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Cancer is one of the serious threats to public life and health. Early diagnosis, real-time monitoring, and individualized treatment are the keys to improve the survival rate and prolong the survival time of cancer patients. Liquid biopsy is a potential technique for cancer early diagnosis due to its non-invasive and continuous monitoring properties. However, most current liquid biopsy techniques lack the ability to detect cancers at the early stage. Therefore, effective detection of a variety of cancers is expected through the combination of various techniques. Recently, DNA frameworks with tailorable functionality and precise addressability have attracted wide spread attention in biomedical applications, especially in detecting cancer biomarkers such as circulating tumor cells (CTCs), exosomes and circulating tumor nucleic acid (ctNA). Encouragingly, DNA frameworks perform outstanding in detecting these cancer markers, but also face some challenges and opportunities. In this review, we first briefly introduced the development of DNA frameworks and its typical structural characteristics and advantages. Then, we mainly focus on the recent progress of DNA frameworks in detecting commonly used cancer markers in liquid-biopsy. We summarize the advantages and applications of DNA frameworks for detecting CTCs, exosomes and ctNA. Furthermore, we provide an outlook on the possible opportunities and challenges for exploiting the structural advantages of DNA frameworks in the field of cancer diagnosis. Finally, we envision the marriage of DNA frameworks with other emerging materials and technologies to develop the next generation of disease diagnostic biosensors., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Potentiometric sensors based on the molecularly imprinted polymers (MIPs) as the receptors have been successfully developed for determination of various organic and biological species. However, these MIP receptors may suffer from problems of low selectivity. Especially, it would be difficult to distinguish the target analyte from its structurally similar interferents. In this work, we propose a novel strategy that using specific functional monomer to fabricate MIP with high selectivity towards the target molecule. The density functional theory calculations are used to investigate the interactions between the template and the functional monomer. The binding energy between the template and functional monomer can be used as the criterion for identifying the optimal monomer. As a proof-of-concept experiment, bisphenol A (BPA) is chosen as the template and the MIP is synthesized by the precipitation polymerization method using the specific allyl-β-cyclodextrin (allyl-β-CD) with high affinity towards BPA as the functional monomer. The high-affinity MIP is employed as the receptor for the construction of the potentiometric sensor. The proposed potentiometric sensor based on the MIP using allyl-β-CD as the functional monomer shows an improved response performance in terms of selectivity and sensitivity compared to the conventional potentiometric sensor based on the MIP with the common monomer (i.e., methacrylic acid). This allyl-β-CD MIP-based potentiometric sensor shows a detection limit of 0.29 μM for BPA, which is about one order of magnitude lower than that obtained by the conventional MIP-based potentiometric sensor. We believe that utilizing a functional monomer with specific recognition ability towards target in the fabrication of MIP could provide an appealing way to construct highly selective MIP-based electrochemical and optical sensors., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Phenotypic antimicrobial susceptibility testing enables reliable antibiotic screening but requires multiple strategies to identify each phenotypic change induced by different bactericidal mechanisms. Bacteria apoptosis with typical phenotypic features has never been explored for antibiotic screening. Herein, we developed an antibiotic screening method based on the measurement of antibiotic-induced phosphatidylserine (PS) exposure of apoptotic bacteria. Phosphatidylserine externalization of E. coli that can be widely used as an apoptosis marker for antibiotics with different antibacterial mechanisms was explored. A positively charged PS-binding peptide was immobilized on magnetic beads (MBs) to recognize and capture apoptotic E. coli with PS externalization. Apoptotic E. coli binding led to the charge or charge density change of MBs-peptide, resulting in a potential change on a magneto-controlled polymeric membrane potentiometric sensor. Based on the detection of apoptotic E. coli killed by antibiotics, antibiotic screening for different classes of antibiotics and silver nanoparticles was achieved within 1.5 h using a potentiometric sensor array. This approach enables sensitive, general, and time-saving antibiotic screening, and may open up a new path for antibiotic susceptibility testing., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Single and rare cell analysis provides unique insights into the investigation of biological processes and disease progress by resolving the cellular heterogeneity that is masked by bulk measurements. Although many efforts have been made, the techniques used to measure the proteome in trace