Optode Membrane Research Articles

Revolutionizing sensing technologies: Crafting a green, ultra-sensitive bismuth optical sensor via fixation of 5-(2′,4′-dimethyl-phenylazo)-6-hydroxypyrimidine-2,4-dione on PVC membrane

An innovative and exceptionally responsive optical sensing device engineered to selectively identify Bi(III) ions in water-based solutions. The sensing component, 5-(2′,4′-dimethylphenylazo)-6-hydroxypyrimidine-2,4-dione (DMPAHPD), is incorporated into a plasticized polyvinyl chloride (PVC) membrane. The sensor demonstrates an exceptional selectivity for Bi(III) within a broad dynamic range spanning from 7.5 × 10−10 to 4.2 × 10−5 M at pH 2.25. Notably, it achieves lower quantification and detection limits of 7.25 × 10−10 and 2.15 × 10−10 M, respectively. The optode membrane’s response to Bi(III) proves to be entirely reversible, demonstrating remarkable selectivity for Bi(III) ions over a diverse range of other cations and anions. The sensor exhibits favorable performance characteristics, including good reversibility, a wide dynamic range, a prolonged lifespan, sustained response stability over the long term, and high reproducibility. This visual chemical sensor exhibits potential for real-world usage, offering consistent outcomes when assessing Bi(III) levels in matrices such as water, soil, plants, biological and synthetic mixtures. Importantly, the sensor’s performance is comparable to corresponding data achieved from inductively coupled plasma atomic emission spectroscopy (ICP-AES).

PVC membrane bulk optode incorporating 4-nitrobenzo-15-crown-5 and sodium tetrakis(1-imidazolyl) borate for the pico-molar determination of silver ion in pharmaceutical formulation

Silver ion (Ag+) is of harmful effects to both environment and human health. Ag+ soluble compounds and salts is used in treating mental illness, epilepsy, nicotine addiction, gastroenteritis, and infectious diseases, including syphilis and gonorrhea, and as anti-infective dermatological agent for controlling nose bleeding. However, high Ag+ doses cause several harmful effects to human health such as irreversible pigmentation of skin and eye, and problems to liver and kidney. A bulk membrane Optode is proposed in this work to measure the Ag+ concentration in the pharmaceutical formulations. The membrane optode is prepared from the ionophore 4-nitobenzo-15-crown-5, the ion-exchanger sodium tetrakis (imidazolyl) borate, the plasticizer o-nitrophenyl octyl ether, and the chromoionophore ETH 5294; these components are dissolved in the PVC/THF slurry to form the membrane. The optode is studied by atomic force microscope and UV–visible spectrophotometer, and its spectrum exhibits two maximum wavelengths of 550 and 665 nm, and response for Ag+ at these maximum wavelengths is reproducible in the concentration range of 10–11 to 10–8 M using acetate buffer of pH 5.0, with very low detection limit of 8.8 × 10–12 M. The most important feature in this work is the selectivity improvement for Ag+ over all interfering ions; the selectivity coefficient logarithm logKAg+,cationopt\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${logK}_{Ag+, cation}^{opt}$$\\end{document} is found to be − 4.3 for Cu2+, − 5.6 for Ni2+ and − 5.0 for Cd2+. The response mechanism is studied by FTIR, and it depends on ion-exchange of Ag+ and sodium imidazolyl borate, followed by the host–guest complexation between Ag+ and the crown ionophore, which is accompanied by concomitant deprotonation of the chromoionphore. The optode has a response time of 2–3 min within lifetime of 10 days with the same response. The optode can be applied successfully for Ag+ determination in the pharmaceutical formulation, PinkEye Relief® eye drop, which is used for treating inflammation, redness and water discharge of the eye; the high recovery and low standard deviation of the results using calibration curve method confirm the accuracy and precision of the proposed optode for its application in real samples.

