Redox-Active Monolayers Self-Assembled on Gold Electrodes—Effect of Their Structures on Electrochemical Parameters and DNA Sensing Ability
Abstract
:1. Introduction
2. Results
2.1. Electrochemical Characterization of Gold Electrodes Modified with Symmetric TPY/M(II)/TPY Complexes
2.2. Electrochemical Characterization of Gold Electrodes Modified with Asymmetric DPM/M(II)/TPY Complexes
2.3. Comparison of Electrochemical Parameters of Symmetric TPY/M(II)/TPY and Asymmetric DPM/M(II)/TPY Sensing Platforms Functionalized with Ethanolamine and ssDNA
2.4. Electrochemical Determination of Target ssDNA Using Gold Electrodes Modified with Symmetric TPY/M(II)/TPY-ssDNA and Asymmetric DPM/M(II)/TPY-ssDNA Complexes
3. Discussion
4. Materials and Methods
- The spontaneous self-assembly of 0.01 mM AHT and 1 mM MBL layer formation—3 h, room temperature (RT), DCM: MeOH (1:1, v/v); the electrodes were immersed in tubes containing 180 µL of modifying solution; after modification electrodes were carefully rinsed with a mixture of DCM: MeOH
- Reaction between the amine groups of AHT and NHS of 0.1 mM TPY-NHS—1h, RT, DCM: MeOH (1:1); the electrodes were immersed in tubes containing 180 µL of modifying solution; after modification electrodes were carefully rinsed with a mixture of DCM: MeOH
- Complexation of 1mM Me (II) (Co (II) or Cu (II)) metal ions by 0.1 mM TPY-NHS—1h, RT, DCM: MeOH (1:1); the electrodes were immersed in tubes containing 180 µL of modifying solution; after modification electrodes were carefully rinsed with a mixture of DCM: MeOH
- The closure of the coordination sphere of the Me (II) metal ions by 0.1 mM TPY-NHS—1h, RT, DCM: MeOH (1:1 volume ratio); the electrodes were immersed in tubes containing 180 µL of modifying solution; after modification electrodes were carefully rinsed with: a mixture of DCM: MeOH, MeOH, sterilized Milli-Q water and MES buffer pH 7.0
- Reaction between amine groups of 10 μM NH2-NC3 probe and NHS of 0.1 mM TPY-NHS—1h, RT, MES pH 7.0, the electrodes were fixed upside down, 5 µL droplets of solution were spotted on each surface and the electrodes were covered with tubes; after modification electrodes were carefully rinsed with MES pH 7.0 and PBS pH 7.4
- Deactivation of unbound NHS groups with 1 M solution of EA, 10 min PBS pH 7.4, the electrodes were fixed upside down, 5 µL droplets of solution were spotted on each surface and electrodes were covered with tubes.
- The spontaneous self-assembly of 0.01 mM DPM-SH and 1 mM MBL layer formation—3 h, RT; the electrodes were immersed in tubes containing 180 µL of modifying solution; after modification electrodes were carefully rinsed with a mixture of DCM: MeOH
- Complexation of 1 mM M (II) (Co (II) or Cu (II)) metal ions by 0.1 mM TPY-NHS—1 h, RT; the electrodes were immersed in tubes containing 180 µL of modifying solution; after modification electrodes were carefully rinsed with a mixture of DCM: MeOH
- The closure of the coordination sphere of the M(II) metal ions by 0.1 mM TPY-NHS—1 h, RT; DCM: MeOH (1:1) the electrodes were immersed in tubes containing 180 µL of modifying solution; after modification electrodes were carefully rinsed with: a mixture of DCM: MeOH; MeOH, sterilized Milli-Q water and MES buffer pH 7.0
- Reaction between amine groups of 10 μM NH2-NC3 probe and NHS of 0.1 mM TPY-NHS—1 h, RT; MES pH 7.0; the electrodes were fixed upside down, 5 µL droplets of solution were spotted on each surface and the electrodes were covered with tubes; after modification electrodes were carefully rinsed with MES pH 7.0 and PBS pH 7.4
- Deactivation of unbound NHS groups with 1 M solution of EA, 10 min, PBS pH 7.4, RT; the electrodes were fixed upside down, 5 µL droplets of solution were spotted on each surface and the electrodes were covered with tubes.
