Communication
significant optical changes observed (Δ) were considered as logic gates with other novel technologies, such as “lab-on-a-
2
+
output = 1, else output = 0. As expected, the presence of Fe
1 ppm) in a water solution of 2 (15 ppm, 0.048 m ) resulted range of applications in the analytical and materials sciences.
in an increase in the absorbance intensity at λabs = 560 nm
output A). The output A = 1 level (here Δ ≥ 0.1 au) was not
chip” and even “lab-on-a-molecule”, could bring about a broad
(
M
CCDC 1427073 (for 4) contains the supplementary crystallographic
(
5
2+
60
3+
3+
Figure 6).
(
Acknowledgments
Research supported by the University of Ontario Institute of
Technology, start-up grant (156057-2700) and by the Natural
Sciences and Engineering Research Council of Canada (NSERC)
through a Discovery Grant (RGPIN-2016-05823).
Keywords: Sensors · Cations · Metal–ligand recognition ·
Molecular logic · N ligands
Figure 6. Logic circuit for the four-input and four-output logic gate system.
Each output is separated for clarity. Given that the output at λabs = 560 nm
[1] a) O. Han, Metallomics 2011, 3, 103–109; b) D. J. A. Netz, M. Stuempfig,
C. Dore, U. Muehlenhoff, A. J. Pierik, R. Lill, Nat. Chem. Biol. 2010, 6, 758–
depends only on the presence of Fe2+, the logic circuit is not shown.
7
65.
[
2] C. P. Wen, J. H. Lee, Y.-P. Tai, C. Wen, S. B. Wu, M. K. Tsai, D. P. H. Hsieh,
H.-C. Chiang, C. A. Hsiung, C. Y. Hsu, X. Wu, Cancer Res. 2014, 74, 6589–
The response at 400 nm (output B) was positive (here Δ
0.012 au) in the presence of Ru (trial 3). The presence of
4
00
3+
≥
6
597.
2
+
3+
Zn together with Ru resulted in disappearance of the signal,
[3] G. M. Bishop, S. R. Robinson, Q. Liu, G. Perry, C. S. Atwood, M. A. Smith,
2+
that is, output B = 0 (trial 10). Thus, by using Zn ions as an
input, NOT gate was implemented followed by AND gate join-
ing Zn and Ru inputs, which resulted in an INHIBIT logic
Dev. Neurosci. 2002, 24, 184–187.
4] A. S. Prasad, Ann. Intern. Med. 1996, 125, 142–143.
5] J. C. King, Am. J. Clin. Nutr. 2011, 94, 679S–684S.
6] J. M. Flinn, P. L. Bozzelli, P. A. Adlard, A. M. Railey, Front. Aging Neurosci.
[
[
[
2
+
3+
3+
2+
gate. On the other hand, a mixture of Ru with either Fe OR
2014, 6, 00174.
3
+
3+
Fe (trial 6 or 9, respectively) as well as a mixture of Ru with
[7] L. C. Costello, R. B. Franklin, Mol. Cancer 2006, 5, 17.
[8] G. J. Fosmire, Am. J. Clin. Nutr. 1990, 51, 225–227.
[9] a) B. A. Albani, B. Peña, N. A. Leed, N. A. B. G. de Paula, C. Pavani, M. S.
Baptista, K. R. Dunbar, C. Turro, J. Am. Chem. Soc. 2014, 136, 17095–
2
+
3+
3+
2+
3+
both Fe AND Fe (trial 12) and even Ru with Fe , Fe ,
2
+
and Zn (trial 16) resulted in a positive (output B = 1) response.
The presence of Zn2+ together with either Fe (trial 8) or Fe
trial 11) resulted in an insignificant optical response (out-
put B = 0, Δ400 < 0.012 au). The output at 290 nm was positive
2+
3+
1
7101; b) B. Peña, A. David, C. Pavani, M. S. Baptista, J.-P. Pellois, C. Turro,
(
K. R. Dunbar, Organometallics 2014, 33, 1100–1103.
[10] P. Westerhoff, S. Lee, Y. Yang, G. W. Gordon, K. Hristovski, R. U. Halden, P.
Herckes, Environ. Sci. Technol. 2015, 49, 9479–9488.
11] a) C. Luo, S. Wang, H. Liu, Angew. Chem. Int. Ed. 2007, 46, 7636–7639;
Angew. Chem. 2007, 119, 7780–7783; b) M. A. Hanif, I. I. Ebralidze, J. H.