Simple Synthesis of Cellulose Triacetate from HVS Paper Waste and Its Application for Optode

The optode membrane is a membrane that can identify ions in an aqueous solution. One of the most widely used optode membranes is cellulose triacetate based. Cellulose triacetate (CTA) has the characteristics of hydrophobic, transparent, elastic, and affordable. There are sources of cellulose triacetate that can be utilized and waste paper is one of them. Waste paper is extracted to obtain the cellulose, then by acetylization reaction to produce cellulose triacetate. The resultant cellulose triacetate has a degree of substitution (DS) of 2.89 and an acetyl group percentage (% AG) of 43.64. The standard and synthesized CTA optode membrane are tested for performance with various parameters, ie optimum pH, optimum immersion time, working range, limit of detection (LOD), and limit of quantification (LOQ). The standard CTA optode membranes and synthesized worked at pH 3 and 4 with optimum immersion time for 15 min, respectively. The optode produced a linear response in detecting Cr(VI) ion in the concentration range of 0.02-1 mg/L for standard CTA with an R2 of 0.9726 and 1-25 mg/L for synthesized CTA with an R2 of 0.9764, The limit of detection (LOD) and limit of quantitation (LOQ) were 0.0015 mg/L and 0.0051 mg/L for standard CTA, while 0.0224 mg/L and 0.0749 mg/L for synthesis CTA respectively. Since both optode membranes' performance test results are adequate, the synthesis results of CTA optode membranes can be employed as one source of cellulose triacetate.

Development of an innovative colorimetric optical sensor for the detection of silver ions in environmental and biological samples

ABSTRACT A recently developed optical chemical sensor for silver assessment relies on polymer inclusion membranes (PIM) and avoids the use of plasticisers. This innovative optical sensor is constructed through a physical immobilisation process known as the encapsulation technique, resulting in an optical chemical membrane. The suggested PIM integrates 2-(2`-hydroxynaphthylazo)benzo-thiazole (HNABT) was used as a colorimetric reagent, polyvinyl chloride (PVC) as the foundational polymer, and dinonyl naphthalene sulphonic acid (DNNS) as an extractant. The created PIM demonstrates heightened responsiveness within the described approach, credited to the sensor membrane, in contrast to the optical sensor without PIM. The achieved results demonstrated that the sensor response was based on some factors such as plasticiser, film thickness, stirring effect, HNABT concentration, DNNS concentration and pH of the aqueous solution. Within the measurement range spanning from 7.5 to 250 ng mL−1 of Ag+ at pH 7.75, the absorbance response exhibits a notable correlation, achieving detection and quantification limits of 2.3 and 7.3 ng mL−1, respectively. The λmax for the PIM-based sensor registers at 577 nm. Additionally, the reproducibility and repeatability of the system are characterised by RSD of 2.25% and 1.13%, respectively, with a swift response time of approximately 3.0 min. The optode membrane’s selectivity is scrutinised in pH-buffered solutions concerning Ag+ ions. The proposed sensor is effectively applied for Ag+ assessment in food, water, environmental, and biological samples. The obtained results are corroborated by the FAAS procedure.

Innovative assembled optode device for enhanced in-situ ceric ions (Ce4+) evaluation and preconcentration in its real human, foods, water, and alloy samples

Cerium (Ce) are the most widely distributed rare earth element. However, humans exposed to Ce through inhalation have been reported to experience heat sensitivity, itching, and heightened taste and odour perception. The present study aims to develop an optical sensor device with a short response time and high selectivity for Ce amongst other ions in various environments. The potential applicability of a 6-hydroxy-5-((4-hydroxy-2-methylphenyl)diazenyl)pyrimidine-2,4(1H,3H)-dione (HHMDPD) assembled ligand as aceric ion (Ce4+)-selective caption optode was examined. After generating an ion pair with Tetra-n-octylammonium bromide (TOABr) and immobilizing on a tri-acetyl cellulose (TAC) membrane, the solubility of the HHMDPD ligand is improved. The constructed optode membrane reacts with Ce4+ by turning its orange colour to violet in Thiel buffer (pH of 5.5), which can be detected spectrophotometrically at λmax 667 nm. The measurement linearity was in the range of 0.70 – 18.7 × 10−6 mol/L of Ce4+ concentration with detection and quantification limits of 0.23 × 10−6 and 0.70 × 10−6 mol/L, respectively. Whatever the Ce4+ concentration in its real samples, the response time of the constructed device was 5.0 min. Additionally, it recorded repeatability and reproducibility with a %RSD of 1.37 and 2.55, respectively (n = 3). The proposed optode device exhibited complete reversibility, for multiple measurements, which could be easily achieved with the aid of a solution of HCl, 0.01 mol/L. The applicability of the proposed device has been effectively extended to analyze synthetic mixes corresponding to different Ce4+ real human, foods, water, and magnesium-based Ce4+ alloys.

