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Title: Electrochemical pH regulation in droplet microfluidics

Journal Article · · Lab on a chip (Print)
DOI: https://doi.org/10.1039/d1lc00952d · OSTI ID:1978800

Here we report a method for electrochemical pH regulation in microdroplets generated in a microfluidic device. The key finding is that controlled quantities of reagents can be generated electrochemically in moving microdroplets confined within a microfluidic channel. Additionally, products generated at the anode and cathode can be isolated within descendant microdroplets. Specifically, ~5 nL water-in-oil microdroplets are produced at a T-junction and then later split into two descendant droplets. During splitting, floor-patterned microelectrodes drive water electrolysis within the aqueous microdroplets to produce H+ and OH-. This results in a change in the pHs of the descendant droplets. The droplet pH can be regulated over a range of 5.9 to 7.7 by injecting controlled amounts of charge into the droplets. When the injected charge is between -6.3 and 54.5 nC nL-1, the measured pH of the resulting droplets is within ±0.1 pH units of that predicted based on the magnitude of the injected charge. This technique can likely be adapted to electrogeneration of other reagents within microdroplets.

Research Organization:
University of Texas, Austin, TX (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); Robert A. Welch Foundation
Grant/Contract Number:
FG02-06ER15758
OSTI ID:
1978800
Journal Information:
Lab on a chip (Print), Journal Name: Lab on a chip (Print) Journal Issue: 3 Vol. 22; ISSN 1473-0197
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (56)

Fabrication of microfluidic systems in poly(dimethylsiloxane) journal January 2000
Effects of buffering conditions and culture pH on production rates and glycosylation of clinical phase I anti-melanoma mouse IgG3 monoclonal antibody R24: Buffering in Production and Glycosylation of MAb R24 journal May 2003
The Mechanism of Water Oxidation: From Electrolysis via Homogeneous to Biological Catalysis journal June 2010
Prediction of Ph-dependent Properties of Proteins journal May 1994
Graphene-polyaniline modified electrochemical droplet-based microfluidic sensor for high-throughput determination of 4-aminophenol journal June 2016
Electrochemical assessments of droplet contents in microfluidic channels. Application to the titration of heterogeneous droplets journal April 2021
“Smart” delivery of antisense oligonucleotides by anionic pH-sensitive liposomes journal April 2004
Thin-film IrO pH microelectrode for microfluidic-based microsystems journal August 2005
Size control over spherical silver nanoparticles by ascorbic acid reduction journal December 2010
The comparison of pKa determination between carbonic acid and formic acid and its application to prediction of the hydration numbers journal July 2008
Electrochemical detection of droplet content in microfluidic devices: Evidence of internal recirculating convection within droplets journal July 2017
Quantitative electrolysis of droplet contents in microfluidic channels. Concept and experimental validation journal October 2021
Electrochemical detection of droplet contents in polystyrene microfluidic chip with integrated micro film electrodes journal July 2014
An in line non-invasive optical system to monitor pH in cell and tissue culture journal June 2006
Generation of Natural pH Gradients in Microfluidic Channels for Use in Isoelectric Focusing journal June 2000
Sampling from Nanoliter Plugs via Asymmetrical Splitting of Segmented Flow journal August 2010
Continuous-Flow Polymerase Chain Reaction of Single-Copy DNA in Microfluidic Microdroplets journal January 2009
Measuring Rapid Enzymatic Kinetics by Electrochemical Method in Droplet-Based Microfluidic Devices with Pneumatic Valves journal June 2009
Recent Advances in Droplet Microfluidics journal November 2019
Emerging Droplet Microfluidics journal May 2017
Synthesis of Cesium Lead Halide Perovskite Nanocrystals in a Droplet-Based Microfluidic Platform: Fast Parametric Space Mapping journal February 2016
Compact Nanowire Sensors Probe Microdroplets journal July 2016
Unveiling the Shape Evolution and Halide-Ion-Segregation in Blue-Emitting Formamidinium Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform journal January 2018
Pick a Color MARIA: Adaptive Sampling Enables the Rapid Identification of Complex Perovskite Nanocrystal Compositions with Defined Emission Characteristics journal May 2018
Microfluidic Encapsulation of Pickering Oil Microdroplets into Alginate Microgels for Lipophilic Compound Delivery journal March 2016
An Integrated Microfluidic Processor for DNA-Encoded Combinatorial Library Functional Screening journal February 2017
Exploration of Near-Infrared-Emissive Colloidal Multinary Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform journal May 2018
Fast Detection and Flexible Microfluidic pH Sensors Based on Al-Doped ZnO Nanosheets with a Novel Morphology journal November 2019
Sensitive Detection of MMP9 Enzymatic Activities in Single Cell-Encapsulated Microdroplets as an Assay of Cancer Cell Invasiveness journal March 2017
Fluorescence-Activated Droplet Sorting for Single-Cell Directed Evolution journal May 2019
Optimum pH for Cr 6+ Co-removal with Mixed Cu 2+ , Zn 2+ , and Ni 2+ Precipitation journal January 2006
Light-Responsive and pH-Responsive DNA Microcapsules for Controlled Release of Loads journal July 2016
Concentration Enrichment, Separation, and Cation Exchange in Nanoliter-Scale Water-in-Oil Droplets journal January 2020
Substituent Effects and pH Profiles for Stability Constants of Arylboronic Acid Diol Esters
  • Martínez-Aguirre, Mayte A.; Villamil-Ramos, Raul; Guerrero-Alvarez, Jorge A.
  • The Journal of Organic Chemistry, Vol. 78, Issue 10 https://doi.org/10.1021/jo400617j
journal May 2013
External control of reactions in microdroplets journal July 2015
Rails and anchors: guiding and trapping droplet microreactors in two dimensions journal January 2011
Measuring rapid kinetics by a potentiometric method in droplet-based microfluidic devices journal January 2012
A droplet-based pH regulator in microfluidics journal January 2014
Electrochemistry, biosensors and microfluidics: a convergence of fields journal January 2015
Calculating the volume of elongated bubbles and droplets in microchannels from a top view image journal January 2015
Controlled droplet microfluidic systems for multistep chemical and biological assays journal January 2017
A microfluidic platform with pH imaging for chemical and hydrodynamic stimulation of intact oral biofilms journal January 2016
Glutathione- and pH-responsive nonporous silica prodrug nanoparticles for controlled release and cancer therapy journal January 2015
Microfluidic screening system based on boron-doped diamond electrodes and dielectrophoretic sorting for directed evolution of NAD(P)-dependent oxidoreductases journal January 2020
Microdroplet synthesis of azo compounds with simple microfluidics-based pH control journal January 2020
In-flow electrochemical detection of chemicals in droplets with pyrolysed photoresist electrodes: application as a module for quantification of microsampled dopamine journal January 2021
Filtering and continuously separating microplastics from water using electric field gradients formed electrochemically in the absence of buffer journal January 2021
pH-Responsive mechanised nanoparticles gated by semirotaxanes journal January 2009
Electrolysis in nanochannels for in situ reagent generation in confined geometries journal January 2011
Electrostatic charging and control of droplets in microfluidic devices journal January 2013
Single-enzyme analysis in a droplet-based micro- and nanofluidic system journal January 2013
Highly reproducible chronoamperometric analysis in microdroplets journal January 2013
Droplet Actuation by Electrowetting-on-Dielectric (EWOD): A Review journal May 2012
Monitoring and external control of pH in microfluidic droplets during microbial culturing journal January 2020
Real-time optical pH measurement in a standard microfluidic cell culture system journal January 2013
A Microfluidic pH Measurement Device with a Flowing Liquid Junction journal July 2017