A Disposable Planar Paper‐Based Potentiometric Ion‐Sensing Platform

Ion‐selective electrodes (ISEs) are widely used tools for fast and accurate ion sensing. Herein their design is simplified by embedding a potentiometric cell into paper, complete with an ISE, a reference electrode, and a paper‐based microfluidic sample zone that offer the full function of a conventional ISE setup. The disposable planar paper‐based ion‐sensing platform is suitable for low‐cost point‐of‐care and in‐field testing applications. The design is symmetrical and each interfacial potential within the cell is well defined and reproducible, so that the response of the device can be theoretically predicted. For a demonstration of clinical applications, paper‐based Cl^? and K⁺ sensors are fabricated with highly reproducible and linear responses towards different concentrations of analyte ions in aqueous and biological samples. The single‐use devices can be fabricated by a scalable method, do not need any pretreatment prior to use, and only require a sample volume of 20 μL.     

Mussel-Inspired Surface-Imprinted Sensors for Potentiometric Label-Free Detection of Biological Species

Using sensors to quantify clinically relevant biological species has emerged as a fascinating research field due to their potential to revolutionize clinical diagnosis and therapeutic monitoring. Taking advantage of the wide utility in clinical analysis and low cost of potentiometric ion sensors, we demonstrate a method to use such ion sensors to quantify bioanalytes without chemical labels. This is achieved by combination of chronopotentiometry with a mussel-inspired surface imprinting technique. The biomimetic sensing method is based on a blocking mechanism by which the recognition reaction between the surface imprinted polymer and a bioanalyte can block the current-induced ion transfer of an indicator ion, thus causing a potential change. The present method offers high sensitivity and excellent selectivity for detection of biological analytes. As models, trypsin and yeast cells can be measured at levels down to 0.03 U mL⁻¹ and 50 CFU mL⁻¹, respectively.     

Novel Biomedical Sensors for Flow Injection Potentiometric Determination of Creatinine in Human Serum

Coated‐wire (CW) and tubular (Tu) type membrane sensors for creatinine are developed. These consist of creatinine tungstophosphate(CTP), creatinine molybdophosphate (CMP) and creatinine picrolonate (CPC) ion‐pair complexes as electroactive materials dispersed in plasticized poly(vinyl chloride) matrix membranes. Electrochemical evaluation of these sensors under static (batch) mode of operation reveals near‐Nernstian response with slopes of 62.9, 58.1, and 55.2 mV decade^?1 over the concentration range 1×10^?2–5.0×10^?6, 1×10^?2–7.5×10^?5, and 1×10^?2?3.1×10^?5 mol L^?1. The lower detection limits are 0.39, 3.49, and 2.20 μg mL^?1 creatinine with CTP, CMP and CPC membrane based sensors plasticized with o‐NPOE, respectively. Tubular and coated wire CTP membrane sensors are incorporated in flow‐through cells and used as detectors for flow injection analysis (FIA) of creatinine. The intrinsic characteristics of the detectors under hydrodynamic mode of operation in a low dispersion manifold are determined and compared with data obtained under static mode of operation. With 10^?2 mol L^?1 phosphate buffer of pH 4.5 as a carrier solution, the tubular and coated wire CTP detectors exhibit rapid response of 58.9 and 50.7 mV decade^?1 over the concentration range 1×10^?2–1×10^?5 mol L^?1 and detection limits of 0.39 μg mL^?1 and 0.85 μg mL^?1, respectively. Validation of the assay methods with the proposed sensors by measuring the lower detection limit, range, accuracy, precision, repeatability and between‐day‐variability reveals good performance characteristics confirming applicability for continuous determination of creatinine. The sensors are used for determining creatinine in human blood serum at an input rate of 40 samples per hour. No interferences are caused by creatine, most common anions, cations and organic species normally present in biological fluids. The results favorably compare with data obtained using the standard spectrophotometric method.     

A Three‐Dimensional Origami Paper‐Based Device for Potentiometric Biosensing

Current paper‐based potentiometric ion‐sensing platforms are planar devices used for clinically relevant ions. These devices, however, have not been designed for the potentiometric biosensing of proteins or small molecule analytes. A three‐dimensional origami paper‐based device, in which a solid‐contact ion‐selective electrode is integrated with an all‐solid‐state reference electrode, is described for the first time. The device is made by impregnation of paper with appropriate bioreceptors and reporting reagents on different zones. By folding and unfolding the paper structures, versatile potentiometric bioassays can be performed. A USB‐controlled miniaturized electrochemical detector can be used for simple and in situ measurements. Using butyrylcholinesterase as a model enzyme, the device has been successfully applied to the detection of enzyme activities and organophosphate pesticides involved in the enzymatic system as inhibitors. The proposed 3D origami paper device allows the potentiometric biosensing of proteins and small molecules in a simple, portable, and cost‐effective way.     

