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.

Microfluidic paper-based analytical device with a preconcentration system for the measurement of anionic surfactants using an optode detector.

The paper discusses the development of a low-cost, simple, and sensitive on-site measurement system for anionic surfactants (AS), specifically sodium alkylbenzene sulfonate (LAS), using a microfluidic paper-based analytical device (µPAD) with an optode as a detector. The need arises due to the discharge of AS-containing wastewater into natural environments, posing risks to aquatic organisms. Traditional methods for AS measurement have drawbacks like the use of harmful solvents, time-consuming procedures, and the need for expensive equipment, prompting the exploration of alternative approaches. The µPAD incorporates a sample solution preconcentration system using filter paper modified with chitosan. The optode, a chemical sensor detecting analytes optically, is employed for AS detection. When a large volume of AS is added to a positively charged modified filter paper with chitosan, the AS is adsorbed and concentrated on the filter paper. The concentrated AS is eluted with a small volume of alkaline solution, and the eluted AS is detected by the optode in the µPAD. The µPAD with preconcentration provides improved sensitivity and a broader range of detection compared to the method without preconcentration. In the present µPAD method, linear alkylbenzenesulfonate (LAS) in the concentration range of 0.1 to 10 µmol dm-3 was measured. The developed µPAD offers advantages such as portability, cost-effectiveness, and negligible interference from coexisting substances in environmental water samples. The µPAD method was applied for the determination of LAS in tap water and river water.

Optical fiber chemical sensing of anionic surfactants using a microfluidic polymer chip with embedded ion-selective fluorescence optode.

This study introduces a novel microfluidic polymer chip system that employs an embedded anionic surfactant (AS) ion-selective fluorescence optode (AS fluorescence optode) as a detector for measuring AS. The AS fluorescent optode comprises a lactone form of rhodamine B (L-RB) embedded in 2-nitrophenyl octyl ether plasticized poly (vinyl chloride) membrane. The AS fluorescence optode demonstrated a linear correlation between fluorescence intensity peak heights and AS concentrations within the range of less than 20 µM under optimal flow conditions. The limit of detection for AS was approximately 0.06 µM. The microfluidic system was utilized to measure AS levels in environmental samples, such as river water and tap water.

Development of an Optode Detector for Determination of Anionic Surfactants by Flow Injection Analysis.

A flow-injection analysis (FIA) method for assaying an anionic surfactant (AS) using AS optode detector was demonstrated. The optode membrane consists of 2-nitrophenyl octyl ether as a plasticizer, lactone form rhodamine B (L-RB) and poly(vinyl chloride). The linear response concentration range of the AS optode to AS was 20 - 100 µmol dm-3 in the FIA system. The sampling rate for an AS ion (40 µmol dm-3 sodium dodecylbenzenesulfonate) in the proposed FIA system was ca. 5 samples h-1. The AS level in commercially available laundry detergents by the proposed FIA system was determined.

Optical sensor of anionic surfactants using solid-phase extraction with a lactone-form rhodamine B membrane.

An optical sensor for the detection of anionic surfactants was developed. The optical sensing membrane is a 2-nitrophenyloctyl ether-plasticized poly(vinyl chloride) membrane incorporating a lactone-form Rhodamine B (L-RB). The response of the optical membrane to anionic surfactants was a result of the ion-pair coextraction of an anionic surfactant and a proton into the PVC membrane. The L-RB forms an ion associate with the extracted anionic surfactant; simultaneously, the formed L-RB ion associate is accompanied by a spectral change. Namely, the extracted anionic surfactant changes the color of the membrane from light pink to dark pink (absorption maximum; 558 nm). The optical membrane responds to anionic surfactants, such as dodecylbenzenesulfonate, dodecylsulfate and di-2-ethylhexyl sulfosuccinate in the concentration range from 1 to 50 microM.

Potentiometric titration of polyhexamethylene biguanide hydrochloride with potassium poly(vinyl sulfate) solution using a cationic surfactant-selective electrode.

