Journal Pre-proof

Cellulose-based Fluorescent Sensor for Visual and Versatile Detection of

Amines and Anions

Haq Nawaz (Data curation) (Writing - original draft), Jinming Zhang

(Conceptualization) (Methodology) (Writing - review and editing)
(Funding acquisition), Weiguo Tian (Resources) (Investigation),
Kunfeng Jin (Validation), Ruonan Jia (Resources) (Investigation),
Tiantian Yang (Resources) (Investigation), Jun Zhang
(Conceptualization) (Methodology) (Writing - review and editing)
(Funding acquisition)

PII: S0304-3894(19)31673-5
DOI: https://doi.org/10.1016/j.jhazmat.2019.121719
Reference: HAZMAT 121719

To appear in: Journal of Hazardous Materials

Received Date: 15 July 2019

Revised Date: 13 November 2019
Accepted Date: 18 November 2019

Please cite this article as: Nawaz H, Zhang J, Tian W, Jin K, Jia R, Yang T, Zhang J,
Cellulose-based Fluorescent Sensor for Visual and Versatile Detection of Amines and Anions,
Journal of Hazardous Materials (2019), doi: https://doi.org/10.1016/j.jhazmat.2019.121719
This is a PDF file of an article that has undergone enhancements after acceptance, such as
the addition of a cover page and metadata, and formatting for readability, but it is not yet the
definitive version of record. This version will undergo additional copyediting, typesetting and
review before it is published in its final form, but we are providing this version to give early
visibility of the article. Please note that, during the production process, errors may be
discovered which could affect the content, and all legal disclaimers that apply to the journal
pertain.

© 2019 Published by Elsevier.

 Cellulose-based Fluorescent Sensor for Visual and Versatile Detection of Amines
and Anions

Haq Nawaz†, Jinming Zhang†,*, Weiguo Tian†, Kunfeng Jin†,‡, Ruonan Jia†,‡, Tiantian Yang†,‡, Jun
Zhang†,‡,*

†
CAS Key Laboratory of Engineering Plastics, CAS Research/Education Center for Excellence in
Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing, 100190,
China.

‡University
of Chinese Academy of Sciences, Beijing, 100049, China.

of

Corresponding authors.
E-mail address: zhjm@iccas.ac.cn (J.M. Zhang); jzhang@iccas.ac.cn (J. Zhang).

ro
Mailing address: Zhongguancun North First Street 2,100190 Beijing, PR China
1

Graphical Abstract
-p
re
lP
na
ur
Jo

Highlights
 Visual and ultrasensitive detection of various amines and three anions
 A cellulose-based multi-responsive fluorescent sensor was fabricated
 A new sensor can give a quantitative detection of anions in mixture solution
Abstract
It is practical and challenging to construct ultrasensitive and multi-responsive sensors for visual
and real-time monitoring of the environment. Herein, a cellulose-based multi-responsive
fluorescent sensor (Phen-MDI-CA) is fabricated, and realizes a visual and ultrasensitive detection
of not only various amines but also three anions based on the change of the fluorescence and/or
visible colors. Once exposure to various amines in both the solution and vapor state, the Phen-
MDI-CA solution and test paper exhibit different fluorescence colors, which can be used to
distinguish triethylamine, ethylenediamine, methylamine, aniline, hydrazine and pyrrolidine from
other amines. Moreover, via combining the Phen-MDI-CA with the Phen-MDI-CA/malachite green
ratiometric system, phosphate (PO43-), carbonate (CO32-) and borate (B4O72-) can be visually and
accurately recognized depending on the change of the visible and fluorescence colors. In

of
fluorescent mode, the LOD for B4O72-, PO43- and CO32- ions is as low as 0.18 nmol, 0.69 nmol and
0.86 nmol, respectively. Significantly, the Phen-MDI-CA can readily make a qualitative and

ro
quantitative detection of B4O72-, PO43- and CO32- anions in the mixture of anions. The state-of-the-
art responsive behavior of Phen-MDI-CA originates from the amplification effect of cellulose
-p
polymer chain and the differentiated interactions between the sensor and analytes.
re
Keywords: Multi-responsive sensor; Ultrasensitive detection; Amines; Anions; Cellulose
derivatives
lP
na
ur
Jo

2
1. Introduction
Selective recognition and sensing of various amines are currently of significant importance,
because aliphatic and aromatic amines are important raw materials or intermediates in chemical
industry, food industry, biological progress, dyeing process, material chemistry and fine chemical
engineering [1-3]. For example, ethylenediamine (EDA), methylamine (MA), aniline (ANL) and
pyrrolidine (PYR) have been extensively used as intermediates in dye chemistry and dyeing process.
Hydrazine (HYD) and triethylamine (TEA) have been used in military operations as additives in
rocket and fighter jet fuel [4-6]. Despite the multipurpose applications of organic amines, they are
hazardous to the environment and human health [7,8]. Therefore, the presence of amines should
be identified sensitively in order to prevent any possible harm. Currently, several methods,
including electrochemical devices, gas and liquid chromatography, and various chemical sensors,

