L. Xu, K. Wu, R. Han et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 261 (2021) 120016
the spoilage extent evaluation [7,8]. And consequently, visualiza-
tion detection is realized. Nowadays, various methods have been
developed for viscosity determination, including the capillary vis-
cometer, damping vibration viscometer, falling ball viscometer,
rotating viscometer, and so on [9-12]. Whereas, these methods
are usually explored for macroscopic detection of viscosity, rela-
tively large amounts of samples were required, with the defects
of time-consuming and complex pretreatment processes [13].
Hence, the method with easy operation, rapid detection, with high
sensitivity, and especially, towards microscopic viscosity detection
is obliged to be exploited [14].
probes with aggregation induced emission (AIE) can display strong
signal even in the aggregation state, is suitable to be applied in the
poor solvent [45-50]. To satisfy the request of drinking liquid qual-
ity control, the AIEgens have initially applied to monitor various
indicators from multiple aspects, including the determination of
acetaldehyde [51], toxic organic pollutants [52], toxic volatile ami-
nes [53], metal cations [54-56], anions [57,58], even the gram bac-
teria [59,60], etc. Particularly, Wu et al. have tried to achieved the
application of AIE probe for sensing of triacylglycerol polymers in
the frying oil, this AIEgen probe was designed to detect the viscos-
ity response during the frying times enhancement of oil, which dis-
played a rapid screening pathway towards food hazards degree
[61]. Roche et al. explored two kinds of spectroscopic probes that
were used to expose the molecular level changes in hydration shell
water interactions, the major focus was on the use of pyranine
probe as a function of added osmolytes detection, this model can
be accounted for the preferential hydration and water/osmolyte-
mediated conformational changes [62]. Du et al. designed a lipo-
philic azo dye which was approved to monitor the micro-
viscosity of oil confined in colloidal fat crystal networks, and the
fluorescence intensity in the degree of oil confinement were deter-
mined [63]. Whereas, the fluorescence-based rotors with large
Stokes shift and AIE feature for fluid viscosity measuring, especially
for liquid food spoilage tracking and food safety inspection are still
lacking.
To date, fluorescence imaging technology has become increas-
ingly attractive, and has become one of qualitative pattern towards
viscosity sensing, which can be employed in the microscopic vis-
cosity determination attracted the interests of viscosity detection,
due to the beneficial advantages such as noninvasive, excellent
selectivity, in situ detection, and so on [15-18]. In fact, several
kinds of fluorescence-based dyes have been developed for environ-
ment viscosity detection [19,20], physiological viscosity change
process tracking [21-24], even the exosome size determination
[25,26], etc. However, most of the existing fluorescence-based dyes
for viscosity detection have been explored in the biological system,
especially for living cells imaging, as presented in Table S1 (in the
supplementary data). These dyes not only displayed short Stokes
shift, but also were hydrophobic and preferred to be aggregated
in aqueous media, which may be harmful towards fluorescence
signal releasing [27]. Usually, an intramolecular hydrogen bonding
interaction between a hydrogen bond donor (AOH) and a hydrogen
bond acceptor (@NA and C@O) is favorable to build the excited
state intramolecular proton transfer (ESIPT) event [28-31]. Indeed,
ESIPT is a unique four-level photochemical process, with the elec-
tronic ground state of ESIPT fluorophores typically existing in an
enol (E) form. Upon photoexcitation, an extremely fast enol to keto
phototautomerization (kESIPT > 1012 sÀ1) event takes place, with the
excited state enol form (E*) rapidly converting to its excited keto
form (K*). After decaying radiatively back to its electronic ground
state, a reverse proton transfer (RPT) takes place to produce the
original E form [32]. Herein, the phenolic hydroxyl group in the
para-position with the Schiff base was designed in the structure,
and the major role of this ESIPT effect is to enlarge the extension
of the conjugated structure and enhance the Stokes shift, which
will be better for fluorescence performance. Moreover, the normal
fluorescence band is generated by a locally excited (LE) state while
the anomalous band corresponds to emission from an intramolec-
ular charge transfer (ICT) state, many theories such as the wagged
ICT (WICT), rehybridized ICT (RICT), planar ICT (PICT), and twisted
ICT (TICT), have been applied to explain this process. The WICT was
proposed by the Schuddeboom et al. [33], which suggests that the
N atom in the amino group of the electron donor will transform the
sp2 hybrid planar configuration to the sp3 hybrid conical configura-
tion. This model is the least supported. Second, the RICT theoretical
research is proposed by Sobolewski et al. [34], considered that the
ICT reaction occurs during the transformation of the geometry of
electron acceptor. However, there exists a high energy barrier
between the LE state and RICT state [35], and this model has been
denied by the Femtosecond instantaneous infrared spectroscopy
[36]. Third, in the PICT model is supported mainly by the fact that
ICT emission is also observed in rigidized systems that can hardly
abandon the planar conformation [37], and its application has been
limited [38]. In comparison, the TICT model proposed by Grabow-
ski and co-workers [39], is supported by large amount of experi-
ments, and has become the most convincing physical model for
the interpretation of dual fluorescence phenomenon [40]. Based
on several previous studies [41-44], the TICT mechanism can be
afforded to explain the photophysics of typical triphenylamine
based fluorescent probe herein. Interestingly, the fluorescent
Herein, we designed an activatable molecular rotor with AIE
characteristic for tracking food spoilage process via responding
towards viscosity. The rotor TPA-PBZ is composed by the electron
donor (D, triphenylamine) and the electron acceptor (A, benzoni-
trile), which formed into the typical D-A type compound through
the single bond. This rotor TPA-PBZ possesses the AIE feature, a
large Stokes shift and a ‘turn-on’ signal towards viscosity incre-
ment. In most cases, the aromatic ring in the triphenylamine, and
the benzene ring (p-bridge), benzonitrile single bond can rotate
freely without any inhibition, the radiative pathways can be chan-
ged [64-66]. With the microenvironmental viscosity enhanced, the
signal was occurred at 568 nm, exhibited a 35.7-fold fluorescence
enhancement at the maximum. Moreover, this rotor performed
excellent anti-interference capability towards viscosity change,
good photo-stability in commercial beverages with the existence
of various food additives, stable fluorescence signal in common
range of pH values. The emission properties of the rotor TPA-PBZ
in various polarity solvents were investigated as well, its universal-
ity has been demonstrated towards complex medium. The temper-
ature factor is considered, corresponding fluorescent spectra have
been recorded. What’s more, the molecular rotor TPA-PBZ was
applied to visualize the thickening effects of the food thickeners
and the viscosity in various liquid food. Moreover, this rotor was
successfully employed to detect the viscosity variation during the
deterioration process as well, for food quality and safety
inspection.
2. Experimental
2.1. Synthesis of the molecular rotor TPA-PBZ
The synthesis route and detailed preparation procedure for the
molecular rotor TPA-PBZ were shown in Scheme S1 and experi-
mental section (see supplementary data), and the corresponding
structural characterizations were described in Fig. S1–S4.
2.2. Spectroscopic properties
Similar as previous reports [67,68], the stock solutions of poten-
tial substances (including NaCl, CaCl2, KNO3, MgSO4, beet molasses,
2