Voltammetry as a Virtual Potentiometric Sensor in Modeling of a Metal‐Ligand System and Refinement of Stability Constants. Part 1. Polarographic and Glass Electrode Potentiometric Study of a Dynamic Cd‐Glycine System

A mathematical conversion of data coming from nonequilibrium and dynamic voltammetric techniques (a direct current sampled (DC) and differential pulse (DP) polarography) into potentiometric sensor type of data is described and tested on a dynamic metal‐ligand system. A combined experiment involving DCP, DPP and glass electrode potentiometry (GEP) was performed on a single solution sample containing a fixed [L_T] : [M_T] ratio (acid‐base titration). Dedicated potentiometric software ESTA was successfully employed in the refinement operations performed on virtual potentiometric (VP) data obtained from DC and DP polarography. It was possible to refine stability constants either separately, from VP‐DC or VP‐DP, or simultaneously from any combination of VP‐DC, VP‐DP and GEP. The concept of VP‐DC or VP‐DP is reported for the first time and numerous documented and possible advantages are discussed. The proposed procedure can be easily utilized also by nonelectrochemists who are interested in, e.g., the ligand design strategies.     

Novel Copper(II)-Selective Potentiometric Sensor Based on a Folic Acid-Functionalized Carbon Nanotube Material

Abstract

A folic acid-functionalized carbon nanotube nanomaterial was prepared by immobilizing folic acid molecules on the carbon nanotubes through covalent bonds. The material was characterized using Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy and scanning electron microscopy. Fourier transform infrared spectroscopy confirmed that folic acid molecules were grafted on the carbon nanotube surfaces through the amide bonds between the carboxylic acid functional groups of the oxidized carbon nanotubes and the amine groups of the folic acid molecules. The folic acid molecules bonded to carbon nanotube surfaces led to appreciable changes in the morphology. By using currently obtained folic acid-functionalized carbon nanotube nanomaterial as electroactive material in a polyvinyl chloride membrane, a potentiometric copper (II)-selective sensor was developed. Membrane optimization studies showed that the composition exhibiting the best potentiometric properties was 4.0% (w/w) folic acid–carbon nanotube, 64.0% (w/w) o-nitrophenyl octylether, and 32.0% (w/w) polyvinyl chloride. The developed sensor displayed a linear response in the copper (II) concentration ranging from 1.0?×?10^–6 to 1.0?×?10^–1 M with a correlation coefficient of 0.9993 and a slope of 29.8?±?0.6?mV/decade of activity. The response time, detection limit, and pH working range were determined to be 4?s, 3.8?×?10^–7 M and 4.0–8.0, respectively. The developed sensor showed highly selective and satisfactory potentiometric response for the determination of copper (II) in a Turkish coin.     

Flow‐Through Potentiometric Sensors for Alizarin Red S Dye and Their Application for Aluminum Determination

