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Article history: Using a smartphone with camera function, simultaneous color sensing of oxygen and pH could be realized.
Received 27 January 2015 In the sensing film, chitosan was selected as a matrix, and platinum tetrakis pentafluorophenyl porphin,
Received in revised form 4 May 2015 a sensitive dye towards oxygen with red color emission, was immobilized in this matrix. A sensitive pH
Accepted 9 May 2015
sensing dye, fluorescein isothiocyanate with green fluorescence emission, was selected and covalently
Available online 4 June 2015
bonded to chitosan. In addition, the doped 4,40-bis(2-benzoxazolyl) stilbene with blue color emission in
the matrix played the role of reference. In the red–green–blue (RGB) sensor, the emission color of the
Keywords:
oxygen dye matched the red channel of the smartphone, while the emission of the pH indicator matched
pH
Oxygen its green channel. The reference dye was emitted in the blue channel. All the dyes were excited using
Sensor a 385 nm ultraviolet lamp. The sensor allowed simultaneous sensing of both pH and oxygen in a single
Ratiometric fluorescence RGB digital photo and showed quite good stability.
RGB © 2015 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2015.05.088
0925-4005/© 2015 Elsevier B.V. All rights reserved.
W. Xu et al. / Sensors and Actuators B 220 (2015) 326–330 327
2.2. Instrument
Fig. 3. Emission spectra of the sensor in different pH (pO2 5% (a)) and pO2 (pH 7 (b)).
Fig. 4. Emission spectra of the sensor (black line) and the typical response for the
Smartphone RGB-channels (the dashed red, green and blue lines). (For interpretation
of the references to color in this figure legend, the reader is referred to the web
version of this article.)
Fig. 5. Response time and luminescence intensity (645 nm) of the dual sensor at different pO2 (a) and reverisibility of the pH sensor (b).
W. Xu et al. / Sensors and Actuators B 220 (2015) 326–330 329
Fig. 7. (a) The pO2 signal is the ratio of the red channel divided by the blue channel (R/B). (b) The pH signal is the ratio of the green channel divided by the blue channel (G/B).
(For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Table 1
pH and O2 detection in water samples using the dual sensor compared with a commercial pH meter and dissolved oxygen meter.
Mineral water 7.3 ± 0.2 7.32 ± 0.05 8.3 ± 0.5 7.49 ± 0.05
Rain water 6.0 ± 0.2 6.24 + 0.05 4.2 ± 0.5 4.34 ± 0.05
Pure water 6.8 ± 0.2 6.74 ± 0.05 7.1 ± 0.5 6.81 ± 0.05
Lake water 7.4 ± 0.2 7.63 ± 0.05 3.6 ± 0.5 3.84 ± 0.05
In the sensing responses, neither oxygen signals (R/B) nor pH between FITC solution and the sensor, the result indicates the pho-
signals (G/B) showed cross-sensitivity to each other. The average tostability has improved in this sensor, however, the fluorescein
intensity of the three channels could be used to calculate the R/B still suffered form photobleaching. In practical applications, the
nd G/B ratio, as shown in Figs. 6 and 7. lifetime of the sensor could be further prolonged since an impulse
The calibration curve of pO2 from 0 to 1 was obtained using a trigger was generally applied for the LED emission. The effect of
mono-exponential function, as in the following equation: aging time on the G/B and R/B sensor is shown in Fig. S4. After
being stored in the dark for 30 days, no significant reduction of the
ln R/B − y0 /a
pO2 [%] = − (1) oxygen and pH sensing properties was observed. The color pictures
b of sensor prepared in different batches at pH 4, pO2 = 0.5 is shown
The calibration curve for pH (based on the ratios of green and in Fig. S4, and the R/B and G/B ratio with an RSD < 10% confirmed
blue channel ratios G/B from 4 to 8 approximately follows a four- that the sensing films was reproducible.
parametric sigmoidal fit [16], as in the following equation:
y + a − G/B 3.4. Sample analysis
0
pH = xo − ln ×b (2)
G/B − y0
The optical dual sensor was applied in the sensing of pH and
3.3. Stability of the optical dual sensor dissolved oxygen in water samples. In the experiments, mineral
water, rain water and the other water samples were selected. The
Indicator leaching or photobleaching in a sensing film generally obtained results were compared with the results from commercial
limits its applications. In order to investigate the leaching situation electrochemical pH meter and oxygen meter. As shown in Table 1,
of our sensing film, it was immersed into pure water for several the results from the optical dual sensor were comparable to those
hours and then treated with ultrasonication for 30 min. After this from the commercial meters. The results from the dual sensor were
procedure, the fluorescence intensity of this solution was tested easy readout using the G/B and R/B ratio.
and the results revealed that the fluorescence intensities of the
solution at 515 nm and 645 nm were both ignorable, indicating that 4. Conclusions
there was no obvious leaching of PtTFPP or FITC from the sensing
film (Fig. S2). Next, the sensor photostability was studied. We illu- Simultaneous optical sensing of O2 and pH with chitosan as a
minated the sensor continuously using an LED with a maximum matrix was achieved using a smartphone. In the sensor, triple emis-
emission wavelength of 385 nm for 1 h (Fig. S3). The RSD of the sion for the RGB channels included reference dye BBS for blue, pH
fluorescence intensity was less than 5%, indicating its good photo- sensitive FITC for green and oxygen sensitive PtTFPP for the red
stability. Generally, it is a common phenomenon that fluorescein channel were applied. The sensor exhibited good response to dif-
is easy to photobleaching, we performed the compare experiment ferent pH values from 4 to 8 and oxygen concentrations from 0
330 W. Xu et al. / Sensors and Actuators B 220 (2015) 326–330
to 100%, and indicated good stability towards leaching and photo- [16] R.J. Meier, S. Schreml, X.D. Wang, M. Landthaler, P. Babilas, O.S. Wolfbeis, Simul-
bleaching. Ongoing research will be focused on the development of taneous photographing of oxygen and pH in vivo using sensor films, Angew.
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optical sensors using phase modulation technique, in: R.A. Lieberman (Ed.), Yiying Chen, is currently a senior in the Department of Chemistry and Chemical
Chemical, Biochemical, and Environmental Fiber Sensors, vol X, 1999, pp. Engineering at Xiamen University. Her research interests are in the fields of 3D
19–27. graphene and 3D graphene based materials.
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ferling, Referenced dual pressure- and temperature-sensitive paint for digital she holds the position of Associate Professor at Xiamen University. Her current
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luminescence sensing of two species using optical probes of different decay Chemical Engineering at Xiamen University, Xiamen. Her research interests are in
time, and its application to an enzymatic reaction at varying temperature, Anal. the fields of new separation medium, new pretreatment techniques and devices for
Bioanal. Chem. 393 (2009) 1199–1207. solid-phase microextraction.
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cent sensor material for simultaneous imaging of pressure and temperature on Xi Chen, is a full Professor in the Department of Chemistry at Xiamen University,
surfaces, Adv. Funct. Mater. 18 (2008) 1399–1406. China. He received his PhD (1996) in Analytical Chemistry from the Kyoto Institute of
[15] A.S. Kocincova, S.M. Borisov, C. Krause, O.S. Wolfbeis, Fiber-optic microsensors Technology, Japan. Dr. Chen’s research interests cover electroanalytical chemistry,
for simultaneous sensing of oxygen and pH, and of oxygen and temperature, bio-chemical sensors and solid-phase microextraction. He has published over 180
Anal. Chem. 79 (2007) 8486–8493. scientific research articles in archival scientific journals.