to DNA1, it can be selectively recognized by DNA1-functionalized gold-coated nanopores. The target (miRNA-21) can induce the opening of hairpin DNA and HCR reaction after the introduction of hairpin DNA H1 and H2. The concentration of miRNA-21 will affect the combination of H1 and H2 on the inner wall of the nanopore, and its surface charge will change with the internal modification, thereby changing the ion current rectification ratio . Under the condition that the concentration of H1, H2 and HCR reaction time are constant, the change of ICR ratio is linearly correlated with the logarithm of miRNA-21 concentration within a certain range, which shows that the sensing strategy we designed can achieve target miRNA-21 detection. This ultrasensitive miRNA holds great promise in the field of cancer diagnosis.

研究领域: 生物化学 · 分子生物学 · 纳米技术 · 医学诊断
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Journal of Materials Chemistry C · 2022 ·Vol. 10 ·期 43 ·16388-16396 · IF 8.067

Heterostructured nanochannels with modulated ionic current rectification for ultrasensitive detection of Hg2+

Wenrui Ma,Lulu Liu,Xu Zhang,Xingfei Liu,Yi Xu,Shunbo Li,Muling Zeng

Artificial membranes with asymmetric nanopores are similar to biological membranes with ion channels. The selective and rectified ion transport property of artificial membranes is of great significance for developing electrochemical sensors with highly sensitive detection performance. Herein, we propose a fast and facile approach for the sensitive detection of metal ions or charged molecules by constructing an asymmetric nanochannel structure using a cation-selective Nafion membrane and a DNA-functionalized anodic aluminum oxide (AAO) membrane. Arising from the varying charge distributions induced by the recognition of targets by DNA probes, the Nafion/AAO heterostructured nanochannels exhibit high ionic current rectification and excellent Hg2+ regulated current responses. The present sensor with heterostructured nanochannels can realize the detection of Hg2+ with a low detection limit of 1 pM, due to the unique ionic transport property of asymmetric nanochannels and the sensitive electrochemical detection method. The sensing mechanism is also confirmed by numerical simulations, demonstrating that the differences in the rectification ratios in the heterostructured nanochannels are caused by the varying surface charge densities in AAO nanochannels. This simple and facile heterostructured sensor has the advantages of simple preparation, easy modification, simple instrumentation and high sensitivity, which possesses great potential in the detection of metal ions or charged molecules.

研究领域: 生物传感器 · 电化学检测 · 纳米技术 · 分析化学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2021 ·Vol. 413 ·期 20 ·4939-4945 · IF 4.157

Ultrasensitive detection of trypsin in serum via nanochannel device

Guan Shulin,Yue Jing,Sun Weihan,Xu Weiqing,Liang Chongyang,Xu Shuping

A highly sensitive trypsin sensing system in serum was developed by using an anodic alumina oxide (AAO)-based, trypsin substrate-decorated hybrid ion permeation membrane. Owing to the trypsin-triggered peptide hydrolyzation reaction, the surface electrical feature of the peptide-decorated hybrid ion membrane changed. The electric double layer effect reduces the effective ion current diameter in the AAO nano unit, so that the ion current rectification ratio will be enhanced, realizing the quantitative detection of trypsin. The lowest detection concentration can be achieved as low as 0.1 pM. This method is no need for sample pre-preparation, easy to operate, highly sensitive, and also applicable to other enzyme evaluation systems by changing corresponding substrates. This study provides a new idea for selective measurements of proteases in complex biological samples. Graphical abstract

CAS / MDL: 51805-45-9
研究领域: 生物化学 · 医学检测 · 纳米技术
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ANALYST · 2021 ·Vol. 146 ·期 22 ·6815-6821 · IF 4.616

Controllable ion transport induced by pH gradient in a thermally crosslinked submicrochannel heterogeneous membrane

Yuan-Ju Tang,Shu-jie Zhang,Zi-Tao Zhong,Wen-Ming Su,Yuan-Di Zhao

Solid-state nanochannels have attracted considerable attention for their similar ion transport properties to biological ion channels. The construction of porous ion channels with good stability at the submicro/micrometer scale is very beneficial to develop large-area ion channel devices. In this manuscript, based on in-situ thermal crosslinking of a small organic molecule containing triphenylamine and styrene groups, we construct a heterogeneous membrane with asymmetrical charge and wettability on cylindrical anodic aluminum oxide (AAO) channels (D ≈ 319 nm). This heterogeneous membrane has typical ion current rectification characteristics with a high rectification ratio of 36.9 and good stability. This work provides an effective strategy for the construction of submicrochannel heterogeneous membranes and also broadens the application range of bionic ion channels.