Novel selective and sensitive poly (vinyl chloride) membrane sensors are developed for measuring alizarin red S (AR) based on the use of aliquate 336, Mg^IIphthalocyanine (MgPc), Cu^IIphthalocyanine (CuPc) and Fe^II phthalocyanine (FePc) plasticized poly (vinyl chloride) membrane. The sensors display Nernestian response with slopes of ‐50.6 ± 0.6 , ‐37.4 ± 0.5 , ‐37.7 ± 0.8 and ‐35.0 ± 0.7 mV decade^?1 over the range of 5.2 × 10^?6 to 1 × 10^?2 mol L^?1 for all of them and detection limits of 5.9 × 10^?7, 1.9 × 10‐^?6 2.3 × 10^?6 and 1.9 × 10^?6 mol L^?1 for aliquate, MgPc, CuPc and FePc membrane based sensor, respectively. The sensors exhibit long life span, long term potential stability, high reproducibility, fast response and good discrimination ability towards alizarinate ion in comparison with many other anions. A tubular detector based on aliquate, MgPc, CuPc and FePc was further developed and coupled to a flow‐injection system for alizarin (AR) determination. Under optimized conditions, the linearity range is 1.0 × 10^?5‐ 1.0 × 10^?1 mol L^?1, with a slope of ‐52.1 ± 0.8, 20.9 ± 0.7, 23.6 ± 0.4 and 25 ± 1.1 mV decade^?1 and a reproducibility of ± 0.8 mV (n = 6) for aliquate, MgPc, CuPc and FePc membrane based sensors, respectively. The sensor based on aliquate is further utilized for a potentiodynamic quantification of aluminum in sludge samples and deodorants. The buffered solution of alizarin was allowed to react in a flow system with aluminum. The calibration curve of Al was found to be linear over a concentration range of 0.1 to 1.8 and 1.0 ‐ 40 μg mL^?1 with a slope = 16.9 (r² = 0.993) and 1.76 (r² = 0.994) mV (μg/mL)^?1 and a detection limit of 0.08 and 0.5 μg mL^?1 for 10^?4 and 10^?3 mol L^?1 AR^? as a carrier, respectively. The method was successfully used for determining aluminum in sludge samples and deodorants. The data agree fairly well the nominal values and with results obtain by continuous flow hydride generation inductively coupled plasma (ICP) method.     

Highly Selective Nd(III) Sensors: Novel Macrocyclic Compounds for Potentiometric Determination of Neodymium

Conductometric studies on the complexation properties of two newly synthesized lariat ethers viz 1,5‐di(cyanoethane)‐2,4 : 7,8 : 13,14‐tribenzo‐1,5‐diaza‐9,12‐dioxacyclopentadeca‐2,7,13‐triene (L₁) and 1,5‐di(cyanoethane)‐2,3,4‐pyridine‐7,8 : 13,14‐dibenzo‐1,3,5‐triaza‐9,12‐dioxa cyclopentadeca‐2,7,13‐triene (L₂) towards various metal ions in acetonitrile solutions revealed the formation of 1 : 1 ligand metal complexation. These compounds were explored as neutral ionophores for the fabrication of Nd³⁺ selective and sensitive membrane coated graphite electrodes (CGEs). Among all the electrodes prepared, CGEs with membrane composition L₁(5%) : NaTPB(3%) : NPOE (57%) : PVC (35%) and L₂(5%) : NaTPB(3%) : NPOE (53%) : PVC (39%) showed best performance. Both the electrodes showed Nernstian response towards Nd³⁺ ions over a wide concentration range with detection limits 3.8×10^?8 mol L^?1 and 1.6×10^?8 mol L^?1 respectively. These electrodes showed a fast response time of <15 s and could be used over a period of three months without significant divergence in their characteristics. The proposed electrodes revealed very good selectivity for Nd³⁺ ions over several ions. However, higher concentration of Co²⁺, La³⁺, Pr³⁺ and Yb³⁺ caused some interference. The potentiometric response of these electrodes was excellent in the range of pH 3.5 to 7.6 and they could tolerate up to 20% (v/v) nonaqueous media in the test solutions. These electrodes were used successfully as indicator electrode in the potentiometric titration of Nd³⁺ against EDTA and also in the quantitative determination of Nd³⁺ ions from binary mixtures and water samples.     

Novel Potentiometric PVC‐Membrane and Coated Graphite Sensors for Lanthanum(III)

Preliminary theoretical studies revealed the selective complexation of bis (2‐mercaptoanil) diacetyl (BMDA) with La³⁺ over several alkali, alkaline earth and heavy metal ions. Thus, novel PVC‐based membrane (PBM) and coated graphite membrane (CGM) sensors for La(III) based on BMDA were prepared. The electrodes display Nernstian behavior over wide concentration ranges (i.e., 1.0×10^?5–1.0×10^?1 M for PBM and 1.0×10^?6–1.0×10^?1 M for CGM). The potential response of sensors was pH independent in the range of 4.0–8.0. The sensors possess satisfactory reproducibility, fast response time (<15 s), and specially excellent discriminating ability for La³⁺ ions with respect to most of the cations. The membrane sensor was used as an indicator electrode in potentiometric titration of lanthanum ions with EDTA. The coated graphite membrane electrode was applied in determination of fluoride ions in mouth wash preparations.     

