Fluorescence-based thin plastic film ion-pair sensors for oxygen

A general method of preparation of thin-film sensors for O-2, incorporating the dye ion-pair tris(4,7-diphenyl-1,10-phenanthroline) rutheninm(II) ditetraphenylborate, in a variety of different thin film polymer/plasticizer matrices is described, The sensitivity of the sensor depends upon the nature of the polymer matrix and plasticizer, A detailed study of one of these systems utilising the polymer poly(methyl methacrylate), PMMA, is reported. The sensitivity of this O-2 sensor depends markedly upon the plasticizer concentration and is largely independent of temperature (24,5-52.5 degrees C) and age (up to 30 d), When exposed to an alternating atmosphere of O-2 and N-2, a typical oxygen film sensor in PMMA exhibits a 0-90% response and recovery time of 0.4 and 4.5 s, respectively.

Thin plastic film colorimetric sensors for carbon dioxide: Effect of plasticizer on response

Different plasticizers, including phosphate-, phthalate-and adipate-based types were used in the creation of a range of colorimetric plastic film sensors for CO2, The different types of plasticizer used in the formulation of a colorimetric plastic film sensor for CO2 affect the response and recovery times of the sensor differently, An effective plasticizer was taken as one that decreased the response and recovery times of the final film sensor when exposed to an alternating atmosphere of 0-5% CO2. On this basis, the most efficient plasticizers appeared to be phosphate-based, followed by phthalate- and adipate-based plasticizers, This trend appears to reflect the degree of the polymer-plasticizer compatibility. Increasing the amount of plasticizer in the film formulation decreased the response and recovery times of the sensor dramatically, The sensitivity of the film sensor towards CO2 appears to decrease with increasing plasticizer effectiveness; thus, the general order of film CO2 sensitivity with respect to plasticizer type was found to be adipate > phthalate > phosphate. In general, the response of the optical films towards CO2 was found to be temperature sensitive [typically, Delta H = -(44-55) kJ mol(-1)], The phosphate-based plasticized films appear to be less temperature sensitive than the other plasticized films, and 2-ethylhexyl diphenylphosphate appears particularly effective in this respect (Delta H = -18.5 kJ mol(-1)).

Plastic colorimetric film sensors for gaseous ammonia

The preparation and characterization of three different plastic thin-film colorimetric sensors for gaseous ammonia is described. In the film sensors, the neutral form of a pH-sensitive dye (Bromophenol Blue, Bromocresol Green or Chlorophenol Red) was encapsulated in a plastic medium, either poly(vinyl butyral) or ethylcellulose plasticized with tributyl phosphate. Each of these film optodes gave a reproducible and reversible response towards gaseous ammonia. The sensitivity of the film sensors towards ammonia was found to be strongly dependent upon the pK(a) of the encapsulated dye. Thus, the film with Chlorophenol Red (pK(a) = 6.25), proved to be very insensitive (operating range: 0.29%

EFFECT OF ULTRASOUND ON THE KINETICS OF OXIDATION OF OCTAN-2-OL AND OTHER SECONDARY ALCOHOLS WITH SODIUM-BROMATE, MEDIATED BY RUTHENIUM TETRAOXIDE IN A BIPHASIC SYSTEM

The initial rate of oxidation of octan-2-ol and other secondary alcohols to their ketones with NaBrO3, mediated by RuO4 in an aqueous-CCl4 biphasic system, is greater with ultrasonic irradiation than by stirring alone. Under ultrasonic irradiation the initial rate of oxidation of octan-2-ol increases with increasing % duty cycle, [RuO4] and [NaBrO3]. The kinetics of alcohol oxidation appear to be closely linked with the oxidative dissolution of RuO2 to RuO4 by NaBrO3. The observed enhancement in rate with ultrasonic irradiation appear to be association, at least in part, with the increase in interfacial surface area via the formation of an emulsion of aqueous microdroplets containing NaBrO3 in the CCl4 layer containing the non-water-soluble secondary alcohol.

EFFECT OF ULTRASOUND ON THE KINETICS OF REDUCTION OF HEXACYANOFERRATE(III) BY THIOSULFATE IONS MEDIATED BY RUTHENIUM DIOXIDE HYDRATE

Ultrasound promotes the reduction of hexacyanoferrate(III) by thiosulfate ions mediated by RuO2 . xH(2)O under diffusion-controlled conditions. There is a strong correlation between the measured first-order rate constant and the absorbance of the dispersion, which, in turn, is closely related to the specific surface area of the catalyst. The enhancement in rate with ultrasonic irradiation appears to be largely associated with the dispersive action of the ultrasound on the aggregated particles of RuO2 . xH(2)O. The rate of reaction increases with increasing %duty cycle and ultrasonic intensity. The measured overall activation energies for the reaction with and without ultrasound, i.e. 18 +/- 1 and 20 +/- 1 kJ mol(-1), respectively, are very similar to those expected for a diffusion-controlled reaction. The homogeneous reaction is not promoted by ultrasound.