of
have been developed to detect various amines in solution and vapor states [9-12]. Among them,
optical sensors, especially fluorescent sensors, exhibit significant advantages over these methods,

ro
because they can give a simple, visual, sensitive and rapid detection for the analytes [13-16].
Although numerous sensors have been developed, it is still appealing, pressing and challenging to
-p
construct multi-responsive and ultrasensitive sensors for visual and real-time monitoring of
various amines [17-21].
Similarly, rapid, sensitive and selective detection of some anions, such as phosphate (PO43-),
re
carbonate (CO32-) and borate (B4O72-) ions, is also indispensable in industrial process, life science
and environmental monitoring [22,23]. Phosphate is widely distributed in agricultural and
lP

industrial sectors, such as synthetic fertilizer, food and drink additives, local detergents and animal
feed. At present, as a result of the fast development and economy competition, a large amount of
phosphate is released into aqueous environment via agricultural, industrial and sanitary
na

wastewater, which causes serious threats to environmental security associated with

eutrophication of water bodies [24,25]. Carbonate compounds have broad application in human
society and manufacturing industry, such as soap, paper, textile industry and rechargeable
ur

batteries [23]. Previously, several analytical methods have been developed for the detection of
anions, including calorimetry, chromatography, ion-selective electrodes and sensors [26-31].
Jo

Despite all this, to develop simple, rapid, visual, multi-responsive and ultrasensitive sensors for
anions is promising and practical in both industrial process and environmental monitoring
nowadays.
In present work, taking advantage of the reactive hydroxyl groups along cellulose chain, we have
designed and synthesized a cellulose-based multi-responsive fluorescent sensor, phenanthroline-
4,4’-methylene diphenyl diisocyanate-cellulose acetate (Phen-MDI-CA), by using cellulose acetate
(CA) as the skeleton, phenanthroline (Phen) moiety as the chromophore and 4,4’-methylene

3
diphenyl diisocyanate (MDI) as the bridge, as shown in Figure 1 and Figure S1. The resultant Phen-
MDI-CA realizes a visual, ultrasensitive and selective detection of various amines and three anions
(Figure 1) based on the change of the fluorescence and visible colors.

of
ro
-p
Figure 1. (A) Chemical structure of the tested amines. (B) Chemical structure of the tested anions. (C)
Synthesis route of cellulose-based sensor Phen-MDI-CA.
re
2. Results and discussions
lP

The Phen-MDI-CA exhibits bright blue fluorescence with an emission peak at 443 nm in both
solution and solid states (Figure 2), like powders, film and coating, because the synergistic effect
of the anchoring and diluting effect of cellulose backbone effectively inhibit the - stacking of
na

Phen groups [32,33]. In addition, benefiting from the excellent solubility and formability of
cellulose derivatives, the Phen-MDI-CA solution has been readily fabricated into the test papers by
the coating method (Figure 2B and 2C). After adding amines into the Phen-MDI-CA solution or onto
ur

the Phen-MDI-CA test paper, the Phen-MDI-CA solution and test paper immediately exhibit
different fluorescence colors for the different amines (Figures 2A, 2B and S2). Moreover, the Phen-
Jo

MDI-CA test paper can also recognize amine vapors based on the change of the fluorescence color
(Figure 2C). For instance, the blue fluorescence of Phen-MDI-CA changes to light blue by using
triethylamine (TEA) as the analyte, to green by diethylamine (DEA), to cyan by methylamine water
(MAW), and quenches gradually as the addition of ammonia aqueous solution (AMM) increases.
In fluorescence spectra (Figure 2D), the emission intensity of the peak at 443 nm decreases
significantly after adding the amines. Meanwhile, a new emission peak at 525 nm appears, and its
emission intensity strongly depends on the chemical structure of amines. According to the different
fluorescence colors, the Phen-MDI-CA solution and test paper can make a facile and visual
4
identification of various amines, such as TEA, DEA, MAW, hydrazine (HYD), pyrrolidine (PYR), etc.

of
ro
Figure 2. (A) Photographs of Phen-MDI-CA/DMSO (1.9 mL, 7.23 x 10-6 M) after adding 100 µL of various
-p
amines under visible light (top) and UV-light at 365 nm (bottom). (CONT, Phen-MDI-CA/DMSO; AMM,
ammonia aqueous solution (25%); TEA, trimethylamine; EDA, ethylenediamine; MAW, methylamine
aqueous solution (30%); HYD, hydrazine; PYR, pyrrolidine.) (B) Photographs of Phen-MDI-CA coated test
re
strips after adding 1-2 drops of various amines under visible light (top) and UV-light at 365 nm (bottom).
(CONT, Phen-MDI-CA coated test strips) (C) Photographs of Phen-MDI-CA coated test strips after
exposure to various amine vapors under visible light (top) and UV-light at 365 nm (bottom). (CONT,
lP

Phen-MDI-CA coated test strips) (D) Fluorescence spectra of Phen-MDI-CA/DMSO (1.9 mL, 7.23 x 10-6
M) after adding 28 µL of various amines. (E) 1H-NMR spectra of Phen-MDI-CA/DMSO-d6 before and after
adding 1 drop of various amines.
na

