UV-Light Photoelectrochemical Sensor Based on the Copper Tetraamino-Phthalocyanine-modified ITO Electrode for the Detection of Nifedipine in Drugs and Human Serum

Article abstract of DOI:10.1002/bkcs.11667

In this study, a new photoelectrochemical (PEC) sensor based on the copper tetraamino-phthalocyanine-modified ITO electrode (CuTAPc/ITO) was designed for the determination of nifedipine. The prepared CuTAPc materials were characterized using UV–Visible spectrophotometry (UVS), Fourier transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). Then, the CuTAPc solution was coated on the ITO electrode surface to fabricate a simple PEC sensing platform. Then, the photoelectrochemical behavior of nifedipine at the CuTAPc/ITO electrode was investigated by chronoamperometry under ultraviolet light irradiation. The obtained results indicated that the modified electrode showed a higher response signal than the blank electrode. The photocurrent of CuTAPc/ITO increased with the increasing concentration of nifedipine. The peak photocurrents were linearly dependent on the nifedipine concentration in the range of 0.25–18.0 μmol/L, thereby providing the detection limit of 0.15 μmol/L (S/N = 3). Due to the good responses for the determination of nifedipine, this sensor can be used as an alternative analysis tool for the detection of nifedipine in various real samples with high sensitivity, low detection limit, and wide linearity range.

Full text of DOI:10.1002/bkcs.11667

Article
DOI: 10.1002/bkcs.11667
BULLETIN OF THE
J. Peng et al.
KOREAN CHEMICAL SOCIETY
UV-Light Photoelectrochemical Sensor Based on the Copper
Tetraamino-Phthalocyanine-modified ITO Electrode for the Detection
of Nifedipine in Drugs and Human Serum
†,‡,
‡
†
†
†
*
Jinyun Peng,
Wenfeng Zhuge, Yingying Huang, Cuizhong Zhang, and Wei Huang
†College of Chemistry and Chemical Engineering, Guangxi Normal University for Nationalities,
Chongzuo 532200, China
‡
School of Pharmacy, Henan University of Traditional Chinese Medicine, Zhengzhou 450046, China.
*E-mail: pengjinyun@yeah.net
Received August 6, 2018, Accepted December 17, 2018
In this study, a new photoelectrochemical (PEC) sensor based on the copper tetraamino-phthalocyanine-
modified ITO electrode (CuTAPc/ITO) was designed for the determination of nifedipine. The prepared
CuTAPc materials were characterized using UV–Visible spectrophotometry (UVS), Fourier transform
infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). Then, the CuTAPc solution was coated on
the ITO electrode surface to fabricate a simple PEC sensing platform. Then, the photoelectrochemical
behavior of nifedipine at the CuTAPc/ITO electrode was investigated by chronoamperometry under ultra-
violet light irradiation. The obtained results indicated that the modified electrode showed a higher
response signal than the blank electrode. The photocurrent of CuTAPc/ITO increased with the increasing
concentration of nifedipine. The peak photocurrents were linearly dependent on the nifedipine concentra-
tion in the range of 0.25–18.0 μmol/L, thereby providing the detection limit of 0.15 μmol/L (S/N = 3).
Due to the good responses for the determination of nifedipine, this sensor can be used as an alternative
analysis tool for the detection of nifedipine in various real samples with high sensitivity, low detection
limit, and wide linearity range.
Keywords: Photoelectrochemical sensor, Copper tetraamino-phthalocyanine, Nifedipine
1
5
Introduction
workstation and a photoelectric instrument. The light
source is used to irradiate the photoactive materials to give
rise to charge transfer and the electrochemical workstation
is responsible for performing tasks and recording the
Nifedipine [1,4-dihydro-2,6-dimethyl-4-(2-nitrophenyl)-
,5-pyridinedicarboxylic acid dimethyl ester] (NP) is a dihy-
dropyridine calcium antagonist that is used for the treatment
of angina pectoris due to coronary heart disease, and in par-
ticular for variant angina pectoris and angina pectoris caused
by coronary artery spasm, high blood pressure and cardio-
The NP dosage must be strictly con-
trolled. Excessive use of NP can trigger hypotension and
proarrhythmic effects. Therefore, the determination of NP
3
16
strength of the photocurrent signal. PEC sensors combine
the advantages of optical methods and chemical sensors
due to their simultaneous application of light irradiation
and electrochemical detection. Moreover, due to the sepa-
ration of the light source and the detection signal, PEC sen-
sors effectively reduce the background signal interference
17
1–3
vascular disease.