amounts of samples or in single cells still lag behind those for DNA and RNA due to the inherent non-amplifiable nature of proteins and the sensitivity limitation of current mass spectrometry. Here, we report an MS/MS spectra merging strategy termed SPPUSM (same precursor-produced unidentified spectra merging) for improved low-input and single-cell proteome data analysis. In this method, all the unidentified MS/MS spectra from multiple test files are first extracted. Then, the corresponding MS/MS spectra produced by the same precursor ion from different files are matched according to their precursor mass and retention time (RT) and are merged into one new spectrum. The newly merged spectra with more fragment ions are next searched against the database to increase the MS/MS spectra identification and proteome coverage. Further improvement can be achieved by increasing the number of test files and spectra to be merged. Up to 18.2% improvement in protein identification was achieved for 1 ng HeLa peptides by SPPUSM. Reliability evaluation by the "entrapment database" strategy using merged spectra from human and E. coli revealed a marginal error rate for the proposed method. For application in single cell proteome (SCP) study, identification enhancement of 28%-61% was achieved for proteins for different SCP data. Furthermore, a lower abundance was found for the SPPUSM-identified peptides, indicating its potential for more sensitive low sample input and SCP studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Two-dimensional carbon-coated molybdenum disulfide (MoS 2 @C) hollow nanorods are combined with nucleic acid signal amplification strategies and DNA hexahedral nanoframework to construct a novel self-powered biosensing platform for ultra-sensitive dual-mode detection of tumor suppressor microRNA-199a. The nanomaterial is applied on carbon cloth and then modified with glucose oxidase or using as bioanode. A large number of double helix DNA chains are produced on bicathode by nucleic acid technologies including 3D DNA walker, hybrid chain reaction and DNA hexahedral nanoframework to adsorb methylene blue, producing high E OCV signal. Methylene blue also is reduced and an increased RGB Blue value is observed. For microRNA-199a detection, the assay shows a extensive linear range of 0.0001-100 pM with a low detection limit of 4.94 amol/L (S/N = 3). The method has been applied to the detection of actual serum samples, providing a novel method for the accurate and sensitive detection of tumor markers., Competing Interests: Declaration of competing interest The authors declared that they have no conflicts of interest to this work., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Single-cell analysis has received much attention in recent years for elucidating the widely existing cellular heterogeneity in biological systems. However, the ability to measure the proteome in single cells is still far behind that of transcriptomics due to the lack of sensitive and high-throughput mass spectrometry methods. Herein, we report an integrated strategy termed "SCP-MS1" that combines fast liquid chromatography (LC) separation, deep learning-based retention time (RT) prediction and MS1-only acquisition for rapid and sensitive single-cell proteome analysis. In SCP-MS1, the peptides were identified via four-dimensional MS1 feature (m/z, RT, charge and FAIMS CV) matching, therefore relieving MS acquisition from the time consuming and information losing MS2 step and making this method particularly compatible with fast LC separation. By completely omitting the MS2 step, all the MS analysis time was utilized for MS1 acquisition in SCP-MS1 and therefore led to 65%-138% increased MS1 feature collection. Unlike "match between run" methods that still needed MS2 information for RT alignment, SCP-MS1 used deep learning-based RT prediction to transfer the measured RTs in long gradient bulk analyses to short gradient single cell analyses, which was the key step to enhance both identification scale and matching accuracy. Using this strategy, more than 2000 proteins were obtained from 0.2 ng of peptides with a 14-min active gradient at a false discovery rate (FDR) of 0.8%. Comparing with the DDA method, improved quantitative performance was also observed for SCP-MS1 with approximately 50% decreased median coefficient of variation of quantified proteins. For single-cell analysis, 1715 ± 204 and 1604 ± 224 proteins were quantified in single 293T and HeLa cells, respectively. Finally, SCP-MS1 was applied to single-cell proteome analysis of sorafenib resistant and non-resistant HepG2 cells and revealed clear cellular heterogeneity in the resistant population that may be masked in bulk studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Molecularly imprinted polymer (MIP)-based polymeric membrane potentiometric sensors are ideal candidates for detection of organic species. The development of such sensors has opened new attractive horizons for potentiometric sensing. However, it should be noted that in the preparation of these MIP receptors, the selection of the functional monomer usually depends on empirical trial- and error-based optimization, which involves tedious and time-consuming experiments. In this work, the computer-aided design and synthesis of an MIP receptor are applied in the fabrication