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The deposition of nanoliter and subnanoliter volumes is important in chemical and biochemical droplet-based microfluidic systems. There are several techniques that have been established for the deposition/generation of small volumes including the use of surfaces with patterned differences in wettability. Many such methods require complex and time-consuming lithographic techniques. Here, we present a facile method for the fabrication of superhydrophobic surfaces with patterned hydrophilic regions by laser micromachining. A comprehensive study of fabrication parameters (laser machining speed, laser power, and patch size) on the material, patch wettability, and droplet volume is presented. Patch sizes as small as 100 μm diameter and as large as 1500 μm diameter were investigated, and volumes as low as 400 pL were observed. As an example application of such patterned materials and the deposition of small volumes, halide salts were preconcentrated on the hydrophilic patches, and their fluorescence quenching constants were rapidly calculated using a 3D-printed device coupled to a fluorescence spectrometer.

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Magnetic actuation is a droplet manipulation mechanism in digital microfluidics (DMF), where droplets can be actuated over a (super)hydrophobic surface with a magnetic force. Superparamagnetic particles or ferromagnetic liquids are added to the droplets to provide a "handle" by which the magnet can exert a force on the droplet. In this study, we present a novel method of magnetic manipulation, where droplets instead contain paramagnetic salts with molar magnetic susceptibilities (χ) approximately ≈10 000× < that for superparamagnetic particles. Droplet actuation is facilitated by low surface friction on fluorous silica nanoparticle-based superhydrophobic coatings, where <2 μN is required for reproducible droplet actuation. Different paramagnetic salts with χ from ≈4500 to 72 000 (× 10 cm mol) were used to make aqueous solutions of different concentration and tested for droplet actuation and sliding angle using permanent magnets (1.8-2.1 kG). Paramagnetic salts are compared in terms of solubility, minimum required concentration, and maximum droplet velocity before disengagement. There is a strong correlation between the magnetic susceptibility of the salt solution, its concentration, and ease of actuation. As an application example, droplets containing a paramagnetic salt and doxorubicin (leukemia drug) are magnetically actuated and interrogated using laser-induced fluorescence. Signal attenuation due to the MnCl salt was examined, and the Stern-Volmer quenching constant was determined.

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