A Novel 2-Phenyl-1,2,3-Triazole Derived Fluorescent Probe for Recyclable Detection of Al3+ in Aqueous Medium and Its Application

Article abstract of DOI:10.1134/S1068162020040214

Abstrast: —A novel 2-phenyl-1,2,3-triazole derived fluorescent probe HPTC ((2-hydroxybenzylidene)-2-phenyl-2H-1,2,3-triazole-4-carbohydrazide) has been designed and synthesized for recyclable detection of Al³⁺ in DMSO/Tris-HCl (pH 7.4) 1 : 100 v/v with high sensitivity and selectivity. A fluorescence enhancement of 97 folds at 457 nm can be realized upon addition of 10.0 equiv. Al³⁺ with excitation at 375 nm. The binding constant of HPTC with Al³⁺ and the detection limit of HPTC toward Al³⁺ were 1.67 × 10⁵ M^–1 and 8.875 × 10^–8 M, respectively. In addition, the probe HPTC can detect Al³⁺ repeatedly in DMSO/Tris-HCl (pH 7.4) 1 : 100 v/v and the detection effect is not changed. The probe HPTC showed an excellent detection ability in a wide pH range from 3 to 10 and also in living cells. Furthermore, the Al³⁺ sensing mechanism was confirmed based on Job’s plot, ¹H NMR titration, HR-MS, and DFT studies. Finally, HPTC-doped agarose hydrogel experiment suggests that the HPTC can recognize the Al³⁺ in solid state.

Full text of DOI:10.1134/S1068162020040214

ISSN 1068-1620, Russian Journal of Bioorganic Chemistry, 2020, Vol. 46, No. 4, pp. 627–641. © Pleiades Publishing, Ltd., 2020.
A Novel 2-Phenyl-1,2,3-Triazole Derived Fluorescent Probe
for Recyclable Detection of Al3+ in Aqueous Medium
and Its Application
Zhengfeng Xiea, 1, Yunpeng Haoa, Zhen Lib, Fanghua Suna, Junchi Maa, Xin Chena,
Wei Shia, and Shun Fengb, 2
aOil and Gas Field Applied Chemistry Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering,
Southwest Petroleum University, Chengdu, 610500 China
bSchool of Life Science and Engineering, Southwest Jiaotong University, Chengdu, 610031 China
Received July 25, 2019; revised August 9, 2019; accepted September 16, 2019
Abstrast—A novel 2-phenyl-1,2,3-triazole derived fluorescent probe HPTC ((2-hydroxybenzylidene)-2-
phenyl-2H-1,2,3-triazole-4-carbohydrazide) has been designed and synthesized for recyclable detection of
Al3+ in DMSO/Tris-HCl (pH 7.4) 1 : 100 v/v with high sensitivity and selectivity. A fluorescence enhance-
ment of 97 folds at 457 nm can be realized upon addition of 10.0 equiv. Al3+ with excitation at 375 nm. The
binding constant of HPTC with Al3+ and the detection limit of HPTC toward Al3+ were 1.67 × 105 M–1 and
8.875 × 10–8 M, respectively. In addition, the probe HPTC can detect Al3+ repeatedly in DMSO/Tris-HCl
(pH 7.4) 1 : 100 v/v and the detection effect is not changed. The probe HPTC showed an excellent detection
ability in a wide pH range from 3 to 10 and also in living cells. Furthermore, the Al3+ sensing mechanism was
confirmed based on Job’s plot, 1H NMR titration, HR-MS, and DFT studies. Finally, HPTC-doped agarose
hydrogel experiment suggests that the HPTC can recognize the Al3+ in solid state.
Keywords: fluorescent probe, 2-phenyl-1,2,3-triazole, aluminum ion, bioimaging
DOI: 10.1134/S1068162020040214
INTRODUCTION
[20], carbon dots [21], metal-organic framework [22],
and photochromic diarylethene [23] probes. Among
them, acylhydrazone compounds have gained interest
due to the CONHN=CH moiety with strong coordi-
nation power and relative ease of synthesis; until now,
julolidine [24], chromen [20, 25, 26], pyrazine [27,
28], pyridine [29], benzothiazole [30], rhodamine
[31–34], naphthalene [35–39], naphthalimide [13],
and benzene [40–42] have been employed as the fluo-
rophore, and the acylhydrazone structure has been
adopted as a selectively reactive moiety.
