Optical sensor arrays: one-pot, multiparallel synthesis and cellulose immobilization of pH and metal ion sensitive azo-dyes

A sixteen component array of acid-base and metal ion sensors was synthesized and covalently immobilized onto a transparent cellulose-based membrane. Dye synthesis and cellulose dyeing were carried out in one-pot, parallel, microscale reactions not requiring any isolation or purification steps. In addition, pH and metal ion optical sensing properties of the sixteen component array have been tested using a high-throughput screening based on digital imaging analysis.     

Selective lanthanum ions optical sensor based on covalent immobilization of 4-hydroxysalophen on a hydrolyzed triacetylcellulose membrane

An optical sensor membrane is described for the determination of lanthanum(III) ions based on the immobilization of 4-hydroxysalophen on a hydrolyzed triacetylcellulose membrane. 4-Hydroxysalophen is covalently bonded to a transparent hydrolyzed triacetylcellulose film. The sensing membrane in contact with lanthanum ions at pH 4.0 changes color from white-yellow to orange (323 to 433 nm). Under the optimum conditions, the proposed membrane displayed a linear range from 1.0 × 10⁻⁶ to 1.0 × 10⁻² M La(III) with a limit of detection of 1 × 10⁻⁷ M. The response time of the membrane was within 5–6 min depending on the concentration of La(III) ions. The selectivity of the probe towards lanthanum ions was found to be excellent. The sensor was successfully applied to the determination of La(III) in water, industrial waste water, and in NIST-615 (glass matrix) and NIST-3127a (lanthanum solution) samples with satisfactory results.     

Phenolphthalein immobilized membrane for an optical pH sensor

A phenolphthalein immobilized cellulose membrane for an optical pH sensor was described. The phenolphthalein was first reacted with the formaldehyde to produce a series of prepolymers with many hydroxymethyl groups. In this paper, the prepolymers was abbreviated to phenolphthalein-formaldehyde (PPF). Then the PPF was covalently immobilized to the diacetylcellulose membrane via hydroxymethyl groups. Finally the membrane was hydrolyzed in the 0.1 M NaOH solution for 24 h to reduce the response time. Advantageous features of the pH-sensitive membrane include (a) a large dynamic range from pH 8.0 to 12.50, or even broader, (b) rapid response time (2–30 s), (c) easy of fabrication, and (d) a promising material for determination of high pH values. The immobilized PPF has a broader dynamic range from 8.0 to 12.50 than the free phenolphthalein from pH 8.0 to 11.0, and this was due to the newly produced methylenes in our investigation.     

Development of a D-amino acids electrochemical sensor based on immobilization of thermostable D-proline dehydrogenase within agar gel membrane

A novel biosensor for determination of d-amino acids (DAAs) in biological samples by using an electrode based on immobilization of a thermostable d-Proline dehydrogenase (d-Pro DH) within an agar gel membrane was developed. The electrode was simply prepared by spin-coating the agar solution with the d-Pro DH on a glassy carbon (GC) electrode.An electrocatalytic oxidation current of 2,6-dichloroindophenol (DCIP) was observed at −100 mV vs. Ag/AgCl with the addition of 5 and 20 mmol L⁻¹d-proline. The current response and its relative standard deviation were 0.15 μA and 7.6% (n = 3), respectively, when it was measured in a pH 8.0 phosphate buffer solution containing 10 mmol L⁻¹d-proline and 0.5 mmol L⁻¹ DCIP at 50 °C. The current response of d-proline increased with increase of the temperature of the sample solution up to 70 °C. The electrocatalytic response at the d-Pro DH/agar immobilized electrode subsequently maintained for 80 days. Finally, the d-Pro DH/agar immobilized electrode was applied to determination of DAAs in a human urine sample. The determined value of DAAs in the human urine and its R.S.D. were 1.39 ± 0.12 mmol L⁻¹ and 8.9% (n = 3), respectively.     