The excellent amine-responsive behavior of Phen-MDI-CA originates from the differentiated

interactions between the sensor Phen-MDI-CA and various amines. In 1H-NMR spectra (Figure 2E),
ur

the aromatic protons and the protons adjacent to nitrogen atom of Phen-MDI-CA shift to upfield
or downfield, after adding different amines, and the change degree of their chemical shift is related
to the amines. In FTIR spectra of Phen-MDI-CA (Figure S3), the peak corresponding to C=N bond
Jo

(1662 cm-1) shifts to 1666 cm-1, 1614 cm-1 and 1658 cm-1 after adding MAW, HYD and PYR,
respectively. These phenomena confirm the differentiated interactions between the Phen-MDI-CA
and various amines, which has a prominent impact on the intramolecular charge transfer (ICT)
process of Phen-MDI-CA, leading to the multicolor transformation.
Based on the fluorescence change, Phen-MDI-CA can accurately detect the concentration of
amines. From the fluorescence spectra, the limit of detection (LOD) for various amines are
determined by plotting exponential equation (Figure S4). Presumably owing to the amplification
5
effect of cellulose polymer chain [32,33], the LOD for TEA, EDA, methylamine, aniline (ANL), HYD
and PYR is as low as 0.90 mol, 0.99 mol, 1.7 mol, 0.46 mol, 0.63 mol and 0.75 mol,
respectively, which is comparable to those of previous amines sensors (Table 1).

The Phen-MDI-CA not only recognizes various amines but also responds to different anions. The
Phen-MDI-CA can distinguish phosphate (PO43-), carbonate (CO32-) and borate (B4O72-) from other
anions via the change of both the fluorescence and visible color, as shown in Figure 3A. After
adding one drop of PO43- and B4O72- aqueous solutions into Phen-MDI-CA/DMSO solution, the
visible color changes to deep yellow and the fluorescence quenches; after adding CO32- solution,
the visible color changes to light yellow and the fluorescence color changes to light blue; while for
other anions, including H2PO4-, HCO3-, NO3-, NO2-, Ac-, Cl-, Br-, SO42- and SO32-, neither the visible

of
color nor the fluorescence has a change. In the UV-Vis absorption spectra (Figure 3B, 3D and 3F),
two new peaks at 320 nm and 396 nm appear after the addition of PO43-, B4O72- and CO32- anions.

ro
In the fluorescence spectra (Figure 3C, 3E and 3G), the emission intensity of the peak at 443 nm
decreases in varying degrees after addition of the PO43-, B4O72- and CO32- anions. Meanwhile, a new
-p
and weak emission peak at 525 nm appears after the addition of PO43- and B4O72- anions. 1H-NMR
spectra (Figure 3H and 3I) prove that only the PO43-, B4O72- and CO32- anions form strong
interactions with Phen-MDI-CA [39-42], while other anions, such as NO3-, Cl- and SO42-, have no
re
interaction with Phen-MDI-CA. These strong interactions between Phen-MDI-CA and anions affect
the ICT process of Phen-MDI-CA, causing the color change.
lP
na
ur
Jo

6
 of
ro
-p
re
lP
na

Figure 3. (A) Photographs of Phen-MDI-CA/DMSO (1.9 mL, 7.23 x 10-6 M) after adding 40 µL of anions
aqueous solutions (1.88 x 10-2 M) under visible light (top) and UV-light at 365 nm (bottom). (B, D and
ur

F) UV-Vis absorption spectra and (C, E and G) Fluorescence spectra of Phen-MDI-CA/DMSO (1.9 mL,
7.23 x 10-6 M) before and after adding 40 µL of anions aqueous solutions (1.88 x 10-2 M). Inset images
Jo

in (B-G) are photographs of Phen-MDI-CA/DMSO after adding anions aqueous solutions under visible
light and UV-light at 365 nm. (H) and (I) 1H-NMR spectra of Phen-MDI-CA/DMSO-d6 before and after
adding 2 drop of anions aqueous solutions.

In order to distinguish between PO43- and B4O72- anions, an anion-irresponsive dye, malachite
green (M-G), is used to construct a ratiometric system, Phen-MDI-CA/M-G. The resultant Phen-
MDI-CA/M-G ratiometric system can clearly discriminate PO43- and B4O72- anions by naked eye
(Figure 4). After adding the PO43- anion, the visible color changes to pink, and the fluorescence

7
color changes to light blue; while after adding the B4O72- anion, the visible color changes to deep
yellow, and the fluorescence color changes to dark pink. Therefore, by combining the Phen-MDI-
CA with the Phen-MDI-CA/M-G ratiometric system, B4O72-, PO43- and CO32- anions can be visually
and accurately recognized.

of
Figure 4. Discrimination of B4O72- and PO43- ions by the ratiometric system of Phen-MDI-CA/malachite

ro
green (M-G) (ratio, 8:1) under visible light (top) and UV-light at 365 nm (bottom).

