Chromogenic Chemosensors Based on Phenolic Imines for the Detection of Alkylamines and Lidocaine in Water and in the Vapor Phase

Ribeiro, Eduardo A.; Machado, Vanderlei G.

doi:10.21577/0103-5053.20210089

Eduardo A. Ribeiro

Departamento de Química, Universidade Federal de Santa Catarina (UFSC), 88040-900 Florianópolis-SC, Brazil

Instituto Federal de Santa Catarina (IFSC), 88813-600 Criciúma-SC, Brazil

Vanderlei G. Machado ^**e-mail: vanderlei.machado@ufsc.br

Departamento de Química, Universidade Federal de Santa Catarina (UFSC), 88040-900 Florianópolis-SC, Brazil

https://orcid.org/0000-0002-6995-6591

*e-mail: vanderlei.machado@ufsc.br

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Figure 1
Molecular structures of dyes 1 and 2.

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Scheme 1
Molecular structures of compounds 3a-5a, colorless in solution, and their deprotonation to generate the colored forms 3b-5b.

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Scheme 2
Route for the synthesis of compounds 3a-5a.

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Figure 2
Solutions of compounds 3a (a), 4a (b), and 5a (c) in water in the absence and after the addition of amines at 25.0 .C. The concentration of the amines was 2.0 × 10-4 mol L^-1.

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Figure 3
Solutions of compounds 3a (a), 4a (b), and 5a (c) in aqueous CTAB solution in the absence and after the addition of aliphatic and aromatic amines at 25.0 .C. The concentrations of the amines and CTAB were 2.0 × 10^-4 and 1.0 × 10-3 mol L^-1, respectively.

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Figure 4
UV-Vis spectra for the aqueous solutions of 3a (a) and 5a (b) at 25.0 °C containing BTA, DEA, TEA, ANI, NMA, and NNDA. (c), (d) Corresponding relative absorbances at 515 and 668 nm for the appearance of 3b and 5b, respectively. The concentrations of the chemosensors and amines were 4.0 × 10^-5 and 2.0 × 10^-4 mol L^-1, respectively, and of CTAB was 1.0 × 10^-3 mol L^-1.

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Figure 5
Values of pKa at 25.0 .C of compounds 3a-5a in (a) water and in (b) aqueous CTAB solution and comparison with the pKa values of the protonated aliphatic and aromatic amines.

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Figure 6
(a) UV-Vis spectra at 25.0 °C showing the behavior of 3a (4.0 × 10^-5 mol L^-1) in water with the addition of increasing amounts of BTA and the corresponding titration curve (b). The final concentration of BTA was 3.17 × 10^-4 mol L^-1 and the absorbance values were collected at 490 nm. The inset displays a Job plot for 3a and the amine.

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Figure 7
(a) UV-Vis spectra at 25.0 °C showing the behavior of 5a (4.0 × 10^-5 mol L^-¹) in aqueous CTAB solution (1.0 × 10^-3 mol L^-1) with the addition of increasing amounts of BTA. (b) Corresponding titration curve with BTA. The final concentration of BTA was 1.07 × 10^-4 mol L^-1 and the absorbance values were collected at 668 nm. The inset displays a Job plot for 5a and the amine.

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Scheme 3
Proposed model for stoichiometries of the chemosensors with the amines in pure water and in aqueous CTAB solution. In (a) compounds 3a and 4a interact with the amines following a 1:2 chemosensor:amine stoichiometry while the 1:3 stoichiometry (b) occurs with 5a in CTAB system in the presence of the alkylamines.

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Figure 8
Photographs of test strips for 3a in contact with vapors of BTA at different concentrations in argon atmosphere.

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Figure 9
Photographs of test strips for 3a in aqueous CTAB solution (1.0 × 10^-3 mol L^-1) in the absence and presence of increasing amounts of BTA.

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Figure 10
Solutions of 3a (4.0 × 10^-5 mol L^-¹) in water in the absence (a) and presence of CTAB (1.0 × 10^-3 mol L^-1) (b), without and after the addition of TEA and lidocaine at 25.0 .C, with c (TEA) = 2.0 × 10^-4 mol L^-1 and c (lidocaine) = 3.0 × 10^-3 mol L^-1.

