Microliquid/Liquid Interfacial Sensors: Biomimetic Investigation of Transmembrane Mechanisms and Real-Time Determinations of Clemastine, Cyproheptadine, Epinastine, Cetirizine, and Desloratadine.

Antihistamines relieve allergic symptoms by inhibiting the action of histamine. Further understanding of antihistamine transmembrane mechanisms and optimizing the selectivity and real-time monitoring capabilities of drug sensors is necessary. In this study, a micrometer liquid/liquid (L/L) interfacial sensor has served as a biomimetic membrane to investigate the mechanism of interfacial transfer of five antihistamines, i.e., clemastine (CLE), cyproheptadine (CYP), epinastine (EPI), desloratadine (DSL), and cetirizine (CET), and realize the real-time determinations. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques have been used to uncover the electrochemical transfer behavior of the five antihistamines at the L/L interface. Additionally, finite element simulations (FEMs) have been employed to reveal the thermodynamics and kinetics of the process. Visualization of antihistamine partitioning in two phases at different pH values can be realized by ion partition diagrams (IPDs). The IPDs also reveal the transfer mechanism at the L/L interface and provide effective lipophilicity at different pH values. Real-time determinations of these antihistamines have been achieved through potentiostatic chronoamperometry (I-t), exhibiting good selectivity with the addition of nine common organic or inorganic compounds in living organisms and revealing the potential for in vivo pharmacokinetics. Besides providing a satisfactory surrogate for studying the transmembrane mechanism of antihistamines, this work also sheds light on micro- and nano L/L interfacial sensors for in vivo analysis of pharmacokinetics at a single-cell or single-organelle level.

Study on the effect and mechanism of chicken breast on the gel properties of silver carp (Hypophthalmichtys molitrix) surimi.

BACKGROUND: Adding appropriate exogenous substances is an effective means to improve the quality of freshwater fish surimi. The present study investigated the effects of chicken breast on the gel properties of mixed minced meat products. RESULTS: With the increase in the proportion of chicken breast, the breaking force of mixed gels gradually increased. When the addition ratio was 30:70, the gel strength of mixed gels had the highest strength of 759.00 g cm-1 and also the highest water holding capacity of 87.36%. Compared with surimi gels (0:100), the hardness, adhesiveness and chewiness of mixed gels were significantly improved. The increase in the proportion of chicken breast increased the thermal stability of the mixed sol and improved the rheological properties of the mixed sol. When the proportion was 40:60, the area of immobile water (A22 ) in the mixed gel increased significantly, and the highest A22 was 3463.24. The hydrophobic interactions and disulfide bonds in the mixed gel were significantly increased as a result of the addition of chicken breast. The results of microstructure, electrophoresis and Raman spectroscopy indicated that the addition of chicken breast promoted the cross-linking of the proteins in mixed gels, which facilitated the transformation of the protein secondary structure from α-helical to ß-folded structure, thus forming a more uniform and orderly network structure. CONCLUSION: These results suggest that improving the gel properties of silver carp surimi by use of chicken breast has practical implications for the development of new blended products for surimi processing. © 2023 Society of Chemical Industry.

Monitoring Bipolar Electrochemistry and Hydrogen Evolution Reaction of a Single Gold Microparticle under Sub-Micropipette Confinement.

Herein, an approach to track the process of autorepeating bipolar reactions and hydrogen evolution reaction (HER) on a micro gold bipolar electrode (BPE) is established. Once blocking the channel of the sub-micropipette tip, the formed gold microparticle is polarized into the wireless BPE, which induces the dissolution of the gold at the anode and the HER at the cathode. The current response shows a periodic behavior with three regions: the bubble generation region (I), the bubble rupture/generation region (II), and the channel opening region (III). After a stable low baseline current of region I, a series of positive spike signals caused by single H2 nanobubbles rupture/generation are recorded standing for the beginning of region II. Meanwhile, the dissolution of the gold blocking at the orifice will create a new channel, increasing the baseline current for region III, where the synthesis of gold occurs again, resulting in another periodic response. Finite element simulations are applied to unveil the mechanism thermodynamically. In addition, the integral charge of the H2 nanobubbles in region II corresponds to the consumption of the anode gold. It simultaneously monitors autorepeating bipolar reactions of a single gold microparticle and HER of a single H2 nanobubble electrochemically, which reveals an insightful physicochemical mechanism in nanoscale confinement and makes the glass nanopore an ideal candidate to further reveal the heterogeneity of catalytic capability at the single particle level.