The fluorescence change of Phen-MDI-CA is employed to detect the concentration of PO43-, B4O72-
-p
and CO32- anions in aqueous solution (Figure 5). From the fluorescence spectra, the linear graph
was plotted between the decrease in the emission intensity of Phen-MDI-CA and the concentration
re
of the anions. The LOD for the anions were determined from the linear graph by taking the reading
for 10 blank samples and using the equation 3δ/S, where δ is standard deviation of blank sample
lP

and S is the slope of the graph. The LOD for PO43-, B4O72- and CO32- anions is as low as 0.69 nmol,
0.18 nmol and 0.86 nmol, respectively, which is comparable to those of previous the best anions
sensors (Table 2). The ultrasensitive responsiveness of Phen-MDI-CA presumably originates from
na

the amplification effect of cellulose polymer chain.

ur
Jo

8
 of
ro
-p
Figure 5. Fluorescence quenching phenomena of Phen-MDI-CA/DMSO solution after adding various
anions solutions with different amounts of anions. (A) and (B) B4O72- ion; (C) and (D) PO43- ion; (E) and
re
(F) CO32- ion.

The above inspiring results encourage us to detect anions in the mixed solution of anions, because
lP

the practical solution generally contains various anions, such as PO43-, CO32-, NO3-, SO42- and Cl-
anions. Meanwhile, the common anions, including NO3-, SO42- and Cl- anions, have far higher
concentration than other anions. Thus, we firstly made a mixture of anions, which includes NO3-,
na

SO42- and Cl- anions, then added the analyte anions into the mixture. In the mixture, the
concentrations of SO42-, NO3- and Cl- anions are the same, 8.5  10-2 M, which is 10 times as high
as the concentrations of PO43-, B4O72- and CO32- anions (8.5  10-3 M). Subsequently, the Phen-MDI-
ur

CA is used to detect PO43-, B4O72- and CO32- anions in the mixture. As shown in Figure 6, there is no
change of the visible and fluorescence colors when only SO42-, NO3- and Cl- anions are present in
Jo

the mixture; if the anions mixture includes B4O72- anion, the visible color changes to deep yellow
meanwhile the fluorescence color change to green; if the anions mixture includes PO43- anion, the
visible color changes to deep yellow meanwhile the fluorescence color change to cyan; if the
anions mixture includes CO32- anion, the visible color changes to light yellow meanwhile the
fluorescence color change to light blue. In the UV-Vis absorption spectra (Figure 6A), two new
peaks at 320 nm and 396 nm appear if the anions mixture includes PO43-, B4O72- and CO32- anions.
In the fluorescence spectra (Figure 6B), the emission intensity of the peak at 443 nm decreases in

9
varying degrees, meanwhile, a new and weak emission peak at 525 nm appears. According to the
fluorescence change of Phen-MDI-CA (Figure S5), the LOD for PO43-, B4O72- and CO32- anions in the
mixture of anions can achieve 24 nmol, 20 nmol and 28 nmol, respectively. Therefore, Phen-MDI-
CA exhibits an excellent responsiveness to make a qualitative and quantitative detection of B4O72-,
PO43- and CO32- ions in the mixture of anions.

of
ro
-p
re
Figure 6. (A) UV-Vis absorption spectra and (B) fluorescence spectra of Phen-MDI-CA/DMSO (1.9 mL,
7.23 x 10-6 M) before and after adding 40 µL of the mixture of anions. (C) Visible images and (D)
lP

fluorescence images (365 nm) of Phen-MDI-CA/DMSO (1.9 mL, 7.23 x 10-6 M) after adding 40 µL of the
mixture of anions. (Cont: Phen-MDI-CA/DMSO solution; Mixture (Mix): the solution of SO 42-, NO3- and
Cl- ions; Concentration of SO42-, NO3- and Cl-: 8.5  10-2 M; Concentration of B4O72-, PO43- and CO32-: 8.5
na

 10-3 M)

Conclusion
ur

A cellulose-based multi-responsive fluorescent sensor, Phen-MDI-CA, has been designed and

synthesized by using cellulose chain as a skeleton, phenanthroline moiety as a chromophore and
urea group as a bridge. Owing to the amplification effect of cellulose polymer chain and the
Jo

differentiated interactions between sensor and analytes, the resultant Phen-MDI-CA realizes a
visual, ultrasensitive and selective detection of various amines and three anions based on the
change of the fluorescence and visible color. The Phen-MDI-CA solution and test paper respond to
the different amines in both the solution and vapor states. The LOD for TEA, EDA, methylamine,
ANL, HYD and PYR is 0.90 mol, 0.99 mol, 1.7 mol, 0.46 mol, 0.63 mol, and 0.75 mol,
respectively. In addition, the Phen-MDI-CA/M-G ratiometric system is constructed. Via combining
the Phen-MDI-CA with Phen-MDI-CA/M-G ratiometric system, B4O72-, PO43- and CO32- anions can
10
be distinguished from other anions, even in the mixture of anions, depending on the change of
visible and fluorescence color. The LOD for B4O72-, PO43- and CO32- ions is as low as 0.69 nmol, 0.18
nmol and 0.86 nmol, respectively. Moreover, in consideration of excellent biodegradability,
nontoxicity, low-cost, and good formability of cellulose-based derivatives [63-65], the multi-
responsive and chromogenic Phen-MDI-CA exhibits a huge potential in the detection of amines
and anions.

