Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 304 (2024) 123349

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Spectrochimica Acta Part A:

Molecular and Biomolecular Spectroscopy
journal homepage: www.journals.elsevier.com/spectrochimica-acta-part-a-
molecular-and-biomolecular-spectroscopy

A novel multifunctional fluorescent capillary-based sensor for simultaneous

monitoring of pH, O2 and CO2
Xiaohui Wang a, *, Yuanxiangyi Feng a, Zhe Li a, Jinhua Liu b, Dandan Sun a, Wei Yang a,
Xiaowei Xing c, Wenjun Liu c, Hongxin Zhang a
a
Beijing Key laboratory of Work Safety Intelligent Monitoring, School of Electronic Engineering, Beijing University of Posts and Telecommunications, Beijing 100876,
China
b
Department of Pulmonary and Critical Care Medicine, The Third Hospital of Changsha, Changsha 410015, China
c
School of Science, Beijing University of Posts and Telecommunications, Beijing 100876, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• A capillary sensor doped with O2 indi­

cator RuDP, pH and CO2 indicator HPTS
is designed for detecting pH, O2, and
CO2.
• The multifunctional sensor can be
excited at the same wavelength and
realize the monitoring of multiple ana­
lyte at the different sensing position.
• The fluorescent capillary sensor exhibits
favorable stability, low-cost and real-
time monitoring.
• The optical multi-analyte fluorescent
capillary sensor possesses a sensitive
fluorescence response to pH, O2 and
CO2.

A R T I C L E I N F O A B S T R A C T

Keywords: A fluorescent capillary sensor for detecting the bioanalytically and biologically relevant analytes pH, O2, and CO2
pH detection has been designed. The sensor is based on single capillary tube with 2 mm inner diameter, which is simultaneous
O2 sensing doped with emissive O2-sensitive indicator Ru(dpp)3(PF6)2 (RuDP), pH-sensitive and CO2-sensitive indicator 8-
CO2 measurement
hydroxypyrene-1, 3,6-trisulfonic acid trisodium salt (HPTS). The multifunctional sensor can be excited at the
Capillary
Optical sensor
same wavelength and realize multi-parameter optical monitoring at the different sensing position. Studies in
Fluorescence phosphate-buffered solutions display the excellent feasibility of the capillary sensor for fluorescence detection of
pH, O2, and CO2. Overall, the multifunctional capillary sensor exhibits great potential in real-time blood gas
analysis, and clinical application of multi-parameter biological detection.

1. Introduction been increasingly applied for monitoring biologically and bio­

analytically relevant analytes[1]. Optical strategies are mainly paied
In recent years, the chemical sensing with optical techniques has attention to achieve spectral and intensity changes in absorption/

* Corresponding author.
E-mail address: [email protected] (X. Wang).

https://doi.org/10.1016/j.saa.2023.123349
Received 4 July 2023; Received in revised form 1 September 2023; Accepted 4 September 2023
Available online 7 September 2023
1386-1425/© 2023 Elsevier B.V. All rights reserved.
X. Wang et al. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 304 (2024) 123349