of an MIP-based potentiometric sensor. The density functional theory calculation with the B3LYP model and 6-31G(d) basis set is used to study the interactions between the functional monomer and template molecules. The binding energies of the complexations between the template molecule and different functional monomers are used as a criterion for the selection of the proper monomer. The designed MIP is then synthesized and employed as the receptor for the fabrication of the potentiometric sensor. As a proof-of-concept experiment, the antibiotic sulfadiazine has been selected as a model and 4 functional monomers, 2-hydroxyethyl methacrylate, methyl methacrylate, N-isopropylacrylamide and N-phenylacrylamide, have been chosen. The designed MIP-based sensor exhibits excellent sensitivity with a linear range of 1-10 μM and also shows a good selectivity. We believe that the proposed computer-aided synthesis technique for the MIP receptor selection can provide a general and facile way to replace the traditional empirical MIP preparation method in the fabrication of MIP-based electrochemical and optical sensors., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Diabetic nephropathy is one of the common complications of diabetes, which has high risk of renal function. Dipeptidyl peptidase 4 (DPP4) is considered to be one of the good dynamic monitoring indicators for early diabetic nephropathy. Therefore, real-time monitoring of changes in the activity of DPP4 in organisms is helpful to the diagnosis and treatment of diabetes and its complications-diabetic nephropathy. A near-infrared fluorescent probe GP-DCMNH 2 is designed to detect the activity of DPP4. GP-DCMNH 2 is catalyzed and hydrolyzed by DPP4 into the near-infrared fluorescent dye DCMNH 2 , to achieve the purpose of detecting DPP4 in organisms. Based on the excellent near-infrared spectroscopy characteristics displayed by the probe GP-DCMNH 2 in vitro, in living cells and diabetic mouse models, GP-DCMNH 2 has been further applied in the visual fluorescence imaging of diabetic complications-diabetic nephropathy. Compared with the control group and the treatment group, GP-DCMNH 2 showed a stronger near-infrared fluorescence signal in the kidney tissue and blood of diabetic nephropathy mice. Because GP-DCMNH 2 shows high sensitivity in real-time dynamic monitoring of changes in the activity of DPP4 in organisms, and shows strong practicability in the spectral test of mouse models of diabetes and diabetic nephropathy. In clinical medicine, GP-DCMNH 2 is expected to be used in the early diagnosis, prevention and treatment of diabetes and diabetic nephropathy., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The modulation of the ion-fluxes across a polymeric membrane is important for designing attractive methodologies. As an alternative to the commonly used dynamic electrochemistry approaches, light can be used as an external stimulus and provides a very convenient way to manipulate ions release and/or extraction into a polymeric membrane. Herein, we designed a solid-contact polymeric membrane ion-selective sensor that exhibits dynamic response by light irradiation at 375 nm. The electrode membrane contains a light-sensitive lipophilic salt (bis(4-tert-butylphenyl)iodonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (R + -R - , BTDT-TFPB) instead of traditional ion exchanger. Under light illumination, the decomposition of the lipophilic cation makes the membrane with ion-exchange properties. The solid-contact ion-selective electrodes based on potentiometry and constant potential coulometry have been explored for direct ion sensing. Copper was selected as a mode analyte and can be determined at micromole levels. The proposed dynamic ion sensors show promise for on-demand ion sensing., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Leucine aminopeptidase (LAP) as an important proteolytic enzyme, has been mainly found in hepatobiliary cells, and overexpressed in hepatoma cells. Herein, a new highly selective red-emitting fluorescent probe (DCDHF-Ala) for LAP has been synthesized based on 2-dicyanomethyldiene-3-cyano-2, 5-dihydrofuran (DCDHF) as fluorophore, and alanine (Ala) as the detection group. More importantly, it's the first time to use Ala as a reactive group for LAP. DCDHF-Ala has a low detection limit (0.20 U/L), excellent water solubility and cell membrane permeability. In addition, the probe has been successfully applied to fluorescent imaging in cells and zebrafish. It's especially worth mentioning that, DCDHF-Ala has a high biosafety and enables a real-time detection of LAP levels in mice model. What's the most important is that DCDHF-Ala may be an effective tool to qualitatively monitor the upregulation of LAP induced by liver injury and liver cancer., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In this work, we describe a novel method to improve the detection limits of the non-classical polymeric membrane ion-selective electrodes (ISEs) which are conditioned with highly discriminated ions instead of primary ions. It is based on a thin-layer ISE membrane with a thickness of 5 μm, which is coated on ordered mesoporous carbon used as solid contact. The diffusion of the primary ion from the surface of the sensing membrane to the bulk of the membrane could be avoided by the proposed