Author Contribution Statement

Haq Nawaz: Data curation, Writing- Original draft

preparation. Jinming Zhang and Jun Zhang:

of
Conceptualization, Methodology, Writing-review & editing,

ro
Funding acquisition. Weiguo Tian, Ruonan Jia and
Tiantian Yang: Resources, Investigation. Kunfeng Jin:
Validation.
-p
re
lP

Acknowledgement
This work was supported by the National Natural Science Foundation of China (Nos. 51425307,
51573196, 51773210 and 51803220), the CAS President’s International Fellowship Initiative (PIFI)
na

and the Youth Innovation Promotion Association CAS (No. 2018040).

References
ur

[1] T. Gao, E.S. Tillman, N.S. Lewis, Detection and classification of volatile organic amines and
carboxylic acids using arrays of carbon black-dendrimer composite vapor detectors. Chem.
Jo

Mater. 17 (2005) 2904.

[2] E. Akceylan, M. Bahadir, M. Yılmaz, Removal efficiency of a calix[4]arene-based polymer for
water-soluble carcinogenic direct azo dyes and aromatic amines. J. Hazard. Mater. 162 (2009)
960.
[3] Y. Chen, K. Ma, T. Hu, B. Jiang, B. Xu, W.J. Tian, J.Z. Sun, W.K. Zhang, Investigation of the binding
modes between aie-active molecules and dsdna by single molecule force spectroscopy,
Nanoscale, 7 (2015) 8939.
11
[4] H. Greim, The MAK collection for occupational health and safety. Wiley-VCH: New York, Vol.
13, (2012) pp 267−280.
[5] D.L. Ellis, M.R. Zakin, L.S. Bernstein, M.F. Rubner, Conductive polymer films as ultrasensitive
chemical sensors for hydrazine and monomethylhydrazine vapor. Anal. Chem. 68 (1996) 817.
[6] S.D. Zelnick, D.R. Mattie, P.C. Stepaniak, Occupational exposure to hydrazines: treatment of
acute central nervous system toxicity. Aviat. Space Environ. Med. 74 (2003) 1285.
[7] X.H. Cao, Q.Q. Ding, N. Zhao, A.P. Gao, Q.S. Jing, Supramolecular self-assembly system based
on naphthalimide boric acid ester derivative for detection of organic amine. Sensors and
Actuators B 256 (2018) 711.
[8] J. Zhang, W. Gao, M. Dou, F. Wang, J. Liu, Z. Li, J. Ji, Nanorod-constructed porous Co3O4
nanowires: highly sensitive sensors for the detection of hydrazine. Analyst, 140 (2015) 1686.

of
[9] S.W. Thomas, G.D. Joly, T.M. Swager, Chemical sensors based on amplifying fluorescent
conjugated polymers, Chem. Rev. 107 (2007) 1339.

ro
[10] Y.H. Gui, K. Tian, J.X. Liu, L.L. Yang, H.Z. Zhang, Y. Wang, Superior triethylamine detection at
room temperature by {-112} faceted WO3 gas sensor. J. Hazard. Mater. (2019) 120876.
-p
[11] Y. Xiong, W.W. Xu, D.G. Ding, W.B. Lu, L. Zhu, Z.Y. Zhu, Y. Wang, Q.Z. Xue, Ultra-sensitive NH3
sensor based on flower-shaped SnS2 nanostructures with sub-ppm detection ability. J. Hazard.
Mater. 341 (2018) 159-167.
re
[12] G.J. Mohr, N. Tirelli, C. Lohse, U.E. Spichiger-Keller, Development of chromogenic copolymers
for optical detection of amines. Adv. Mater. 10 (1998) 1353.
lP

[13] X. Pang, X. Yu, H. Lan, X. Ge, Y. Li, X. Zhen, T. Yi, Visual recognition of aliphatic and aromatic
amines using a fluorescent gel: application of a sonication-triggered organogel. ACS Appl.
Mater. Interfaces 7 (2015) 13569.
na

[14] Z. Jiao, Y. Zhang, W. Xu, X. Zhang, H. Jiang, P. Wu, Y. Fu, Q. He, H. Cao, J. Cheng, Highly efficient
multiple-anchored fluorescent probe for the detection of aniline vapor based on synergistic
effect: chemical reaction and PET. ACS Sens. 2 (2017) 687.
ur

[15] Y.J. Zhao, K. Miao, Z. Zhu, L.J. Fan, Fluorescence Quenching of a conjugated polymer by
synergistic amine-carboxylic acid and π−π interactions for selective detection of aromatic
Jo

amines in aqueous solution. ACS Sens. 2 (2017) 842.

[16] P. Xue, J. Ding, Y. Shen, H. Gao, J. Zhao, J. Sun, R. Lu, Aggregation-induced emission nanofiber
as a dual sensor for aromatic amine and acid vapor. J. Mater. Chem. C 5 (2017) 11532.
[17] N.A. Rakow, A. Sen, M.C. Janzen, J.B. Ponder, K.S. Suslick, Molecular recognition and
discrimination of amines with a colorimetric array. Angew. Chem. Int. Ed. 44 (2005) 4528.
[18] Y.S. Zhou, H.Y. Gao, F.M. Zhu, M.L. Ge, G.D. Liang, Sensitive and rapid detection of aliphatic
amines in water using self-stabilized micelles of fluorescent block copolymers. J. Hazard.