Defined Ion-Transfer Voltammetry of a Single Microdroplet at a Polarized Liquid/Liquid Interface.

A strategy for the fast analysis of ion transfer/facilitated ion transfer toward a tiny (femtoliter) water-in-oil droplet has been established. This scenario is embodied by the fusion of a w/o microdroplet at the micro liquid/liquid (L/L) interface, with the use of Fourier transform fast-scan cyclic voltammetry (FT-FSCV) to express the apparent half-wave potentials of anions or cations encapsulated inside the w/o microdroplet. First, the half-wave potential is in strict accordance with the transfer Gibbs free energy of either cations or anions. Second, the half-wave potential has been found to be positively proportional to the logarithmic concentration of ions, shedding thermodynamic insight into ion transfer. Third, as an instance of multivalent biopolymers, the transfer of protamine inside the single w/o microdroplet has been investigated. Obvious discrepancies in the behaviors of the fusion impacts at different pH, as well as in the absence and presence of the cationic surfactant DNNS-, are revealed. The internal mechanism of protamine transfer has been thoroughly investigated. This work proposes a strategy to sensitively and quickly determine the transfer Gibbs energy and the concentration of ions encapsulated in a single microdroplet, and it provides the possibility of analyzing the interfacial transfer properties of trace biomacromolecules inside an aqueous micro- or nanoscale droplet.

Electrochemiluminescent sensor based on an aggregation-induced emission probe for bioanalytical detection.

In recent years, with the rapid development of electrochemiluminescence (ECL) sensors, more luminophores have been designed to achieve high-throughput and reliable analysis. Impressively, after the proposed fantastic concept of "aggregation-induced electrochemiluminescence (AIECL)" by Cola, the application of AIECL emitters provides more abundant choices for the further improvement of ECL sensors. In this review, we briefly report the phenomenon, principle and representative applications of aggregation-induced emission (AIE) and AIECL emitters. Moreover, it is noteworthy that the cases of AIECL sensors for bioanalytical detection are summarized in detail, from 2017 to now. Finally, inspired by the applications of AIECL emitters, relevant prospects and challenges for AIECL sensors are proposed, which is of great significance for exploring more advanced bioanalytical detection technology.

Electrochemical Polymerization Induced Chirality Fixation of Crystalline Pillararene-Based Polymer and Its Application in Interfacial Chiral Sensing.

A new strategy has been developed for the direct chirality fixation, which is induced by electrochemical polymerization, of macrocyclic hosts pillar[5]arene. Taking advantage of electrochemical polymerization, thiophene-modified pillar[5]arene monomers (Th-P[5]A) have been regularly arranged under the action of an electric field to form chiral nanofiber-like crystalline pillar[5]arene-based polymers (poly-Th-P[5]A), showing a significant circular dichroism (CD) signal. With the active photochemical properties, poly-Th-P[5]A is first used as a photoelectrochemical (PEC) chiral sensor for the identification and determination of l- and d-ascorbic acid (l-AA, d-AA) without adding any extra photoactive probes. Importantly, the chiral recognition between poly-Th-P[5]A and l-AA also triggers a polarity conversion for the photocurrent of the polymer, and it greatly results in a broad chiral detection range for l-AA, crossing 6 orders of magnitude. This work provides a promotional strategy for building a PEC chiral recognition platform based on pillararenes.

Ion Selective Detection Based on the Nuances of the Kinetic Fingerprint for Ion Transfer at Soft Interfaces.