Recently, we have reported a series of highly selec-
tive and sensitive fluorescence probes [43–50], some
of them based on 2-phenyl-1,2,3-triazole-4-yl back-
bone, which is a novel fluorophore with strong emis-
sion and good conjugation [51, 52]. In 2016, we
designed and synthesized a novel fluorescent probe
2-hydroxy-((2-phenyl-2H-1,2,3-triazol-4-yl)methy-
lene)benzohydrazide by the condensation reaction of
phenyl-2H-1,2,3-triazole-4-carbaldehyde and sali-
cylhydrazide. This acylhydrazone-based probe
responded to Al3+ in ethanol with excellent selectivity
and low detection limit [53]. Here, in continuation of
our previous research, we synthesized (2-hydroxyben-
As the third most abundant metal in the crust, alu-
minum is extensively used in industries and modern
daily life, such as alloy materials, conductive materi-
als, packaging materials, pharmaceuticals, food addi-
tives, water purifying agent, etc. [1–8]. Because of the
wide application of aluminum, the research has found
that when the concentration of Al3+ is present in over-
load quantities, it can cause serious risks to the health
of animals and plants and even put away with many
species in the ecosystem [9–11]. The excessive Al3+ in
the human body may also lead to the emergence of
diseases, such as Alzheimer’s disease, neurasthenia,
breast cancer, osteomalacia, and Parkinson’s disease.
Hence, it is urgently desirable to synthesize a high sen-
sitivity, good selectivity, simplicity, wide range of pH,
and short-time Al3+ fluorescent probe in environmen-
tal and biological systems [12, 13].
In recent years, a series of probes for Al3+ have been
reported, including imine [14–19], acylhydrazone
1 Corresponding author: phone: +86 28 83037306; fax: +86 28
83037305; e-mail: xiezhf@swpu.edu.cn.
2 Corresponding author: e-mail: fengshunxd@hotmail.com.
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1
The 13C NMR and H NMR spectra (δ, ppm) were
zylidene)-2-phenyl-2H-1,2,3-triazole-4-carbohydra-
zide (HPTC) by condensation reaction of 2-phenyl-
2H-1,2,3-triazole-4-carbohydrazide with salicylalde-
hyde. The probe possessed the 2-phenyl-1,2,3-tri-
azole unit as a fluorophore and CONHN=CH skele-
ton as recognition site. In Table 1, we summarize some
Al3+ probes containing the CONHN=CH skeleton
with comparison to the probe synthesized in this
paper. From the Table 1 we can find that as long as
there is a chromophore with oxygen, nitrogen, or sul-
fur atoms on either side of the CONHN=CH skeleton,
it could usually be used as an aluminium ion probe,
and the large conjugated chromophore is beneficial to
the bathochromic shift of fluorescence emission.
Here, the HPTC probe is shown to exhibit high sensi-
tivity and selectivity in aqueous medium with a wide
pH range from 3 to 10 by cyclic detection and also
applied in living cells.
obtained from a VARIAN Inova-400 spectrometer.
Bioimaging was obtained with an Olympus CKX41
fluorescence microscope (Tokyo, Japan). HR-MS
(TOF-MS) spectra were recorded on a Waters Q-TOF
Premier apparatus.
Synthesis
Synthesis of HPTC
The synthetic route of HPTC ((2-hydroxyben-
zylidene)-2-phenyl-2H-1,2,3-triazole-4-carbohydra-
zide) is shown in Scheme 1. Glacial acetic acid
(0.5 mL) was added to a solution of 2-phenyl-2H-1,2,3-
triazole-4-carbohydrazide (0.203 g, 1 mmol) and
2-hydroxybenzaldehyde (0.135 g, 1.11 mmol) in 5 mL
ethanol, and the reaction was refluxed for 6 h. After
cooling to room temperature, the precipitate was fil-
tered and washed with cold ethanol to afford the white
solid powder in 83.9% yield. mp 198–200°C. IR:
3242, 1632, 1544, 1491, 1305, 755. 1H NMR
(400 MHz, DMSO-d6): 12.34 (s, 1 H), 11.07 (s, 1 H),
8.77 (s, 1 H), 8.62 (s, 1 H), 8.14 (d, J = 8.0 Hz, 2 H),
7.62–7.66 (m, 2 H), 7.58–7.60 (m, 1 H), 7.50–7.54
(m, 1H), 7.30–7.34 (m, 1 H), 6.91–6.94 (m, 2 H). 13C
NMR (100 MHz, DMSO-d6): 157.60, 155.63, 148.99,
143.00, 139.00, 137.33, 131.85, 130.06, 129.33, 129.01,
119.61, 119.29, 118.97, 116.61. HR-MS (TOF-MS+),
m/z: [M + Na]+ calcd. for C16H13N5O2Na 330.0967,
EXPERIMENTAL
Materials and Apparatus
All reagents and solvents were supplied by Adamas
Chemical Co. and used without purification. All of the
metal ions were dissolved in distilled water (10 mL) to
afford 1 × 10–1 mol/L aqueous solution from their
hydrochloride or nitrate salts.