Coumarin‐3‐Aldehyde as a Scaffold for the Design of Tunable PET‐Modulated Fluorescent Sensors for Neurotransmitters

NeuroSensor 521 (NS521) is a fluorescent sensor for primary‐amine neurotransmitters based on a platform that consists of an aryl moiety appended to position C4 of the coumarin‐3‐aldehyde scaffold. We demonstrate that sensors based on this platform behave as a directly linked donor–acceptor system that operates through an intramolecular acceptor‐excited photoinduced electron transfer (a‐PET) mechanism. To evaluate the PET process, a series of benzene‐ and thiophene‐substituted derivatives were prepared and the photophysical properties, binding affinities, and fluorescence responses toward glutamate, norepinephrine, and dopamine were determined. The calculated energy of the highest occupied molecular orbital (E_HOMO) of the pendant aryl substituents, along with oxidation and reduction potential values derived from the calculated molecular orbital energy values of the platform components, allowed for calculation of the fluorescence properties of the benzene sensor series. Interestingly, the thiophene derivatives did not fit the typical PET model, highlighting the limitations of the method. A new sensor, NeuroSensor 539, displayed enhanced photophysical properties aptly suited for biological imaging. NeuroSensor 539 was validated by selectively labeling and imaging norepinephrine in secretory vesicles of live chromaffin cells.     

Novel Potentiometric Sensors for Determination of Melatonin and Oxomemazine in Biological Samples and in Pharmaceutical Formulations

Simple, selective and accurate sensors were developed for the determination of melatonin and oxomemazine in biological samples (urine) and in pharmaceutical preparations. Potentiometric measurements were based on bismus tetraiodate‐drug ion‐pair as novel electroactive materials incorporating a plasticized PVC membrane with o‐nitrophenyl octyl ether or dioctyl phthalate. Each sensor was conditioned for at least two days in 0.1 M drug solution before use. It exhibited fast and stable Nernstian response for melatonin and oxomemazine over the concentration range of 1.0×10^?6–1.0×10^?2 M and 1.0×10^?5–1.0×10^?2 M, pH range of 3.0–6.5 and 3.5–6.0 for melatonin and oxomemazine sensors, respectively. Results with an average recovery not more than 101 % and a mean standard deviation less than 1.0 % of the nominal were obtained for the four sensors. The sensors showed reasonable selectivity towards investigated drugs in presence of many cations.     

Deoxyribonucleoside‐Modified Squaraines as Near‐IR Viscosity Sensors

Deoxyribonucleoside‐modified squaraines were synthesized by Sonogashira coupling reactions using an unsymmetrical, terminal alkynylated benzothiazolium squaraine dye. These non‐natural nucleosides exhibited fluorescent ‘turn‐on’ properties in viscous conditions with an enhancement of >300‐fold. The viscosity‐dependent fluorescence enhancement was attributed to a combination of hampering both molecular aggregation and intramolecular bond rotation of the squaraine probe. Fluorescence microscopy allowed visualization of highly viscous regions during various stages of cellular mitosis.     

Potentiometric Iodide Selectivity of Polymer‐Membrane Sensors Based on Co(II) Triazole Derivative

The 3‐amion‐5‐mercapto‐1,2,4‐triazole cobalt(II) [Co(II)AMETR] was used as a new carrier for preparing polymeric membrane selective sensor which exhibited high affinity for iodide ion. The effects of membrane composition, pH, the influence of lipophilic ion additives and plasticizer on the response characteristics of the sensor were investigated. The sensor showed a near Nernstian slope of ?56.6 mV/decade for I^? ion over a wide concentration range from 8.5×10^?7 to 1.0×10^?1 M with a low detection limit of 5.1×10^?7 M. The sensor has a fast response time and could be used over a wide pH range of 2–8. The response mechanism is discussed in view of the AC impedance technique. The sensor was successfully applied to direct determination of iodide content in environmental water samples and mouth wash samples.     

