Response Patterns of Chromoionophore-Based Bulk Optodes Containing Lipophilic Electrolytes: Toward Background-Independent pH-Sensing.

Despite a number of advantages of ion-selective optical sensors (optodes), their practical application is limited by their response mechanism, which leads to the dependence of the signal on the activity of two ions (analyte ion and the so-called reference ion) in the solution at the same time. Here, we show that the introduction of a lipophilic electrolyte into the polymeric optode membrane allows assessing the ionic activity of H+ cations regardless of the concentration of the background electrolyte containing a hydrophilic cation, with NaCl as an example of such an electrolyte. For the first time, the applicability of this approach is proven theoretically utilizing the numerical simulation of optode response. A correlation between the interfacial potential stability and the single-ion optical response is established. The predicted optical response is independent of background cation concentration to a significant extent. Theoretical conclusions are supported by experimental data obtained with chromoionophore-based optodes doped with various lipophilic electrolytes, including ionic liquids, by thin-film spectrophotometry and macrophotography coupled with digital color analysis. Most of the experimental sensor characteristics, such as the response range and its median, as well as its independence from the background electrolyte concentration are in quantitative agreement with the proposed theoretical description.

Structurally engineered ion-receptor probe immobilized porous polymer platform as reusable solid-state chromogenic sensor for the ultra-trace sensing and recovery of mercury ions.

This study reports an efficacious solid-state optical sensor through the synergistic coalescences of an original chromoionophoric probe and a structurally engineered porous polymer monolith for the selective and sensitive colorimetric spotting of ultra-trace toxic mercury ions. The unique properties of the bimodal macro-/meso-pore structured polymer, i.e., poly(AAm-co-EGDMA) monolith, offer voluminous and uniform anchoring of probe molecules, i.e., (Z)-N-phenyl-2-(quinoline-4-yl-methylene)hydrazine-1-carbothioamide (PQMHC). The structure/surface features of the sensory system, i.e., surface area, pore dimensions, monolith framework, elemental mapping, and phase composition, were examined by p-XRD, XPS, FT-IR, HR-TEM-SAED, FE-SEM-EDAX, and BET/BJH analysis. The sensor's ion-capturing ability was established through naked eye color transition and UV-Vis-DRS response. The sensor exhibits a strong binding affinity for Hg2+, with a linear signal response in the concentration range of 0-200 µg/L (r2 >0.999), with a detection limit of 0.33 µg/L. The analytical parameters were optimized to facilitate pH-dependent visual sensing of ultra-trace Hg2+ in ≤ 30 s. The sensor exhibits high chemical/physical stability characteristics, with reliable data reproducibility (RSD ≤1.94 %), while testing with natural/synthetic water and cigarette samples. The proposed work offers a cost-effective and reusable naked-eye sensory system for the selective sensing of ultra-trace Hg2+, with potential prospects of commercialization considering their simplicity, viability, and reliability.

Simple colorimetric copper(II) sensor - Spectral characterization and possible applications.

New o-hydroxyazocompound L bearing pyrrole residue was obtained in the simple synthetic protocol. The structure of L was confirmed and analyzed by X-ray diffraction. It was found that new chemosensor can be successfully used as copper(II) selective spectrophotometric regent in solution and can be also applied for the preparation of sensing materials generating selective color signal upon interaction with copper(II). Selective colorimetric response towards copper(II) is manifested by a distinct color change from yellow to pink. Proposed systems were effectively used for copper(II) determination at concentration level 10-8 M in model and real samples of water.

Macrocyclic chemosensors with anthraquinone signaling unit built into ionophore. Experimental and computational studies (part I) - synthesis and effect of proton binding on spectrophotometric and electrochemical properties.

Two macrocyclic chemosensors with anthraquinone signaling unit incorporated into ionophore system (via positions 1 and 8) have been synthesized and subsequently their physicochemical properties became the subject of our extensive research. First ligand, labeled in the paper as AQ-Ncrown is characterized by a cyclic structure of a crown ether, while second one AQ-Ncrypt includes an additional ethoxy bridge, which ensures the bicyclic character of a cryptand. The studied macrocycles possess both oxygen and nitrogen heteroatoms in the ionophore cavity. Dualistic (chromophore and electrophore) signaling nature of described compounds, makes them potentially attractive molecular recognition systems. The aim of our research was to synthesize and analyze the spectroscopic, acid-base and redox properties of aforesaid macrocycles. Furthermore, we have combined experimental approach together with theoretical investigations. The equilibrium structures of AQ-Ncrown and AQ-Ncrypt were determined with the use of DFT calculations. The sensitivity of studied macrocycles towards interactions with protons was scrutinized. The complete pH-spectrophotometric characteristic of studied ligands together with their protolytic forms and corresponding pKa values were determined. The influence of medium (aprotic and protic solvent) on spectral effects was described. Furthermore, the molecular electrostatic potential maps for ligands and differential electron densities for their mono and dianions were calculated. The redox reactions was investigated at different pHs by cyclic voltammetry. Electrochemical results have presented intriguing phenomenon: the specific stabilization of the reduced form of the protonated molecules. The calculations have revealed that this is a consequence of barrierless intramolecular proton transfer (from the macrocycle cavity onto the anthraquinone moiety) that might occur during the reduction process in acidic medium.