4
18
and improves the detection sensitivity. PEC sensors have
level in pharmaceutical formulations is indispensable for the
control of industrial product quality and for ensuring the
suitable dose for the patients. Modern instrumental analysis
techniques such as high-performance liquid chromatography
been successfully applied to the detection of environmental
19
20
21
pollutants, food additives, drug content, pesticide
22,23
24
residues,
and enzymes. Generally, PCE sensors have
bright prospects for use in a wide range of applications.
As the paramount tetrapyrrole derivatives, metallophtha-
locyanine (MPc) compounds have been intensively studied
in the recent years. MPc compounds have a highly deloca-
lized 18 π-electron macrocyclic conjugate system with
special optical, conductive, electron-donor, and electron-
5,6
7,8
(
HPLC),
chromatography, and spectrophotometry
lished and applied to the determination of NP. Although
gas chromatography,
capillary gas
9
10,11
were estab-
1
2–14
HPLC and other combination technologies
have high
sensitivity and selectivity, these analytical methods involve
costly and time-consuming processes. It is urgently neces-
sary to develop a method with simple operation, fast
response, and low cost for use in NP detection.
Photoelectrochemical (PEC) sensors are an emerging
analytical tool that is operated with an electrochemical
25
acceptor properties. In addition, MPc shows unique ther-
mal and chemical stability and photosensitivity and has also
been widely used in the fabrication of photoelectrochemical
26
sensors. MPc also possesses a strong modifiable struc-
27
ture that can accommodate different substituents that are
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introduced to improve its functions and overcome the dis-
advantage of poor solubility. For example, the properties of
metal tetraamino-phthalocyanine (MTAPc) are not only
superior to those of MPc, but MTAPc is also soluble in
Patients who provided blood samples were given the right
to know about and to agree to participate in the trials.
Synthesis of CuTAPc materials. Following the reports in
33,34,
the literature
as follows.
Synthesis
the CuTAPc materials were synthesized
2
8
general organic solvents. MTAPc compounds have been
used in various applications, such as electrochemical
of
Copper Tetranitro-Phthalocyanine.
2
9
30
31
sensors, l2ight-effect transistor, optical sensor, and
4-nitrophthalimide (4.10 g), urea (10.15 g), and molybdic
acid (0.05 g) were ground evenly in a mortar. The resulting
powder was then placed in a 250-mL flask and placed in an
electric heating jacket to heat and melt. After all of the
solid had melted, ground copper chloride powder (1.40 g)
was added to the flask under stirring. The reaction tempera-
3
solar cells.
In this work, CuTAPc was dripped onto the ITO-coated
glass electrode, producing a uniform, highly conductive,
robust and strongly adherent coating. The modified elec-
trode served as the working electrode of the PEC sensor for
nifedipine detection. The PEC sensors exhibited high sensi-
tivity, good selectivity, and low detection limits with satis-
factory results.
ꢁ
ture was maintained at 160 C for 1 h. The solid product
was ground and boiled for 1 h with an HCl solution
(1 mol/L, 300 mL) and a NaOH solution (1 mol/L,
3
00 mL), respectively. The product was vacuum filtered,
Experimental
neutralized with water, and dried.
Synthesis of Copper Tetraamino-Phthalocyanine.
CuTNPc (1.05 g) and sodium sulfide (7.14 g) were placed
into a 250-mL three-necked flask, and then DMF (45 mL)
Apparatus. The photoelectrochemical experiments were
carried out using a CHI 760E Electrochemical Workstation
ꢁ
(Chenhua Instrument Co., Shanghai, China) and a PEAC
was added. The temperature was kept at 60 C under stir-
2
00A photoelectric alignment collimator (Tjaida Instrument
ring for 1 h. The solid product was separated from the reac-
tion mixture by centrifuging and was treated with a
1 mol/L HCl solution followed by the treatment with a
1 mol/L of NaOH solution. The suction filtered CuTAPc
was washed to neutral with distilled water and dried to get
obtain a dark green solid.