研究领域: 材料科学 · 仿生学
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SENSORS · 2024 ·Vol. 24 ·期 13 ·4264 · IF 3.4

An Insulin-Modified pH-Responsive Nanopipette Based on Ion Current Rectification

Xu-Fan Wang,Yi-Fan Duan,Yue-Qian Zhu,Zi-Jing Liu,Yu-Chen Wu,Tian-Hao Liu,Ling Zhang,Jian-Feng Wei,Guo-Chang Liu

The properties of nanopipettes largely rely on the materials introduced onto their inner walls, which allow for a vast extension of their sensing capabilities. The challenge of simultaneously enhancing the sensitivity and selectivity of nanopipettes for pH sensing remains, hindering their practical applications. Herein, we report insulin-modified nanopipettes with excellent pH response performances, which were prepared by introducing insulin onto their inner walls via a two-step reaction involving silanization and amidation. The pH response intensity based on ion current rectification was significantly enhanced by approximately 4.29 times when utilizing insulin-modified nanopipettes compared with bare ones, demonstrating a linear response within the pH range of 2.50 to 7.80. In addition, insulin-modified nanopipettes featured good reversibility and selectivity. The modification processes were monitored using the I-V curves, and the relevant mechanisms were discussed. The effects of solution pH and insulin concentration on the modification results were investigated to achieve optimal insulin introduction. This study showed that the pH response behavior of nanopipettes can be greatly improved by introducing versatile molecules onto the inner walls, thereby contributing to the development and utilization of pH-responsive nanopipettes.

研究领域: 生物化学 · 纳米技术 · 分析化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2024 · IF 8

Cell membrane-inspired COF/AAO hybrid nanofluidic membrane with ion current rectification properties for ultrasensitive detection of E. coli

Mengyuan Chen,Chong Wang,Jing Tan,Jin Wang,Chen Wang

Nanofluidic membranes hold great prospects in sensitive and rapid detection of bioanalysts, while remaining lacking robust and general approaches for specificity. In this work, we introduce a cell membrane-inspired nanofluidic membrane with excellent ion current rectification properties as a simple and robust platform for label-free and ultrasensitive biosensing. The asymmetric nanofluidic membrane is prepared by coupling a two-dimensional covalent organic framework (COF) membrane to an anodic aluminum oxide (AAO) nanochannel via hydrogen bonding. The prepared COF/AAO membrane presents selective ion transport due to the asymmetric structure and anion selectivity of COF. With the large surface area and abundant functional modification sites of COF, further grafting of the recognition unit can be easily achieved to mimic the recognition process of receptors and ligands on cell membranes. As a proof of concept, the application in bacterial detection is demonstrated by covalently bonded Concanavalin A as recognition units. The highly amplified ionic current based on ion current rectification properties of the COF/AAO membrane allows sensitive and selective bioanalysis. Specifically, the proposed asymmetric nanofluidic membrane presents a linear detection range from 10 to 10 6 CFU/mL with an ultralow detection limit of 7 CFU/mL for E. coli . This work reveals the great potential of COF/AAO hybrid nanofluidic membrane as a sensor for rapid and precise bioanalysis.

