4D-Printed Elution-Peak-Guided Dual-Responsive Monolithic Packing for the Solid-Phase Extraction of Metal Ions.

Four-dimensional printing (4DP) technologies are revolutionizing the fabrication of stimuli-responsive devices. To advance the analytical performance of conventional solid-phase extraction (SPE) devices using 4DP technology, in this study, we employed N-isopropylacrylamide (NIPAM)-incorporated photocurable resins and digital light processing three-dimensional printing to fabricate an SPE column with a [H+]/temperature dual-responsive monolithic packing stacked as interlacing cuboids to extract Mn, Co, Ni, Cu, Zn, Cd, and Pb ions. When these metal ions were eluted using 0.5% HNO3 solution as the eluent at a temperature below the lower critical solution temperature of polyNIPAM, the monolithic packing swelled owing to its hydrophilic/hydrophobic transition and electrostatic repulsion among the protonated units of polyNIPAM. These effects resulted in smaller interstitial volumes among these interlacing cuboids and improvements in the elution peak profiles of the metal ions, which, in turn, demonstrated the reduced method detection limits (MDLs; range, 0.2-7.2 ng L-1) during analysis using inductively coupled plasma mass spectrometry. We studied the effects of optimizing the elution peak profiles of the metal ions on the analytical performance of this method and validated its reliability and applicability by analyzing the metal ions in reference materials (CASS-4, SLRS-5, 1643f, and Seronorm Trace Elements Urine L-2) and performing spike analyses of seawater, groundwater, river water, and human urine samples. Our results suggest that this 4D-printed elution-peak-guided dual-responsive monolithic packing enables lower MDLs when packed in an SPE column to facilitate the analyses of the metal ions in complex real samples.

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.

Materials Engineering of Violin Soundboards by Stradivari and Guarneri.

We investigated the material properties of Cremonese soundboards using a wide range of spectroscopic, microscopic, and chemical techniques. We found similar types of spruce in Cremonese soundboards as in modern instruments, but Cremonese spruces exhibit unnatural elemental compositions and oxidation patterns that suggest artificial manipulation. Combining analytical data and historical information, we may deduce the minerals being added and their potential functions-borax and metal sulfates for fungal suppression, table salt for moisture control, alum for molecular crosslinking, and potash or quicklime for alkaline treatment. The overall purpose may have been wood preservation or acoustic tuning. Hemicellulose fragmentation and altered cellulose nanostructures are observed in heavily treated Stradivari specimens, which show diminished second-harmonic generation signals. Guarneri's practice of crosslinking wood fibers via aluminum coordination may also affect mechanical and acoustic properties. Our data suggest that old masters undertook materials engineering experiments to produce soundboards with unique properties.

3D-Printed Column with Porous Monolithic Packing for Online Solid-Phase Extraction of Multiple Trace Metals in Environmental Water Samples.

In this study, we used a multimaterial three-dimensional printing (3DP) technology and porous composite filaments (Lay-Fomm, Gel-Lay, and Lay-Felt) to fabricate solid phase extraction (SPE) columns for the enhanced extraction of multiple metal ions. When employed as sample pretreatment devices in an automatic flow injection analysis/inductively coupled plasma mass spectrometry (ICP-MS) system, these 3D-printed SPE columns performed the near-complete extractions of Mn, Co, Ni, Cu, Zn, Cd, and Pb ions from natural water samples prior to ICP-MS determination. After optimizing the column fabrication, the extraction conditions, and the automatic analysis system, the column packed with the porous composite Lay-Fomm 40 was found to provide the highest extraction performance-the extraction efficiencies of the listed metal ions were all greater than 99.2%, and the detection limits of the method ranged from 0.3 to 6.7 ng L-1. The detection of these metal ions in several reference materials (CASS-4, SLEW-3, 1640a, and 1643f) validated the reliability of this method; spike analyses of collected water samples (groundwater, river water, and seawater) demonstrated the applicability of the method. The nature of the printing materials enhanced the analytical performance of 3D-printed sample pretreatment devices. Such approaches will be useful to diversify the range of sample preparation schemes and analytical methods enabled by 3DP technologies.