12
 Mater. 368 (2019) 630.
[19] S. Bettini, Z. Syrgiannis, R. Pagano, L. Đorđević, L. Salvatore, M. Prato, G. Giancane, L. Valli,
Perylene bisimide aggregates as probes for subnanomolar discrimination of aromatic
biogenic amines. ACS Appl. Mater. Interfaces 11 (2019) 17079.
[20] S. Fredrich, A. Bonasera, V. Valderrey, S. Hecht, Sensitive assays by nucleophile-induced
rearrangement of photoactivated diarylethenes. J. Am. Chem. Soc. 140 (2018) 6432.
[21] V. Valderrey, A. Bonasera, S. Fredrich, S. Hecht, Light-activated sensitive probes for amine
detection. Angew. Chem. Int. Ed. 56 (2017) 1914.
[22] L.W. He, B.L. Dong, Y. Liu, W.Y. Lin, Fluorescent chemosensors manipulated by dual/triple
interplaying sensing mechanisms. Chem. Soc. Rev. 45 (2016) 6449.
[23] N.N. Sun, B. Yan, Rapid and facile ratiometric detection of CO32- based on hetero-bimetallic

of
metal-organic frameworks (Eu/Pt-MOFs). Dyes and Pigments 142 (2017) 1.
[24] N.A. Esipenko, P. Koutnik, T. Minami, L. Mosca, V.M. Lynch, G.V. Zyryanov, P. Anzenbacher,

ro
First supramolecular sensors for phosphonate anions. Chem. Sci. 4 (2013) 3617.
[25] C. Warwick, A. Guerreiro, A. Soares, Sensing and analysis of soluble phosphates in
-p
environmental samples: A review. Biosens. Bioelectron. 41 (2013) 1.
[26] H. Zhao, S.J. Park, F. Shi, Y. Fu, V. Battaglia, P.N. Ross, G. Liu, Propylene carbonate (PC)-based
electrolytes with high coulombic efficiency for lithium-ion batteries. J. Electrochem. Soc. 16
re
(2014) A194.
[27] M.S. Han, D.H. Kim, Naked-eye detection of phosphate ions in water at physiological pH: a
lP

remarkably selective and easy-to-assemble colorimetric phosphate sensing probe. Angew.

Chem. Int. Ed. 41 (2002) 3809.
[28] J.B. Quintana, R. Rodil, T. Reemtsma, Determination of phosphoric acid mono- and diesters
na

in municipal wastewater by solid-phase extraction and ion-pair liquid chromatography -

Tandem mass spectrometry. Anal. Chem. 78 (2006) 1644.
[29] W.C. Mak, K.K. Sin, C.P. Chan, L.W. Wong, R. Renneberg, Biofunctionalized indigo-
ur

nanoparticles as biolabels for the generation of precipitated visible signal in immunodipsticks.

Biosens. Bioelectron. 26 (2011) 3148.
Jo

[30] H.K. Lee, H. Oh, K.C. Nam, S. Jeon, Urea-functionalized calix[4]arenes as carriers for
carbonate-selective electrodes. Sens. Actuators B Chem. 106 (2005) 207.
[31] L. Fabbrizzi, A. Leone, A. Taglietti, A chemosensing ensemble for selective carbonate detection
in water based on metal–ligand interactions. Angew. Chem. Int. Ed. 40 (2001) 3066.
[32] H. Nawaz, W.G. Tian, J.M. Zhang, R.N. Jia, Z.Y. Chen, J. Zhang, Cellulose-based sensor
containing phenanthroline for the highly selective and rapid detection of Fe2+ ions with naked
eye and fluorescent dual modes. ACS Appl. Mater. Interfaces 10 (2018) 2114.

13
[33] H. Nawaz, W.G. Tian, J.M. Zhang, R.N. Jia, Z.Y. Chen, J. Zhang, Visual and precise detection of
pH values under extreme acidic and strong basic environments by cellulose-based superior
sensor. Anal. Chem. 91 (2019) 3085.
[34] A. Mallick, B. Garai, M.A. Addicoat, P.S. Petkov, T. Heine, R. Banerjee, Solid state organic
amine detection in a photochromic porous metal organic framework. Chem. Sci. 6 (2015)
1420.
[35] P. Xue, B. Yao, P. Wang, P. Gong, Z. Zhang, R. Lu, Strong fluorescent smart organogel as a dual
sensing material for volatile acid and organic amine vapors. Chem. Eur. J. 21 (2015) 17508.
[36] H.Q. Zhong, C.C. Liu, W.J. Ge, R.C. Sun, F. Huang, X.H. Wang, Self-assembled conjugated
polymer/chitosan-graft-oleic acid micelles for fast visible detection of aliphatic biogenic
amines by “turn-on” FRET. ACS Appl. Mater. Interfaces 9 (2017) 22875.