Potentiometric Anion Selectivity and Analytical Applications of Polymer Membrane Electrodes Based on Novel Mn(III)‐ and Mn(IV)‐Salophen Complexes

New Mn(III)‐L and Mn(IV)‐L complexes were prepared from the highly lipophilic salophen ligand (L): phenol 2,2′‐[(4,5‐dimethyl‐1,2‐phenylene)bis[(E)‐nitrilomethylidyne]]bis[4,6‐bis(1,1‐dimethylethyl). The prepared complexes were fully characterized and used for the construction of thiocyanate membrane electrodes. Optimized membrane electrodes contained 33.0 mg PVC, 66.0 mg o‐nitrophenyloctylether, 50 or 5 (mole %) tetrakis(trifluoromethyl)phenyl borate and 1 mg Mn(III)‐L (sensor 2) or Mn‐(IV)‐L (sensor 12), respectively. Such electrodes exhibited linear responses toward thiocynate in a concentration range of 10^?1–10^?5 M and detection limits of 8.3×10^?6, 8.9×10^?6 M for sensor 2 and 12, respectively. Optimized membrane electrodes exhbited high selectivty toward thiocayante compared to more lipophilic anions. The observed thiocyanate selectivity of the optimized membranes was confirmed by formation constant calculations for Mn(III)‐L and Mn(IV)‐L with SCN^?, β=10^14.1 and 10^12.5, which was measured potentiometrically using the sandwich membrane method. Furthermore, computational study using DFT calculations was performed to at DFT/B3LYP level of theory to confirm the observed selectivity data. The response times were 3 and 0.5 min for low and high concentrations. The lifetimes of the optimized electrodes were ～4–6 weeks. The analytical utility of the optimized membrane electrodes was demonstrated by the analysis of thiocyanate level in different saliva samples.     

Fixed‐Component Lanthanide‐Hybrid‐Fabricated Full‐Color Photoluminescent Films as Vapoluminescent Sensors

Full‐color lanthanide (Ln) photoluminescent materials have attracted considerable interest owing to their potential applications in display systems and lighting technologies. Herein, full‐color photoluminescent films have been designed and fabricated facilely with a fixed‐component Ln‐based (Ln=Tb and Eu) polymer hybrid doped with a proton‐sensitive amide‐type β‐diketonated photosensitizer, N‐(2‐pyridinyl)benzoylacetamide (HPBA). The tunable photoluminescence emissions of the films are achieved by changing the amounts of OH^? in the hybrid rather than varying the relative concentrations of the lanthanide ions and photosensitizers, thus representing a new paradigm for full‐color displays. The emission color can also be finely tuned through the variation of the excitation wavelength, and white‐light emission can be achieved when the given film is excited at the visible region (405 nm). The photophysical properties and the mechanisms of the intra‐ and intermolecular energy transfer before and after deprotonation have been investigated in detail. Meanwhile, the films might find application as vapoluminescent sensors due to their good stability, sensitivity, reversibility, and quick response when triggered by a base–acid vapor.     

Preparation of Functional Polyamine Scaffolds via Mitsunobu Post‐Polymerization Modification Reactions

A Mitsunobu reaction of trifluoroacetamide (TFA amide) and alcohols is used in a post‐polymerization modification process. The reaction is conducted on polystyrene (PSt) bearing 20 mol% TFA amide groups with 4‐methyl benzyl alcohol in the presence of a N,N,N′,N′‐tetramethylazodicarboxamide and tributylphosphine as mediators. The Mitsunobu reaction on polymer proceeds efficiently, as confirmed by the obvious precipitation generation during the reaction and the conversion of TFA amide moiety reached 88.6% confirmed by ¹⁹F NMR measurement, yielding PSt bearing tertiary TFA amide moieties. The obtained polymers featuring tertiary TFA amide moieties are deprotected in the presence of tetrabutylammonium hydroxide as a base to afford corresponding polymers featuring functionalized polyamine scaffolds with 92.5% conversion. In addition, the precise structural assignment is proven by synthesis and analysis of the model monomeric compounds and the respective model polymers.

     

p‐Quaterphenylene as an Aggregation‐Induced Emission Fluorogen in Supramolecular Organogels and Fluorescent Sensors

Two dumbbell‐shaped organogelators with a p ‐quaterphenylene core were synthesized, and their self‐assembly properties were investigated. These low‐molecular‐weight gelators could form self‐supporting gels in many apolar organic solvents with an H‐type aggregation form through a synergic effect of π–π stacking, intermolecular translation‐related hydrogen bonding, and van der Waals forces. In comparison to the p ‐terphenylene‐cored gelator, the extended π‐conjugated segment improved the gelation efficiency significantly with enhanced gelation rate. Additionally, these p ‐quaterphenylene‐centered gelators exhibited strong fluorescence emission induced by aggregation, which not only provided an in situ method to optically monitor the gelation process, but also endowed these self‐assemblies with substantial applications in sensing explosives.