Biodistribution of Graphene Oxide Determined through Postadministration Labeling with DNA-Conjugated Gold Nanoparticles and ICPMS.

Recent research has revealed the use of graphene oxide (GO) and its derivatives as a potential biomaterial because of their attractive physicochemical characteristics and functional properties. However, if GO and related derivatives are to become useful materials for biomedical applications, it will be necessary to evaluate their biodistribution for health and safety considerations. To obtain a more accurate biodistribution for GO, we (i) developed a postadministration labeling strategy employing DNA-conjugated gold nanoparticles (DNA-AuNPs) to selectively label administered GO in Solvable-treated tissue samples and (ii) constructed an automatic sample pretreatment scheme (using a C18-packed minicolumn) to effectively separate the DNA-AuNP-labeled GO from the unbound DNA-AuNPs and the dissolved tissue matrices, thereby enabling ultrasensitive, interference-free quantification of GO through measurement (inductively coupled plasma mass spectrometry) of the Au signal intensities. The DNA-AuNPs can bind to GO in a concentration- and time-dependent manner. After optimizing the labeling conditions (DNA length, incubation pH, DNA-AuNP concentration, and incubation time) and the separation scheme (sample loading flow rate, rinsing volume, and eluent composition), we found that A20R20-AuNPs (R20: random DNA sequence including A, T, C, and G) had the strongest binding affinity for labeling of the administered GO (dissociation constant: 36.0 fM) and that the method's detection limit reached 9.3 ag L-1 with a calibration curve having a working range from 10-1 to 1010 fg L-1. Moreover, this approach revealed that the intravenously administered GO accumulated predominantly in the liver and spleen at 1 and 12 h post administration, with apparent discrepancies in the concentrations measured using pre- and postadministration labeling strategies.

3D-printed CuO nanoparticle-functionalized flow reactor enables online fluorometric monitoring of glucose.

An online flow reactor was fabricated by using a fused deposition modeling three-dimensional printing (3DP) technology along with thermoplastic poly(lactic acid) filaments incorporating copper oxide nanoparticles (CuO NPs). In the presence of glucose, the flow reactor displays multi-catalytic activities because accelerates the oxidation of 2',7'-dichlorodihydrofluorescein to form fluorescein which displays green fluorescence under 480 nm excitation (emission wavelength: 530 nm). The CuO NPs exert two functions to mediate electron transfer at a basic reaction condition, viz. direct oxidation of glucose to generate reactive oxygen species (ROS), and prompting the ROS to oxidize 2',7'-dichlorofluorescin diacetate. The flow reactor coupled to a microdialysis sampler and a fluorometer was applied for online fluorometric monitoring of brain extracellular glucose levels in living rats based on scanning of time-resolved fluorescence intensities. After optimization of (a) the manufacture of the flow reactor, (b) the reaction conditions (pH 10; 50 °C), and (c) the online analytical system, the detection limit of the method (when using 10-µL samples of microdialysate) is as low as 6.1 µM (linear range: 0.05-5 mM) with a sampling frequency of 7.5 h-1. To illustrate the method's applicability, analyses of spiked off-line-collected rat brain microdialysates were conducted. In addition, rat brain extracellular glucose levels were monitored in-vivo and online upon neuronal depolarization triggered by perfusing a high-K+ medium. The results demonstrate that functionalizing raw 3DP materials with appropriate nanomaterials can simplify the manufacturing of analytical devices and related analytical procedures. This will extend the diversity and adaptability of current 3DP-enabling analytical strategies. Graphical abstract Schematic presentation of an online flow reactor fabricated using a fused deposition modeling 3D printer along with poly(lactic acid) (PLA) filaments incorporating CuO NPs. The manufactured flow reactor displays multi-catalytic activities and simplifies online fluorometric monitoring of living rat brain extracellular glucose.