An innovative approach in titanium determination based on incorporating 2-amino-4-((4-nitrophenyl)diazenyl)pyridine-3-ol in a PVC membrane.

A pioneering optical sensor has been effectively developed to achieve precise and reliable detection of titanium ions. The sensor employs an optode membrane composed of 2-amino-4-((4-nitrophenyl)diazenyl)pyridine-3-ol (ANPDP) and sodium tetraphenylborate (NaTPB) incorporated into a plasticized PVC matrix, with dioctyl sebacate (DOS) acting as the plasticizer. When exposed to Ti4+ ions at pH 8.25, the color of the sensing membrane undergoes a distinctive transformation from yellow-orange to violet. Extensive investigations were carried out to assess and optimize various factors influencing the efficiency of ion uptake. Through careful experimentation, the optimum conditions were determined to be 60.0% DOS, 6.0% ANPDP, 30% PVC, and 4.0% NaTPB, with a rapid response time of 5.0 min. Within these conditions, the developed optode demonstrates an impressive linear range of 3.0-225 ng mL-1, boasting detection (LOD) and quantification (LOQ) limits of 0.91 and 2.95 ng mL-1, respectively. Moreover, the precision of the sensor, as indicated by the relative standard deviation (RSD%), remained consistently below 1.55% in six replicate determinations of 100 ng mL-1 Ti4+ across diverse membranes. The selectivity of the sensor was rigorously examined for a range of cations and anions, successfully establishing the tolerance limits for interfering species. Notably, the presence of EDTA as a masking agent did not compromise the high selectivity of the sensor. Consequently, the innovative probe holds significant potential as a reliable analytical tool for quantifying titanium content in various samples, including water, geological materials, soil, plants, paints, cosmetics, and plastics.

Optimization of innovative optical sensor for zirconium determination and capturing from environmental samples

A highly sensitive bulk optode membrane, specifically engineered for the identification of zirconyl (ZrO2+) ions, has been successfully created. The membrane is composed of plasticized polyvinyl chloride (PVC), dibenzodylmethane (DBM) acting as the chromoionophore, 2-amino-4-(3-chlorophenylazo)pyridine-3-ol (ACPAP) serving as the ionophore, and sodium tetraphenylborate (NaTPB) included as an ionic additive. The sensing membrane undergoes a color change from orange to blue when exposed to ZrO2+ ions at pH 6.5. The preparation parameters of the sensor and the determination of ZrO2+ ions were meticulously optimized. In addition to showcasing reproducibility, extended stability, and a comparatively long lifespan, the suggested sensor membrane displays remarkable selectivity for ZrO2+ ions, effectively discerning them from a spectrum of alkaline earth, heavy and transition metal ions, and actinides. The sensor delivers a calibration response tailored for ZrO2+ ions across a concentration spectrum spanning 7.5–185 ng mL−1, establishing limits of quantification and detection at 7.3 and 2.2 ng mL−1, respectively. Demonstrating a rapid response within a timeframe of under 5.0 min. The sensor consistently delivered highly reproducible results, as evidenced by relative standard deviation (RSD) of 1.67 % and 1.55 % for Zr4+ concentrations at 100 and 150 ng mL−1.This underscores the precision and reliability of the sensor. Regeneration of the optode can be easily accomplished by employing 0.05 M HCl. Effectively employed across a spectrum of samples, including water, soil, plant materials, and ore solutions, the proposed optical sensor proves to be a valuable instrument for determining ZrO2+ ions in diverse environmental and analytical scenarios.

Detection of Hexavalent Chromium Ion in Water by Optode Membrane

Chromium is a heavy metal that is often found as a water pollutant. High concentrations of hexavalent chromium (Cr(VI)) ion in nature are toxic and carcinogenic, so their presence in water needs to be monitored. Detection of heavy metals in water was carried out using an optical sensor membrane (optode). The optode was fabricated from cellulose triacetate polymer with plasticizers (oleic acid and acetophenone), aliquot 336, and the chromoionophore 1.5-diphenylcarbazide (DPC). The success synthesis of optode was evidenced by FTIR and SEM characterization. The optode performance produces a linear response in detecting Cr(VI) ion in the concentration range of 0.02-0.40 mg/L with an R2 of 0.9930, as well as the best conditioning at pH 3. The detection and quantitation limits are 0.0055 mg/L and 0.0165 mg/L. The sensitivity of the chromium optode was excellence, with a molar absorptivity value of 8.8303 × 106 M-1cm-1. The performance test results of the chromium optode were acceptable because they meet the specified requirements for minimum detection concentration value.