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Figure 11
(a) Influence of the addition of increasing amounts of a standard pharmaceutical lidocaine on the UV-Vis spectrum of 3a (4.0 × 10^-5 mol L^-1) in water containing CTAB (1.0 × 10^-3 mol L^-1) at 25.0 °C. (b) Corresponding titration curve for the absorbances collected at 515 nm. The inset displays a Job plot for 3a and lidocaine.

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Scheme 4
Proposal for the interaction of 3a with lidocaine in solution.

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Figure 12
(A) UV-Vis spectra of 3a in water with CTAB (1.0 × 10^-3 mol L^-1) at 25.0 °C without (a) and with 1.02 × 10^-5 (b), 3.04 × 10^-5 (c), and 6.99 × 10^-5 mol L^-1 (d) of a commercial sample of lidocaine. (B) Titration curve at 515 nm for the titration of 3a (5.0 × 10^-5 mol L^-1) with increasing amounts of a standard pharmaceutical lidocaine. The red circles correspond to the commercial samples of lidocaine.

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Table 1
Values of λ_max and ε_max for dyes 3b-5b in water at 25.0 ºC in the absence and presence of CTAB (1.0 × 10^-3 mol L^-1)

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Table 2
Values of pK_a determined for compounds 3a-5a in water at 25.0 ºC in the absence and presence of CTAB

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Table 3
Values of equilibrium constants K₁₂ for 3a-5a and K₁₃ for 5a with the amines in water at 25.0 °C

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Table 4
Values of limit of detection (LOD) and quantification (LOQ) for compounds 3a-5a with the amines in water at 25.0 °C

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Table 5
Comparison between limits of detection (LOD) for the detection of aliphatic amines in water, obtained from the literature and for compounds 3a-5a

(1)

(2)

(3)

(4)

(5)

Compound	Water		Aqueous CTAB solution		Δλ_max^a a Δλmax = λmax (aqueous CTAB solution) - λmax (water). CTAB: cetyltrimethylammonium bromide; λmax: maximum wavelength; εmax: molar absorptivity coefficient. / nm
Compound	λ_max / nm	ε_max / (L mol^-1 cm^-1)	λ_max / nm	ε_max / (L mol^-1 cm^-1)
3b	490	(1.804 ± 0.006) × 10⁴	515	(1.833 ± 0.001) × 10⁴	+25
4b	480	(1.719 ± 0.003) × 10⁴	508	(1.415 ± 0.012) × 10⁴	+28
5b	615	(1.774 ± 0.012) × 10⁴	668	(1.785 ± 0.001) × 10⁴	+53

Compound	pK_a (without CTAB)	pK_a (with CTAB)^a a c (surfactant) = 1.0 × 10-3 mol L-1. CTAB: cetyltrimethylammonium bromide.
3a	9.12 ± 0.01	8.57 ± 0.01
4a	5.91 ± 0.01	4.40 ± 0.01
5a	12.25 ± 0.02	10.08 ± 0.04

Compound		BTA	DEA	TEA
3a	K₁₂ / (L² mol^-2)	(1.463 ± 0.048) × 10⁸	(1.070 ± 0.027) × 10⁸	(1.729 ± 0.055) × 10⁸
3a ^a a With cetyltrimethylammonium bromide (CTAB) 1.0 × 10-3 mol L-1.BTA: n-butylamine; DEA: diethylamine; TEA: triethylamine.	K₁₂ / (L² mol^-2)	(1.162 ± 0.050) × 10⁸	(1.173 ± 0.049) × 10⁸	(8.511 ± 0.262) × 10⁷
4a	K₁₂ / (L² mol^-2)	(8.797 ± 0.191) × 10⁸	(1.721 ± 0.044) × 10⁸	(2.237 ± 0.080) × 10⁸
5a ^a a With cetyltrimethylammonium bromide (CTAB) 1.0 × 10-3 mol L-1.BTA: n-butylamine; DEA: diethylamine; TEA: triethylamine.	K₁₂ / (L² mol^-2)	(8.959 ± 0.219) × 10⁷	(1.240 ± 0.279) × 10⁸	(1.844 ± 0.325) × 10⁸
	K₁₃ /(L³ mol^-3)	(2.012 ± 0.043) × 10⁵	(7.160 ± 0.182) × 10⁴	(7.780 ± 1.099) × 10⁴