A Highly Stable Framework of Crystalline Zinc Phosphite with Selective Removal, Recovery, and Turn-On Sensing Abilities for Mercury Cations in Aqueous Solutions.

A highly stable framework of organic-inorganic hybrid zinc phosphite (NTOU-4) and its cobalt analogue (NTOU-4a) were synthesized under the hydro(solvo)thermal conditions and structurally characterized by single-crystal X-ray diffraction. Their frameworks consisted of inorganic metallophosphite chains, in which the metal atoms were interlinked through 1H-1,2,4-triazole-3,5-diamine and 1,4-benzenedicarboxylate linkers to form new crystalline materials. It is extremely difficult to achieve the consolidation of three distinct coordinations of metal-carboxylate, metal-triazolate, and metal-phosphite bonds into one crystal, resulting in the synthesis of the first mixed-ligand terephthalate-metallophosphite solids in the absence of organic molecules as templates or space-filling counters in their structures. Interestingly, the zinc compound not only exhibits high thermal stability (up to 400 °C in air) and chemical resistance to seawater, aqueous solutions (pH 3-11), and organic solvents at boiling conditions, but also shows selective removal, recovery, and "turn-on" sensing abilities of toxic mercury ions in aqueous solutions. Furthermore, the synthesis, characterization, and the difference of the framework stabilities between isostructural zinc and cobalt compounds are also reported.

3D-printed, TiO2 NP-incorporated minicolumn coupled with ICP-MS for speciation of inorganic arsenic and selenium in high-salt-content samples.

To extend the applicability of solid phase extraction devices manufactured using 3D printing technologies, a stereolithographic 3D printer and resins incorporating titanium dioxide nanoparticles (TiO2 NPs) were employed to fabricate a demountable minicolumn with TiO2 NP-incorporated packing as a sample pretreatment device for the selective extraction of inorganic As and Se species from high-salt-content samples, and to facilitate their analyses when coupled to an inductively coupled plasma mass spectrometer. After optimization, the automatic system enabled highly sensitive determinations of As and Se species with detection limits as low as 0.004-0.033 µg L-1 for As and 0.061-0.128 µg L-1 for Se. Reliability was confirmed through analyses of the reference materials 1643f, SLEW-3, CASS-4, and 2670a, as well as spike analyses of samples of water and human urine. These 3D-printed minicolumns appear to be very useful for multi-elemental speciation of these elements from high-salt-content samples. Thus, the incorporation of active nanomaterials into raw printing resins can enable 3D printing technologies-not only to fabricate functionalized devices for diverse sample pretreatment applications but also to encourage the future development of multifunctional devices for analytical science. Graphical abstract Schematic presentation of a demountable minicolumn fabricated using a stereolithographic 3D printer and the resins incorporating with TiO2 NPs. They were used to selectively extract As and Se species through controlling the sample acidities.

Enzyme-Immobilized 3D-Printed Reactors for Online Monitoring of Rat Brain Extracellular Glucose and Lactate.

In this study we constructed a highly sensitive system for in vivo monitoring of the concentrations of rat brain extracellular glucose and lactate. This system involved microdialysis (MD) sampling and fluorescence determination in conjunction with a novel sample derivatization scheme in which glucose oxidase and lactate oxidase were immobilized in ABS flow bioreactors (manufactured through low-cost three-dimensional printing (3DP)), via fused deposition modeling, for online oxidization of sampled glucose and lactate, respectively, in rat brain microdialysate. After optimizing the experimental conditions for MD sampling, the manufacture of the designed flow reactors, the enzyme immobilization procedure, and the online derivatization scheme, the available sampling frequency was 15 h(-1) and the system's detection limits reached as low as 0.060 mM for glucose and 0.059 mM for lactate, based on a 20-µL conditioned microdialysate; these characteristics were sufficient to reliably determine the concentrations of extracellular glucose and lactate in the brains of living rats. To demonstrate the system's applicability, we performed (i) spike analyses of offline-collected rat brain microdialysate and (ii) in vivo dynamic monitoring of the extracellular glucose and lactate in living rat brains, in addition to triggering neuronal depolarization by perfusing a high-K(+) medium from the implanted MD probe. Our analytical results and demonstrations confirm that postprinting functionalization of analytical devices manufactured using 3DP technology can be a powerful strategy for extending the diversity and adaptability of currently existing analytical configurations.

