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MOHAMMADI, KHOSHSOROOR, KHALILI

Rapid, sensitive and


selective detection of
arginine using a simple azo-
based colorimetric and
fluorescent chemosensor
Journal of Photochemistry & Photobiology

PRESENTED BY ONG, VALENZUELA, WALTHERN


LBYBIBI N01B DR. RAFAEL ESPIRITU
ThiCS
THIAZOLE-BASED COLORIMETRIC
AND FLUORESCENT CHEMOSENSOR
Detection of Arginine
INTRODUCTION
BIOLOGICAL APPLICATIONS SIGNIFICANT INFLUENCE
molecular transporters, photocatalyst, human brain chemistry, including blood vessel
supramolecular nanofiber, nanostructures, dilation, immune responses and
protein-based biopharmaceuticals, and neurotransmission
forming immediate NO, urea, ornithine and
agmatine
OTHER METHODS FOR ARG OBJECTIVES
DETECTION Chemosensor containing thioazole for
high-performance liquid chromatography determination of Arg
(HPLC), gas chromatography (GC), liquid In partial aqeous medium and blood plasma
chromatography-tandem mass spectrometry
(LC–MS), molecular recognition technology,
and capillary electrophoresis
ThiCS
ADVANTAGES IN ARGININE DETECTION

Low detection limit Rapid response time

Wide linear detection High selectivity


range
Arg-ThiCS interaction
METHODOLOGY
OVERVIEW
Materials and Reagents
Apparatus
General procedure for the synthesis of ThiCS
Materials
double distilled water
& Reagents
deionized water
arginine (Arg), cysteine (Cys), phenylalanine
(Phe), glycine (Gly), tryptophan (Trp), glutamic (Glu), histidine
(His), tyrosine (Tyr), lysine (Lys), isoleucine (Ile), leucine (Leu), hydroxyproline
(Hyp), valine (Val), alanine (Ala), methionine (Met)
Apparatus
Apparatus
General 2-Aminothiazole (3 mmol)
procedure for hydrochloric acid (4.5 ml)
water (3 ml)
the synthesis 40 °C for about 2 h

of ThiCS

Orojloo,  Zolgharnein, Solimannejad, Amani (2017)


diazotized at 0–3 °C  solution containing salicylaldehyde
sodium nitrite (3 mmol) diazonium salt solution (dropwise)
water (2 ml) In basic conditions
30 min at 0–5 °C
Neutralized with 0.1M HCl
stirred for 1 hour Vacuum filter
(precipitate will form) washed several times with
deionized water
METHODOLOGY AND
RESULTS & DISCUSSION
1. Spectroscopic characterization of ThiCS
2. Colorimetric and UV–vis spectral studies
3. pH and Time-dependence of ThiCS-Arg
complex
4. Fluorescent responses of ThiCS toward
different amino acids
5. Practical application of ThiCS in human
blood plasma
PRESENTED BY ONG, VALENZUELA, WALTHERN
LBYBIBI N01B DR. RAFAEL ESPIRITU
1 METHODOLOGY
- Diazo coupling reaction for sensor
1

Fig. 1. The FT-IR spectrum of ThiCS.


2 METHODOLOGY

10 equiv. 15 AA +
3.0 x 10^-5 M ThiCS
2

Fig. 2a. Colorimetric response of ThiCS.


2 METHODOLOGY

Absorption spectroscopy Acetonitrile-water


(8:2, vlv)
2

Fig. 2b. UV–vis spectra for ThiCS (3.0 × 10−5 M) in ACN-H2O in the
presence of amino acids.
23 METHODOLOGY

Spectrophotometric titration
2

Fig. 3. Change in UV–vis spectra for ThiCS (3 × 10−5 M) in ACN-


H2O with various amounts of Arg.
23 METHODOLOGY

Job plot analysis Benesi-Hildebrand plot


2

Fig. 4a. Job plots between ThiCS and Arg in CH3CN-H2O solution.
2

Fig. 4b. Benesi-Hildebrand plot of ThiCS:Arg complex.


(Patel & Menon, 2009; Rawat & Kailasa, 2014)
2

Fig. 5. A linear calibration curve between the absorbance of ThiCS


and the equivalents of Arg.
2

Fig. 6. Change in UV–vis spectra for ThiCS in ACN-H2O upon the


addition of different amino acids.
132 METHODOLOGY

Time-dependence of ThiCS-Arg Effect of pH on ThiCS-Arg in


through UV-vis absorption spectra acidic, neutral, and basic solutions
3

Fig. 7. Response time of ThiCS toward Arg in CH3CN-H2O solution.


3

Fig. 8. The effect of pH on the sensing performance of ThiCS upon


addition of Arg in aqueous solution.
4 METHODOLOGY

probe of ThiCS + Acetonitrile-water


(8:2, vlv) 
4

Fig. 9a. The absorption spectra of ThiCS in acetonitrile-water (3 × 10−5 M).


4

Fig. 9b. The emission spectra of ThiCS in acetonitrile-water (3 × 10−5 M).


4
Principles
Emission Spectrum vs Excitation Spectrum

(Davidson, 2019)
4

Fig. 10. Fluorescence responses of ThiCS (3 × 10−5 M) in the presence of 10


equiv. of various amino acids in acetonitrile-water solution (λex = 409 nm).
4

Fig. 11a. The changes of the fluorescence spectra of ThiCS


with different equiv. of Arg in acetonitrile-water solution.
4
1

Fig. 11b. A linear calibration curve between the relative fluorescence


intensity (I545/I486) and Arg concentration (λex = 409 nm).
5 METHODOLOGY

Human Blood Plasma 


Centrifuge (1hr)
5

Fig. 12. Change in UV–vis spectra for ThiCS upon the addition of
human blood plasma at different concentrations.
5

Fig. 13. ThiCS-paper test strips upon addition of Arg at different


concentrations.
Conclusion significant red shift in UV–vis spectra

vivid color change visible to the naked-eye

red-shift in fluorescence emission

detect arginine in human blood plasma


Reference
G. Patel, S. Menon, Recognition of lysine, arginine and histidine by novel p-sulfo- natocalix
[4] arene thiol functionalized gold nanoparticles in aqueous solution, Chem. Commun. 24
(2009) 3563–3565.
Davidson, M. (2019). Fluorescence filter spectral transmission profiles. Retrieved November 27,
2019, from https://micro.magnet.fsu.edu/primer/java/fluorescence/fluorocubes/index.html.
K.A. Rawat, S.K. Kailasa, Visual detection of arginine, histidine and lysine using quercetin-
functionalized gold nanoparticles, Microchim. Acta 181 (15–16) (2014) 1917–1929.
Mohammadi, A., Khoshsoroor, S., Khalili, B. (2019). Rapid, sensitive and selective detection
of arginine using a simple azo-based colorimetric and fluorescent chemosensor. Journal of
Photochemistry & Photobiology, 384(2019) 112035.
M. Orojloo, P. Zolgharnein, M. Solimannejad, S. Amani, Synthesis and characterization of
cobalt (II), nickel (II), copper (II) and zinc (II) complexes derived from two Schiff base
ligands: spectroscopic, thermal, magnetic moment, electrochemical and antimicrobial
studies, Inorg. Chim. Acta 467 (2017) 227–237.

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