Non-Enzymatic Phenylboronic Acid-Based Optode Membrane for Glucose Monitoring in Serums of Diabetic Patients and in the Culture Medium of Human Embryos.

Monitoring glucose levels is important not only for diabetics, but also for tracking embryonic development in human embryo culture media. In this study, an optochemical sensor (glucose-selective polymer membrane) was fabricated for the determination of glucose in serum from diabetic patients and the culture media of human embryos. The optode membranes were formulated using polyvinyl chloride (PVC) as the polymer matrix and 4',5'-dibromofluorescein octadecyl ester (ETH 7075) as the chromoionophore. The sensitivity of the optode membranes was optimized using two different plasticizers (tricresyl phosphate-TCP and nitrophenyloctyl ether-NOPE) and three ionophores (nitrophenylboronic acid-NPBA, trifluorophenyboronic acid-TFPBA, 4'-nitrobenzo-15-crown-5) and tested for glucose detection. The best optode membrane was formulated from 49.5% PVC, 49.5% TCP, 1% NPBA, and 1% ETH 7075. It showed a linear dynamic range of 10-3 M to 10-1 M, with a detection limit of 9 × 10-4 M and a response time of 2 min. The detection mechanism involves H-bonding between NPBA and glucose, which was confirmed by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR). The reaction also involves the formation of boronate esters in basic media with deprotonation of the chromoionophore (ETH 7075), leading to a decrease in UV-Vis absorbance at λmax = 530 nm. The membrane optode was used for glucose determination in synthetic culture medium, commercial embryo culture medium (GLOBAL® TOTAL® W/HEPES), and serum from normal and diabetic patients, showing good accuracy and precision of the optode.

Novel Diazocrowns with Pyrrole Residue as Lead(II)Colorimetric Probes.

Novel 18- and 23-membered diazomacrocycles were obtained with satisfactory yields by diazocoupling of aromatic diamines with pyrrole in reactions carried under high dilution conditions. X-ray structure of macrocycle bearing five carbon atoms linkage was determined and described. Compounds were characterized as chromogenic heavy metal ions receptors. Selective color and spectral response for lead(II) was found in acetonitrile and its mixture with water. Complexation properties of newly obtained macrocycles with a hydrocarbon chain were compared with the properties of their oligoether analogs. The influence of the introduction of hydrocarbon residue as a part of macrocycle on the lead(II) binding was discussed. Selective and sensitive colorimetric probe for lead(II) in aqueous acetonitrile with detection limit 56.1 µg/L was proposed.

Colorimetric ratiometry with ion optodes for spatially resolved concentration analysis.

The deprotonation degree of the lipophilic pH indicator dye (chromoionophore) in ionophore-based ion optodes (so-called bulk optodes) has traditionally been measured spectrophotometrically. This makes it difficult to obtain spatially resolved concentration information, for example in the study of heterogenous systems. This article reports on a new colorimetric method that relies on a ratiometric image analysis. The acquision of image data allows one to map the deprotonation degree in two dimensions, which in turn is used to obtain the spatially-resolved ion concentration of the image. Using the detection of potassium as an example, the deprotonation degree data calculated on the basis of image analysis correlate quantitatively with those from spectrophotometry. They showed no dependence on the type of camera used in spite of their different gamma correction values and spectral sensitivities, as expected from theory. As an example, the method is successfully applied to the pixel level analysis of an ensemble of pictures acquired at different times to spatially and temporally observe potassium ion diffusion into an agarose gel containing a potassium-selective optical sensor microemulsion.

Solid-state ion recognition strategy using 2D hexagonal mesophase silica monolithic platform: a smart two-in-one approach for rapid and selective sensing of Cd2+ and Hg2+ ions.

The possibility of a multifunctional and reversible solid-state colorimetric sensor is described for the identification and quantification of ultra-trace Cd2+ and Hg2+ ions, using a honeycomb-structured mesoporous silica monolith conjoined with an indigenous chromoionophoric probe, i.e., 4-hexyl-6-((5-mercapto-1,3,4-thiadiazol-2-yl)diazenyl)benzene-1,3-diol (HMTAR). The amphiphilic probe is characterized using NMR, FT-IR, HR-MS, and CHNS elemental analysis. The structural and surface properties of the monolithic template have been characterized using p-XRD, XPS, TEM-SAED, SEM-EDAX, FT-IR, TG-DTA, and N2 isotherm analysis. The unique structural features and distinct analytical properties of the solid-state sensor proffer a strong response in selectively signaling the target analytes. The probe (HMTAR) exhibits a 1:1 stoichiometric binding ratio with the target ions (Cd2+ & Hg2+), with a visual color change from pale orange to dark red for Cd2+ (525 nm, λmax), and to purple for Hg2+ (530 nm, λmax), respectively, in the pH range 7.0-8.0. The influence of various analytical criteria such as pH, temperature, response kinetics, critical probe concentration, sensor quantity, matrix tolerance, linear response range, reusability, the limit of detection (LOD), and quantification (LOQ) has been investigated to validate the sensor performance. The proposed method displays a linear signal response in the concentration range 5-100 µg/L, with a LOD value of 2.67 and 2.90 µg/L, for Cd2+ and Hg2+, respectively. The real-world efficacy of the sensor material has been tested with real and synthetic water samples with a significant recovery value of ≥ 99.2%, to authenticate its data reliability and reproducibility (RSD ≤ 3.53%). Graphical abstract.