Compound	BTA		DEA		TEA
Compound	LOD / (mol L^-1)	LOQ / (mol L^-1)	LOD / (mol L^-1)	LOQ / (mol L^-1)	LOD / (mol L^-1)	LOQ / (mol L^-1)
3a	2.36 × 10^-6	7.88 × 10^-6	1.61 × 10^-6	5.36 × 10^-6	1.45 × 10^-6	4.18 × 10^-6
3a ^a	6.89 × 10^-7	2.29 × 10^-6	5.29 × 10^-7	1.76 × 10^-6	6.27 × 10^-7	2.09 × 10^-6
4a	9.71 × 10^-7	3.23 × 10^-6	1.84 × 10^-6	6.54 × 10^-6	1.42 × 10^-6	4.75 × 10^-6
5a ^a	7.00 × 10^-7	2.33 × 10^-6	6.99 × 10^-7	2.33 × 10^-6	5.08 × 10^-7	1.69 × 10^-6

Technique	LOD / (mol L^-1)	Reference
HPLC	1.6 × 10^-13	⁹⁵95 Cao, L. W.; Wang, H.; Li, J. S.; Zhang, H. S.; J. Chromatogr. A 2005, 1063, 143.
GC-NPD^a a GC with a nitrogen phosphorus detector;	7.7 × 10^-11	⁹⁶96 Ábalos, M.; Bayona, J. M.; Ventura, F.; Anal. Chem. 1999, 71, 3531.
GC	9.0 × 10^-11	⁹⁷97 Kamarei, F.; Ebrahimzadeh, H.; Yamini, Y.; J. Hazard. Mater. 2010, 178, 747.
HPLC	6.8 × 10^-9	¹¹11 Lloret, S. M.; Legua, C. M.; Andrés, J. V.; Falcó, P. C.; J. Chromatogr. A 2004, 1035, 75.
GC-MS	4.1 × 10^-8	¹⁰10 Akyüz, M.; Ata, Ş.; J. Chromatogr. A 2006, 1129, 88.
Fluorescence	4.3 × 10^-8to 9.3 × 10^-8	³²32 Yu, J.; Zhang, C.; J. Mater. Chem. C 2020, 8, 16463.
Fluorescence	6.6 × 10^-8	⁹⁸98 Mallick, A.; El-Zohry, A. M.; Shekhah, O.; Yin, J.; Jia, J.; Aggarwal, H.; Emwas, A.-H.; Mohammed, O. F.; Eddaoudi, M.; J. Am. Chem. Soc. 2019, 141, 7245.
UV-Vis spectrophotometry	1.0 × 10^-7 to 1.0 × 10^-6	⁹⁹99 Chan, W. H.; Lee, A. W. M.; Wang, K.; Analyst 1994, 119, 2809.
Electrophoresis	1.4 × 10^-5to 3.3 × 10^-5	¹⁰⁰100 Matchett, W. H.; Brumley, W. C.; J. Liq. Chromatogr. Relat. Technol. 1997, 20, 79.
UV-Vis spectrophotometry^b b amines in ionic liquids. HPLC: high performance liquid chromatography; GC: gas chromatography; GC-MS: gas chromatography mass spectrometry; CTAB: cetyltrimethylammonium bromide.	5.0 × 10^-4 to 1.0 × 10^-3	¹⁰¹101 Stark, A.; Braun, O.; Ondruschka, B.; Anal. Sci. 2008, 24, 681.
Fluorescence	1.0 × 10^-3	¹⁰²102 Mohr, G. J.; Klimant, I.; Spichiger-Keller, U. E.; Wolfbeis, O. S.; Anal. Chem. 2001, 73, 1053.
3a and 4a (without CTAB)	9.71 × 10^-7-2.36 × 10^-6	this work
3a and 5a (with CTAB)	5.08 × 10^-7-7.00 × 10^-7	this work

Abs = \frac{{Abs}_{0} + {Abs}_{12} K_{12} {(c (a \min e))}^{2} + {Abs}_{13} K_{12} K_{13} {(c (a \min e))}^{3}}{1 + K_{12} {(c (a \min e))}^{2} + K_{12} K_{13} {(c (a \min e))}^{3}}

[1] *e-mail: vanderlei.machado@ufsc.br

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Chromogenic Chemosensors Based on Phenolic Imines for the Detection of Alkylamines and Lidocaine in Water and in the Vapor Phase