thin membrane configuration. Since the detection sensitivity of the non-classical ISEs depends on the accumulation of the primary ion in the interfacial layer of the sensing membrane, a lower detection limit can be obtained. By using the copper ion as a model, the present potentiometric sensor shows a significantly improved detection sensitivity compared to the conventional ISE with a membrane thickness of ca. 200 μm. Low detection limits of 0.29 and 0.53 nM can be obtained in 0.01 and 0.5 M NaCl, respectively. In addition, the proposed sensor exhibits an excellent reversibility by using a neutral proton-selective ionophore incorporated in the thin membrane., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Traditional potentiometric NO 3 - -selective electrodes suffer from a fundamental limitation of the Nernst slope (59.1 mV/dec at 25 °C) due to the relationship between the potential and the logarithmic of ionic activity. Herein, a coulometric signal readout is proposed instead of the potentiometric response for detection of NO 3 - based on an ordered mesoporous carbon (OMC)-based solid-contact ion-selective electrode (ISE). The mechanism for obtaining the coulometric signal is based on the electrical double layer capacitance of OMC compensating the potential change at the ion-selective membrane/solution interface during the measurements under the control of a constant applied potential. Under the optimized conditions, the coulometric signal for the OMC-based solid-contact NO 3 - -ISE shows two linear responses in the activity range of 1.0 × 10 -6 -8.0 × 10 -6  M and 8.0 × 10 -6 -8.0 × 10 -4  M, and the detection limit is 4.0 × 10 -7  M (3σ/s). The proposed coulometric response also shows excellent reproducibility and stability in the presence of O 2 and CO 2 and light on/off. Additionally, the coulometric response shows acceptable and reliable results for detection of NO 3 - in mineral water as compared to the traditional potentiometric response and the ion chromatography. This work provides a promising alternative signal readout for detection of ions by using solid-contact ion-selective electrodes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Neutrophil elastase (NE), a representative protease which is closely related to many diseases, acts an indispensable role in inflammatory diseases and clinical medicine. In this work, one activity-based non-peptide ratiometric fluorescent probe DCDF was designed with pentafluoropropionic anhydride as identification group. To our knowledge, this is the first probe capable of detecting NE in ratio. After the addition of the NE, the emission spectrum of DCDF has obvious bathochromic-shift phenomenon, and there is large Stokes shifts of ∼60 nm. Compared to only a few reported NE probes, DCDF is sensitive and selective and has very low detection limit (0-14 μg/mL, DL = 30.8 ng/mL). A possible response mechanism was proposed and verified by HPLC and HRMS spectra. What's more, DCDF is capable of endogenous recognition imaging in biological cells without interference from other enzymes under the ratio signal. A549 and HeLa cells were used for endogenous cell imaging experiments of NE and the feasibility of DCDF for the specific detection of NE in cells was proved. This experimental result makes probe DCDF a very promising tool for the clinical diagnosis and treatment of NE related diseases., Competing Interests: Declaration of competing interest The authors declare that they have no known competing interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The dissolution kinetics of silver nanoparticles (Ag NPs) to Ag + ions is a critical factor determining the toxicity of silver nanoparticles. In this work, a solid-contact Ag + -selective electrode (Ag + -ISE) is fabricated and used to monitor the dissolution of Ag NPs. Ordered mesoporous carbon is compared with disordered mesoporous carbon as the solid-contact material for the Ag + -ISE. The ordered mesoporous carbon based solid-contact Ag + -ISE shows a linear potential response in the range of 1.0 × 10 -6 -1.0 × 10 -3  M AgNO 3 with the slope of 55.6 ± 0.8 mV/dec (n = 7) and the detection limit of 10 -6.8  M. The solid-contact Ag + -ISE is used to monitor the concentration changes of Ag + during spontaneous dissolution of Ag NPs in deionized water, and the dissolution kinetics of Ag NPs is consistent with that obtained by inductively coupled plasma-mass spectrometry (ICP-MS). Stimulated dissolution of Ag NPs induced by addition of H 2 O 2 to the Ag NP solution is also investigated by the proposed solid-contact Ag + -ISE. This work provides a fast tool for charactering the dissolution of Ag NPs to Ag + in real time, which is important for studying the toxicology of nanoparticles., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Protein N-glycosylation plays crucial roles in many biological processes and has close association with the occurrence and development of various cancers. Therefore, it is necessary to analyze the abnormal changes of N-glycopeptides in complex biological samples for biomarker discovery. However, due to their low abundance and poor ionization, N-glycopeptides identification in complex samples by mass spectrometry (MS) is still a challenging task. In this work, a novel magnetic hydrophilic material was prepared by serial functionalization of