A novel approach has been developed for the selective determination of cations or anions based on the application of Fourier transformed staircase sinusoidal voltammetry (FT-SC-SV) in combination with the interface between two immiscible electrolyte solutions (ITIES) in the four-electrode configuration. The electrochemistry at the ITIES provides a very simple yet sensitive platform for the detection of a broad spectrum of redox inactive ions and even the neutral (bio)molecules that can be charged (e.g., protonated in appropriate pH). FT-SC-SV employs a complex potential excitation, i.e., a large-amplitude sine wave superimposed onto a dc bias potential that is stepped/scanned throughout the potential window. The response current is subsequently analyzed in the frequency domain by FT. Although the ions have close standard/formal transfer potential, discrimination and selective detection can be achieved by the higher harmonics. Feasibility and reliability of the proposed approach were verified with two pairs of ions that have very close transfer potentials across the ITIES and were chosen as the model systems. Besides, the additivity of the ionic current magnitude on concentration measured either in the mixture of ionic analytes or in individually prepared solutions containing the separate ionic analyte was tested. The experimental results prove that the principle of additivity holds. Compared with the traditional voltammetry, FT-SC-SV is simpler and more efficient in discrimination and quantification of apparently indistinguishable ion transfer from the viewpoint of thermodynamics. This demonstration may provide a new way for analytical detection of a broad range of redox inactive ions in terms of both fundamentals and applications.

Confined Synthesis of Silver Wire at the Nanopipette-Liquid/Liquid Interface.

Herein, silver wire is synthesized electrochemically within a nanopipette using the nanopipette-liquid/liquid interface. The i-t curve characterizes the growth state of the silver wire. The higher rate of current increase indicates the faster electron transfer and the faster growth of the silver wire; conversely, when the current does not increase significantly with time, i.e., the rate of increase of the current is small, the growth rate of the silver wire is slow. The main driving force for the growth of silver into a linear structure is the theoretical current differential between the water and oil, caused by the concentration difference between the silver nitrate and ferrocene. The growth of the silver wire is also influenced by the shape of the nanopipette. If the diameter of the pipet increases quickly, silver wire tends to produce multibranched structures, while a smaller diameter makes it easier to obtain silver wire with fewer branches due to the confinement effect. This method is also applicable to the synthesis of gold within a nanopipette. The combination of nanopipette and metallic material using a liquid-liquid interface results in a broader application of nanopipettes for nanopore sensors, nanopore electrodes, bipolar electrodes, etc.

A ferrocene-linked metal-covalent organic polymer as a peroxidase-enzyme mimic for dual channel detection of hydrogen peroxide.

A novel ferrocene-linked metal-covalent organic polymer (MCOP-NFC) was synthesized through the Claisen-Schmidt condensation reaction of 1,1'-diacetyl ferrocene and tris(4-formylphenyl)amine. MCOP-NFC acts as a highly efficient artificial enzyme for mimicking peroxidase, and shows good stability in harsh chemical environments including strong bases and acids, and boiling water. Based on the peroxidase-like activity of MCOP-NFC, a highly sensitive dual channel detection method for hydrogen peroxide was developed. For the colorimetric detection strategy, the limit of detection (LOD) reached 2.1 µM, while the limit of detection was found to be as low as 0.08 µM based on the electrochemical detection channel. This study offers a new strategy for the development of an enzyme mimetic on the basis of the covalent assembly of nanostructures, and the proposed electrochemical-colorimetric sensor for H2O2 detection has great potential for applications in biology and biomedicine.

A Fourier Transform-Induced Data Process for Label-Free Selective Nanopore Analysis under Sinusoidal Voltage Excitations.

Nanopore analysis based on a resistive-pulse technique is an attractive tool for single-molecule detection in different fields, but it suffers a great drawback in selectivity. A common solution to this challenge is to add extra sensing aptamers and labels to analytes by improving the sensitivity of their pulses for distinguishing. Compared to the labeling methods, we alternatively develop and demonstrate a novel data process for label-free nanopore analysis that enables the conversion of resistive current signals to more specific frequency domain phase angle features with the contribution from both sinusoidal voltage excitation and Fourier transform. In particular, we find that the transmural capacitance induced by nanoparticle translocations under a sinusoidal voltage plays an important role in this process, making phase angle features more pronounced. In practical applications, the method is successfully applied to directly distinguish the translocation events through a nanopipette by their unique phase angles for similarly sized SiO2, Ag, and Au nanoparticles and soft living organisms of HeLa and LoVo and even in a more complicated case of a SiO2, Ag, and Au nanoparticle mixture.