Co., Tianjin, China) equipped with a 10-W light-emitting
diode (LED). The LED provided the source of a 375-nm
UV-light. The electrochemical workstation was directly
connected to a three-electrode cell system. The CuTAP-
c/ITO electrode was used as the working electrode. A Pt
wire was employed as the counter electrode and a saturated
Ag/AgCl served as the reference electrode. The sizes and
structures of the experimental materials were characterized
by SEM (Hitachi S-4800, Tokyo, Japan; 5 kV), UVS (UV-
Construction of the Modified ITO-coated Glass
Electrode. The ITO-coated glass electrode was ultrasoni-
cally washed with acetone, then anhydrous ethanol, and
then distilled water, and then was dried under an infrared
lamp. The modifier was prepared with CuTAPc (1 mg) and
DMF (1 mL) and ultrasonically dispersed for 30 min. Then,
10 μL of the modifier was dripped onto the ITO electrode.
The area of the material covering the electrode is
6100S, Metash, Shanghai, China), FT-IR (Spectrum 65, Per-
kin Elmer, Santa Clara, CA, USA), and FS (RF-5301PC,
Shimadzu, Japan) techniques. A pH meter (pHS 3C, Rex,
Shanghai, China) was used to measure the pH of the
solutions.
2
5 × 15 mm . After the modified electrode was dried natu-
Chemicals and Materials. NP was purchased from Alad-
din Biochemical Technology Co., Ltd. (Shanghai, China).
The human serum sample was originally obtained from
Chongzuo People’s Hospital (Guangxi, China). Sodium sul-
fate, copper chloride [CuCl ꢀ2H O], and ammonium
rally, a green film was formed on the surface.
NP sample preparation. The solutions were prepared in a
darkened room. The coating of the NP tablets was
removed, and the tablets were ground, and weighed pre-
cisely. An appropriate amount of methanol was added, and
NPs were dissolved by ultrasonication. The initial solution
of the sample (contains 1 × 10− mol/L NP) was diluted
with the B-R buffer solution to the scale. The filtrate was
collected for the filtration. The pretreatment process of the
serum refers to the previous studies reported in the litera-
2
2
molybdate were provided by Xilong Scientific Co., Ltd.
3
(Guangdong, China). Concentrated sulfuric acid, fuming
nitric acid and N,N-dimethylformamide (DMF), and other
chemicals used in this work were obtained from the
Chengdu Kelong chemical reagent plant (Chengdu, China).
All of the reagents used in this study were of analytical
grade. All of the solutions were prepared using double dis-
tilled water. Britton-Robinson (B-R) buffer solution
35
ture. The serum samples were thawed at room tempera-
ture. Serum and methanol were placed in centrifuge tubes
to precipitate the proteins at a volume ratio of 1: 3. The
mixture was shaken vigorously for 2 min and then was cen-
trifuged at 10000 rpm for 20 min.
(0.04 mol/L) was prepared by mixing phosphoric acid,
boric acid, and glacial acetic acid. A 0.2 mol/L NaOH solu-
tion was used to adjust the pH of the buffer solution. ITO-
coated glass slices (6 Ω, 50 × 5 × 1.1 mm) were provided
by Xiangcheng Technology Co., Ltd. (Shenzhen, China).
All of the experiments were carried out under the National
Law and Related Institutional Committee Regulations.
Results and Discussion
Characterization of CuTAPc Materials. The characteris-
tic functional groups of CuTAPc were identified by FT-IR
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Photoelectrochemical Sensor for Detection of Nifedipine
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spectroscopy (Figure 1(a)). A double peak was observed in
−1
the wavelength range of 3500–3200 cm that corresponds
3
4
to the presence of amino groups (νNH2). The sharp peak
−
1
at 1606 cm (δNH) further proved the presence of amino
36
groups. The absorption peaks observed at 1136, 1083,
−
1
1
047, 939, 817, and 743 cm 7were due to the vibrations
3
of the phthalocyanine skeleton.
The UV–Vis spectra of CuTAPc in DMF are shown in
Figure 1(b). Two absorption bands, the B band (341 nm),
and the Q band (730 nm), appeared in the representative
spectrum. Both of these absorption peaks are due to the
π-electron transition on the ring of the tetraamine copper
phthalocyanine. The B band is due to the 4a2u ! 6e tran-
g
sition, and the Q band is due to the 2a1u ! 6e transition.
g
This finding is consistent with the previous reports in the
28,38
literature.