ultra-thin two-dimensional molybdenum disulfide with Fe 3 O 4 nanoparticles, gold nanowire and glutathione (MoS 2 -Fe 3 O 4 -Au/NWs-GSH) for efficient N-glycopeptides enrichment. The advantage of using the new nanocomposite is threefold. First, the introduction of magnetic Fe 3 O 4 nanoparticles efficiently simplifies the enrichment process. Second, the gold nanowire modification enlarges the surface area of the nanocomposites to facilitate interaction with N-glycopeptides. Third, the employment of highly hydrophilic glutathione leads to specific HILIC-based retention of N-glycopeptides. Low femtomolar detection sensitivity and 1:1000 enrichment selectivity can be achieved using MoS 2 -Fe 3 O 4 -Au/NWs-GSH enrichment and bio-mass spectrometry analysis. Successful applications in human urine exosome and serum proteins were demonstrated by the enrichment and identification of 1250 and 489 N-glycopeptides, respectively. This remarkable data set of N-glycoproteome indicates the application potential of the novel nanocomposites for N-glycopeptides enrichment in complex biological samples and for related glycoproteome studies., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Accurate, simple and economical methods for quantifying N-glycans are continuously required for discovering disease biomarkers and quality control of biopharmaceuticals. Quantitative N-glycomics based on MS using exogenous isotopic labeling internal standards is promising as it is simple and accurate. However, it is largely hampered by the lack of available glycan internal standard libraries with good coverage of the natural glycan structural heterogeneity as well as broad dynamic mass and ion abundance range. To overcome this limitation, we developed a novel method, providing 'Bionic Glycome' as internal standards for glycan quantitation by MALDI-MS. Bionic Glycome was produced using N-glycome from pooled samples to be analyzed as substrate by one step of glycan reducing and isotope labeling (Glycan-RAIL). Each bionic glycan has 3 Da mass increment over its corresponding glycan analyte based on hemiacetals/alditols and H/D mass difference. In addition, Bionic Glycome has the same glycome composition and similar glycome profile in abundance with N-glycome to be analyzed from biological sample. Through the investigation of single glycan standard and complex glycans released from model glycoprotein and serum, the results demonstrate that the method has good quantitative accuracy and high reproducibility. Lastly, this method was successfully used for discovery of lung cancer specific glycan markers by comparing the serum glycans from each sample in lung cancer group (n = 16) and healthy controls (n = 16), indicating its potential in clinical applications., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Here, we designed and synthesized two fluorescent probes for detecting phosgene by nucleophilic substitution reaction using BODIPY as a fluorophore and 2-aminobenzylamine as reactive functional group. For the first time, we have studied the similarities and differences between asymmetric monosubstituted (1) and symmetric disubstituted (2) probes. A monosubstituted probe 1 (having a 2-aminobenzylamine group at the 3-position of BODIPY) has fluorescence-enhancing (weak green fluorescence to strong green fluorescence) responce to phosgene in 30 s with a large Stokes shift (∼70 nm) and sensitive property (DL = 0.81 nM); while the disubstituted probe 2 (having two 2-aminobenzylamine groups at the 3, 5-position of BODIPY) has a ratiometric fluorescent responce to phosgene in 2 min. The linear range of the response is wider than that of the monosubstitution probe 1, and the detection limit is also lower (2.36 nM). In addition, probes 1 and 2 can effectively eliminate the interference of other substances with similar chemical structure as phosgene. They can not only detect phosgene in solution environment, but also in gaseous environment quickly and sensitively., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Methods for in-situ measurements of heavy metal ions in coastal sediment pore water to elucidate fine-scale biogeochemical and environmental processes are highly required but have rarely been reported. In this work, an all-solid-state lead-selective microelectrode (Pb 2+ -ISμE) based on a poly(3,4-ethylenedioxythiophene)-poly(sodium 4-styrenesulfonate) (PEDOT/PSS) modified gold wire with a diameter of 14 μm has been fabricated. The proposed Pb 2+ -ISμE is capable of in-situ measurement of Pb 2+ in coastal sediment pore water at millimeter depth intervals. The Pb 2+ -ISμE shows a Nernstian response for Pb 2+ within the activity range of 2.1 × 10 -9 -2.1 × 10 -4  M (S = 28.1 ± 1.3 mV/dec, R 2  = 0.998) in 0.5 M NaCl, and the detection limit is 6.4 × 10 -10  M. By lowering the microelectrode into a coastal sediment core with a micro-manipulator, the proposed Pb 2+ -ISμE allows the direct measurement of the vertical distribution profile of Pb 2+ in the pore water. The in-situ measurement of Pb 2+ using the microsensor could avoid the problems of sample handling. Moreover, the detection system can be extended to assess the vertical distribution profiles of other heavy metal ions in sediment pore water by using different ion-selective microelectrodes., (Copyright © 2019 Elsevier B.V. All rights reserved.)