A potentiometric titration method using a cationic surfactant as an indicator cation and a plasticized poly(vinyl chloride) membrane electrode sensitive to the cationic surfactant is proposed for the determination of polyhexamethylene biguanide hydrochloride (PHMB-HCl), which is a cationic polyelectrolyte. A sample solution of PHMB-HCl containing an indicator cation (hexadecyltrimethylammonium ion, HTA) was titrated with a standard solution of an anionic polyelectrolyte, potassium poly(vinyl sulfate) (PVSK). The end-point was detected as a sharp potential change due to an abrupt decrease in the concentration of the indicator cation, HTA, which is caused by its association with PVSK. The effects of the concentrations of HTA ion and coexisting electrolytes in the sample solution on the degree of the potential change at the end-point were examined. A linear relationship between the concentration of PHMB-HCl and the end-point volume of the titrant exists in the concentration range from 2.0 x 10(-5) to 4.0 x 10(-4) M in the case that the concentration of HTA is 1.0 x 10(-5) M, and that from 1.0 x 10(-6) to 1.2 x 10(-5) M in the case that the concentration of HTA is 5.0 x 10(-6) M, respectively. The proposed method was applied to the determination of PHMB-HCl in some contact-lens detergents.

Determination of Sulfate Ion with 2-Aminoperimidine Hydrobromide Using an Optode Based on Tetrabromophenolphthalein Ethyl Ester Membrane.

An optode method for the determination of sulfate ion was developed. The optode membrane is 2-nitrophenyl octyl ether-plasticized poly(vinyl chloride) membrane containing tetrabromophenolphthalein ethyl ester. The method is based on formation of an ion associate between the excess of 2-aminoperimidine hydrobromide (Ap) and sulfate ion in the sample solution, and detection of the concentration of the remaining Ap ion by the optode. Under the optimal conditions, a good linear relationship was found to exist between the absorbance of the optode membrane, and concentrations of sulfate ion in a concentration range from 20 to 400 µM. The developed optode method was applied to the determination of sulfate ion in environmental water samples.

A New Microfluidic Polymer Chip with an Embedded Cationic Surfactant Ion-selective Optode as a Detector for the Determination of Cationic Surfactants.

A new microfluidic polymer chip with an embedded cationic surfactant (CS) ion-selective optode (CS-optode) as a detector of flow-injection analysis (FIA) for the determination of CSs was developed. The optode sensing membrane is based on a poly(vinyl chloride) membrane plasticized with 2-nitrophenyl octyl ether containing tetrabromophenolphthalein ethyl ester. Under the optimal flow conditions of the FIA system, the CS-optode showed a good linear relationship between the peak heights in the absorbance, and the concentrations of CS in a concentration range from 50 to 400 µmol dm-3. The sample throughput of the present system for the determination of a CS ion (300 µmol dm-3 zephiramine) was ca. 11 samples h-1. The proposed FIA system was applied to determine the level of CS in dental rinses.

Microfluidic polymer chip integrated with an ISFET detector for cationic surfactant assay in dental rinses.

A cationic surfactant ion-selective field-effect transistor (cationic surfactant-ISFET) has been developed based on the tetraphenylborate derivative known as sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The cationic surfactant-ISFET shows an almost Nernstian response to tetradecyldimethylbenzylammonium chloride (Zephiramine) over a concentration range between 1.0 x 10(-6) M and 1.0 x 10(-3) M, with a slope of 58.5 +/- 1.7 mV/decade. The cationic surfactant-ISFET can be used over a range of pH values, between pH 3 and 9. The cationic surfactant-ISFET shows excellent selectivity for Zephiramine over small inorganic cations, but shows similar selectivity for other cationic surfactants, such as hexadecyltrimethylammonium and stearyltrimethylammonium ions. A microfluidic polymer chip was integrated with the cationic surfactant-ISFET, and this was fabricated using polystyrene plates and stainless wires as a template for the channel. Cationic surfactant-ISFETs used in a batch system and microchips integrated with cationic surfactant-ISFETs showed very similar performance in terms of low detection limits, slope sensitivity and the stability of the potential response. The microfluidic polymer chip was then applied to the determination of cationic surfactants in dental rinses.

Sequential injection analysis of thiocyanate ions using a microfluidic polymer chip with an embedded ion-selective electrode.

A sequential injection analysis (SIA) system for the determination of SCN(-) ion using a microfluidic polymer chip with an embedded SCN(-) ion-selective electrode (SCN(-)-ISE) as a detector was developed. Under the optimal flow conditions of the SIA system, the SCN(-)-ISE showed a good linear relationship between peak heights and logarithmic concentrations of SCN(-) ion with a Nernstian slope of 59.4 ± 3.8 mV decade(-1) in a concentration range from 1.0 × 10(-5) to 1.0 × 10(-1) mol dm(-3). Sample throughput of the present system for the determination of SCN(-) ion was approximately 12 samples h(-1). The proposed SIA system was applied to the determination of the level of SCN(-) ion in human saliva samples.

Determination of polyhexamethylene biguanide hydrochloride using photometric colloidal titration with crystal violet as a color indicator.

