Enhanced Chemical Synthesis at Soft Interfaces: A Universal Reaction-Adsorption Mechanism in Microcompartments

Fallah-Araghi, Ali; Meguellati, Kamel; Baret, Jean‐Christophe; Harrak, Abdeslam El; Mangeat, Thomas; Karplus, Martin; Ladame, Sylvain; Marques, Carlos M.; Griffiths, Andrew D.

doi:10.1103/physrevlett.112.028301

Cited by 239 publications

(316 citation statements)

References 27 publications

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“…Thus, the present study strongly supports the idea that the accelerated reaction rate for the systems we have studied originates from microdroplet confinement. This same mechanism agrees with a previous study by FallahAraghi et al (39) in which they reacted a nonfluorescent amine with a very weakly fluorescent aldehyde to form a fluorescent imine in water droplets (16-68 μm in diameter) surrounded by fluorinated oil. Again, a significant enhancement in reaction rate compared with the bulk was observed, and the rate was reported to be inversely proportional to the radius of the microdroplet.…”

Section: Discussionsupporting

confidence: 81%

“…It is becoming well established that the reaction rate in microdroplets is remarkably faster than the same reaction in bulk solution (20,21,(37)(38)(39). Moreover, in some cases products are found in the droplet reactions that are different from those in the bulk (40).…”

Section: Discussionmentioning

confidence: 99%

“…Again, a significant enhancement in reaction rate compared with the bulk was observed, and the rate was reported to be inversely proportional to the radius of the microdroplet. Clearly, these results have many important possible implications ranging from the kinetics of reactions inside a cell to the possible role confinement has played in the origin of life (39,41,42).…”

Section: Discussionmentioning

confidence: 99%

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Microdroplet fusion mass spectrometry for fast reaction kinetics

Lee

Kim

Nam

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

206

258

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We investigated the fusion of high-speed liquid droplets as a way to record the kinetics of liquid-phase chemical reactions on the order of microseconds. Two streams of micrometer-size droplets collide with one another. The droplets that fused (13 μm in diameter) at the intersection of the two streams entered the heated capillary inlet of a mass spectrometer. The mass spectrum was recorded as a function of the distance x between the mass spectrometer inlet and the droplet fusion center. Fused droplet trajectories were imaged with a high-speed camera, revealing that the droplet fusion occurred approximately within a 500-μm radius from the droplet fusion center and both the size and the speed of the fused droplets remained relatively constant as they traveled from the droplet fusion center to the mass spectrometer inlet. Evidence is presented that the reaction effectively stops upon entering the heated inlet of the mass spectrometer. Thus, the reaction time was proportional to x and could be measured and manipulated by controlling the distance x. Kinetic studies were carried out in fused water droplets for acid-induced unfolding of cytochrome c and hydrogen-deuterium exchange in bradykinin. The kinetics of the former revealed the slowing of the unfolding rates at the early stage of the reaction within 50 μs. The hydrogendeuterium exchange revealed the existence of two distinct populations with fast and slow exchange rates. These studies demonstrated the power of this technique to detect reaction intermediates in fused liquid droplets with microsecond temporal resolution.mass spectrometry | liquid microdroplets | reaction kinetics | protein unfolding | hydrogen-deuterium isotope exchange T ime-resolved measurements of reaction intermediates are crucial for understanding the fast kinetics of chemical reactions. Various approaches have been implemented to improve the temporal resolution of kinetic measurements in liquid reactions (1, 2), which are often limited by the mixing time. One approach for improving the mixing time involves the use of turbulent flow to increase the shear stress in fluid channels (3). Another approach is to stimulate the rapid initiation of a reaction by photo-triggered initiation (4), electron transfer (5), or temperature jump/rise (6). A small-size reactor was also used for rapid mixing so that the time required for diffusion-dependent mixing is minimized (7-10).Among various methods for detecting reaction intermediates, mass spectrometry has been a powerful tool for probing reaction products because it can discriminate similar species by their mass-to-charge ratio while simultaneously measuring multiple species. Time-resolved mass spectrometry (11) has been widely used for measuring the kinetics of protein-ligand complexation, organometallic compound formation, and enzyme-catalyzed processes. Despite these efforts for improving temporal resolution, time-resolved mass spectrometry has been limited to the millisecond timescale, with a recent achievement of 300 μs (12).A major obstacle for imp...

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Section: Discussionsupporting

confidence: 81%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Microdroplet fusion mass spectrometry for fast reaction kinetics

Lee

Kim

Nam

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

206

258

View full text Add to dashboard Cite

show abstract

“…Performing reactions within droplets can have a profound impact on the reaction kinetics. For example, when imine synthesis was performed in emulsion droplets, the apparent equilibrium constant and the forward rate constant were found to be inversely proportional to the droplet radius [60].…”

Section: Droplet-based Chemical Synthesismentioning

confidence: 99%

Droplet microfluidics: A tool for biology, chemistry and nanotechnology

Mashaghi

Abbaspourrad

Weitz

et al. 2016

TrAC Trends in Analytical Chemistry

311

188

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The ability to perform laboratory operations on small scales using miniaturized devices provides numerous benefits, including reduced quantities of reagents and waste as well as increased portability and controllability of assays. These operations can involve reaction components in the solution phase and as a result, their miniaturization can be accomplished through microfluidic approaches. One such approach, droplet microfluidics, provides a high-throughput platform for a wide range of assays and approaches in chemistry, biology and nanotechnology. We highlight recent advances in the application of droplet microfluidics in chipbased technologies, such as single-cell analysis tools, small-scale cell cultures, in-droplet chemical synthesis, high-throughput drug screening, and nanodevice fabrication.

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“…When additional species are added to the system, these may accumulate at the interface; this is exemplified by amphiphilic surfactants, the adsorption of which to interfaces can be used to modify interfacial properties, such as surface tension. This adsorption of molecules also allows the interfaces to be used as platforms for chemical synthesis [6] and formation of nanoparticles [7]. It has long been recognised that liquid interfaces potentially provide elegant and convenient templates for the construction of dense and ordered structures.…”

Section: Introductionmentioning

confidence: 99%

Complex Molecules at Liquid Interfaces: Insights from Molecular Simulation

Cheung

2014

Advances in Chemistry

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The behaviour of complex molecules, such as nanoparticles, polymers, and proteins, at liquid interfaces is of increasing importance in a number of areas of science and technology. It has long been recognised that solid particles adhere to liquid interfaces, which provides a convenient method for the preparation of nanoparticle structures or to modify interfacial properties. The adhesion of proteins at liquid interfaces is important in many biological processes and in a number of materials applications of biomolecules. While the reduced dimensions of these particles make experimental investigation challenging, molecular simulations provide a natural means for the study of these systems. In this paper I will give an overview of some recent work using molecular simulation to investigate the behaviour of complex molecules at liquid interfaces, focusing on the relationship between interfacial adsorption and molecular structure, and outline some avenues for future research.

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Enhanced Chemical Synthesis at Soft Interfaces: A Universal Reaction-Adsorption Mechanism in Microcompartments

Cited by 239 publications

References 27 publications

Microdroplet fusion mass spectrometry for fast reaction kinetics

Microdroplet fusion mass spectrometry for fast reaction kinetics

Droplet microfluidics: A tool for biology, chemistry and nanotechnology

Complex Molecules at Liquid Interfaces: Insights from Molecular Simulation

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