Ion Transfer-Resolved Fusion Impacts of Single Droplets Probed at the Liquid/Liquid Interface.

An ion transfer-resolved configuration has been introduced to study the fusion impact of a tiny (femtoliter) water-in-oil droplet probed at the micro liquid/liquid (L/L) interface. A periodic linear potential signal with a high frequency is applied in this configuration, and typical (facilitated) ion transfer voltammograms and capacitive voltammograms of single fusion events have been obtained. The responses with voltammetric characteristics allow us to identify ion transfer potentials and elucidate the mechanism in single fusion events. The aqueous droplets encapsulating femtomoles of different quaternary ammonium ions are successfully tracked by fusing with the L/L interface and are identified by their ion transfer potentials. In addition, a capacitive fusion impact is recorded in the obtained current response when no biphasic ion translocation event occurs during a single fusion process, revealing a new mechanism of charge exchange between the electrode surface and polarized interface in the alternating electric field. In addition, a single fusion impact revealed by the facilitating ion transfer is reported, and the obvious discrepancy of fusion event voltammograms with and without ionophore participation is established. By providing new physiochemical insights, this study enables extra trace analysis at the femtomole scale and provides a possible method to electrochemically characterize micro-/nanoscale heterogeneous media.

Ag nanoparticles decorated into metal-organic framework (Ag NPs/ZIF-8) for electrochemical sensing of chloride ion.

In this work, silver nanoparticles (Ag NPs) were decorated into the cavities of ZIF-8 to fabricate a novel Ag NPs/ZIF-8 modified glassy carbon electrode (GCE) for electrochemical sensing of chloride ion. Benefiting from the synergistic properties of ZIF-8 and Ag NPs, the Ag NPs/ZIF-8/GCE showed favorable performance towards chloride ion. For comparison, the electrochemical activity of Ag NPs wrapped by ZIF-8 (Ag NPs@ZIF-8) and Ag NPs coating on ZIF-8 (Ag NPs-on-ZIF-8) were also investigated and it was found that Ag NPs/ZIF-8 possessed the best performance. Some experimental parameters including pH of the supporting electrolyte and scan rate were also investigated. Under optimal conditions, the proposed sensor exhibited excellent stability, reproducibility and selectivity for the determination of chloride ion with a wide linear detection range from 5 to 4000 µmol dm-3 and a low detection limit of 0.61 µmol dm-3 (S/N = 3). The proposed sensor was successfully applied to the determination of chloride ion spiked in human serum. All these results indicated that the developed Ag NPs/ZIF-8/GCE sensor was superior.

Simple and ultrasensitive electrochemical sensor for oxalic acid detection in real samples by one step co-electrodeposition strategy.

Oxalic acid (OA), naturally available in vegetables and foodstuffs derived from them, easily combines with calcium and iron to form insoluble oxalates. Their chelation will result in various renal diseases; thus, the accurate determination of OA is quite significant in the evaluation of food quality and healthcare settings. Here, we developed an electrochemically induced alcohol-free sol-gel method to obtain platinum nanoparticles (PtNPs) adhered with porous silica on glassy carbon electrode (PSiO2-PtNPs/GCE) by a one-step process, which can be potentially used as an excellent catalyst towards electrochemical oxidation of OA for the first time. Without any redox mediator, PSiO2-PtNPs/GCE exhibited a low oxidation overpotential and a significantly high current signal, achieving a wide linear range of concentration from 0 to 45 µM and a detection limit as low as to 25 nM for OA detection. Moreover, this present alcohol-free sol-gel approach towards OA determination was verified in real samples, which is promising for foodstuff analysis and clinical diagnosis. Graphical abstract.

