Background: To integrate valves, manifolds, and solid-phase extraction (SPE) columns into a compact device is technically difficult. Four-dimensional printing (4DP) technologies, employing stimuli-responsive materials in three-dimensional printing (3DP), are revolutionizing the fabrication, functionality, and applicability of stimuli-responsive analytical devices that can show time-dependent shape programming to enable more complex geometric designs and functions. However, 4D-printed stimuli-responsive actuators and valves utilized to control flowing streams in SPE applications remain rare. The tunable stimuli-responsive 4D-printed flow control actuators and valves with the capability of the programmable actuation can be used to manipulate flowing streams and simplify the automation of a conventional SPE scheme.
Results: We employed digital light processing three-dimensional printing (3DP), bisphenol A ethoxylate dimethacrylate-based photocurable resins, and 2-carboxyethyl acrylate (CEA)-incorporated flexible photocurable resins to fabricate an SPE column positioned between two [H]-responsive flow-actuated needle valves. The two valves sequentially close after loading an alkaline sample (pH > pK of CEA) due to swelling of the stem. Subsequently, they sequentially open upon loading an acidic eluent (pH < pK of CEA; deswelling of the stem). The optimized device enabled a semi-automatic SPE scheme for Mn, Co, Ni, Cu, Zn, Cd, and Pb ions and showed competitive performance when coupled with inductively coupled plasma mass spectrometry-with the method detection limits ranging from 0.5 to 5.9 ng L. We validated the reliability and applicability of this method by analyzing the metal ions in reference materials (CASS-4, SLRS-5, 1643f, and Trace Elements Urine L-2) and spike analyses of natural water and human urine samples.
Significance: To the best of our knowledge, our device is the first demonstration of an SPE scheme performed by the programmable actuation of 4D-printed stimuli-responsive flow control valves, highlighting the analytical applicability of the tunable stimuli-responsive 4D-printed parts and the promising capability of 4DP technologies in advancing conventional sample pretreatment devices.
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| http://dx.doi.org/10.1016/j.aca.2024.343536 | DOI Listing |
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