A Selective Fluorescent Optode for Lead(II) Based on the Dansylamidopropyl Pendant Arm Derivative of 1,4-Dioxa-7,13-dithia-10-azacyclopentadecane ([15]aneNS2O2)

In this study, a novel highly sensitive and selective fluorescent optode membrane aimed at the determination of Pb(II) ion is proposed by incorporating N-(3-(1,4-dioxa-7,13-dithia-10-azacyclopentadecan-10-yl)propyl)-5-(dimethylamino)naphthalene-1-sulfonamide (L) as fluoroionophore in polyvinyl chloride (PVC) containing 2-nitrophenyl octylether (NPOE) as a plasticizer. In addition to high stability and reproducibility, the proposed optosensor showed a unique selectivity toward Pb(II) ion, with a wide linear range of molar concentrations (1.0 × 10−9–1.0 × 10−3 M) and a low detection limit of 7.5 × 10−10 M in solution at pH 5.0. The formation constants of the Pb(II) complexes with the fluoroionophore were evaluated by fitting the fluorescence data with a nonlinear least-squares curve-fitting program, and further information about the structures of the complexes were evaluated based on hybrid-DFT calculations. The optosensor exhibited a fast response time of less than three min, being easily regenerated by exposure to a solution of dithiothreitol. The sensor was applied to the determination of Pb(II) in real samples (canned tuna fish), and it provided satisfactory results comparable to those obtained via atomic absorption spectrometry (AAS).

Utilization of a novel PVC- optical sensor for high sensitive and selective determination of zinc ion in real samples

A novel and highly specific bulk membrane optode was developed for the ultra-sensitive detection of zinc(II) in biological, pharmaceutical, and water samples. The polymer inclusion membrane (PIM) utilized in this study consists of 50% polyvinyl chloride (PVC) as a base polymer, 9.00% DOP (dioctylphthalate) as the plasticizer, and 40.0% D2EHPA (di(2-ethlyhexyl)phosphoric acid) as the carrier. To facilitate the spectrophotometric determination of zinc(II), a colorimetric reagent, namely 4-(2-arsonophenylazo) salicylic acid (APASA) {1.00%, m/v}, was employed. When Zn(II) was extracted into the PIM, it led to the creation of the zinc-D2EHPA complex. This complex then underwent a reaction with APASA, resulting in the formation of a red Zn − APASA complex with a maximum absorption wavelength (λmax) of 558 nm. To optimize the response of the optode, a central composite design was employed, considering variables such as the amount of additive and reagent, response time, and pH. When operated under the specific optimal conditions, the sensor demonstrated a limit of quantification (LOQ) of 0.74 ng/mL (equivalent to 1.17 × 10−8 M) and a limit of detection (LOD) of 0.22 ng/mL (equivalent to 3.44 × 10−9 M). The optode membrane demonstrated excellent reproducibility, stability, and a relatively long lifespan, making it suitable for precise and accurate monitoring of Zn(II) ion content. Regeneration of the optode was achieved effectively using 0.25 nitric acid solution, and its response exhibited reversibility and reproducibility, showed a relative standard deviation of less than 1.33%. Moreover, the PIM-APASA optode exhibited a high level of effectiveness in accurately determining the presence of Zn(II) ions in real environmental samples.

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.

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.

Phosphorous (V) Corrole Fluorophores for Nitrite Assessment in Environmental and Biological Samples

Two phosphorous (V) corrole complexes, [5,10,15-pentafluorophenyl corrole] phosphorous (V) (PFCorr) and [10-(4-trimethylsilylphenyl)-5,15-dimesityl-corrole] phosphorous (V) (PCorr) were synthesized and tested as nitrite-sensitive fluorophores. Fluorimetry studies on ligand sensitivity towards anions were carried out in solution, then inside polymeric membrane optodes deposited on glass, and finally by functionalized SiO2 nanoparticles deposited on a paper support. The selective fluorescence quenching was registered upon addition of an increasing amount of NO2− ions for both ligands. The influence on the PFCorr optode’s response of the lipophilic sites’ functionalization was investigated. The sensors’ suitability for nitrite assessment in natural waters at levels 10-fault lower than the WHO’s recommended maximum concentration level of 3 mg/L was demonstrated.