A solution of polyhexamethylene biguanide hydrochloride (PHMB-HCl) was titrated with a standard solution of potassium poly(vinyl sulfate) (PVSK) using crystal violet (CV) as an photometric indicator cation. The end point was detected by a sharp absorbance change due to an abrupt decrease in the concentration of CV. A linear relationship between the concentration of PHMB-HCl and the end-point volume of the titrant existed in the concentration range from 2 to 10 × 10(-6) eq mol L(-1). Back-titration was based on adding an excess amount of PVSK to a sample solution containing CV, which was titrated with a standard solution of poly(diallyldimethylammonium chloride) (PDADMAC). The calibration curve of the PHMB-HCl concentration to the end point volume of the titrant was also linear in the concentration range from 2 to 8 × 10(-6) eq mol L(-1). Both photometric titrations were applied to the determination of PHMB-HCl in a few contact-lens detergents. Back-titration showed a clear end point, but direct titration showed an unclear end point. The results of the back-titration of PHMB-HCl were compared with the content registered in its labels.

Microfluidic polymer chip with an embedded ion-selective electrode detector for nitrate-ion assay in environmental samples.

A nitrate ion-selective electrode (NO(3)(-)-ISE) has been developed based on tetradodecylammonium bromide as an anion exchanger and 2-nitrophenyl octyl ether as a plasticizer. The NO(3)(-)-ISE shows an almost Nernstian response to nitrate ion over a concentration range between 1.0 x 10(-6) and 1.0 x 10(-1) M, with an anionic slope of -57.7 +/- 0.7 mV/decade. The selectivity coefficients of the NO(3)(-)-ISE for nitrate ion against chloride and sulfate (log k(NO(3)(-)Cl(-))(pot) = -2.42 and log k(NO(3)(-)SO(4)(2-))(pot) = -4.33) were obtained. A microfluidic polymer chip was fabricated using polystyrene plates and stainless-steel wires as a template for the channel. The microfluidic polymer chip is composed of a mixing chip and a NO(3)(-)-ISE detector chip. The microfluidic polymer chip, integrated with a NO(3)(-)-ISE detector consisting of the NO(3)(-)-ISE and a Na(+)-ISE as a reference electrode, showed an almost Nernstian response to nitrate ion over a concentration range between 1.0 x 10(-5) and 1.0 x 10(-1) M, with an anionic slope of -54.3 +/- 1.3 mV/decade. The microfluidic polymer chip was then applied to the determination of nitrate ion in environmental water samples, such as a tap water, a well-water sample and water for agricultural use.

Flow immunoassay for nonioinic surfactants based on surface plasmon resonance sensors.

A rapid, sensitive immunoassay based on a surface plasmon resonance sensor in a flow system for the determination of alkylphenol polyethoxylate (APEO) is described. The method is based on an indirect competitive reaction between an anti-APEO antibody in the sample solution and APEO immobilized on a sensor chip and APEO in the same sample solution. A sensor chip was prepared by immobilizing an APEO-horseradish peroxidase (APEO-HRP) conjugate on the thin gold film of the sensor chip. The adsorption constants for the APEO-HRP conjugate on the sensor chip and the surface density of the APEO-HRP adsorbed on the sensor chip at the saturated state were estimated to be 4.7 x 10(5) M(-1) and 5.0 x 10(-14) mol/mm(2), respectively, using a Langmuir adsorption isotherm equation and results from the adsorption experiments. The affinity constants for the immunocomplexes of the anti-APEO antibody with the APEO conjugate on the sensor chip and for APEO in the sample solution were estimated to 2.0 x 10(6) and 5.1 x 10(6) M(-1), respectively. A typical sigmoid calibration curve for APEO was obtained in the concentration range from 1 ppb to 1000 ppb. The detection limit, defined as the concentration of APEO, at which 85% of the sensor signal was observed, was ca. 10 ppb. The assay was applied to the determination of APEO in tap water in conjunction with a solid phase extraction pretreatment; APEO levels of approximately 50 ppt were successfully determined.

Sequential injection chemiluminescence immunoassay for nonionic surfactants by using magnetic microbeads.