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Sample Availability: Samples of the Terpy NHS ester are available from the authors. |
TPY | TPY/Co(II) | TPY/Co(II)/TPY/EA | TPY/Co(II)/TPY/ssDNA | ||||
---|---|---|---|---|---|---|---|
CV Reduction | |||||||
ERED, mV | IRED, µA | ERED, mV | IRED, µA | ERED, mV | IRED, µA | ERED, mV | IRED, µA |
271 ± 9 | 0.08 ± 0.01 | 263 ± 3 | 0.23 ± 0.006 | 266 ± 278 | 0.14 ± 0.05 | 294 ± 14 | 0.21 ± 0.03 |
CV Oxidation | |||||||
EOX, mV | IOX, µA | EOX, mV | IOX, µA | EOX, mV | IOX, µA | EOX, mV | IOX, µA |
317 ± 7 | 0.007 ± 0.0005 | 309 ± 2 | 0.09 ± 0.002 | 346 ± 9 | 0.09 ± 0.006 | 320 ± 8 | 0.11 ± 0.005 |
OSWV | |||||||
E, mV | I, µA | E, mV | I, µA | E, mV | I, µA | E, mV | I, µA |
326 ± 5 | 1.43 ± 0.07 | 273 ± 4 | 1.94 ± 0.07 | 329 ± 24 | 1.90 ± 0.27 | 288 ± 16 | 1.20 ± 0.23 |
TPY | TPY/Cu(II) | TPY/Cu(II)/TPY/EA | TPY/Cu(II)/TPY/ssDNA | ||||
CV Reduction | |||||||
ERED, mV | IRED, µA | ERED, mV | IRED, µA | ERED, mV | IRED, µA | ERED, mV | IRED, µA |
271 ± 5 | 0.08 ± 0.02 | 181 ± 21 | 0.11 ± 0.03 | 216 ± 34 | 0.09 ± 0.03 | 196 ± 10 | 0.09 ± 0.02 |
CV Oxidation | |||||||
EOX, mV | IOX, µA | EOX, mV | IOX, µA | EOX, mV | IOX, µA | EOX, mV | IOX, µA |
317 ± 7 | 0.007 ± 0.0005 | 242 ± 10 | 0.25 ± 0.06 | 250 ± 17 | 0.12 ± 0.02 | 250 ± 7 | 0.12 ± 0.01 |
OSWV | |||||||
E, mV | I, µA | E, mV | I, µA | E, mV | I, µA | E, mV | I, µA |
326 ± 5 | 1.43 ± 0.07 | 292 ± 47 | 2.80 ± 0.92 | 304 ± 24 | 1.91 ± 0.60 | 330 ± 36 | 1.51 ± 0.09 |
DPM | DPM/Co(II) | DPM/Co(II)/TPY/EA | DPM/Co(II)/TPY/ssDNA | ||||
---|---|---|---|---|---|---|---|
CV Reduction | |||||||
ERED, mV | IRED, µA | ERED, mV | IRED, µA | ERED, mV | IRED, µA | ERED, mV | IRED, µA |
252 ± 7 | 0.26 ± 0.05 | 247 ± 7 | 0.24 ± 0.02 | 267 ± 15 | 0.15 ± 0.02 | 273 ± 17 | 0.14 ± 0.02 |
CV Oxidation | |||||||
EOX, mV | IOX, µA | EOX, mV | IOX, µA | EOX, mV | IOX, µA | EOX, mV | IOX, µA |
316 ± 5 | 0.12 ± 0.01 | 341 ± 5 | 0.09 ± 0.002 | 304 ± 18 | 0.08 ± 0.02 | 314 ± 13 | 0.12 ± 0.002 |
OSWV | |||||||
E, mV | I, µA | E, mV | I, µA | E, mV | I, µA | E, mV | I, µA |
335 ± 2 | 1.64 ± 0.27 | 267 ± 3 | 1.70 ± 0.70 | 304 ± 13 | 1.79 ± 0.20 | 321 ± 23 | 1.34 ± 0.24 |
DPM | DPM/Cu(II) | DPM/Cu(II)/TPY/EA | DPM/Cu(II)/TPY/ssDNA | ||||
CV Reduction | |||||||
ERED, mV | IRED, µA | ERED, mV | IRED, µA | ERED, mV | IRED, µA | ERED, mV | IRED, µA |
252 ± 7 | 0.13 ± 0.05 | 230 ± 4 | 0.17 ± 0.02 | 212 ± 25 | 0.07 ± 0.02 | 201 ± 8 | 0.07 ± 0.03 |
