TiO2 nanoparticle-Coated 3D-Printed porous monoliths enabling highly sensitive speciation of inorganic Cr, As, and Se.

Post-printing functionalization can enhance the functionality and applicability of analytical devices manufactured using three-dimensional printing (3DP) technologies. In this study we developed a post-printing foaming-assisted coating scheme-through respective treatments with a formic acid (30%, v/v) solution and a sodium bicarbonate (0.5%, w/v) solution incorporating titanium dioxide nanoparticles (TiO2 NPs; 1.0%, w/v)-for in situ fabrication of TiO2 NP-coated porous polyamide monoliths in 3D-printed solid phase extraction columns, thereby enhancing the extraction efficiencies of Cr(III), Cr(VI), As(III), As(V), Se(IV), and Se(VI) for speciation of inorganic Cr, As, and Se species in high-salt-content samples when using inductively coupled plasma mass spectrometry. After optimizing the experimental conditions, the 3D-printed solid phase extraction columns with the TiO2 NP-coated porous monoliths extracted these species with 5.0- to 21.9-fold enhancements, relative to those obtained with the uncoated monolith, with absolute extraction efficiencies ranging from 84.5 to 98.3% and method detection limits ranging from 0.7 to 32.3 ng L-1. We validated the reliability of this multi-elemental speciation method through determination of these species in four reference materials [CASS-4 (nearshore seawater), SLRS-5 (river water), 1643f (fresh water), and Seronorm Trace Elements Urine L-2 (human urine); relative errors between certified and measured concentrations: 5.6 to +4.0%] and spike analyses of seawater, river water, agriculture waste, and human urine samples (spike recoveries: 96-104%; relative standard deviations of these measured concentrations all below 4.3%). Our results demonstrate that post-printing functionalization has great potential for future applicability in 3DP-enabling analytical methods.

Solution Foaming-Treated 3D-Printed monolithic packing for enhanced solid phase extraction of trace metals.

Post-printing treatment is a promising means of enhancing the performance of devices manufactured using conventional three-dimensional printing (3DP) technologies. In this study we developed a post-printing solution foaming process-involving respective treatment with formic acid (60%, v/v) and sodium bicarbonate (5%, w/v) solutions to generate CO2 as a foaming agent-to increase the surface roughness and porosity of the polyamide 6 (PA6) monolithic packing in a multimaterial fused deposition modeling 3D-printed solid phase extraction (SPE) column, thereby enhancing the extraction of Mn, Co, Ni, Cu, Zn, Cd, and Pb ions from complicated real samples prior to their determination using inductively coupled plasma mass spectrometry. After optimizing the column fabrication process, the solution foaming treatment process, the extraction conditions, and the automatic analytical system, the 3D-printed SPE column incorporating the solution foaming-treated PA6 monolithic packing extracted these metal ions with 18.9- to 42.0-fold enhancements, relative to those of the as-printed column, with absolute extraction efficiencies all greater than 94.3% and method detection limits ranging from 0.2 to 7.7 ng L-1. We verified the reliability and applicability of this method through analyses of the tested metal ions in several reference materials (CASS-4, SLEW-3, 1643f, and 2670a) and spike analyses of seawater, river water, ground water, and urine samples. We conclude that post-printing treatment can dramatically improve the performance of 3D-printed analytical devices.

4D-Printed Temperature-Controlled Flow-Actuated Solid-Phase Extraction Devices.

Four-dimensional printing (4DP) technologies can extend the functionality and applicability of manufactured analytical devices through employing stimuli-responsive materials. In this study, we used a photocurable resin of stimuli-responsive shape-memory polymers and digital light processing three-dimensional printing (3DP) to fabricate a smart sample pretreatment device featuring a solid-phase extraction (SPE) column and a temperature-controlled flow-actuated valve. Through manipulation of the temperatures and flow rates of the sample, eluent, and rinsing streams, we used this 4D-printed SPE device to extract Mn, Co, Ni, Cu, Zn, Cd, and Pb ions from high-salt content samples and remove the sample matrix prior to their determination by inductively coupled plasma mass spectrometry. After optimizing the valve design and operation and the analytical scheme, this device displayed competitive analytical performance-the method detection limits (MDLs) ranged from 0.7 to 22.1 ng L-1 for these metal ions (the MDLs ranged from 0.5 to 18.8 ng L-1 when validating the same printed SPE column using an online automatic system equipped with electric switching valves). Furthermore, we performed analyses of these metal ions in three reference materials (CASS-4, 1643f, and 2670a) and spike analyses of collected samples (seawater, ground water, river water, and human urine) to confirm the reliability and applicability of this analytical method. For the first time, 4DP has been used to fabricate a multi-functional, stimuli-responsive sample pretreatment device displaying analytical performance equal to that of a commercial apparatus. This novel approach builds upon the functionality and diversity of 3DP-enabling devices with the goal of developing more efficient analytical schemes.