A novel freestanding all-solid-state polymeric membrane Cu 2+ -selective electrode (Cu 2+ -ISE) is proposed based on three-dimensional graphene sponge (3D GS). The 3D GS electrode has been characterized by cyclic voltammetry, electrochemical impedance spectroscopy, and contact angle measurements. Experiments show that 3D GS possesses a large electrical double layer capacitance, good conductivity, and high hydrophobicity. Based on these superior properties, 3D GS has been applied as both electrode substrate and solid contact for construction of a freestanding all-solid-state polymeric membrane Cu 2+ -ISE. The 3D GS-based Cu 2+ -ISE shows a good Nernstian response ranging from 1.0 × 10 -8 to 7.9 × 10 -4  M with a low detection limit of 2.5 × 10 -9  M. Moreover, the proposed Cu 2+ -ISE exhibits a stable potential response with a reduced water layer at the sensing membrane/3D GS interface and is not affected by interferences from light, O 2 and CO 2 ., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Calcium is closely related to the oceanic biosphere and carbonate system. Potentiometry based on a calcium-selective electrode (Ca-ISE) represents a promising tool for detection of calcium ion activities in seawater. This technique, however, generally is limited by the low sensitivity for the inherent Nernstian response (i.e. ca 30 mV/dec). A current pulse based ion-selective electrode with enhanced sensitivity for chronopotentiometric measurements of calcium in seawater is proposed. The Ca 2+ -selective membrane containing lipophilic salt ETH 500 instead of traditional ion-exchanger is galvanostatically controlled. An applied constant cathodic current pulse can leads to the extraction of the calcium ions into the membrane to produce a chronopotential response, which shows a stable and reproducible super-Nernstian response in a narrow calcium activity range. The super-Nernstian region of the electrode depends on not only the the magnitude and duration of the applied current pulse but also the interfering ions. Under optimal conditions, the proposed Ca-ISE exhibits a super-Nernstian response between the calcium concentrations of 10 -2.5 -10 -1.5  M with a slope of ca 80 mV/dec. The current pulse based Ca-ISE has been applied to determination of calcium in seawater with satisfactory results., (Copyright © 2018. Published by Elsevier B.V.)

A method integrating capillary electrophoresis (CE) and gold nanoparticle aggregation-based colorimetry (AuNP-ABC) was described. By using a dual-sheath interface, the running buffer was isolated from the colorimetric reaction solution so that CE and AuNP-ABC would not interfere with each other. The proof-of-concept was validated by assay of polyamidoamine (PAMAM) dendrimers that were fortified in human urine samples. The factors influencing the CE-AuNP-ABC performances were investigated and optimized. Under the optimal conditions, the dendrimers were separated within 8 min, with detection limits of 0.5, 1.2 and 2.6 μg mL -1 for PAMAM G1.0, G2.0 and G3.0, respectively. The sensitivity of CE-AuNP-ABC was comparable to or even better than those of liquid chromatography-fluorimetry and liquid chromatography-mass spectrometry. The results suggested that the proposed strategy can be applied to facile and quick determination of analytes of similar properties in complex matrices., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A magnetic field-directed self-assembly solid contact has been proposed for developing an all-solid-state polymeric membrane Ca 2+ -selective electrode. The solid contact is prepared by physically adsorbing magnetic graphene powder on a magnetic gold electrode under the direction of the magnetic field. The proposed method for preparing solid contact avoids using the aqueous solutions and is simple, fast and general as compared to the multilayer drop-casting and electrodeposition methods. The all-solid-state Ca 2+ -selective electrode based on magnetic graphene as solid contact shows a stable potential response in the linear range of 1.0 × 10 -6 -1.0 × 10 -3  M with a slope of 28.2 mV/decade, and the detection limit is about 4.0 × 10 -7  M. Additionally, the magnetic graphene-based electrode shows a comparable potential stability performance to other graphene-based all-solid-state ion-selective electrodes, such as reduced undesirable water layer and insensitive to the interferences of O 2 , CO 2 and light. This work provides a favorable way to prepare solid contact for use in the field of all-solid-state ion-selective electrodes., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Nanomaterial-based peroxidase-mimetics are an emerging research field that promises to produce alternatives to horseradish peroxidase for a variety of