IR spectra (ν, cm–1) were recorded on an Equinox
55 FT-IR spectrometer with KBr pellets. Absorption
spectra were obtained by a Metash UV-6000 pc UV-
Vis spectrometer. Fluorescence spectra were obtained
found 330.0955, [M + H]+ calcd. for C16H14N5O2
by a F-320 spectrometer (Gangdong Technology). 308.1142, found 308.1132.
H
H
N
N
N
N
N
N
NH2
N
N
N
AcOH
O
O
O
+
EtOH, 6 h
OH
HO
HPTC
Scheme 1. The synthetic procedure for receptor HPTC.
Intracellular Imaging
thrice with bioclean PBS buffer, and then further
incubated for additional 1 h in the medium containing
30 μM Al3+. After being rinsed again with PBS buffer,
inverted fluorescence microscope with a 40× lens
(375 nm excitation) was used to obtain fluorescence
HeLa cells were seeded into a 96-well plate and
cultured in DMEM medium supplemented with 10%
FBS for 24 h. Before in vitro experiments, the cells
were incubated for 1 h except that 10 μM HPTC was
added in the medium. After incubation, it was rinsed intracellular images of the cells. The cells were cul-
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350
300
250
200
150
100
50
Blank
Al3+
Co2+
Cr3+
Cu2+
Hg2+
Ni2+
Pb2+
Zn+2+
Ag
Al3+
Fe3+
Cd2+
Ba2+
Ca2+
Na+
K+
Blank and other ions
Mg2+
0
400
500
600
Wavelength, nm
Fig. 1. Fluorescence spectra (λex = 375 nm) of HPTC (10.0 μM) and upon the addition of metal ions (10.0 equiv.) of Cr3+, Ag+,
Ba2+, Ca2+, Cd2+, Co2+, Cu2+, Fe3+, Hg2+, K+, Na+, Mg2+, Ni2+, Pb2+, Zn2+, and Al3+ in DMSO/Tris-HCl buffer ( pH 7.4)
1 : 100, v/v.
of HPTC with various metal ions (Ag+, Al3+, Ba2+,
Ca2+, Cd2+, Co2+, Cu2+, Fe3+, Hg2+, K+, Mg2+, Ni2+,
Pb2+, Zn2+, Na+, and Cr3+) in 100 : 1 (v/v) Tris-HCl
buffer (pH 7.4) : DMSO were recorded and the
remarkable enhancement in fluorescence intensity
tured and incubated were all done at 37°C under 5%
CO2 in a humidity incubator.
HPTC Doped Agarose Gels
With the following method, HPTC-doped agarose (ca. 97-folds) was discovered only in the presence of
Al3+ (Fig. 1). This fluorescence enhancement could be
explained by the chelation-enhanced fluorescence
(CHEF) through the coordination of hydrazide-O,
azomethine-N, and phenolic hydroxyl-O to Al3+ ion
[20, 24]. The solution of HPTC demonstrated a signif-
icant fluorescence enhancement from colorless to
bright blue in the presence of Al3+, while other ions did
not enhance fluorescence, which could easily be dis-
criminated with bare eye under the ultraviolet lamp
(Fig. 2). Therefore, the probe exhibited excellent
selectivity for Al3+ compared with other metal ions.
gels were obtained. Agarose 20 mg was thoroughly dis-
solved in 2 mL of boiling water. After the aqueous
solution was cooled to 70°C, 40 µL of HPTC solution
in DMSO (10.0 mM) was added and the mixture was
rapidly stirred with ultrasound for 2 min. Then the
aqueous solution was placed at room temperature until
the gel was formed.