excitation and/or luminescence and luminescence lifetime[2,3]. Among and CO2 parameters simultaneously were never reported. It is therefore
the readout techniques, luminescence measurements are frequently critically important to design multianalyte capillary sensors for the
employed for online in-situ detection and sensing owing to its multi­ practical application in biological systems.
parametric nature, rapid response, high spatial resolution and simple In this study, we immobilized the pH, O2 and CO2 probes on front,
operation [1,4]. Luminescence sensing of optically inactive analytes like middle and back parts of the capillary tube for the detection of pH, O2
metal ions, small organic molecules and gases, are based on the optical and CO2 in solution. As for pH-, O2– and CO2-responsive sensor dyes, we
property changes of sensing indicators or probe selectively after inter­ chose typical optical sensing materials HTPS, Ru(dpp)3(PF6)2 and HTPS
action with the target analytes[5,6]. These sensing indicators and probes respectively. These complexes can be excited at wavelength region from
are often loaded into matrices like polymers films to generate sensor, 450 to 480 nm, and thus can be operated with single-wavelength exci­
and directly interact with the analyte during the monitoring process[7]. tation. Subsequently, the pH, O2 and CO2 sensing behavior and stability
As for the biologically relevant parameters, pH, O2 and CO2 are of multianalyte sensor were assessed in buffer solutions. The multi­
mostly frequently monitored because of their relevance for biological functional capillary sensor exhibits high sensitivity, favorable stability,
processes and diseases diagnosis. The optical sensors for pH, O2 or CO2 low-cost and real-time monitoring, indicating great significance for
detection were rapidly developed in analytical science, environment efficient and rapid detection in the biological field.
engineering and medicine, which are essential to detect environmental
changes and human health [8–10]. Typically, the blood hypoxia and 2. Experimental section
acid-base balance are usually determined by human artery blood gas
analysis, namely measuring the blood acidity (pH normal range: 7.35 ~ 2.1. Reagents
7.45), blood O2 partial pressure (normal range: 80 ~ 100 mmHg) and
CO2 partial pressure (normal range:35 ~ 45 mmHg). Accurate and Sodium 8-hydroxy-pyrene-1,3,6-trisulfonate (HPTS), ethyl­
timely blood gas monitoring of pH, O2 and CO2, can realize the effective triethoxysilane (ETEOS), (3-glycidyl) trimethylsilane (GPTMS), 1-
assessment of human health state, and reflect respiratory failure in pa­ methimidazole (MI), tetraoctylammonium bromide, silver oxide
tients. Typical oxygen sensing fluorescence indicators are commonly (Ag2O) were purchased from J&K Scientific. Hexadecyl trimethyl
made of metalloporphyrins like the platinum(II) porphyrin complex ammonium Bromide, ethanol, 2-methacryloyloxyethyl phosphorylcho­
[11], and ruthenium polypyridyl complex[12]. The phosphorescent line (MPC), azodiisonititrile (2,2′-Azobis(2-methylpropionitrile)) and n-
transition-metal complex sensors are attractive owing to their highly butyl methacrylate (BMA) were obtained from Aladdin Industrial Cor­
oxygen-sensitive MLCT (metal-to-ligand charge transfer) emitting state. poration. Ru(dpp)3(PF6)2 (RuDP)was bought from Heowns. All reagents
Typically used luminescent pH-sensitive dyes include 8-hydroxypyrene- were adopted without further purification.
1,3,6-trisulfonate (HPTS)[13], fluorescein(FITC)[14] and rhodamine
derivatives[15]. Thereinto, H + ion can reacts with the deprotonated 2.2. Characterization
form of the HPTS dye, and the fluorescence of HPTS decreases accord­
ingly. For CO2 sensing, commonly used fluorescence indicators are HPTS Emission spectra were investigated using a Hitachi F-4600 fluores­
[16] and neutral red [17]. It should be noted that HPTS exhibits pH- cence spectrometer (https://www.hitachi.com). Absorption spectra
dependent emission spectrum. To avoid the interference of pH, the were detected on a UV-3600 plus spectrophotometer (Shimadzu).