研究领域: 生物传感器 · 材料科学 · 微生物学
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BIOSENSORS & BIOELECTRONICS · 2018 · IF 8.173

Conical nanofluidic channel for selective quantitation of melamine in combination with β-cyclodextrin and a single-walled carbon nanotube

Zhipeng Xie,Jinlong Lei,Mingfeng Yang,Youji Li,Xinhua Geng,Simin Liu,Jiahai Wang

Amine group-bearing small molecules tend to adsorb onto the nanochannel surfaces, which degrades the efficiency of nanochannel sensors. In this study, we utilized host-guest knowledge to eliminate the influence of excessive small molecules. In combination with single-walled carbon nanotubes (SWNTs), β-cyclodextrin (β-CD) provided an excellent sensing performance for the conical nanochannel coated with polyethyleneimine (PEI) and zirconium ion (Zr 4+ ). By taking detection of melamine as a prototype, the as-prepared nanochannel could selectively detect melamine-elicited double-stranded DNA (dsDNA). Both excessive melamine and single-stranded DNA were removed via the addition of β-CD and SWNTs. The nanochannel sensing platform for the detection of melamine has a detection limit of as low as 4.3 nM with a suitable sensitivity, an excellent reproducibility and stability. Therefore, it is highly promising that a nanochannel sensor based on ion current rectification (ICR) can be used to detect other possible targets.

研究领域: 分析化学 · 纳米技术 · 食品科学
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ANALYTICAL CHEMISTRY · 2022 · IF 8.008

Polydopamine-Induced Modification on the Highly Charged Surface of Asymmetric Nanofluidics: A Strategy for Adjustable Ion Current Rectification Properties

Zhixiao Si,Hongquan Xu,Meihua Lin,You Jiang,Qiujiao Du,Haotian Ma,Huageng Liang,Pengcheng Gao,Fan Xia

Surface charge effects in nanoconfines is one of the fundamentals in the ion current rectification (ICR) of nanofluidics, which provides entropic driving force by asymmetric surface charges and causes ion enrichment/depletion by the electrostatic interaction of fixed surface charges. However, the surface charge effect causes a significant electrostatic repulsion in nanoconfines, restricting additional like charge or elaborate chemistry on the highly charged confined surface, which limits ICR manipulation. Here, we use polydopamine (PDA), a nearly universal adhesive, that adheres to the highly positive-charged poly(ethyleneimine) (PEI) gel network in a nanochannel array. PDA enhances the ICR effect from a low rectification ratio of 9.5 to 92.6 by increasing the surface charge and hydrophobicity of the PEI gel network and, meanwhile, shrinking its gap spacing. Theoretical and experimental results demonstrate the determinants of the fixed surface charge in the enrichment/depletion region on ICR properties, which is adjustable by PDA-induced change in a nanoconfined environment. Chemically active PDA brings Au nanoparticles by chloroauric reduction for further hydrophobization and the modification of negative-charged DNA complexes in nanochannels, whereby ICR effects can be manipulated in versatile means. The results describe an adjustable and versatile strategy for adjusting the ICR behaviors of nanofluidics by manipulating local surface charge effects using PDA.

研究领域: 材料科学 · 生物物理学 · 纳米技术
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TALANTA · 2025 · IF 6.1

Dummy Molecularly Imprinted Polymer Nanochannel Sensor for Ultrasensitive Detection of Aniline Compounds

Ya Sun,Ziwen Zhao,Jie Zhao,Lide Hu,Yawei Shi,Mengqi Li

Aniline pollutants can cause great harm to human health and the ecosystem, while rapid and selective quantification of aniline compounds in environment samples at trace levels is a highly complex target. In this study, a novel, efficient nanochannel sensor based on dummy molecularly imprinted polymer (DMIP) was fabricated. The sensor works on the principle of the ion current rectification across the asymmetric charged nanoporous capillary. With the help of the electric-concentration multi-field coupling model and controlled experiments, the ion distribution and transport in the nanoporous capillary. and the key influencing factors were examined for optimization of the sensor. At the concentration of 1 nmol/L ∼ 0.1 mmol/L, the rectification ratio of the nanosensor and logarithm aniline concentration exhibited a good linear relationship with the limit of detection of 0.2 nmol/L. The concentration of anilines in the real seawater sample was tested with the DMIP nanochannel sensor, and the average recovery rate was 88.31%. The prepared DMIP nanochannel based sensor has established itself a promising method for trace aniline detection in real environmental samples, with the advantages of low cost, small size, simple operation, high accuracy and excellent reproducibility.

研究领域: 环境科学 · 分析化学
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