Full-range optical pH sensor based on imaging techniques

A new colour-based disposable sensor array for a full pH range (0-14) is described. The pH sensing elements are a set of different pH indicators immobilized in plasticized polymeric membranes working by ion-exchange or co-extraction. The colour changes of the 11 elements of the optical array are obtained from a commercial scanner using the hue or H component of the hue, saturation, value (HSV) colour space, which provides a robust and precise parameter, as the analytical parameter. Three different approaches for pH prediction from the hue H of the array of sensing elements previously equilibrated with an unknown solution were studied: Linear model, Sigmoid competition model and Sigmoid surface model providing mean square errors (MSE) of 0.1115, 0.0751 and 0.2663, respectively, in the full-range studied (0-14). The performance of the optical disposable sensor was tested for pH measurement, validating the results against a potentiometric reference procedure. The proposed method is quick, inexpensive, selective and sensitive and produces results similar to other more complex optical approaches for broad pH sensing.     

Full-range optical pH sensor array based on neural networks

A neural network multivariate calibration is used to predict the pH of a solution in the full-range (0–14) from hue (H) values coming from imaging an optical pH sensor array based on 11 sensing elements with immobilized pH indicators. Different colorimetric acid-base indicators were tested for membrane preparation fulfilling the following conditions: 1) no leaching; 2) change in tonal coordinate by reaction and 3) covering the full pH range with overlapping between their pH responses. The sensor array was imaged after equilibration with a solution using a scanner working in transmission mode. Using software developed by us, the H coordinate of the colour space HSV was calculated from the RGB coordinates of each element.The neural network was trained with the calibration data set using the Levenberg–Marquardt training method. The network structure has 11 input neurons (each one matching the hue of a single element in the sensor array), 1 output (the pH approximation value) and 1 hidden layer with 10 hidden neurons. The network provides an MSE = 0.0098 in the training data, MSE = 0.0183 in the validation data and MSE = 0.0426 in the test data coming from a set of real water samples. The resulting correlation coefficient R obtained in the Pearson correlation test is R = 0.999.     

Development of pH sensor based on aromatic polyurethane matrix

The synthesized aromatic polyurethane (APU)-based all-solid-state (ASS) pH sensor was developed with the same APU-based reference site in an ASS multi sensing electrode. The best analytical performance (the linear range of pH 3.0–11.5, slopes of 57 mV pH⁻¹) was obtained with the membrane composition of 33:66:1 (wt.%) of APU/plasticizer (NPOE)/ionophore (N,N-dioctadecylmethylamine) with the addition of lipophilic additive (KTpClPB, 5 mol.%). This ASSE exhibits more advantages of increasing stability, reducing membrane resistance and reducing anion interference.     

Hydrophilic sensor membrane based on cation-selective protic chromoionophore

The first potassium optode based on a protic chromoionophore immobilized in a hydrogel matrix is presented. The highly selective protic chromoionophore consists of a cryptohemispherand moiety and a trinitroanilino chromophore part. The acidifying power of potassium ions over sodium ions is 0.6 pH units. This correlates with the findings in solution. In contrast to several crown and aza-crown based chromophores the highly pre-organized moiety allows ion detection even in aqueous environment. The detection limit for potassium ions at pH 7.7 is 5 microM.     

Hydrophilic sensor membrane based on cation-selective protic chromoionophore

The first potassium optode based on a protic chromoionophore immobilized in a hydrogel matrix is presented. The highly selective protic chromoionophore consists of a cryptohemispherand moiety and a trinitroanilino chromophore part. The acidifying power of potassium ions over sodium ions is 0.6 pH units. This correlates with the findings in solution. In contrast to several crown and aza-crown based chromophores the highly pre-organized moiety allows ion detection even in aqueous environment. The detection limit for potassium ions at ¶pH 7.7 is 5 μM.     

Urea sensors based on PVC membrane pH electrode

Several procedures of urease immobilization on the surface of the polymeric membrane pH electrode with tri-n-dodecylamine as a neutral carrier were compared. The best results were obtained for the urea sensor with covalently bound urease. The sensor characteristics including the effect of buffer, pH and concentration and the effect of stirring rate are presented. These effects are in good agreement with theoretical expectations.     