applications. Generally, some peroxidase-mimetics substrates are used in acidic condition (pH ≤ 7). Then, it is necessary to screen some peroxidase-mimetics substrates suitable for basic condition because that some peroxidase-mimetics leached ions in acidic solution. In this paper, using Ni/Co layered double hydroxides (LDHs) as a nano-peroxidase mimic model, we evaluated three fluorogenic substrates suitable for basic condition though experimental conditions, reaction kinetic and glucose detection assay. And the detection of glucose method based on homovanillic acid (HVA) as fluorescent substrate gave wide linear range (0.02-20 μM) and low detection limit (0.01 μM). We also developed a novel platform that could study the inhibitory effects of ascorbic acid and glutathione based on the system of Ni/Co LDHs-HVA-H 2 O 2 ., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A solid-contact ion-selective electrode (SC-ISE) for potassium with MoO 2 microspheres as ion-to-electron transducer is described. MoO 2 microsphers can be synthesized via the reduction of MoO 3 nanobelts in an isopropanol solvent with a mild process, and the obtained MoO 2 microspheres have been characterized by X-ray diffraction and field-emission scanning electron microscopy. With the application of MoO 2 microspheres, the newly fabricated SC-ISE for K + exhibits a stable and rapid potential response. A near Nernstian slope of 55 mV/decade to potassium activities in the range of 10 -5 ‒ 10 -3  M is found and the detection limit is 10 -5.5  M. Impedance spectra and chronopotentiometry results show that a smaller resistance together with a larger double layer capacitance is guaranteed due to the introduction of the intermediate layer of MoO 2 microspheres. Additionally, light, O 2 and CO 2 do not induce significant influences to the present SC-ISE, and a reduced water layer between the ion selective membrane and the underlying conductor is formed. Thus, it is clear that MoO 2 microspheres, as metallic analogues, can be used as a good candidate for the new type of transducing layer in SC-ISEs., (Copyright © 2017 Elsevier B.V. All rights reserved.)

An all-solid-state polymeric membrane Pb(2+) ion-selective electrode (Pb(2+)-ISE) based on bimodal pore C60 (BP-C60) as solid contact has been developed. A BP-C60 film can be readily formed on the surface of a glassy carbon electrode by electrochemical deposition. Cyclic voltammetry and electrochemical impedance spectroscopy have been employed to characterize the BP-C60 film. The large double layer capacitance and fast charge-transfer capability make BP-C60 favorable to be used as solid contact for developing all-solid-state ISEs. The all-solid-state BP-C60-based Pb(2+)-ISE shows a Nernstian response in the range from 1.0×10(-9) to 1.0×10(-3)M with a detection limit of 5.0×10(-10)M. The membrane electrode not only displays an excellent potential stability with the absence of a water layer between the ion-selective membrane and the underlying BP-C60 solid contact, but also is insensitive to interferences from O2, CO2 and light. The proposed solid-contact Pb(2+)-ISE has been applied to determine Pb(2+) in real water samples and the results agree well with those obtained by anodic stripping voltammetry., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A flow injection system incorporated with a polycation-sensitive polymeric membrane electrode in the flow cell is proposed for potentiometric determination of heparin. An external current in nano-ampere scale is continuously applied across the polymeric membrane for controlled release of protamine from the inner filling solution to the sample solution, which makes the electrode membrane regenerate quickly after each measurement. The protamine released at membrane-sample interface is consumed by heparin injected into the flow cell via their strong electrostatic interaction, thus decreasing the measured potential, by which heparin can be detected. Under optimized conditions, a linear relationship between the potential peak height and the concentration of heparin in the sample solution can be obtained in the range of 0.1-2.0 U mL(-1), and the detection limit is 0.06 U mL(-1). The proposed potentiometric sensing system has been successfully applied to the determination of heparin in undiluted sheep whole blood., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A simple and robust approach for the development of solid-state ion-selective electrodes (ISEs) using nanomaterials as solid contacts is described. The electrodes are fabricated by using the mixture of an ionic liquid (IL) and a nanomaterial as intermediate layer, formed by melting the IL. Tetradodecylammonium tetrakis(4-chlorophenyl)borate (ETH 500) is chosen as