HPTS molecules in CO2 sensors are combined with water molecules to Scanning electron microscopy (SEM) images were obtained with a
form ion pairs, and then fixed on polymers film, which can be passed Hitachi S-4800 electron microscope at 15 kV.
through by gas such as CO2, but not be passed by protons[18].
Although numerous materials are used to optically detect the 2.3. Preparation of multi-analyte capillary sensors
changes of pH, O2 or CO2, it is still necessary to design multianalyte
sensors for the integration of related multi-parameter measurement in Firstly, the capillary was washed with ethanol and dried at room
biological processes [7,19,20]. Furthermore, it is extremely advanta­ temperature for further experiments. Subsequently, pH, O2 and CO2
geous to obtain simultaneously the information about the changes of sensing units were coated to the capillary inner wall in sequence.
multiple analyte parameters using single wavelength excitation for For the pH sensing part, HPTS was used for pH sensing probe. The ion
controlling biologically relevant characteristics. The realization of pair (HPTS-IP) was synthesized by adding 0.38 mmol of HPTS aqueous
multifunctional sensors at a single excitation wavelength requires solution into CTAB aqueous solution (0.76 mmol, 25 mL) at 50 ◦C. The
analyte-responsive dyes with similar absorption features. Multi-analyte precipitate of HPTS-IP was filtered and dried at 70 ◦C for 12 h. Then, the
sensors are commonly fabricated by doping multiple indicators into matrix film of pH sensing unit was prepared by a mixture of ETEOS-
matrix materials, in which each indicator responding to a single analyte based and GPTMS-derived sols[28]. The ETEOS-based sol was formed
[21–23]. As far as know, there are only a few reports on multifunctional by mixing ETEOS, HCl (0.1 M) and EtOH at 1:0.007:6.25 M ratio. The
optical sensors that can sense three of the pH, O2 and CO2 parameters GPTMS-based sol was formed by mixing GPTMS, MI, water and EtOH at
simultaneously. A quadruple sensor composed of two spatially separated 1:0.69:4:6.25 M ratio. The ETEOS-GPTMS hybrid sol was obtained by
sensing layers was reported for O2/CO2 and pH/temperature sensing mixing the two sols in 1:1 M ratios. Then, the HPTS-IP solutions were
[24]. This multianalyte sensor is based on planar thin films, which are mixed with the prepared ETEOS-GPTMS hybrid sol to achieve a final
not applicable in real-time biological studies at a flowing liquid envi­ silane/dye ratio of 103. Lastly, the final mixture was dip-coated onto the
ronment. Meanwhile, it is complicated to operate this multi-analyte inner wall of capillary tube, and heated at 140 ◦C for 4 h.
sensor duo to dual-wavelength excitation. It is very essential to find a As for the O2 sensing unit, the Ru(dpp)3(PF6)2 was used for O2
portable sensing carrier to realize rapid detection in solution. Signifi­ fluorescence indicator, and the polymer MPC-co-BMA was synthetized
cantly, the capillary usually can be used to measure liquid samples for the sensing substrates[29,30]. Specifically, 2-methacryloyloxye-thyl
because of its microcavity structure, low cost, portability, and is very phosphorylcholine (MPC) (2 g) and azobisisobuty-ronitrile (9 mg) were
suitable for the carrier of liquid detection[25]. Some optical sensors added into a 2% n-butyl methacrylate (BMA) solution in ethanol (50
based on capillary have been reported for detection of liquid materials. mL). Then the mixture was heated and refluxed for 8 h. After cooling
Wang et al. reported the capillary sensors composed of CdTe quantum down, 500 mL ether was added to the above solution and the deposit was
dots for real-time in situ detection of Cu2+[26]. Zhang reported a visual dried. Subsequently, 1 mL Ru(dpp)3(PF6)2 (1 mg/mL, in THF) was
quantitative distance-based sensor by capillary force alteration in a added into 10 mL MPC-co-BMA solution. The resultant mixture was
capillary tube to achieve the detection of miRNAs with high sensitivity stirred well. 50uL of mixture solution was removed by a syringe, and
and specificity[27]. While capillary-based sensors for sensing pH, O2 slowly injected into the middle part of the capillary. The capillary was