CV Oxidation | |||||||
EOX, mV | IOX, µA | EOX, mV | IOX, µA | EOX, mV | IOX, µA | EOX, mV | IOX, µA |
275 ± 5 | 0.05 ± 0.01 | 359 ± 3 | 0.29 ± 0.02 | 241 ± 13 | 0.11 ± 0.01 | 265 ± 8 | 0.14 ± 0.05 |
OSWV | |||||||
E, mV | I, µA | E, mV | I, µA | E, mV | I, µA | E, mV | I, µA |
335 ± 2 | 1.64 ± 0.27 | 331 ± 14 | 3.57 ± 1.41 | 295 ± 12 | 1.85 ± 0.11 | 275 ± 6 | 1.45 ± 0.25 |
TPY-Co(II)-TPY | TPY-Cu(II)-TPY | DPM-Co(II)-TPY | DPM-Cu(II)-TPY | |||||
---|---|---|---|---|---|---|---|---|
EA | ssDNA | EA | ssDNA | EA | ssDNA | EA | ssDNA | |
α | 0.52 ± 0.006 | 0.63 ± 0.02 | 0.24 ± 0.05 | 0.27 ± 0.006 | 0.60 ± 0.01 | 0.77 ± 0.003 | 0.23 ± 0.02 | 0.38 ± 0.03 |
k [s−1] | 1.06 ± 0.01 | 1.71 ± 0.20 | 0.84 ± 0.01 | 1.11 ± 0.16 | 1.08 ± 0.12 | 1.41 ± 0.09 | 1.22 ± 0.13 | 1.25 ± 0.07 |
Surface Coverage (Γ) [×10−11 mol/cm2] | ||||||||
---|---|---|---|---|---|---|---|---|
TPY-M(II)-TPY | DPM-M(II)-TPY | |||||||
EA | ssDNA | EA | ssDNA | |||||
ox | red | ox | red | ox | red | ox | red | |
Co(II) | 4.29 | 4.61 | 4.81 | 6.54 | 2.28 | 4.37 | 3.44 | 5.17 |
Cu(II) | 3.53 | 2.35 | 3.69 | 2.77 | 2.88 | 1.76 | 3.57 | 2.45 |
Type of SAM | LOD, fM | Rij = Sj/Si | The Tested Linear Concentration Range, fM |
---|---|---|---|
TPY-Co(II)-TPY-ssDNA | 2.13 | 0.22 | From 1 to 20 |
TPY-Cu(II)-TPY-ssDNA | 1.58 | 0.13 | From 1 to 20 |
DPM-Co(II)-TPY-ssDNA | 5.43 | 0.23 | From 1 to 20 |
DPM-Cu(II)-TPY-ssDNA | 1.01 | 0.30 | From 1 to 20 |
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Malecka, K.; Menon, S.; Palla, G.; Kumar, K.G.; Daniels, M.; Dehaen, W.; Radecka, H.; Radecki, J. Redox-Active Monolayers Self-Assembled on Gold Electrodes—Effect of Their Structures on Electrochemical Parameters and DNA Sensing Ability. Molecules 2020, 25, 607. https://doi.org/10.3390/molecules25030607
Malecka K, Menon S, Palla G, Kumar KG, Daniels M, Dehaen W, Radecka H, Radecki J. Redox-Active Monolayers Self-Assembled on Gold Electrodes—Effect of Their Structures on Electrochemical Parameters and DNA Sensing Ability. Molecules. 2020; 25(3):607. https://doi.org/10.3390/molecules25030607
Chicago/Turabian StyleMalecka, Kamila, Shalini Menon, Gopal Palla, Krishnapillai Girish Kumar, Mathias Daniels, Wim Dehaen, Hanna Radecka, and Jerzy Radecki. 2020. "Redox-Active Monolayers Self-Assembled on Gold Electrodes—Effect of Their Structures on Electrochemical Parameters and DNA Sensing Ability" Molecules 25, no. 3: 607. https://doi.org/10.3390/molecules25030607