Fully 3D-Printed Preconcentrator for Selective Extraction of Trace Elements in Seawater.

In this study, we used a stereolithographic 3D printing technique and polyacrylate polymers to manufacture a solid phase extraction preconcentrator for the selective extraction of trace elements and the removal of unwanted salt matrices, enabling accurate and rapid analyses of trace elements in seawater samples when combined with a quadrupole-based inductively coupled plasma mass spectrometer. To maximize the extraction efficiency, we evaluated the effect of filling the extraction channel with ordered cuboids to improve liquid mixing. Upon automation of the system and optimization of the method, the device allowed highly sensitive and interference-free determination of Mn, Ni, Zn, Cu, Cd, and Pb, with detection limits comparable with those of most conventional methods. The system's analytical reliability was further confirmed through analyses of reference materials and spike analyses of real seawater samples. This study suggests that 3D printing can be a powerful tool for building multilayer fluidic manipulation devices, simplifying the construction of complex experimental components, and facilitating the operation of sophisticated analytical procedures for most sample pretreatment applications.

Quantitatively profiling the dissolution and redistribution of silver nanoparticles in living rats using a knotted reactor-based differentiation scheme.

Whether silver nanoparticles (AgNPs) degrade and release silver ions (Ag(+)) in vivo has remained an unresolved issue. To evaluate the biodistribution and dissolution behavior of intravenously administered AgNPs in living rats, we employed a knotted reactor (KR) device to construct a differentiation scheme for quantitative assessment of residual AgNPs and their released Ag(+) ions in complicated animal tissues; to do so, we adjusted the operating parameters of the KR, namely, the presence/absence of a rinse solution and the sample acidity. After optimization, our proposed differentiation system was confirmed to be tolerant to rat tissue and organ matrix and provide superior reliability of differentiating AgNPs/Ag(+) than the conventional centrifugal filtration method. We then applied this differentiation strategy to investigate the biodistribution and dissolution of AgNPs in rats 1, 3, and 5 days postadministration, and it was found that the administered AgNPs accumulated predominantly in the liver and spleen, then dissolved and released Ag(+) ions that were gradually excreted, resulting in almost all of the Ag(+) ions becoming deposited in the kidney, lung, and brain. Histopathological data also indicated that toxic responses were specifically located in the AgNP-rich liver, not in the Ag(+)-dominated tissues and organs. Thus, the full-scale chemical fate of AgNPs in vivo should be integrated into future assessments of the environmental health effects and utilization of AgNP-containing products.

In-vivo evaluation of the permeability of the blood-brain barrier to arsenicals, molybdate, and methylmercury by use of online microdialysis-packed minicolumn-inductively coupled plasma mass spectrometry.