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X. Wang et al. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 304 (2024) 123349

slowly rotated well, and the mixture was evenly coated on the inner wall about 510 nm and 620 nm, respectively. It indicates that all sensor
for the O2-sensitive part. constituents can be excited at about 460 nm. The design objective for the
As regards the CO2 sensing part, the CO2 sensing solution was pre­ multianalyte capillary sensor is the integration of sensor constituents
pared as previously described [18,31], and then was coated on the inner HPTS and RuDP in the same capillary under single excitation light.
wall of capillary. The hydrophilic fluorescence indicator HTPS was Ascribed to the properties of capillary including small size, light
distributed in hydrophobic sol–gel layer that is permeable for carbon weight and strong light transmission ability, capillary-based sensors are
dioxide, but impermeable for ion. In particular, 1.1 mmol tetraocty­ very convenient and portable for liquid detection. To fabricate multi­
lammonium bromide was dissolved in 10 g ethyl triethoxy silane with 3 analyte capillary sensors, pH, O2 and CO2 sensing films were attached on
drops of dichloromethane. Then, 0.038 mmol HPTS was added into 20 the inner wall of the capillary. SEM imaging displayed that the pH, O2
mL NaOH solution (4 mg/mL), and mixed with the above obtained ethyl and CO2 sensing solution were coated into the capillary and form
triethoxy silane solution. The HPTS mixture was stirred 10 min and left sensing films on the inner wall (Fig. 2A, 2B and 2C). Fig. 2A show that
for 10 min. Subsequently, the organic phase was extracted, and the the pH sensing film on the inner wall of the capillary is dense, smooth
resultant light yellow liquid was added into 0.16 mL of dilute hydro­ and uniform. Fig. 2B demonstrates that the O2 sensing film of capillary
chloric acid at pH 2.0. Afterwards, 2.5 mmol tetraoctylammonium sensor presents bulge island structures (about 2 μm). Meanwhile, the
bromide and 2.5 mmol silver oxide were added in 10 mL methanol, and CO2 sensing film exhibits intensive spherical shape with a size distri­
stirred for 4 h. Then, 0.08 mL of supernatant was mixed with the above bution of 3 μm. Fig. 2D show that the emission spectra of various sensing
HPTS mixture. The final solution was coated on the other end of the films, demonstrating that the capillary sensor still maintains good
capillary, and heated at 70 ◦C for 8 h. fluorescence signals. While expanding the contact area between the film
and pH, O2 and CO2 detection solution, the detection solution can react
with the sensing film on the inner wall of the capillary, and the changes
2.4. Fluorescence measurements of fluorescence signal can be monitored by spectrometer.

The multi-analyte fluorescent capillary sensor was connected to the

peristaltic pump. Various fresh phosphate-buffered solutions of pH 3.2. pH sensing properties of the capillary sensor
including 5.5, 6, 6.5, 7, 7.5, and 8 by adjusting different ratios of
NaH2PO4 and Na2HPO4, was added into capillary to determine the pH The pH-, O2-, and CO2-sensitivity of multifunctional capillary sensor
sensing properties. Various dissolved oxygen concentrations were ob­ are evaluated by detecting the changes of luminescence intensity
tained to determine O2 sensitivity by flowing O2-N2 gas mixtures with accompanying the variations in pH, O2 and CO2. Fig. 3A shows the pH-
different ratios (0%, 5%, 10%, 15%, 20% and 25%), controlled via a sensitivity of sensors derived from the response of luminescence in­
WITT gas mixer. The pre-mixed gases including 0%, 5%, 10%, 20%, 50% tensity to different pH levels. With the increase of pH from 5.8 to 7.8, the
and 100% CO2 were pumped into capillary to detect the CO2 sensitivity. emission intensity of HPTS at 515 nm has obviously increased, showing
Afterwards, the capillary sensor was excited by 460 nm laser, and the high pH-sensitivity. To further detect the response process of pH, the
fluorescence signals at various sensing units produced from the fluo­ pKa value of capillary sensor is calculated as 6.91 via the sigmoidal
rescent indicators were detected by the spectrometer. fitting curve (Fig. 3B), which is consistent with the pKa value of HPTS
[13].
3. Results and discussion
3.3. O2 sensing properties of the capillary sensor
3.1. Design and characterization of multifunctional capillary sensor
Oxygen sensitivity of the capillary sensor is assessed by detecting the
The fabrication of pH, O2 and CO2 multifunctional capillary sensor luminescence intensity of RuDP at 620 nm under various O2 concen­
were illustrated in Fig. 1A. For the multianalyte sensors, RuDP was used trations. As displayed in Fig. 4A, the emission intensity of RuDP grad­
for O2 fluorescence indicator, and HPTS was selected as both pH and ually decreases with the rise of O2 levels. The calibration plot of
CO2 indicator. As illustrated in Fig. 1B, HPTS and RuDP show the luminescent intensity versus O2 concentrations for the multi-analyte
excitation band at about 460 nm, and reveal emission bands centered at capillary sensor was demonstrated in Fig. 4B. The plot is the fit of the