Optical enzymatic formaldehyde biosensor based on alcohol oxidase and pH-sensitive methacrylic-acrylic optode membrane

Optical biosensor for the detection of formaldehyde has been developed based on the transparent enzymatic stacked membranes system on the glass substrate, and employing optical absorption transducer with H+ ion-selective Nile Blue chromoionophore (NBCM) dye-doped methacrylic acrylic (MB28) copolymer membrane as the optode membrane. Alcohol oxidase (AOx) enzymes were entrapped within the biocompatible sol–gel matrix and deposited on top of the pH optode membrane. As the uppermost catalytic membrane catalyzes the oxidative conversion of formaldehyde to formic acid and hydrogen peroxide, the immobilized NBCM undergoes protonation reaction and forms HNBCM+, the dark blue ion-chromoionophore complex via H+ ion transfer reaction within the soft and flexible MB28 polymeric membrane. This rendered the enzymatic optode membrane absorbed a high yellow light intensity from the light source and exhibited maximum absorption peaks at 610 and 660 nm. Optical evaluation of formaldehyde by means on UV–vis absorption transduction of the enzymatic stacked membranes demonstrated rapid response time of 10 min with high sensitivity, good linearity and high reproducibility across a wide formaldehyde concentration range of 1 × 10−3–1 × 103 mM (R2 = 0.9913), and limit of detection (LOD) at 1 × 10−3 mM, which could be useful for formaldehyde assay in industrial, agricultural, environmental, food and beverages as well as medical samples. The formaldehyde concentration in snapper fish, pomfret fish and threadfin fish samples determined by the proposed optical enzymatic biosensor were very much close to the formaldehyde concentration values determined by the UV–vis spectrophotometric NASH standard method based on the statistical t-test. This suggests that the optical biosensor can be used as a reliable method for quantitative determination of formaldehyde levels in food samples.

Paper-Based Optode Devices (PODs) for Selective Quantification of Potassium in Biological Fluids.

This paper describes the design, fabrication, and feasibility of paper-based optode devices (PODs) for sensing potassium selectively in biological fluids. PODs operate in exhaustive mode and integrate with a handheld, smartphone-connected optical reader. This integrated measuring system provides significant advantages over traditional optode membranes and other paper-based designs, by obtaining a linear optical response to potassium concentration via a simple, stackable design and by harnessing a smartphone to provide an easy-to-use interface, thus enabling remote monitoring of diseases.

Development of a microplate-format direct optode sensor for ultra-high-throughput environmental and wastewater monitoring of Pb2+

Although many Pb2+-selective optodes have been developed so far, methods using optical sensor membranes have not become widespread in environmental analytical practice. In order to create a bulk optode sensor, which can overcome all of the main drawbacks in the application of conventional optode membranes, - i.e., pH-dependence, long response time and the leakage of the ionic components - unusually thick PVC membrane was developed, embedded in microtiter plates and operated on a novel concept. This is the first reported work, which applies a plate-format optode as well as a direct optode-type sensing membrane for determination of Pb2+. We reported here also the first example for the application of an ionic component-free bulk optode membrane to avoid the membrane leakage, improve the regenerability and extend the lifetime of the membrane. The reported sensor has a LOD above 4.0 × 10−7 M (∼83 μg L−1), thus it is unsuitable for the effective monitoring of drinking waters, but considered to be a promising method for monitoring contamination episodes. On the other hand, the widest pH-independent working range of 4.3 < pH < 7.0 among bulk optodes reported in the literature was realized and an unprecedentedly fast response time of <10 s was achieved. The effectiveness of the applied method was investigated by measuring Pb2+-spiked multicomponent aqueous solutions as simulated environmental or wastewater samples containing near equimolar amounts of Ag+, Ca2+, Co2+, Cu2+, K+, Mg2+, Na+ and Zn2+ as acetate salts. In the presence of these potential competing ions with a concentration not greater than the typical ionic strength of surface freshwaters (∼10−3 M) the reported sensor proved to be appropriate for the selective detection of Pb2+ without any preparation of the samples (e.g., preconcentration, buffering, addition of excipients, etc.) with a required sample volume of only 100 μL. An outstanding analytical performance could be achieved within an average time of less, than 5 s/sample. The reported fluorescent probe is considered to be a promising method for replacing atomic absorption spectroscopy- (AAS), anodic stripping voltammetry- (ASV) or inductively coupled plasma- (ICP) based techniques as well as conventional ion-selective bulk membranes in high-throughput preliminary environmental monitoring of Pb2+, as it provides a cheap and unprecedentedly fast qualitative analysis of contaminated surface and wastewaters.