RESULT AND DISCUSSION
Fluorescence Studies
The competition experiments. Competition experi-
ments were applied to prove the possibility of using
HPTC as a valuable selective fluorescent probe for
Optical properties of the HPTC probe. HPTC
(3.07 mg, 0.01 mmol) was dissolved in DMSO
(10 mL) and 20 μL of this solution was diluted with
2 mL Tris-HCl buffer (pH 7.4). Fluorescence spectra Al3+. For this reason, HPTC was treated with
Ba
Cu
Mg
Fe
K
Ca
Co
Al
Pb
Ni
Zn
Cd
Cr
Hg
Ag
Fig. 2. Photographs of the fluorescence of HPTC (10.0 μM) in the presence of various metal ions (10.0 equiv.) under por-
table UV lamp.
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635
HPTC + metal ions + Al3+
350
300
250
200
150
100
50
0
Al3+ Cr3+ Hg2+ Pb2+ Ni2+ Cd2+ Ca2+
K+
Co2+ Cu2+
Ag+ Zn2+ Fe3+ Ba2+ Na2+ Mg2+
Fig. 3. Interference from other metal cations in a binary mixture in DMSO/Tris-HCl buffer (pH 7.4) 1 : 100, v/v: HPTC
(10.0 μM) + Al3+ (10.0 equiv.) + Mn+ (10.0 equiv.), where Mn+ = Ag+, Ba2+, Ca2+, Cd2+, Co2+, Cu2+, Fe3+, Hg2+, K+, Mg2+
Ni2+, Pb2+, Zn2+, Na+, Cr3+ (λex = 375 nm).
,
10.0 equiv. Al3+ in the presence of 10.0 equiv. other
metal ions in DMSO/Tris-HCl buffer (pH 7.4) 1 : 100,
v/v, solution. The competitive metal ions were first
added to the HPTC solution and then the Al3+ ion was
put in the solution. As shown in Fig. 3, the HPTC
probe could efficiently detect Al3+ ion and no interfer-
ence was observed. This result also demonstrated that
the probe exhibited excellent selectivity for Al3+.
Titrations experiments. In fluorescence titration
experiments of HPTC with increasing concentrations
of Al3+ from 0 to 2 × 10–4 M, the fluorescence emis-
sion intensity at 457 nm grew gradually (Fig. 4a),
demonstrating successful coordination. The binding
constant of HPTC with Al3+ was calculated as 1.67 ×
105 M–1 by the Benesi–Hildebrand equation [25], and
the detection limit of HPTC toward Al3+ was also cal-
culated as 8.875 × 10–8 M according to the equation
DL = 3σ/k [54].
and without any interference. Of course, HPTC could
be used under physiological conditions.
Cyclic detection capability. For purpose of finding
practical application for HPTC, the cyclic detection of
Al3+ by HPTC was investigated. As shown in Fig. 6,
addition of 10 equiv. EDTA to the solution of HPTC–
Al3+ resulted in quenching of the fluorescence emis-
sion intensity, indicating the regeneration of HPTC.
Nevertheless, when 10 equiv. Al3+ was added to the
regenerated HPTC, the enhancement of the fluores-
cence luminance occurred again at 457 nm. Alternately
adding Al3+ (10 equiv.) and EDTA (10 equiv.) for 5 times
did not reduce sensitivity of HPTC considerably.
For this reason, it was concluded that HPTC could
be employed as a recyclable fluorescent probe with high
selectivity and sensitivity for Al3+ in a wide pH range over
other environmental and biological metal ions.
Job’s plot measurement. The binding stoichiometry
between the receptor HPTC and the aluminum ion was
confirmed by the Job’s plot. As depicted in Fig. 7, the flu-
orescence emission intensity at 457 nm reached maximum
when the molecular fraction of HPTC was 0.5, which
indicated that HPTC and Al3+ formed a 1 : 1 complex.
The effect of pH. To explore whether the different
pH environments have effect on the detection of Al3+,
the influence of pH on the fluorescence was studied.