Fig. 1. (A)Samatic illustration of the optical detection and fabrication of the multi-analyte capillary sensor;(B) Excitation spectra (dashed curve) and emission
spectra (solid curve) of the HPTS (blue colour) and the RuDP (red colour). (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)

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Fig. 2. (A) pH, (B) O2 and (C)CO2 sensing film on the inner wall of the capillary by SEM. The scale bar is 20 μm. (D)Emission spectra of various sensing films.

Fig. 3. (A) Emission spectra of multifunctional capillary sensor at various pH levels. (B) Fluorescence signal at the pH 5.8–7.8 conditions. Red line represented the
sigmoidal fitting curve of fluorescence intensity as a function of pH. (For interpretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)

Fig. 4. (A) Fluorescence emission spectra under 460 nm excitation at different oxygen concentrations. (B) Fluorescence intensity-based Stern-Volmer plot. The
experimental data (scatter) were obtained from (A) and linearly fitted (solid line).

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linear Stern-Volmer equation, I0/I = 1 + KSV[O2], where I0 is the luminescence intensity of sensors stored for 27 days are measured. As
emission intensity in the absence of oxygen, I as the emission intensity at demonstrated in Fig. 7, the respective emission intensity of pH, O2 and
a given oxygen concentration, KSV as the Stern-Volmer quenching con­ CO2 sensing units shows little changes (less than 15%) during the
stant and [O2] as the oxygen concentration[11]. The linear response detection period, indicating the favorable stability owing to the pro­
towards oxygen demonstrates that RuDP molecules are located in a tective effect of sensing substrates. The luminescence intensity of indi­
homogeneous system, which is favorable for practical oxygen detection. vidual sensor in aqueous solution and phosphate buffered saline (PBS)
solution against with time were detected in Fig. S2 and Fig. S3,
respectively. The results demonstrate that the fluorescence intensity
3.4. CO2 sensing properties of the capillary sensor
shows no obvious fluctuation during the study. The excellent stability in
aqueous solution and PBS solution is attributed to the effective encap­
Luminescence response of the capillary sensor towards CO2 is eval­
sulation of the matrix. The photostability of individual sensor under
uated by detecting the luminescence intensity of HPTS under different
laser irradiation was estimated in Fig. S4. Compared to the 55% in­
CO2 concentrations. Fig. 5A show that the fluorescence signal of HPTS
tensity drops of HPTS in solution, the luminescence of CO2 sensing part
gradually reduces along the increase of CO2 concentration in the envi­
is bleached by 20% under continuous 460 nm illumination for 1 h, and
ronment. The calibration curve for fluorescence intensity versus CO2
the luminescence of pH sensing part has no obvious fluctuation, which is
concentrations is displayed in Fig. 5B. CO2 quenching is expressed by the
attributed to the protection of the immobilization matrix. Furthermore,
linear equation, I0/I = 1 + K [CO2], where I0 is the emission intensities of
the luminescence intensity of O2 sensing part is bleached by 11% after
HPTS without CO2; [CO2] is the CO2 concentration, KSV is the quenching
continuous 460 nm illumination for 1 h. In the measurement in practice,
constant. The data are fitted very well with a linear function, displaying
it should be noted that all individual sensor should be protected from
that I0/I increases proportional to the concentration of CO2 [32]. The
light without during the absence of the measurement to avoided the
CO2 sensitivity has been calculated as about 96% by the overall CO2
continuous exposure of the light source.
quenching response equation of Q = (I0 − I100)/I0, indicating the good
On the other hand, multi-analyte sensor is expected to avoid the
quenching response to CO2 owing to protonation-deprotonation of the
interference from individual probes. Therefore, the dependence of three
pH indicator[32]. This excellent CO2 sensitivity information is similar
sensing units should also be evaluated by measuring the fluorescence
with the CO2 sensitivity of HPTS distributed in polymeric matrices[33],