Construction of a Hydrogel Pectin-Based Triglyceride Optical Biosensor with Immobilized Lipase Enzymes.

A novel and simple optical biosensor to detect triglycerides (TGs) has been successfully constructed by using pectin hydrogel membrane as the indicator pH and chromoionophore ETH 5294 (CI), with lipase as the catalyst. The enzymatic working system against TGs releasing H+ ions will affect the color absorbance of CI. The characterization results show that a TG biosensor has the optimum condition and sensitivity at the phosphate buffer concentration of 50 mM, pH 7, and enzyme loading of 60 µg. The biosensor works at the tripalmitin (TP) concentration range of 100-400 mg/dL. With the sensitivity of 0.001 (∆A/(mg/dL)), the biosensor response reaches stability after five minutes, and the limit of detection (LOD) of the TG optical biosensor is 15 mg/dL. Relative standard deviation (RSD) in a reproducibility test was 2.5%, with a 15-day lifespan.

Preparation and Characterization of a Pectin Membrane-Based Optical pH Sensor for Fish Freshness Monitoring.

In a simple and instant procedure for detecting fish freshness, a hydrogel and hydrophilic pectin matrix membrane was used successfully as an optical pH sensor by immobilizing the chromoionophore ETH 5294 (CI), which is very selective and sensitive for the membrane. The Pe/CI optical pH sensor exhibited excellent linearity between pH 5 and pH 9, with a sensor response time of 5 min and reproducibility of 1.49% relative standard deviation (RSD). The sensor showed response stability for 15 days and a response reduction of 8.6%. The sensor's capability was demonstrated by the detection of fish freshness for 17 days at 4 °C.

Highly selective thiocyanate optochemical sensor based on manganese(III)-salophen ionophore.

We report on the development of optochemical sensor based on Mn(III)-salophen ionophore. The sensor was prepared by embedding the ionophore in a plasticized poly (vinyl chloride) impregnated with the chromoionophore ETH7075. Optical response to thiocyanate occurred due to thiocyanate extraction into the polymer via formation of strong complex with the ionophore and simultaneous protonation of the indicator dye yielding the optical response at 545nm. The developed optochemical sensor exhibited high selectivity for thiocyanate over other anions including the most lipophilic species such as salicylate and perchlorate. For instance, the optical selectivity coefficients, logKSCN,anionopt, were as follow: ClO4-=-5.8; Sal-=-4.0; NO3-˂-6. Further, the thiocyanate optical selectivity obtained using the present optochemical sensor was greatly enhanced in comparison with that obtained using an anion-exchanger based sensor. Also, the optimized optochemical sensor exhibited micro-molar detection limit with 2min response time at pH4.5 using acetate buffer. The reversibility of the optimized sensor was poor due to strong ligation of the thiocyanate to the central Metal ion, log K=14.1, which can be overcome by soaking the optode in sodium hydroxide followed by soaking in buffer solution. The developed sensor was utilized successfully for the determination of thiocyanate in human saliva and in spiked saliva samples.

Continuous Fluorescence Imaging of Intracellular Calcium by Use of Ion-Selective Nanospheres with Adjustable Spectra.

Continuous fluorescence imaging of intracellular ions in various spectral ranges is important for biological studies. In this paper, fluorescent calcium-selective nanospheres, including calix[4]arene-functionalized bodipy (CBDP) or 9-(diethylamino)-5-[(2-octyldecyl)imino]benzo[a]phenoxazine (ETH 5350) as the chromoionophore, were prepared to demonstrate intracellular calcium imaging in visible or near-IR regions, respectively. The fluorescence of the nanospheres was controlled by the chromoionophore, and thus the spectral range for detection was adjustable by choosing the proper chromoionophore. The response time of the nanospheres to calcium was typically 1 s, which allowed accurate measurement of intracellular calcium. These nanospheres were loaded into cells through free endocytosis and exhibited fluorescence for 24 h, and their intensity was correlated with the elevation of intracellular calcium upon stimulation. The successful demonstration of calcium imaging by use of ion-selective nanospheres within two spectral ranges in 24 h supported that these nanospheres could be applied for continuous imaging of intracellular ions with adjustable spectra.