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Reaction kinetic studies by compliance-induced ultra monodisperse microdroplets

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Reaction Kinetic Studies by Compliance-Induced

Ultra Monodisperse Microdroplets

Ali Kalantarifard, Abtin Saateh, Pinar Beyazkilic, and Caglar Elbuken

UNAM – National Nanotechnology Research Center and Institute of Materials Science and Nanotechnology, Bilkent University, Ankara, Turkey

Introduction

Microfluidics offer advantages for studying reaction kinetics due to high spatio-temporal resolution, the use of very low sample volumes and high sensitivity [1,2]. Droplet monodispersity plays a significant role in the reaction kinetic measurements since any variation in droplet size reflects itself as concentration variation. Here, we developed an ultra monodisperse droplet system to study the reaction kinetics involved in Polydopamine (PDA) polymerization and Aggregation Induced Quenching (AIQ) inhibition of PDA. Dopamine is a potential biomarker for neurological diseases such as schizophrenia, Huntington’s and Parkinson’s diseases. Understanding this reaction is a critical towards a functional assay.

Ultra Monodisperse Microdroplets

Microfluidic device

The photoluminescence emission spectra of the polydopamine (PDA) show that the concentration of the reagent and substrate (hydrogen peroxide and dopamine) plays a significant role on reaction kinetics [4,5]. Using our enhanced monodisperse droplet system, we investigate the reaction kinetics of the increased fluorescent emission of PDA.

We demonstrate enhancement of droplet monodispersity using off-chip compliances to minimize fluctuations due to flow sources. By adding compliant off-chip components (flexible tubings), we were able to significantly damp the flow fluctuations. The electrical droplet detection scheme we have developed gives comparable performance to more commonly

used optical detection method [3] and yields real-time droplet length analysis. Figure 3. Schematic of ultra monodisperse droplet system used for reaction kinetics investigation. Merging of H2O2and polydopamine droplets were studied.

Supports

References

Conclusion

1. Song H, Chen DL, Ismagilov RF, Angewandte chemie international edition. 2006;45(44):7336-56.

2. Sjostrom SL, Joensson HN, Svahn HA, Lab on a Chip. 2013;13(9):1754-61. 3. Basu AS, Lab on a Chip. 2013;13(10):1892-901.

4. Zhang X, Wang S, Xu L, Feng L, Ji Y, Tao L, et al, Nanoscale. 2012;4(18):5581-4. 5. Chen X, Yan Y, Müllner M, van Koeverden MP, Noi KF, Zhu W, et al, Langmuir. 2014;30(10):2921-5.

The ultra monodisperse droplet-based system provides a sensitive and automated platform to study precision reaction kinetics. Using an automated microfluidic device results reaction kinetics for varying reagent concentrations can be studied to investigate response curves and limit of detection for potential assays.

This work is supported by TÜBİTAK, The Scientific and Technological Research Council of Turkey, Project No: 215E086.

Time dependent reaction kinetics

The change of the fluorescence intensity of PDA due to the change of reaction time is studied. Time-dependent fluorescence spectra of PDA in the presence of 50 mM H2O2was

investigated with the droplet system (Fig. 5b) and verified with spectrometer results (Fig. 5a) Calculating the coefficient of variation (CV) of the droplet length, droplet monodispersity has

been analyzed. CV of the droplet length decreases from 2.12% to 0.19% using compliance damping. The ultra monodisperse droplets provide very precise concentration control for the segmented fluid.

Monodisperse droplets of two fluids to be mixed are formed individually and mixed so that the concentration of the final droplet is precisely regulated. After droplet merging, five long channel segments with the same length is used to characterize the reaction in the time scale.

Figure 1. Schematic illustration of T-junction monodisperse droplet generation and characterization setup.

Figure 2. Droplet length obtained using 20 cm and 100 cm – long silicone tubings as compliance unit.

Figure 4. Fabricated microfluidic device containing two T-junction droplet generation module, a passive droplet merging unit and long channel segments for temporal study of the reaction.

Figure 5. a) Bulk spectrometer fluorescence intensity at 490 nm in the presence of 1 mM, 5 mM and 10 mM H2O2 . b) Time-dependent fluorescence spectra of PDA inside droplets for 50 mM H2O2.

(a)

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Figure 1. Schematic illustration of T-junction monodisperse droplet generation and characterization setup.

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