XRD was used to characterize and analyze the CuTAPc
crystal structure. The XRD patterns of the CuTAPc pow-
Figure 2. (a) Nyquist plots at ITO and CuTAPc/ITO in the pres-
3−/4−
ence of 3 mmol/L [Fe(CN)
6
]
in 0.1 mol/L KCl. (b) Ampero-
ꢁ
ders showed diffraction peaks in the 2θ range of 10–80
metric i-t curve for 15.0 μmol/L NP on the surfaces of various
electrodes; ITO in the absence (a) and presence of analyte (b),
CuTAPc/ITO in the absence (c), and presence of the analyte (d).
(c) Effect of the electrolyte on the photocurrent in response to
ꢁ
(
Figure 1(c)). The peaks were observed at the 28 plane.
This peak corresponds to the characteristic peak of the
39
CuTAPc materials.
1
5.0 μmol/L NP, and (d) effect of pH (4.5–10.5).
Electrochemical impedance spectroscopy. The electro-
chemical system examined in this work can be viewed as
an equivalent circuit that is a combination of the resistance
of the solution (R , R ), double-layer capacitance (C ), and
ITO electrode exhibited a larger semicircle diameter than
the CuTAP/ITO electrode in the EIS. The electron-transfer
resistance is equal to the semicircle diameter. The results
showed that the modified electrode has a lower resistance
than the ITO electrode. This finding may be because the
CuTAPc film has a reduced mass-transfer resistance of
s
et
dI
41
1
8
Warburg impedance (Z ) in series and in parallel. Elec-
w
trochemical impedance spectroscopy (EIS) is a useful anal-
ysis technique for investigating the electrode surface
4
0
dependent charge transfer process and efficiency. EIS was
3-/4-
[Fe(CN)6]
and, as a result, shows an accelerated elec-
carried out in a 3.0 mmol/L K [Fe(CN) ]/K [Fe(CN) ]
3
6
4
6
tron transfer between the electrolyte and the electrode
surface. The successful modification of the CuTAPc mate-
rial onto the surface of the ITO electrode was confirmed.
solution containing 0.1 mol/L KCl for the characterization
of the ITO and the CuTAPc/ITO electrodes. A small-
amplitude alternating current signal at different frequencies
was applied to the electrochemical system, with the highest
frequency of 100 000 Hz, the lowest frequency of 1 Hz,
and the amplitude of 0.005 V. As seen in Figure 2(a), the
Photoelectrochemical Responses of NP on CuTAPc/ITO
and ITO. The photoelectrochemical responses of NP on
CuTAPc/ITO and ITO were studied under UV-light irradia-
tion. As shown in Figure 2(b), the photocurrent of the bare
ITO electrode in the blank solution is 9.1 nA (curve a),
whereas it is 9.9 nA (curve b) in the electrolyte containing
1
5.0 μmol/L NP. The bare ITO electrode exhibited a weak
response signal. By contrast, the CuTAPc/ITO electrode
showed a good response signal. The photocurrent of the
CuTAPc/ITO electrode in the blank solution is 22.4 nA
(curve c), while in the electrolyte containing 15.0 μmol/L
NP, the photocurrent is 60.2 nA (curve d). It is found that
the signal of NP at CuTAPc/ITO increased significantly
compared to that of ITO, due to the excellent photoelectric
activity and sensitivity of CuTAPc.
Optimization of Experimental Conditions. To obtain the
best photoelectrochemical responses, the experimental con-
ditions, including the bias voltage, material concentration,
electrolyte and pH, were investigated and optimized.
Figure 1. FT-IR spectrum (a), UV-Vis spectrum (b), and X-ray
diffraction (c).
In this work, the concentrations of the introduced
CuTAPc suspensions were 0.5, 1.0, 1.5, and 2.0 mg/mL.
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Photoelectrochemical Sensor for Detection of Nifedipine
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The results indicated that the highest analytical signals were
obtained for the concentration of 1.0 mg/mL. A higher con-
centration of CuTAPc suspension led to an increase in the
background photocurrent. The bias voltage was also opti-
mized by the examination of the voltages of 0, 0.1, 0.15,
linear regression equation given as I (nA) = 21.46 + 2.45CNP
(μmol/L), with the correlation coefficient of 0.9987. The limit
detection of the sensor was 0.15 μmol/L (S/N = 3).