of
[37] B.S. Seenivasagaperumal, S. Shanmugam, Fluorescent β-ketothiolester boron complex:
substitution based ‘‘turn-off’’ or ‘‘ratiometric’’ sensor for diamine. New J. Chem. 42 (2018)

ro
3394.
[38] J. Qiu, Y. Chen, S. Jiang, H. Guo, F. Yang, A fluorescent sensor based on aggregation induced
-p
emission: highly sensitive detection of hydrazine and its application in living cell imaging.
Analyst 143 (2018) 4298.
[39] S.N.K. Elmas, F. Ozen, K. Koran, A.O. Gorgulu, G. Sadi, I. Yilmaz, S. Erdemir, Selective and
re
sensitive fluorescent and colorimetric chemosensor for detection of CO32- anions in aqueous
solution and living cells. Talanta 188 (2018) 614.
lP

[40] C. Han, Z. Cui, Z. Zou, Sabahaiti, D. Tian, H. Li, Urea-type ligand-modified CdSe quantum dots
as a fluorescence “turn-on” sensor for CO32- anions, Photochem. Photobiol. Sci. 9 (2010) 1269.
[41] S.G. Li, C.D. Jia, B. Wu, Q. Luo, X.J. Huang, Z.W. Yang, Q.S. Li, X.J. Yang, A triple anion helicate
na

assembled from a bis(biurea) ligand and phosphate ions. Angew. Chem. Int. Ed. 50 (2011)
5720.
[42] S.G. Li, M.Y. Wei, X.J. Huang, X.J. Yang, B. Wu, Ion-pair induced self-assembly of molecular
ur

barrels with encapsulated tetraalkylammonium cations based on a bis-trisurea stave. Chem.

Commun. 48 (2012) 3097.
Jo

[43] L.S.B. Upadhyay, N. Verma, Alkaline phosphatase inhibition based conductometric biosensor
for phosphate estimation in biological fluids. Biosensors and Bioelectronics 68 (2015) 611.
[44] K.S. Asha, R. Bhattacharjee, S. Mandal, Complete transmetalation in a metal organic
framework by metal ion metathesis in a single crystal for selective sensing of phosphate ions
in aqueous media. Angew. Chem. Int. Ed. 55 (2016) 11528.
[45] P. Chandra Rao, S. Mandal, Europium-based metal−organic framework as a dual
luminescence sensor for the selective detection of the phosphate anion and Fe3+ ion in

14
 aqueous media. Inorg. Chem. 57 (2018) 11855.
[46] N. Gao, J. Huang, L. Wang, J. Feng, P. Huang, F. Wu, Ratiometric fluorescence detection of
phosphate in human serum with a metal-organic frameworks-based nanocomposite and its
immobilized agarose hydrogels. Applied Surface Science 459 (2018) 686.
[47] A.A. Fadhel, M. Johnson, K. Trieu, E. Koculi, A.D. Campiglia, Selective nano-sensing approach
for the determination of inorganic phosphate in human urine samples. Talanta 164 (2017)
209.
[48] S. Sateanchok, N. Pankratova, M. Cuartero, T. Cherubini, K. Grudpan, E. Bakker, In-line
seawater phosphate detection with ion-exchange membrane reagent delivery. ACS Sens. 3
(2018) 2455.
[49] B.B. Chen, R.S. Li, M.L. Liu, H.Y. Zou, H. Liu, Z.C. Huang, Highly selective detection of phosphate

of
ion based on a single-layered graphene quantum dots-Al3+ strategy. Talanta 178 (2018) 172.
[50] X. Tang, Y. Wang, J. Han, L. Ni, L. Wang, L. Li, H. Zhang, C. Li, J. Li, H. Li, A relay identification

ro
fluorescence probe for Fe3+ and phosphate anion and its applications. Spectrochimica Acta
Part A: Molecular and Biomolecular Spectroscopy 191 (2018) 172.
-p
[51] Y. Cheng, H. Zhang, B. Yang, J. Wu, Y. Wang, B. Ding, J. Huo, Y. Li, Highly efficient fluorescence
sensing of phosphate by dual-emissive lanthanide MOFs. Dalton Trans. 47 (2018) 12273.
[52] H. Wu, C. Tong, A Specific Turn-on fluorescent sensing for ultrasensitive and selective
re
detection of phosphate in environmental samples based on antenna effect-improved FRET by
surfactant. ACS Sens. 3 (2018) 1539.
lP

[53] L. Li, B. Zhao, Y. Long, J.M. Gao, G. Yang, C.H. Tung, K. Song, Visual detection of carbonate ions
by inverse opal photonic crystal polymers in aqueous solution. J. Mater. Chem. C 3 (2015)
9524.
na

[54] V. Thimaradka, S. Pangannaya, M. Mohan, D.R. Trivedi, Hydrazinylpyridine based highly

selective optical sensor for aqueoussource of carbonate ions: Electrochemical and DFT
studies. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 193 (2018) 330.
ur

[55] Y.N. Lu, J.L. Peng, X. Zhou, J.Z. Wu, Y.C. Ou, Y.P. Cai, Rapid naked-eye luminescence detection
of carbonate ion through acetonitrile hydrolysis induced europium complexes.
Jo

CrystEngComm 20 (2018) 7574.