The fluorescence intensity of HPTC in the absence
and presence of Al3+was investigated. In Fig. 5, it is
clear that HPTC itself has no fluorescence in a wide
pH range from 3 to 10; when 10 equiv. of Al3+ was
1
1H NMR titration experiments. H NMR titration
experiments were carried out for the sake of elucida-
added, the fluorescence intensity has greatly tion of the mechanism of the HPTC–Al3+ complex
formation. As shown in Fig. 8, when 1.0 equiv. Al3+
increased, which demonstrates that HPTC can be
employed to detect Al3+ in a wide range of pH 3 to 10 was added to HPTC, the –OH proton signal at
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(a)
350
300
250
200
150
100
50
[Al3+]
0
450
500
550
600
Wavelength, nm
(b)
35
30
25
300
225
150
75
y
= a + b × x
Equation
Weight
No weighting
0.37634
Residual sum of
squares
0.99858
0.9967
Pearson’s
r
Adj. R-Square
Value
20.97296
3.55374
Standard error
0.19515
0.07729
Intercept
Slope
B
B
1
2
3
4
[Al3+](10–6)
0
0
100
[Al3+](10–6)
200
Fig. 4. (a) Fluorescence spectra of HPTC (10.0 μM) in DMSO/Tris-HCl buffer (pH 7.4) 1 : 100, v/v, upon the addition of
Al(NO3)3 with an excitation at 375 nm. (b) Fluorescence intensity at 457 nm versus the molar concentration of Al3+ added. Insert:
enlarged figure in the concentration range of 5 × 10–7–4 × 10–6 M of Al3+
.
involvement in bonding with Al3+. The results illus-
11.06 ppm almost disappeared owing to its strong
involvement in bonding with Al3+ [18, 24, 35], but the trate that the two oxygen atoms (–OH and C=O) and
the nitrogen atom (C=N) are coordinated with Al3+.
–NH proton remained unchanged owing to its non-
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To explore the constituent of the HPTC-Al3+ formed
in the solutions, the HR-MS spectra was recorded, the
(calcd. 428.1009) is attributed to the formula
[AlNO3(HPTC)(CH3OH)]. This prove the binding stoi-
peak with a 75% intensity at m/z = 428.0968 chiometry of HPTC–Al3+ is 1 : 1 (Scheme 2).
H
N
H
N
N
N
N
N
N
N
Al3+
N
N
O
O
Al3+
EDTA
O3N
HO
O
H
O
H
H3C
Scheme 2. The proposed mechanism of the HPTC–Al3+ complex formation.
Density functional theory (DFT) studies. Optical acceptability. Therefore, electron transfer becomes easier
properties of HPTC and HPTC–Al3+ could be
explained through a theoretical calculation. The
structures of HPTC and HPTC–Al3+ were optimized
by DFT calculation with the B3LYP method. It was
found that the computed HOMO and LUMO band
gap energy of the HPTC (0.091 eV) is higher than that
of the HPTC–Al3+ (0.009 eV). Similar phenomena
have been reported [16, 20, 36, 38]. The fluorescence
enhancement of HPTC–Al3+ may be attributed to
intramolecular charge transfer (ICT) in HPTC. The
binding of HPTC with Al3+ causes the reduction of the
oxidation potential and the increase of the electron
and the fluorescence emission is enhanced (Fig. 9).
HeLa Cells Imaging Studies
Because HPTC was highly selective and sensitive
for Al3+ ions, we decided to examine the turn-on sens-
ing of Al3+ ions in HeLa cells. As Fig. 10b shows, when
HeLa cells were incubated with HPTC (10 μM) for 1
h at 37°C, no fluorescence was observed. Then, the
binding interactions of HPTC (10 μM) with Al3+ ions
(30 μM) in living cells were investigated; strong blue
fluorescence was observed in the HeLa cells
HPTC
HPTC + Al3+
400
Al3+
300
200
100
0
300
200
100
EDTA
0
2
1
3
5
4
4
6
8
10
Cycle
pH
Fig. 6. Fluorescence intensity changes of HPTC (1.0 × 10–M)
Fig. 5. Effect of pH on fluorescence intensity of the
upon alternate addition of Al3+and EDTA (10 equiv.) in
DMSO/Tris-HCl buffer (pH 7.4) 1 : 100, v/v.
HPTC–Al3+ complex in DMSO/Tris-HCl buffer (pH
7.4) 1 : 100, v/v.