Stability and Reproducibility of the CuTAPc/ITO. The
ꢁ
modified electrode was stored in a refrigerator at 4 C for
0
.2, 0.25, 0.3, and 0.35 V. Under the voltage of 0.25 V,
9 days, and the stability of the PEC sensor was evaluated
by detection of NP in a standard solution at optimal condi-
tions. The experimental results are shown in Figure 3(c),
and the relative standard deviation (RSD) was 2.5%. This
result indicates the stability of the PEC sensor. The repro-
ducibility (Figure 3(d)) of the PEC sensor was also exam-
ined by detecting the photocurrent of NP in the B-R buffer
solution (pH = 7.5) using seven electrodes. The photocur-
rent remained stable after seven consecutive measurements,
and an RSD of 2.9% was obtained, thereby demonstrating
the advantageous reproducibility of the PEC sensor.
the working electrode showed the largest response signal,
but the i-t baseline was not stable. The baseline was more
stable under the open-circuit voltage of 0.26 v. Moreover,
there was no significant difference between the response
signals obtained at 0.26 V and those obtained at 0.25 V.
In addition, the photoelectric effect of NP at the CuTAP-
c/ITO was studied in different media such as a phosphate
buffer solution (PBS), Britton-Robinson buffer solution
(
(
B-R), McIlvaine buffer solution, and borate buffer solution
BBS). As shown in Figure 2(c), it was found that the high-
est photocurrent was for detecting NP was obtained in the
B-R buffer solution. Chronoamperometry studies of NP at
the CuTAPc/ITO were carried out in the B-R buffer solu-
tion with different pH values in the 4.5–10.5 range. It was
found that the NP photocurrent increased gradually with
increasing pH and reached the maximum value at pH 7.5
Interference Studies. The selectivity and utility of the sen-
sor were explored by performing the measurement in the
presence of the interfering substances in the actual sample.
The maximum tolerated interference limit is defined as the
variation of the photocurrent value of a certain concentration
of NP being smaller than 5% before and after the addition of
the interfering substance. As shown in Table 1, the photo-
currents of NP were not affected by most species. However,
the photocurrent is more sensitive to oxalic acid and is sus-
ceptible to its interference. This outcome is because NP
hydrolyzes easily in acidic conditions, thereby hindering the
process of electron transfer to the electrode surface.
Detection of NP in Real Samples. To examine the practi-
cal value of the PEC sensor for detecting NP in clinical
samples, content detection was tested in human serum and
tablets. The samples were collected and pretreated, as
described in the NP sample preparation section. For the
human serum samples, the accuracy of the experimental
results was expressed in terms of recovery (Table 2). For
clinical drugs, the results were compared with the labeled
amount (Table 3). NP levels obtained by the PEC sensors
were also compared with the results obtained by HPLC.
The recovery of NP in the serum, the percentage of NP in
(Figure 2(d)). Then, the photocurrent decreased gradually
until pH 10.5. Therefore, subsequent measurements were
performed in pH 7.5 B-R buffer solution.
PEC Sensor Detection of NP. A PEC sensor was used for
the determination of NP, with pH 7.5 B-R buffer solution.
The photocurrents for different concentrations of NP on the
CuTAPc/ITO were recorded, as shown in Figure 3(a). The
NP photocurrent increases steadily as its concentration
increased from 0.25 to 18.0 μmol/L. The data were fit with a
Table 1. Interference study of some species for the simultaneous
determination of 0.5 μmol/L of NP.
Molar ratio
(
foreign
Foreign species
species/NP)
2
+
−
Mg , Cl , maltose, urea
Mannitol
400
300
250
200
100
Neomycin sulfate
2+
−
2+
2+
3
Ba , NO , Ca , Cu , Sucrose
Figure 3. (a) Response of the PEC sensor under optimized condi-
tions for detection of NP, with NP concentration ranging from
Al , Zn , SO , K , S O , Br−,
3+
2+
2+
+
2−
4
2 3
2+
+
2−
2+
NH , CO , Ni ,Mn ,
CH COO , Chloramphenicol
4
3
−
0
.25 to 18.0 μmol/L. (b) The linear analytical curve. (c) Stability
3
of the PEC sensor during continuous detection of 12.0 μmol/L NP
for 9 days. (d) Detection of the same concentration of NP per-
formed seven times. The applied bias voltage was 0.26 V
Theophylline
50
30
20
2−
SO
3
Oxalic acid
(vs. Ag/AgCl).