an model of IL to provide strong adhesion between the inner glassy carbon electrode and the intermediate layer. Nanomaterials including single-walled carbon nanotubes (SWCNTs) and graphene were used as active ion-to-electron transducers between the glassy carbon electrode and the ionophore-doped ISE membrane. By using the proposed approach, the solid-contact Cu(2+)- and Pb(2+)-selective electrodes based on ETH 500/SWCNTs and ETH 500/graphene as transducers, respectively, have been fabricated. The proposed electrodes show detection limits in the nanomolar range and exhibit a good response time and excellent stability., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A polymeric membrane permanganate-selective electrode has been developed as a current-controlled reagent release system for potentiometric detection of reductants in flow injection analysis. By applying an external current, diffusion of permanganate ions across the polymeric membrane can be controlled precisely. The permanganate ions released at the sample-membrane interface from the inner filling solution of the electrode are consumed by reaction with a reductant in the sample solution thus changing the measured membrane potential, by which the reductant can be sensed potentiometrically. Ascorbate, dopamine and norepinephrine have been employed as the model reductants. Under the optimized conditions, the potential peak heights are proportional to the reductant concentrations in the ranges of 1.0×10(-5) to 2.5×10(-7)M for ascorbate, of 1.0×10(-5) to 5.0×10(-7)M for dopamine, and of 1.0×10(-5) to 5.0×10(-7)M for norepinephrine, respectively with the corresponding detection limits of 7.8×10(-8), 1.0×10(-7) and 1.0×10(-7)M. The proposed system has been successfully applied to the determination of reductants in pharmaceutical preparations and vegetables, and the results agree well with those of iodimetric analysis., (Copyright © 2011 Elsevier B.V. All rights reserved.)

In this work, a novel all-solid-state polymeric membrane Pb(2+)-selective electrode was developed by using for the first time poly(2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene) (MEH-PPV) as solid contact. To demonstrate the ion-to-electron transducing ability of MEH-PPV, chronopotentiometry and electrochemical impedance spectroscopy measurements were carried out. The proposed electrodes showed a Nernstian response of 29.1 mV decade(-1) and a lower detection limit of subnanomolar level. No water film was observed with the conventional plasticized PVC membrane. This work demonstrates a new strategy for the fabrication of robust potentiometric ion sensors., (Copyright © 2011 Elsevier B.V. All rights reserved.)

A capillary electrophoresis (CE)-chemiluminescence (CL) method for determining norfloxacin (NFLX) and prulifloxacin (PFLX) was developed based on the enhanced CL intensity of the cerium(IV)-sulfite-fluoroquinolone (FQ) reaction sensitized by terbium(III). The separation was conducted in buffer composed of 20 mM sodium citrate, 4 mM citric acid and 10 mM sodium sulfite at pH 6.1. The CL reagent solution consisted of 2 mM cerium(IV), 4 mM terbium(III) and 1.1 mM hydrochloric acid. NFLX and PFLX were baseline separated within 11 min with detection limits (S/N=3) of 0.057 and 0.084 microg mL(-1), respectively. The maximum intra- and inter-day relative standard deviations (R.S.D.s) of migration time of the analytes were less than 4.0% and 4.2%, respectively. The proposed method was applied to detect NFLX and PFLX in fortified urine sample and the results were comparable to high-performance liquid chromatography (HPLC)-UV method. Moreover, the high selectivity of the CL detection and the high-separation efficiency of CE render the method the potential of quick analyzing fluoroquinolones in real complex matrix.

A computational approach was developed to screening functional monomers and polymerization solvents for rational design of molecularly imprinted polymer (MIP). It was based on the comparison of the binding energy of the complexes between the template and different functional monomers. The effect of the polymerization solvent was included using the polarizable continuum model. According to the theoretical calculation results, the MIP with aniline as template was prepared by emulsion polymerization method using acrylamide (AAM) as functional monomer and divinylbenzene as cross-linker in carbon tetrachloride. The synthesized MIP was then tested by equilibrium-adsorption method, and the MIP demonstrated high removal efficiency to the aniline. The results of this study have indicated the possibility of using computer aided design for rational selection of functional monomers and solvents capable of removal of aniline from contaminated water.