Optical sensor for sulfur dioxide based on fluorescence quenching

A series of potential indicator dyes is evaluated for use in the development of optical sensors for measuring sulfur dioxide in gaseous samples. Rhodamine B isothiocyanate is selected on the basis of relative sensitivity to dynamic quenching by sulfur dioxide and oxygen. A solid-state fluorometer is described for monitoring the sulfur dioxide induced fluorescence quenching of sensing membranes composed of silicone and rhodamine B isothiocyanate. A modulated blue LED is coupled with the lock-in detection of a photodiode detector to provide high signal-to-noise ratios. The limit of detection is 0.114+/-0.009% for sulfur dioxide in a carrier stream of nitrogen gas. Selectivity measurements indicate no interference from several common gases (HCl, NH(3), NO, and CO(2)). Oxygen alters the sensor response when comparing signals for sulfur dioxide in 0, 20 and 100% oxygen environments.     

Optical behaviour of pH detectors based on sol-gel technology

Acidity is an outstanding parameter that affect the correct preservation of most part of materials engaged in artworks and heritage objects. In spite of the new generation of advanced analytical devices, the conservation/heritage management sector claims for some kind of simple, robust and low-cost device to monitor environmental acidity wherever necessary. The purpose of this paper is to offer a suitable alternative for the estimation of environmental acidity by means of detectors to be used without electrodes, solutions, pH meters, wires or batteries.Doped sol-gel thin coatings have been used as transductors for producing pH detectors. The coatings consist of a partially densified polysiloxane network and an organic dye sensitive to pH changes. The siloxane network behaves as a host for immobilisation of the dye molecules, in such a way that chemical-optical properties of the dye are preserved as far as possible. The transductors were applied on common glass substrates by dipping. Further heat-treatment allows the coating partial densification.The optical response of the detectors was analysed by VIS absorption spectroscopy, since a change of colour took place when the detectors were submitted to different pH buffered solutions. With the aim to investigate their optical behaviour as a function of pH, several experimental measurements were undertaken: absorption intensity; maximum spectral wavelength; colour coordinates; colour purity percentages. Time response and memory effect were also studied. The detector operation conditions for monitoring environmental acidity both indoor and outdoor are discussed.     

A sensor for pH based on an optical reflective device coupled to the swelling of an aminated polystyrene membrane

We have developed a low cost pH sensor based on an optical reflective device (ORD) coupled to a toughened, lightly crosslinked aminated polystyrene membrane. Protonation of the amine group causes the polymer to swell. This is accompanied by a decrease in the turbidity of the membrane. As a result, reflected intensity measured by the ORD is a function of pH. The resulting pH sensor is inexpensive and has modest power requirements. The sensor is stable, provided the membrane is not allowed to dry out and crack. Changing ionic strength affects response both by changing the turbidity of the membrane due to refractive index effects and also by reducing the extent to which the protonated polymer swells. Increasing temperature leads to a larger change in turbidity.     

Optical sensor for sodium based on ion-pair extraction and fluorescence

A reagent phase that responds to sodium ion is used in a sodium-selective fiber-optic sensor. The components of the reagent phase are the ammonium salt of 8-anilino-1- naphthalenesulfonic acid (ANS), copper(II)—polyethyleneimine, and a commercial sodium-selective ionophore [N,N′,N″-triheptyl-N,N′,N″-trimethyl-4,4′,4″-propylidyne- tris(3-oxabutyramide)] immobilized on silica. In the absence of sodium, the ANS binds to the copper(II) polyelectrolyte and fluorescence is quenched. When sodium (20– 200 mM) is added, it forms a cationic complex which forms ion-pairs with some of the ANS, causing it to fluoresce. Response is linear at the lower sodium concentrations but tends to curve toward the concentration axis at higher concentrations. The sensitivity and the range of linear response depend on ANS concentration. Typically, it takes 1–3 min to reach 90% of steady-state response. The response time increases with decreasing temperature, increasing amounts of immobilized ionophore, and higher sodium concentrations. The selectivity of the sensor is established by the selectivity of the ionophore.     

