4D-printed programmable sample-/eluent-actuated solid-phase extraction device for trace metal analysis

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.

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_a of CEA) due to swelling of the stem. Subsequently, they sequentially open upon loading an acidic eluent (pH < pK_a 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^-1. 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.

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.