Experimental and finite element method studies for femtomolar cobalt ion detection using a DHI modified nanochannel.

In this work, a sensing nanochannel based on a N-[3-(triethoxysilyl)propyl]-4,5-dihydroimidazole (DHI) modified nanopipette was prepared and characterized for the ultrasensitive detection of cobalt ions (Co2+) in aqueous solutions. By both experimental and theoretical studies, the detection conditions (chelation balance time, pH of the electrolyte, nanopipette diameter, potentials for ionic current) and parameters (rectification value, resistance and ionic current) have been fully optimized, and the proposed Co2+ sensor shows a significantly wide detection range from 20 fM to 0.2 mM, with an ultra-low detection limit down to 0.94 fM.

A novel electrochemical strategy based on porous 3D graphene-starch architecture and silver deposition for ultrasensitive detection of neuron-specific enolase.

This work was aimed at designing a novel and ultrasensitive electrochemical immunoassay strategy to detect neuron-specific enolase (NSE) with a triple signal amplification strategy. A greatly enhanced sensitive detection of NSE was achieved by using porous three-dimensional graphene-starch architecture (3D-GNS) modified on the immunosensor's surface to construct a unique 3D immunoelectrode, which would greatly accelerate electron transfer and capture more protein molecules. 3D-GNS was prepared with starch as a crosslinking agent and stabilizer, which is biocompatible and environmentally friendly. Aggregation-free gold nanoparticle (AuNP) incorporated ordered mesoporous carbon-silica (OMCSi-Au) with good catalytic activity was synthesized as the tracing tag for labeling signal antibody (Ab2). After a sandwich-type immunoreaction, the OMCSi-Au labeled Ab2 was trapped on the surface of the immunosensor, and the high concentration of AuNPs with high dispersion greatly catalyzed the deposition of silver nanoparticles. The deposited silver nanoparticles (AgNPs) could be tested directly with anodic stripping voltammetric analysis (ASV) in potassium chloride solution to monitor the immunoreactions, which greatly enhanced the sensitivity of protein markers with a detection limit of 0.008 pg mL-1, and a linear range of 0.02 pg mL-1 to 35 ng mL-1 for neuron-specific enolase antigen. This proposed immunosensor displayed acceptable accuracy, good stability, and high sensitivity. Good results were also obtained in agreement with the enzyme-linked immunosorbent assay method, which provides greatly promising potential in clinical applications.

Electrochemical synthesis of a nanocomposite consisting of carboxy-modified multi-walled carbon nanotubes, polythionine and platinum nanoparticles for simultaneous voltammetric determination of myricetin and rutin.

The authors describe a method for electrochemical synthesis of a nanocomposite consisting of carboxylated multi-walled carbon nanotubes, polythionine and platinum nanoparticles (denoted as cMWCNT@pTh@Pt). The composite was placed on a glassy carbon electrode (GCE) to obtain a sensor for simultaneous determination of myricetin and rutin by differential pulse voltammetry, with typical peak voltages of 0.16 and 0.34 V (vs. SCE). Under optimal conditions, the modified GCE has a linear response in the range of 0.01-15 µM myricetin concentration range, and a 3 nM lower detection limit. For rutin, the data are 0.01-15 µM and 1.7 nM, respectively. The sensor is selective, stable and reproducible. It was successfully applied to the simultaneous determination of myricetin and rutin in spiked juice samples, and satisfactory results were obtained. Graphical abstract A nanocomposite consists of carboxy multi-walled carbon nanotube (cMWCNT), polythionine (pTh) and platinum nanoparticles (Pt) was presented for the simultaneous determination of myricetin and rutin. The nanocomposite shows excellent electrochemical determination performances based on a synergistic effect among cMWCNT, pTh and Pt.

Voltammetric determination of levofloxacin using silver nanoparticles deposited on a thin nickel oxide porous film.