A rapid and sensitive immunoassay based on a sequential injection analysis (SIA) using magnetic microbeads for the determination of alkylphenol polyethoxylates (APnEOs) is described. An SIA system was constructed from a syringe pump, a switching valve, a flow-through type immunoreaction cell equipped with a photon counting unit and a neodymium magnet. Magnetic beads, to which an anti-APnEOs monoclonal antibody was immobilized, were used as a solid support in an immunoassay. The introduction, trapping and release of the magnetic beads in and from the immunoreaction cell were controlled by means of a neodymium magnet and adjusting the flow of a carrier solution. The immunoassay was based on an indirect competitive immunoreaction of an anti-APnEOs monoclonal antibody immobilized on the magnetic beads with a sample APnEOs and a horseradish peroxidase (HRP)-labeled APnEOs in the same sample solution, and was based on the subsequent chemiluminscence reaction of HRP on the magnetic microbeads with a luminol solution containing hydrogen peroxide and p-iodophenol. The anti-APnEOs antibody was immobilized on the magnetic microbeads by coupling the antibody with the magnetic beads after activation of a carboxylate moiety on the surface of the magnetic beads that had been coated with a polylactic acid film. The antibody immobilized magnetic beads were introduced in the immunoreaction cell and trapped in it by the neodymium magnet, which was equipped beneath the immunoreaction cell. An APnEOs sample solution containing the HRP-labeled APnEOs at a constant concentration, and a luminol solution containing hydrogen peroxide and p-iodophenol were sequentially introduced into the immunoreaction cell, according to an SIA programmed sequence. Chemiluminescence emission was monitored by means of a photon counting unit located at the upper side of the immunoreaction cell by collecting the emitted light with a lens. A typical sigmoidal calibration curve was obtained, when the logarithm of the concentration of APnEOs was plotted against the chemiluminescence intensity as the number of photons in 100 ms using standard APnEOs sample solutions at various concentrations (0-1000 ppb) under optimum conditions. The lower detection limit defined as IC(80) is ca 10 ppb. The time required for analysis is less than 15 min per a sample. The present method was successfully applied to the determination of APnEOs in river water.

Sequential injection chemiluminescence immunoassay for anionic surfactants using magnetic microbeads immobilized with an antibody.

A rapid and sensitive immunoassay for the determination of linear alkylbenzene sulfonates (LAS) is described. The method involves a sequential injection analysis (SIA) system equipped with a chemiluminescence detector and a neodymium magnet. Magnetic beads, to which an anti-LAS monoclonal antibody was immobilized, were used as a solid support in an immunoassay. The introduction, trapping and release of the magnetic beads in the flow cell were controlled by means of a neodymium magnet and adjusting the flow of the carrier solution. The immunoassay was based on an indirect competitive immunoreaction of an anti-LAS monoclonal antibody on the magnetic beads and the LAS sample and horseradish peroxidase (HRP)-labeled LAS, and was based on the subsequent chemiluminscence reaction of HRP with hydrogen peroxide and p-iodophenol, in a luminol solution. The anti-LAS antibody was immobilized on the beads by coupling the antibody with the magnetic beads after activation of a carboxylate moiety on the surface of magnetic beads that had been coated with a polylactic acid film. The antibody immobilized magnetic beads were introduced, and trapped in the flow cell equipped with the neodymium magnet, an LAS solution containing HRP-labeled LAS at constant concentration and the luminol solution were sequentially introduced into the flow cell based on an SIA programmed sequence. Chemiluminescence emission was monitored by means of a photon counting unit located at the upper side of the flow cell by collecting the emitted light with a lens. A typical sigmoid calibration curve was obtained, when the logarithm of the concentration of LAS was plotted against the chemiluminescence intensity using various concentrations of standard LAS samples (0-500ppb) under optimum conditions. The time required for analysis is less than 15min.

Determination of cationic polyelectrolytes using a photometric titration with crystal violet as a color indicator.

The reaction of the cationic dye, crystal violet (CV) with the anionic polyelectrolytes such as potassium poly (vinyl sulfate) (PVSK) results in a decrease of the absorbance of CV at the maximum absorption wavelength (590 nm). This change of the absorption spectra of the CV has been already applied to the determination of anionic polyelectrolytes using flow injection analysis method. In this paper, CV was applied to the indicator for the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by photometric titration, using a PVSK solution as a titrant. The end-point of the titration is detected as the break point of the titration curve. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 0 to 5 x 10(-5) eq. mol dm(-3) for Cat-floc, glycol chitosan and methylglycol chitosan. The effects of the concentration of CV and coexisting electrolytes in the sample solution and the effect of pH of the sample solution on the degree of the change of absorbance at the end-point were also examined.

Use of marker ion and cationic surfactant plastic membrane electrode for potentiometric titration of cationic polyelectrolytes.

