A CO2 sensor based on Pt-porphyrin dye and FRET scheme for food packaging applications

Abstract An optochemical CO2 sensor is described which uses a phosphorescent reporter dye PtTFPP and a colourimetric pH indicator α-naphtholphthalein incorporated in plastic matrix together with a phase transfer agent tetraoctyl- or cetyltrimethylammonium hydroxide. Good spectral overlap of PtTFPP emission and α-naphtholphthalein absorption at around 650 nm provides efficient energy transfer from PtTFPP via FRET mechanism, thus reducing its phosphorescence lifetime. Experiments were carried out to optimize the composition and working characteristics of such a sensor for the measurement of headspace CO2 in foods packaged under modified atmosphere. The resulting thin film sensor coatings showed robust optical responses to CO2, response (1 min, 99.9%) and recovery times (4 min, 99.9%) from 0 to 100% CO2. As expected, the CO2 sensor showed significant cross-sensitivity to O2 quenching, and this was accounted for by a tandem O2 sensor having similar phosphorescent characteristics but no CO2 sensitivity. Upon storage in an open container, the sensors were stable for at least 14 days at 4 °C and 50 days at −20 °C, however at room temperature they were seen to deteriorate within 7 days loosing colour and sensitivity to CO2. At the same time, in food and modified atmosphere environment the sensor retained its sensitivity to CO2 for 21 days at 4 °C which is sufficient for many packaged products. Migration of sensor components examined with a standard set of standard food stimulants was only detectable in 95% ethanol and in olive oil for PtTFPP (0.06–0.13 μg/ml) and in 50% and 95% ethanol for α-naphtholphthalein (9.86–21.65 μg/ml).

[1]  Colette McDonagh,et al.  Sol-gel based optical carbon dioxide sensor employing dual luminophore referencing for application in food packaging technology. , 2002, The Analyst.

[2]  Colette McDonagh,et al.  Development of an optical sensor probe for the detection of dissolved carbon dioxide , 2006 .

[3]  Yordan Kostov,et al.  Optical Ratiometric Sensor for Alcohol Measurements , 2007 .

[4]  L. Capitán-Vallvey,et al.  A new light emitting diode-light emitting diode portable carbon dioxide gas sensor based on an interchangeable membrane system for industrial applications. , 2011, Analytica chimica acta.

[5]  Kenneth W McMillin,et al.  Where is MAP Going? A review and future potential of modified atmosphere packaging for meat. , 2008, Meat science.

[6]  Dmitri B. Papkovsky,et al.  Study of migration of active components of phosphorescent oxygen sensors for food packaging applications , 2005 .

[7]  Kadriye Ertekin,et al.  Ratiometric sensing of CO2 in ionic liquid modified ethyl cellulose matrix. , 2008, Talanta.

[8]  Yang Tao,et al.  Effect of initial oxygen concentration and film oxygen transmission rate on the quality of fresh-cut romaine lettuce , 2005 .

[9]  Sandhya. Modified atmosphere packaging of fresh produce: Current status and future needs , 2010 .

[10]  Ingo Klimant,et al.  The influence of the lipophilic base in solid state optical pCO2 sensors , 2005 .

[11]  Ricardo Simpson,et al.  Mass transfer of CO2 in MAP systems: Advances for non-respiring foods , 2009 .

[12]  K. Yam,et al.  Package Headspace Composition Changes of Chill‐Stored Perishable Foods in Relation to Microbial Spoilage , 2011 .

[13]  Optical CO(2) sensor of the combination of colorimetric change of alpha-naphtholphthalein in poly(isobutyl methacrylate) and fluorescent porphyrin in polystyrene. , 2005, Talanta.

[14]  L. Capitán-Vallvey,et al.  Phosphorescent sensing of carbon dioxide based on secondary inner-filter quenching. , 2009, Analytica chimica acta.

[15]  Colette McDonagh,et al.  Lifetime-based optical sensor for high-level pCO2 detection employing fluorescence resonance energy transfer , 2003 .

[16]  O. Wolfbeis,et al.  Fiber-optic microsensor for high resolution pCO2 sensing in marine environment , 2000, Fresenius' journal of analytical chemistry.

[17]  Alberto J. Palma,et al.  Hand-held optical instrument for CO2 in gas phase based on sensing film coating optoelectronic elements , 2010 .

[18]  Dmitri B. Papkovsky,et al.  Quality assessment of packaged foods by optical oxygen sensing , 2005, SPIE Optics East.

[19]  Y. Amao,et al.  Optical CO2 sensor with the combination of colorimetric change of α-naphtholphthalein and internal reference fluorescent porphyrin dye , 2004 .

[20]  Ingo Klimant,et al.  Microsecond lifetime-based optical carbon dioxide sensor using luminescence resonance energy transfer , 1999 .

[21]  Andrew Mills,et al.  Equilibrium studies on colorimetric plastic film sensors for carbon dioxide , 1992 .

[22]  R. Parry,et al.  Principles and applications of modified atmosphere packaging of foods , 1993 .

[23]  Joseph R. Lakowicz,et al.  Phase Fluorometric Optical Carbon Dioxide Gas Sensor for Fermentation Off‐Gas Monitoring , 1996, Biotechnology progress.

[24]  J. Kerry,et al.  Physical assessment of composite biodegradable films manufactured using whey protein isolate, gelatin and sodium alginate. , 2010 .

[25]  A. Mills,et al.  Water-based colourimetric optical indicators for the detection of carbon dioxide. , 2010, The Analyst.

[26]  Y. Amao,et al.  An optical sensor with the combination of colorimetric change of α-naphtholphthalein and internal reference luminescent dye for CO2 in water , 2005 .

[27]  Curt R. Eyster,et al.  Optical pH, oxygen and carbon dioxide monitoring using a microdialysis approach , 2000 .

[28]  Karla D. Thrall,et al.  Analysis of exhaled breath by laser detection , 1996, Photonics West.

[29]  Morten Sivertsvik,et al.  A review of modified atmosphere packaging of fish and fishery products – significance of microbial growth, activities and safety , 2002 .

[30]  C. McDonagh,et al.  Ratiometric fluorescence-based dissolved carbon dioxide sensor for use in environmental monitoring applications , 2010, Analytical and bioanalytical chemistry.

[31]  J. Severinghaus,et al.  Electrodes for blood pO2 and pCO2 determination. , 1958, Journal of applied physiology.

[32]  Ingo Klimant,et al.  Strategies To Design pH Optodes with Luminescence Decay Times in the Microsecond Time Regime , 1998 .

[33]  A. Mills,et al.  Breath-by-breath measurement of carbon dioxide using a plastic film optical sensor , 1997 .

[34]  M. Jensen,et al.  Tedlar bag sampling technique for vertical profiling of carbon dioxide through the atmospheric boundary layer with high precision and accuracy. , 2004, Environmental science & technology.

[35]  An Autonomous Sensor and Telemetry System for Low-Level pCO(2) Measurements in Seawater. , 1999, Analytical chemistry.

[36]  Ursula E. Spichiger-Keller,et al.  Optical CO2-sensing layers for clinical application based on pH-sensitive indicators incorporated into nanoscopic metal-oxide supports , 2007 .

[37]  Roger Diels,et al.  Intelligent Infrared Comfort Sensors for the Automotive Environment , 2006 .

[38]  Andrew Mills,et al.  Fluorescence plastic thin-film sensor for carbon dioxide , 1993 .