Horton, Appl. Surf. Sci. 2013, 280, 836–844.
[12] A. Bergamo, C. Gaiddon, J. H. M. Schellens, J. H. Beijnen, G. Sava, J. Inorg.
Biochem. 2012, 106, 90–99.
[13] a) P. L. Croot, P. Laan, Anal. Chim. Acta 2002, 466, 261–273; b) H. Tamura,
K. Goto, T. Yotsuyanagi, M. Nagayama, Talanta 1974, 21, 314–318; c) N.
Donato, D. Aloisio, S. G. Leonardi, G. Neri, IEEE Sens. J. 2015, 15, 3196–
output C = 1, Δ290 ≥ 0.17 au) if Fe3 and/or Ru was/were
+
3+
(
[
present in the system (trials 3, 4, and 9). The presence of either
2
+
2+
2+
2+
Fe or Zn or both Fe AND Zn inhibited output C. The
fluorescence emission output at 360 nm was positive (out-
2+
put D = 1, if Δf360 ≥ 2000 au) in the presence of Zn (trial 5).
However, the presence of Fe AND at least one of the other
ions (Fe or Ru ) INHIBITed fluorescence.
2+
3
+
3+
3
200; d) N. O. Laschuk, I. I. Ebralidze, S. Quaranta, S. T. W. Kerr, J. G. Egan,
S. Gillis, F. Gaspari, A. Latini, O. V. Zenkina, Mater. Des. 2016, 107, 18–25.
14] a) C. R. Lohani, J.-M. Kim, K.-H. Lee, Bioorg. Med. Chem. Lett. 2009, 19,
[
Conclusions
6
069–6073; b) U. Fegade, S. Tayade, G. K. Chaitanya, S. Attarde, A. Kuwar,
In summary, we developed a promising sensing platform for
the rapid and sensitive detection of Fe , Fe , Ru , and Zn
J. Fluoresc. 2014, 24, 675–681; c) A. Luo, H. Wang, Y. Wang, Q. Huang, Q.
Zhang, Spectrochim. Acta Part A 2016, 168, 37–44.
2+
3+
3+
2+
[
15] a) J. Peng, W. Xu, C. L. Teoh, S. Han, B. Kim, A. Samanta, J. C. Er, L. Wang,
L. Yuan, X. Liu, Y.-T. Chang, J. Am. Chem. Soc. 2015, 137, 2336–2342; b)
J. H. Choi, J. Y. Ryu, Y. J. Park, H. Begum, H.-R. Park, H. J. Cho, Y. Kim, J.
Lee, Inorg. Chem. Commun. 2014, 50, 24–27; c) J.-R. Lin, C.-J. Chu, P. Ven-
katesan, S.-P. Wu, Sens. Actuators B 2015, 207, 563–570.
16] a) T. Suoranta, M. Niemelä, P. Perämäki, Talanta 2014, 119, 425–429; b)
E. Zambrzycka, U. Kiedysz, A. Z. Wilczewska, B. Lesniewska, B. Godlewska-
Zylkiewicz, Anal. Methods 2013, 5, 3096–3105.
ions in aqueous solutions; this platform is potentially applicable
for the analysis of environmental, food, biological, and biomedi-
cal systems. Unique responses from these four metal cations
were detected by the combination of UV/Vis and fluorescence
spectroscopy. To get fundamental understanding of this sens-
ing system, metal–ligand stoichiometries were studied. The cor-
responding metal binding events were directly translated into
distinct colorimetric and spectroscopic logic outputs. By utiliz-
ing all acquired knowledge we were able to apply molecular
logic (Boolean logic operations) to describe the interactions be-
tween the ligand (as a logic gate) and the four target cations
[
[17] S. Goodwin, A. M. Gade, M. Byrom, B. Herrera, C. Spears, E. V. Anslyn,
A. D. Ellington, Angew. Chem. Int. Ed. 2015, 54, 6339–6342; Angew. Chem.
2015, 127, 6437–6440.
[
18] a) L. You, D. Zha, E. V. Anslyn, Chem. Rev. 2015, 115, 7840–7892; b) Z.
Zhang, D. S. Kim, C.-Y. Lin, H. Zhang, A. D. Lammer, V. M. Lynch, I. Popov,
O. Š. Miljanić, E. V. Anslyn, J. L. Sessler, J. Am. Chem. Soc. 2015, 137, 7769–
7774.
(
four logical inputs). We believe that the combination of these
Eur. J. Inorg. Chem. 0000, 0–0
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