A plasticized poly (vinyl chloride) (PVC) membrane electrode sensitive to stearyltrimethylammonium (STA) ion is applied to the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by potentiometric titration, using a potassium poly (vinyl sulfate) (PVSK) solution as a titrant. The end-point of the titration is detected as the potential change of the plasticized PVC membrane electrode caused by decrease in the concentration of STA ion added to the sample solution as a marker ion due to the ion association reaction between the STA ion and PVSK. The effects of the concentration of STA ion, coexisting electrolytes in the sample solution and pH of the sample on the degree of the potential change at the end-point were examined. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 2x10(-5) to 4x10(-4) N for Cat-floc, glycol chitosan, and methylglycol chitosan.

Chemiluminescence sequential injection immunoassay for vitellogenin using magnetic microbeads.

A rapid and sensitive immunoassay for the determination of carp vitellogenin (Vg) is described. The method involves a sequential injection analysis (SIA) system equipped with a chemiluminescence detector and a samarium-cobalt magnet. An anti-Vg monoclonal antibody, immobilized on magnetic beads, was used as a solid support for the immunoassay. The introduction, trapping and release of the magnetic beads in the flow cell were controlled by a samarium-cobalt magnet and the flow of the carrier solution. The immunoassay was based on a sandwich immunoreaction of anti-Vg monoclonal antibody (primary antibody) on the magnetic beads, Vg, and the anti-Vg antibody labeled with horseradish peroxidase (HRP) (secondary antibody), and was based on a subsequent chemiluminescence reaction of HRP with hydrogen peroxide and p-iodophenol, in a luminol solution. The magnetic beads to which the primary antibody was immobilized were prepared by coupling the primary antibody with the magnetic beads after an agarose-layer on the surface of the magnetic beads was epoxidized. The primary antibody-immobilized magnetic beads were introduced, and trapped in the flow cell equipped with the samarium-cobalt magnet, a Vg sample solution, an HRP-labeled secondary antibody solution and the luminol solution were sequentially introduced into the flow cell based on an SIA programmed sequence. Chemiluminescence emission was monitored by means of a photomultiplier located at the upper side of the flow cell. The optimal incubation times both for the first and second immunoreactions were determined to be 20min. A concave calibration curve was obtained between Vg concentration and chemiluminescence intensity when various concentrations of standard Vg samples (2-100ngmL(-1)) were applied to the SIA system under optimal conditions. In spite of a narrow working range, the lower detection limit of the immunoassay was about 2ngmL(-1).

Spectrophotometric determination of carp vitellogenin using a sequential injection analysis technique equipped with a jet ring cell.

A sequential injection analysis (SIA) technique, in which antibody-immobilized microbeads were transferred to a jet ring (JR) cell, was used in determination of carp vitellogenin (Vg). The determination is based on a sandwich immunoassay in which two types of reactions between anti carp Vg antibodies and carp Vg are used. Namely, the antibody for the first reaction step was immobilized on microbeads (Sephadex beads), and an antibody labeled with a horseradish peroxidase (HRP) was used in the second step of the reaction. A mixed solution of hydrogen peroxide and o-phenylenediamine (OPD) was used as the source of the chromophore in the reaction. The microbeads-immobilized antibody, Vg analyte, HRP-labeled anitbody and the color developing solution were introduced automatically into the JR cell of the SIA system in a programmed sequence, and the absorbance of the oxidized OPD product was used to determine the amount of Vg present. The optimal incubation times for the immuno-raction for the first and the second steps were determined at 120 and 60 min, respectively, taking into account the sensitivity to the Vg determination. Under these conditions, a good linear correlation was obtained between Vg concentration and the absorbance of the oxidized OPD. The lower detection limit for the determination of Vg was about 5 ng ml(-1) in this system. The method developed here represents a simple, accurate method for the determination method of Vg.

Preparation of refractive index matching polymer film alternative to oil for use in a portable surface-plasmon resonance phenomenon-based chemical sensor method.

In order to simplify the procedure for assembling a surface-plasmon resonance (SPR) sensor, a refractive index matching polymer film was prepared as an alternative to the conventionally used matching oil. The refractive index matching polymer film, the refractive index of which was nearly equal to the prism and sensor chip material (a cover glass) of the SPR sensor, was prepared by casting a tetrahydrofuran solution of poly (vinyl chloride) (PVC) containing equal weights of dioctyl phthalate and tricresyl phosphate. The refractive index matching polymer film was found to have a refractive index of 1.516, which is identical to that of the prism and the cover glass used for the present SPR sensor. The utility of the matching polymer film for the SPR sensor was confirmed by the detection of anti-human albumin, based on an antigen-antibody reaction.