A pH sensor based on force generated by pH-dependent polymer swelling

We have demonstrated the feasibility of a new type of pH sensor by combining a bead of porous lightly crosslinked diethanolamine derivatized poly(vinylbenzyl chloride) with a strain gauge, i.e. a pressure sensitive resistor. The polymer bead is toughened with Kraton G1652, a styrene-ethylene,butylene-styrene triblock copolymer. The sensor is constructed so that the shrunken form of the bead is held in contact with the strain gauge with a small force. Increases in the hydrogen ion concentration protonate the diethanolamine introducing a positive charge onto the polymer backbone. This results in an electrostatic swelling force that causes the polymer to swell. This is detected as a change in strain gauge resistance that is readout via a Wheatstone bridge. When the pH of 0.10 M buffers is changed from 10 to 4, the response time is 390 s for a bead that is 0.25 mm in diameter in the shrunken state. The response varies with the square of the bead radius. The magnitude of the response is highly correlated with the penetration modulus, a measure of the extent to which the bead resists deformation when subjected to an external force. The response to pH appears to be shifted by the application of pressure in the sensor. This instrumentally simple approach to sensing has the potential to be stable and long-lived if the polymer bead can undergo a large number of swelling/shrinking cycles without changing mechanical properties.     

Fabrication of an optical sensor based on the immobilization of Qsal on the plasticized PVC membrane for the determination of copper(II)

A novel optical sensor has been proposed for sensitive determination of Cu(II) ion in aqueous solutions. The copper sensing membrane was prepared by incorporating Qsal (2-(2-hydroxyphenyl)-3H-anthra[2,1-d]imidazole-6,11-dione) as ionophore in the plasticized PVC membrane containing tributyl phosphate (TBP) as plasticizer. The membrane responds to Cu(II) ion by changing color reversibly from yellow to dark red in acetate buffer solution at pH 4.0. The proposed sensor displays a linear range of 6.3 × 10^?7?1.00 × 10^?4 M with a limit of detection of 3.3 × 10^?7 M. The response time of the optical sensor was about 3?C5 min, depending on the concentration of Cu(II) ions. The selectivity of the optical sensor to Cu(II) ions in acetate buffer is good. The sensor can readily be regenerated by hydrochloric acid (0.1 M). The optical sensor is fully reversible. The proposed optical sensor was applied to the determination of Cu(II) in environmental water samples.     

Alcohol-FET sensor based on a complex cell membrane enzyme system

An alcohol -FET sensor was developed by use of a complex enzyme system in a cell membrane and an ion-sensitive field effect transistor (ISFET). The cell membrane of Gluconobacter suboxydans IFO 12528, which converts ethanol to acetic acid, was immobilized on the gate of an ISFET with calcium alginate gel coated with nitrocellulose. This ISFET (1), a reference ISFET without the cell membrane (ISFET 2) and an Ag/AgCl reference electrode were placed in 5 mM Trismalate buffer (pH 5.5, 25°C), and the differential output between ISFETS 1 and 2 was measured. The output of the sensor was stabilized by adding pyrroloquinoline quinone. The response time was ca. 10 min., and there was a linear relationship between the differential output voltage and the ethanol concentration up to 20 mg l^?1. The output of the sensor was stable for 40 h below 30°C. The sensor responded to ethanol, propan- 1-ol and butan- 1-ol, but not to methanol, propan-2-ol and butan-2-ol. The sensor was used to determine blood ethanol.     

Enzyme electrode for glucose based on an iodide membrane sensor

The construction of a new type of enzyme electrode for the potentiometric determination of glucose is reported. The electrode response is based on the enzymecatalyzed reactions: The highly selective iodide sensor monitors the local decrease in the iodide activity at the electrode surface. The properties of the above reactions were examined kinetically, with flow-stream techniques and potentiometric detection. The glucose electrode constructed and the use of flow-stream experiments with two iodide sensors provided accurate and convenient glucose determinations in the absence of some oxidizing and reducing agents.