The authors describe a simplified chemical precipitation method and silver mirror reaction to synthesize a nanocomposite consiting of silver nanoparticles on a thin and porous nickel oxide film. Placed on a glassy carbon electrode (GCE), it allows for the determination of levofloxacin (LEV) via square wave voltammetry (SWV). Under optimal detection conditions, the voltammetric signal (typically measured at around 0.96 V vs. SCE) increases linearly in the 0.25-100 µM LEV concentration range. And the detection limit was calculated as 27 nM (at S/N = 3). The sensor is highly selective, stable and repeatable. It was applied to the determination of LEV in spiked human serum samples, and the satisfactory results confirm the applicability of this sensor to practical analyses. Graphical abstract Schematic of a two-step method to synthesize a nanocomposite consisting of nickel oxide porous thin-film supported silver nanoparticles. The composite was used for improved voltammetric determination of levofloxacin.

Electrochemical Exfoliation of Pillared-Layer Metal-Organic Framework to Boost the Oxygen Evolution Reaction.

Two-dimensional (2D) materials and ultrathin nanosheets are advantageous for elevating the catalysis performance and elucidating the catalysis mechanism of heterogeneous catalysts, but they are mostly restricted to inorganic or organic materials based on covalent bonds. We report an electrochemical/chemical exfoliation strategy for synthesizing metal-organic 2D materials based on coordination bonds. A catechol functionalized ligand is used as the redox active pillar to construct a pillared-layer framework. When the 3D pillared-layer MOF serves as an electrocatalyst for water oxidation (pH 13), the pillar ligands can be oxidized in situ and removed. The remaining ultrathin (2 nm) nanosheets of the metal-organic layers are an efficient catalyst with overpotentials as low as 211 mV at 10 mA cm-2 and a turnover frequency as high as 30 s-1 at an overpotential of 300 mV.

Application of Coal in Electrochemical Sensing.

In this work, we first report a new application of coal as a novel modified electrode material in electrochemical sensing, achieving excellent electrochemical performance similar to graphene and making the utilization of coal become more multipurpose and more meaningful. Raw coal was first ball-milled, then centrifugated, and finally annealed, thus obtaining annealed coal that possesses lots of edge-plane-like defective sites, resulting in good electron-transfer efficiency and excellent electrocatalytic activity, which makes it promising when used as signal amplifier material and as a modified matrix in electrochemical sensing. And we also described an investigation into the electrochemical and spectroscopic properties of annealed coal samples and their application for the detection of electroactive redox molecules (rutin). Compared with other published carbon materials modified sensors, the annealed coal/chitosan/GCE sensor exhibited excellent electrocatalytic activity for the determination of rutin with good sensitivity, providing a wide linear detection range from 0.001 to 10 µmol dm-3 and a low detection limit of 0.2 nmol dm-3 (S/N = 3). Moreover, when the annealed coal/GCE sensor was applied for the determination of ascorbic acid, dopamine, uric acid, guanine, and adenine commonly contained in blood samples and urine samples, it also exhibited excellent detection performance with strong electrocatalytic activity. This research has opened up the application of coal in electroanalytical chemistry and held great promise for the sensing and biosensing application, which can be promising used as an alternative material of graphene.

Single Organic Droplet Collision Voltammogram via Electron Transfer Coupled Ion Transfer.

Single-emulsion toluene oil droplets (femtoliter) containing a hydrophobic redox probe that are dispersed in water stochastically collide with an ultramicroelectrode (UME). The fast-scan cyclic voltammetry (FSCV) or Fourier-transformed sinusoidal voltammetry (FTSV) is applied: the UME was scanned with a fast, repetitive triangular, or sinusoidal potential, and its current in time/frequency domains were monitored. The electron transfer at the UME/oil interface is coupled with ion transfer at the oil/water interface. Thus, the obtained transient voltammograms of a myriad of ions were used to estimate thermodynamics of ion transfer at the toluene/water interface. Additionally, the single-droplet voltammogram combined with finite element simulations reveal the droplet's size and shape distributions. Four collision mechanisms with new physical insights were also uncovered via comprehensive analysis of phase angle in the frequency domain, time domain FSCVs, and finite element simulations.