Direct photoimmobilization of extraction disks on "green state" 3D printed devices.

Post-curing is essential to improve the mechanical properties of 3D printed parts fabricated by stereolithography (SLA), since right after 3D printing they remain in a "green state". It means that the 3D printed parts have reached their final shape, but the polymerization reaction has not been yet completed. Herein, we take advantage of the tacky partially polymerized surface of "green state" SLA 3D printed parts to immobilize extraction disks and miniature magnets, which after UV post-curing, become permanently attached to the 3D printed part resulting in a rotating-disk sorptive extraction device (RDSE). The developed "stick & cure" procedure is reagent-free and does not require any additional preparation time, specialized skills, or instrumentation. As proof of concept, 3D printed RDSE devices with immobilized chelating disks have been applied to the simultaneous extraction of 14 trace metals prior to ICP-OES determination, featuring LODs between 0.03 and 1.27 µg L-1, and an excellent device-to-device reproducibility (n = 5, RSD = 2.7-8.3%). The developed method was validated using certified wastewater and soil reference samples, and satisfactory spiking recoveries were obtained in the analysis of highly polluted solid waste treatment plant leachates (89-110%). In addition, exploiting the versatility of 3D printing, nine RDSE devices with different shapes were fabricated. Their performance was evaluated and compared for the fast extraction of the highly toxic Cr (VI) as its 1,5-diphenylcarbazide complex in reversed-phase mode, showing different extraction performance on depending on the shape of the 3D printed RDSE device.

3D printed device for the automated preconcentration and determination of chromium (VI).

A 3D printed device for the fully automated disk-based solid-phase extraction (SPE) of Cr (VI) from water samples has been fabricated. The compatibility of the use of organic solvents for analyte elution with 3D printed flow devices based on polymers fabricated using stereolithograph​y has been evaluated. The developed methodology comprises the complexation of Cr (VI) with 1, 5-diphenylcarbazide (DPC) in acidic medium and the subsequent retention of the complex in a SBD-RPS disk contained within the 3D printed device. A multisyringe flow injection analysis system with online spectrophotometric detection has been used for the automation of the method. The fabricated 3D printed device integrates the different components of the flow analysis manifold, including connectors and mixers, being a powerful approach towards the reproducible construction of highly integrated flow-based manifolds. The extracted Cr (VI)-DPC complex is eluted with a mixture of methanol- sulfuric acid and quantified at 540 nm. The effect on the analytical signal and the optimization of variables were evaluated using multivariate and univariate techniques. A detection limit of 1 ng Cr (VI) and a linear working range of 3.2-600 ng Cr (VI) were obtained using a sample volume of 2 ml. The intra-day and inter-day RSDs were 4.8% (10 µg L-1, n = 12) and 3.4% (n = 5, different day with a different disk), respectively. The applicability of the fabricated 3D printed device has been proved by the determination of Cr (VI) in groundwater, surface water and leachates.

3D printed device including disk-based solid-phase extraction for the automated speciation of iron using the multisyringe flow injection analysis technique.

The development of advanced manufacturing techniques is crucial for the design of novel analytical tools with unprecedented features. Advanced manufacturing, also known as 3D printing, has been explored for the first time to fabricate modular devices with integrated features for disk-based automated solid-phase extraction (SPE). A modular device integrating analyte oxidation, disk-based SPE and analyte complexation has been fabricated using stereolithographic 3D printing. The 3D printed device is directly connected to flow-based analytical instrumentation, replacing typical flow networks based on discrete elements. As proof of concept, the 3D printed device was implemented in a multisyringe flow injection analysis (MSFIA) system, and applied to the fully automated speciation, SPE and spectrophotometric quantification of Fe in water samples. The obtained limit of detection for total Fe determination was 7ng, with a dynamic linear range from 22ng to 2400ng Fe (3mL sample). An intra-day RSD of 4% (n = 12) and an inter-day RSD of 4.3% (n = 5, 3mL sample, different day with a different disk), were obtained. Incorporation of integrated 3D printed devices with automated flow-based techniques showed improved sensitivity (85% increase on the measured peak height for the determination of total Fe) in comparison with analogous flow manifolds built from conventional tubing and connectors. Our work represents a step forward towards the improved reproducibility in the fabrication of manifolds for flow-based automated methods of analysis, which is especially relevant in the implementation of interlaboratory analysis.