[56] L. He, C. Liu, J.H. Xin, A novel turn-on colorimetric and fluorescent sensor for Fe3+ and Al3+ with
solvent-dependent binding properties and its sequential response to carbonate. Sensors and
Actuators B 213 (2015) 181.
[57] Z. Jarolımova, J. Bosson, G.M. Labrador, J. Lacour, E. Bakker, Ion transfer voltammetry in
polyurethane thin films based on functionalised cationic [6]helicenes for carbonate detection.
Electroanalysis 30 (2018) 1378.

15
[58] M. Saleem, N.G. Choi, K.H. Lee, Facile synthesis of an optical sensor for CO32− and HCO3−
detection. Intern. J. Environ. Anal. Chem. 95 (2015) 592.
[59] T.R. Martz, H.W. Jannasch, K.S. Johnson, Determination of carbonate ion concentration and
inner sphere carbonate ion pairs in seawater by ultraviolet spectrophotometric titration.
Marine Chemistry 115 (2009) 145.
[60] Z. Jarolímová, Z.A. Crespo, X. Xie, M.G. Afshar, M. Pawlak, E. Eric Bakker,
Chronopotentiometric carbonate detection with all-solid-state ionophore-based electrodes.
Anal. Chem. 86 (2014) 6307.
[61] L.D. Chen, D. Mandal, G. Pozzi, J.A. Gladysz, P. Buhlmann, Potentiometric sensors based on
fluorous membranes doped with highly selective ionophores for carbonate. J. Am. Chem. Soc.
133 (2011) 20869.

of
[62] A. Ghorai, J. Mondal, R. Chandra, G.K. Patra, A reversible fluorescent-colorimetric
chemosensor based on a novel Schiff base for visual detection of CO32- in aqueous solution.

ro
RSC Adv. 6 (2016) 72185.
[63] T. Iwata, Biodegradable and bio-based polymers: future prospects of eco-friendly plastics.
Angew. Chem. Int. Ed. 54 (2015) 3210.
-p
[64] R.N. Jia, W.G. Tian, H.T. Bai, J.M. Zhang, S. Wang, J. Zhang, Amine-responsive cellulose-based
ratiometric fluorescent materials for real-time and visual detection of shrimp and crab
re
freshness. Nature Communications 10 (2019) 795.
[65] T.T. Yang, P. Xiao, J.M. Zhang, R.N. Jia, H. Nawaz, Z.Y. Chen, J. Zhang, Multifunctional cellulose
lP

ester containing hindered phenol groups with free-radical-scavenging and UV-resistant

activities. ACS Appl. Mater. Interfaces 11 (2019) 4302.
na
ur
Jo

16
Table 1. Limit of detection (LOD) for different organic amines by various sensors.

Sensors Organic amines LOD References

Naphthalimide boric acid ester TEA 0.47 M [7]

Chitosan-g-oleic acid micelles EDA 10 M [36]

Boron diketonate EDA 0.8 M [37]

PFPE-COOH ANL 64 M [15]

Mg(II) based metal–organic framework (MOF) ANL 10 M [34]

L-Phenylalanine xerogel ANL 769 ppt [35]

PC2VA ANL 0.33 ppb [16]

Diphenylacrylonitrile HYD 3.67 M [38]

of
TEA 0.90 mol
EDA 0.99 mol
Cellulose-based sensor ANL 0.46 mol

ro
This work
Phen-MDI-CA HYD 0.63 mol
Methylamine 1.7 mol
PYR -p 0.75 mol
re
lP
na
ur
Jo

17
 Table 2. LOD for PO43- and CO32- ions by various sensors.

PO43- Sensors LOD References CO32- Sensors LOD References

Conductometric biosensor 50 M [43] Inverse opal photonic crystal 1000 M [53]

Hydrazinylpyridine based
Barium MOF 40 M [44] 110 M [54]
optical sensor

Europium MOF 6.62 M [45] Europium complexes 10 M [55]

Zr-based MOF 2.0 M [46] Bis-Rhodamine derivative BRU 5.1 M [56]

Au nanoparticles 1.8 M [47] Ion-to-electron redox probe 3.2 M [57]

Ion-exchange membranes 0.1 M [48] Organic probe 1.91 M [58]

Ultraviolet spectrophotometric
Graphene quantum dots 0.1 M [49] 1.0 M [59]
titration

of
Phenylthiazole/Biphenyl
0.1 M [50] Ionophore-based electrodes 1.0 M [60]
carbonitrile

ro
Lanthanide MOF 52 nM [51] Ion-selective electrodes 0.93 M [61]

Ciprofloxacin-Eu3+/Sodium
4.3 nM [52] Schiff-base chemosensor 96 nM [62]
dodecylbenzenesulfonate

Cellulose-based sensor
Phen-MDI-CA
0.69 nmol This work
-p
Cellulose-based sensor
Phen-MDI-CA
0.86 nmol This work
re
lP
na
ur
Jo

18