Real-time optical sensing of exhaled acetone concentration utilizing non-Fickian Nafion diffusion inside a flow-through sample chamber

Rapid in-situ chemical analysis of flowing gas streams is of interest in a wide range of applications but requires deconvolution of the time-scales associated with the analyte source concentration, its accumulation within a sampling chamber, and its detection by a sensor. A mathematical analysis is presented on the use of a flow-through sample chamber for rapid, in-situ breath analysis utilizing analyte diffusion through a Nafion membrane optode. We show that this approach yields apparently non-Fickian (anomalous or Case II) transport that varies from t1/2 to t as t → 0 with constant inlet concentration. Such behavior arises due to the transition from membrane-limited to sample chamber-limited transport dynamics depending on test conditions. The model is validated utilizing experimental data obtained from the color response associated with the Friedel-Craft acylation of acetone vapor with resorcinol reagent immobilized in Nafion membrane solid-state catalyst. Reduction of optode membrane thickness and increase in membrane humidification yield an optical response limited only by sample chamber material accumulation. At this limit, the exhaled breath signal for acetone obtained from a healthy individual is found to vary as t2 (apparently Super Case II transport). Utilizing a simplified material balance on the human lung, this observation is ascribed to a constant acetone exhalation rate as opposed to a constant exhaled acetone concentration. This conclusion is shown to have broad implications on the use of exhaled breath biomarkers for medical diagnosis, in particular, lung physiology and permeability.

Determination of Polyhexamethylene Biguanide Hydrochloride Using a Lactone-Rhodamine B-Based Fluorescence Optode.

A new determination method for polyhexamethylene biguanide hydrochloride (PHMB) using a lactone-rhodamine B (L-RB) based fluorescence optode has been developed. The optode membrane consists of 2-nitrophenyl octyl ether as a plasticizer, L-RB, and poly (vinyl chloride). The optode responds to tetrakis (4-fluorophenyl) borate, sodium salt (NaTPBF) in the μM range. The fluorescence intensity of the L-RB film for PHMB solution containing 20 μM NaTPBF decreased linearly as the concentration of the PHMB solution increased in the concentration range from 0 to 8.0 μM, which shows that PHMB with a concentration range of 0 to 8.0 μM is determined by the L-RB film optode. The concentration of PHMB in the contact lens detergents by the proposed method was in accord with its nominal concentration.

A lipophilic ionic liquid-based dye for anion optodes: importance of dye lipophilicity and application to heparin measurement.

Herein, a fully lipophilic ionic liquid (IL) comprising a lipophilic fluorescein anion and a trihexyltetradecylphosphonium cation was synthesized and used as the plasticizer for a plasticized poly(vinyl chloride) (PVC) membrane optode. Systematic investigation of the alkyl chain length of the fluorescein anion proved the significance of lipophilicity for obtaining the reversible absorbance measurements. A PVC membrane fabricated with the synthesized lipophilic IL was observed to comprise an unusually high dye concentration (915 mmol kg-1) and exhibited good sensitivity as well as response time in its sensor performance. The sensitivity of the presented PVC membrane was 26-fold higher than that of a conventional optode membrane with the same membrane thickness and the same lipophilic dye of typical dye content (1 wt%). The response time was observed to be >120-fold faster by using a significantly thinner PVC membrane (approx. 140 nm). Heparin is known to be a polyanionic anticoagulant, and the presented PVC membrane exhibited an extremely fast response (20-150 seconds) to the heparin in diluted serum within the required concentration region. Thus, the lipophilic IL-based dye could significantly improve the sensor performance in conventional optodes, especially for an analyte showing slow diffusion, such as macromolecular heparin.

Development of a Rapid and Highly Sensitive Plasticized PVC Membrane Optode Utilizing an Ionic Liquid Material Composed of Bromothymol Blue

Development of a Rapid and Highly Sensitive Plasticized PVC Membrane Optode Utilizing an Ionic Liquid Material Composed of Bromothymol Blue