changes in presence of other analytes. For pH sensing unit, the fluo­
which is of practical importance in CO2 detection.
rescence intensity has little fluctuation with the increase of O2 concen­
tration (Fig. 6C). When the CO2 is injected gradually, the fluorescent
3.5. Reproducibility and stability of the capillary sensor signal has obviously decreased, owing to the pH values changed with the
CO2 concentration. Meanwhile, the fluorescence signal of O2 sensing
The rapid response and recovery of a sensor is a critical factor for its part is hardly affected by both pH and CO2, indicating the high photo­
sustainable application. Thank you very much for the valuable com­ chemical stability of O2 sensing film. As for the CO2 sensing unit, the O2
ments. In the revised manuscript, the dynamic response and recovery concentration has less interference to the luminescence intensity of CO2
time of the individual sensor were detected in Fig. 6A, B and C, indicator. Furthermore, the HPTS fluorescence signals have less
respectively. The response and recovery time are described by the time dependence on the pH values, because the hydrophobic sol–gel layer is
spent by the individual sensor to reach 90% of its final intensity and 90% permeable for carbon dioxide, but impermeable for ion.
of its initial intensity, respectively. Fig. 6A indicates the response and
recovery of pH sensing unit between pH 7.8 and pH 6.2. The response 4. Conclusions
time for pH to quench 90% of the fluorescence intensity is 4 min, while
the recovery time of 90% quenched intensity is 4.5 min. For the response A multifunctional capillary sensor is developed for simultaneously
and recovery of O2 sensing unit, the sensor is initially placed in the monitoring important chemical parameters pH, O2 and CO2. Three
absence and presence of O2 (Fig. 6B). The fluorescence of RuDP can spatially separated sensing units (pH, O2 and CO2) are integrated inde­
completely recovers after complete quenching at 100% O2. The response pendently on the inner of capillary. All indicators in each unit are
time for O2 to quench 90% of the fluorescence intensity of RuDP is 2.5 carefully chosen with single wavelength excitation to avoid optical in­
min, while the recovery time of 90% initial intensity is about 3.5 min. terferences with the probes in other sensing part. The optical multi-
Similarly, Fig. 6C show that the response and recovery of the sensor for analyte fluorescent capillary sensor possesses a sensitive fluorescence
CO2, which is pumped to 100% CO2 from 100% N2 and then again response to pH, O2 and CO2. The response of sensors to all parameters is
switched back to 100% N2. The response and recovery times for CO2 fully reversible and stable stored for 27 days. All in all, the multi-analyte
sensing unit are calculated to be 1.5 min and 1.5 min, respectively. capillary sensor is of great significance for real-time monitoring of
The stability of an optical sensor is crucial for practical applications. chemical parameters in blood gases analysis and natural environment.
To estimate the stability of the multifunctional capillary sensor, the

Fig. 5. (A) Emission spectra excited at 460 nm under different CO2 concentrations. (B) Fluorescence intensity-based Stern-Volmer plot. The experimental data
(scatter) were achieved from (A) and linearly fitted (solid line).

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Fig. 6. Response and recovery plots of the optical dual sensor for (A) pH, (B) O2 and (C) CO2.

Fig. 7. Luminescence intensity of (A) pH, (B) O2 and (C) CO2 sensing part stored for 27 days. (D) The stability of sensing units under interference of other two
analytes. These O2 and CO2 represent the environment saturated with 100% O2 and 100% CO2, respectively.

CRediT authorship contribution statement Formal analysis, Writing – original draft, Supervision. Yuanxiangyi
Feng: Investigation, Formal analysis, Visualization. Zhe Li: Investiga­
Xiaohui Wang: Conceptualization, Methodology, Investigation, tion, Formal analysis. Jinhua Liu: Methodology, Investigation. Dandan

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X. Wang et al. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 304 (2024) 123349

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