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Table 2. Results for the NP determination in urine samples under
the optimal conditions.
Added
Found
Recovery
Sample
Serum
(μmol/L)
(μmol/L)
(%, n = 5)
RSD (%)
4.2
15.0
14.7
97.9
Table 3. Results for the NP determination in the drug under the
optimal conditions.
Labeled
Found Percentage of labeled RSD
Sample amount (mg)
(mg)
amount (%, n = 5)
(%)
a
S1
S2
a
10.0
20.0
9.7
20.6
96.6
103.1
1.2
3.2
b
NP tablets, Shanxi Taiyuan Pharmaceutical Co., Ltd.
NP sustained—release tablets, Shanxi Yunpeng Pharmaceutical
Co., Ltd.
b
Scheme 1. Schematic of electron transfer of the PEC sensor based
on the CuTAPc/ITO electrode.
donor and transferred electrons to the holes in the valence
band simultaneously; thus, photocurrent signals were gener-
the tablets, and the percentage of NP in the sustained-
release tablets were 95.8, 89.1, and 101.2%, respectively.
There is no significant difference between the results
obtained by the two techniques. Finally, the obtained good
recoveries and RSD values indicated that the PEC sensor
has great practical significance in the detection of NP in
real clinical samples.
ated and further prevented the reorganization of the photo-
26,44
generated electrons and holes.
The photocurrent of the
modified electrode will change based on the NP content.
According to the above mechanism, the PEC sensor based
on the CuTAPc/ITO electrode was developed for NP
detection.
The developed method was compared with a variety of
methods that have been reported in the literature for NP
detection. The distinct features of the proposed method are
shown in Table 4. It is clear that the CuTAPc/ITO PEC
sensor has excellent limit of detection and linear range
for NP.
Conclusion
The establishment of accurate, rapid, and sensitive methods
for the detection of drugs is highly important. In this work,
it was shown that the CuTAPc materials accelerate the elec-
tron transfer on the electrode surface and enhance the pho-
tocurrent signal of the sensor. A PEC sensor based on the
semiconductor CuTAPc materials for NP detection with
low limit of detection and good linear range in real samples
was reported for the first time. The sensor presented in this
work is likely to be widely used due to its small volume
and low cost. Moreover, the proposed method does not
exhibit interference by coexisting ions in biological samples
and drug samples that were obtained without complicated
pretreatment processes. Due to its excellent selectivity and
good stability and reproducibility, the novel PEC sensor is
expected to be an alternative analytical tool in the fields of
analytical detection and photoelectrochemistry.
PEC Sensor Detection Mechanism. The electron-transfer
mechanism of the PEC sensor with CuTAPc/IT as the
working electrode was proposed for the NP-containing B-R
electrolyte (Scheme 1). The UV irradiation source was
turned ON/OFF every 20 s. The sensitivity (A/V) was
−6
1
0 , and the applied potential was 0.26 V. When CuTAP-
c/ITO was stimulated by the UV irradiation source, the
photogenerated electrons transferred from the CuTAPc
valence band (VB) to its conduction band (CB), resulting
in the separation of the photogenerated electrons and holes.
The CB electrons were then transferred to the ITO elec-
trode. Meanwhile, NP served as an outstanding electron
Table 4. Comparison between this work and other reported
methods for NP determination in real samples.
Acknowledgments. The authors acknowledge the National
Natural Science Foundation of China (Grant No. 21465
Method
UVS
Linear rang
Detection limit
References
0
04) and the Guangxi Science Foundation of China (grant
2.0–12.0 μg/mL
0.8–60.0 μmol/L
20–600 μmol/L
1.4 μg/mL
0.72 μmol/L
11 μmol/L
43 μmol/L
0.15 μmol/L
11
42
43
No. 2016GXNSFAA380113) for providing support to
this work.
a
DPV
b
CV
8
0–1000 μmol/L
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Photoelectrochemical Sensor for Detection of Nifedipine
KOREAN CHEMICAL SOCIETY
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