COLORIMETRIC POLYMER FILM SENSORS FOR DISSOLVED CARBON-DIOXIDE

Plasticized and unplasticized polymer colorimetric film sensors for gaseous CO2, containing the dye m-cresol purple, are tested as sensors for dissolved CO2. The plasticized polymer m-cresol purple film sensor develops a measurable degree of opacity when exposed to aqueous solution, especially in neutral, compared with alkaline, solution. However, it is shown that a presoaked, fogged plasticized polymer m-cresol purple film does function as a quantitative sensor for dissolved CO2 over the range 0-4% CO2. An unplasticized polymer m-cresol purple film remains largely dear upon exposure to aqueous solution and also functions as a quantitative sensor for dissolved CO2 over the range 0-4% CO2. However, in both types of films the dye interacts with electrolytes present in solution; invariably the dye appears to be converted from its initial deprotonated form (blue) to its protonated form (yellow) and the rate of this process appears to increase with increasing ionic strength, anionic charge and decreasing pH. The 90% response and recovery times for an unplasticized film are determined as 19 s(CO2:0-->5%) and 21 s (CO2:5-->3.6%), respectively.

TUNING COLOURIMETRIC AND FLUOROMETRIC GAS SENSORS FOR CARBON-DIOXIDE

The basic theory behind conventional colourimetric and fluorimetric optical sensors for CO2 is examined and special attention is given to the effect on sensor response of the key parameters of initial base concentration and dye acid dissociation constant, K(D). Experimental results obtained in aqueous solution using a variety of different dyes and initial base concentrations are consistent with the predictions made by the theoretical model. A series of model-generated pK(D) versus %CO2 curves for different initial base concentrations allow those interested in constructing an optical CO2 sensor to readily identify the optimum dye/initial base combination for their sensor; the response of the sensor can be subsequently fine-tuned through a minor variation in the initial base concentration. The model and all its predictions appear also to apply to the new generation of plastic film CO2 sensors which have just been developed.

THE EFFECT OF POWER ULTRASOUND ON THE OXIDATIVE DISSOLUTION OF RUO2.XH2O BY BROMATE IONS

The effects of continuous sonication and presonication on the kinetics of oxidative dissolution of ruthenium dioxide hydrate by bromate ions under acidic conditions are reported. Compared with unsonicated and presonicated dispersions the overall rate of dissolution of continuously sonicated dispersions is significantly greater due to a reduction in the average particle size and, hence, an increase in the specific surface area. Powder dispersions subjected to continuous ultrasound and presonication exhibit an initial induction period in their corrosion kinetics; the length of this induction period increases with increasing presonication. This corrosion feature is retained in the dissolution kinetics of powder samples which have been subjected to pre-ultrasound, but which are then stirred during the dissolution process. It is believed that this apparent permanent change in the nature of the powder particles is due to the ultrasound induced formation of a very thin layer of a largely unreactive form of ruthenium dioxide (possibly due to partial dehydration) on the surface of the powder particles. A kinetic scheme, based on this model, is used to account for the observed kinetics of dissolution of RuO2 . xH2O which have been subjected to both continuous sonication and presonication.

EQUILIBRIUM STUDIES ON COLORIMETRIC PLASTIC FILM SENSORS FOR CARBON-DIOXIDE

The equilibrium responses of three new colorimetric plastic film sensors for CO2 as a function of % CO2 and temperature are described. The results fit a model in which there is a 1:1 equilibrium reaction between the deprotonated form of the dye (present in the film as an ion pair) and CO2. The 0-50% and 0-90% response and recovery times of each of these films when exposed to an alternating atmosphere of air and 5% CO2 are determined and in two cases are typically less than 3 s. The shelf life of the films is long (many months); however, prolonged use of the films leads to the permanent generation of the protonated form of the dye over a period of 20-100 h. A possible cause of this latter effect is discussed.

Molecular Logic Gates and Luminescent Sensors Based on Photoinduced Electron Transfer

The competition between Photoinduced electron transfer (PET) and other de-excitation pathways such as fluorescence and phosphorescence can be controlled within designed molecular structures. Depending on the particular design, the resulting optical output is thus a function of various inputs such as ion concentration and excitation light dose. Once digitized into binary code, these input-output patterns can be interpreted according to Boolean logic. The single-input logic types of YES and NOT cover simple sensors and the double- (or higher-) input logic types represent other gates such as AND and OR. The logic-based arithmetic processors such as half-adders and half-subtractors are also featured. Naturally, a principal application of the more complex gates is in multi-sensing contexts.