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400
200
0
0
0.2
0.4
0.6
0.8
1.0
[Al3+]/[Al3+] + HPTC
Fig. 7. Job’s plot for the determination of the stoichiometry of HPTC and Al3+ in the complex.
(Fig. 10e). The results demonstrate that HPTC can be more and more bright with the increase of the concen-
used to detect Al3+ in living HeLa cells.
tration of Al3+ (Fig. 11). Therefore, the HPTC probe
could be applied to detect Al3+ in actual samples.
Al3+ Detection by HPTC-Doped Agarose Hydrogels
CONCLUSION
Inspired by the successful application of HPTC to
detect Al3+ in aqueous medium, we further tested Al3+
in solid state. The HPTC-doped agarose hydrogels
(HPTC with an average concentration of 0.2 mM per
gel) were prepared to detect Al3+. These gels were
A novel probe HPTC based on acylhydrazone
structure was designed and synthesized by a facile
condensation reaction. HPTC exhibited excellent
selectivity and sensitivity for Al3+ without interference
immersed in Al3+ aqueous solutions of various con- with 97-folds fluorescence enhancement in aqueous
centrations with pH 7.4. Under the irradiation of UV medium, and was efficient under recycling conditions,
lamp (365 nm excitation), the fluorescence becomes in a wide range of pH, and in cellular environment.
HPTS
HPTC + 0.5 equiv. Al3+
HPTC + 1 equiv. Al3+
13.0 12.5 12.0 11.5 11.0 10.5 10.0
fl, ppm
9.5
9.0
8.5
8.0
7.5
7.0
6.5
Fig. 8. 1H NMR spectral patterns upon adding 0 to 1 equiv. of Al3+ in DMSO-d6.
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LUMO
–0.092 eV
0.091 eV
HOMO
(b)
–0.0183 eV
(a)
LUMO
–0.535 eV
0.009 eV
HOMO
–0.544 eV
Fig. 9. The display of HOMO and LUMO of HPTC (a) and HPTC–Al3+ (b).
(a)
(b)
(c)
(d)
(e)
(f)
Fig. 10. Fluorescence and bright-field images of HeLa cells stained with HPTC (a–c) and with both HPTC and Al3+ (d–f). Left, bright
field image; center, fluorescence image; right, merged image. [HPTC] = 10 μM, [Al3+] = 30 μM. Excitation wavelength 375 nm.
VI
V
IV
III
II
I
Fig. 11. Visual detection of Al3+ using HPTC-doped agarose hydrogels under 457 nm UV light (from I to VI: 0, 0.00002, 0.0002,
0.002, 0.02, 0.2 mM).
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13. Kang, L., Liu, Y.T., Li, N.N., Dang, Q.X., Xing, Z.Y.,
Li, J.L., and Zhang, Y., J. Lumin., 2017, vol. 186,
pp. 48–52.
The results of HPTC-doped agarose hydrogels for
Al3+ indicate that HPTC has good application value.
https://doi.org/10.1016/j.jlumin.2016.12.056
FUNDING
14. Kaur, B., Kaur, N., and Kumar, S., Coord. Chem. Rev.,
2018, vol. 358, pp. 13–69.
The authors thank Youth Science and Technology
Innovation Team of SWPU (project no. 2017CXTD05).
https://doi.org/10.1016/j.ccr.2017.12.002
15. Lee, J.J., Park, G.J., Kim, Y.S., Lee, S.Y., Lee, H.J.,
Noh, I., and Kim, C., Biosens. Bioelectron., 2015,
vol. 69, pp. 226–229.
COMPLIANCE WITH ETHICAL STANDARDS
https://doi.org/10.1016/j.bios.2015.02.038
This article does not contain any studies involving animals
or human participants performed by any of the authors.
16. Kumar, M., Kumar, A., Faizi, Md.S.H., Kumar, S.,
Singh, M.K., Sahu, S.K., Kishor, S., and John, R.P.,
Sens. Actuators. B Chem., 2018, vol. 260, pp. 888–899.
https://doi.org/10.1016/j.snb.2018.01.098
Conflict of Interests
The authors declare that they have no conflict of interests.
17. Selvan, G.T., Kumaresan, M., Sivaraj, R.,
Enoch, I.V.M.V., and Selvakumar, P.M., Sens. Actua-
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