To study the permeability of the blood-brain barrier (BBB) to arsenates, arsenite, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), molybdate, and methylmercury, and the transfer behavior of these species, we constructed an automatic online analytical system comprising a microdialysis sampling device, a minicolumn packed with nonfunctionalized poly(vinyl chloride) beads, and an inductively coupled plasma mass spectrometer for continuous in-vivo measurement of their dynamic variation in the extracellular space of the brains of living rats. By using ion-polymer interactions as a novel working mechanism for sample pretreatment of volume-limited microdialysate, we simplified the operating procedure of conventional solid-phase extraction and reduced the contribution to the blank of the chemicals used. After optimizing this hyphenated system, we measured its performance by analysis of NIST standard reference materials 1640a (trace elements in natural water) and 2672a (trace elements in human urine) and by in-vivo monitoring of the dynamic variation of the compounds tested in the extracellular fluid (ECF) of rat brain. We found that intraperitoneal administration led to observable BBB permeability of arsenates, arsenite, DMA, MMA, and molybdate. Nevertheless, the limited sensitivity of the system and the size of microdialysis samples meant that detection of MeHg in ECF remained problematic, even when we administered a dose of 20 mg MeHg kg(-1) body weight. On the basis of these practical demonstrations, we suggest that our analytical system could be used not only for dynamic monitoring of the transfer kinetics of the four arsenicals and molybdate in the rat brain but also to describe associated neurotoxicity in terms of exposure to toxic metals and their species.

In vivo monitoring of distributional transport kinetics and extravasation of quantum dots in living rat liver.

Although the unique optical properties of surface-modified quantum dots (QDs) have attracted wide interest in molecular biology and bioengineering, there are very few reports of their in vivo biodistribution, due to a lack of analytical techniques for characterizing the dynamic variation of QDs in living animals. In this study, we used an in vivo online monitoring system and a batch-wise elemental analytical method to investigate the biodistribution/extravasation of various surface-modified CdTeSe/ZnS (QDs) in rat liver. It is found that the surface modification dictated not only the blood retention profile but also the degree of extravasation and the clearance of extracellular QDs, making it an important variable for regulating the transfer and exchange process of QDs among three physiological compartments-bloodstream, extracellular space and Kupffer cells/hepatocytes.

Tuning the fabrication of knotted reactors via 3D printing techniques and materials.

Although three-dimensional (3D) printing technologies can customize a diverse range of devices, cross-3D printing technique/material comparisons aimed at optimizing the fabrication of analytical devices have been rare. In this study, we evaluated the surface features of the channels in knotted reactors (KRs) fabricated using fused deposition modeling (FDM) 3D printing [with poly(lactic acid) (PLA), polyamide, and acrylonitrile butadiene styrene filaments], and digital light processing and stereolithography 3D printing with photocurable resins. Also, their ability to retain Mn, Co, Ni, Cu, Zn, Cd, and Pb ions was evaluated to achieve the maximal sensitivities of these metal ions. After optimizing the techniques and materials for 3D printing of the KRs, the retention conditions, and the automatic analytical system, we observed good correlations (R > 0.9793) for the three 3D printing techniques in terms of the surface roughnesses of their channel sidewalls with respect to the signal intensities of their retained metal ions. The FDM 3D-printed PLA KR provided the best analytical performance, with the retention efficiencies of the tested metal ions all being greater than 73.9% and with the detection limits of the method ranging from 0.1 to 5.6 ng L-1. We used this analytical method to perform analyses of the tested metal ions in several reference materials (CASS-4, SLEW-3, 1643f, and 2670a). Spike analyses of complicated real samples verified the reliability and applicability of this analytical method, highlighting the possibility of tuning 3D printing techniques and materials to optimize the fabrication of mission-oriented analytical devices.

4D-printed needle panel meters coupled with enzymatic derivatization for reading urea and glucose concentrations in biological samples.

On-site analytical techniques continue being developed with advances in modern technology. To demonstrate the applicability of four-dimensional printing (4DP) technologies in the direct fabrication of stimuli-responsive analytical devices for on-site determination of urea and glucose, we used digital light processing three-dimensional printing (3DP) and 2-carboxyethyl acrylate (CEA)-incorporated photocurable resins to fabricate all-in-one needle panel meters. When adding a sample having a value of pH above the pKa of CEA (ca. 4.6-5.0) into the fabricated needle panel meter, the [H+]-responsive layer of the needle, printed using the CEA-incorporated photocurable resins, swelled as a result of electrostatic repulsion among the dissociated carboxyl groups of the copolymer, leading to [H+]-dependent bending of the needle. When coupled with a derivatization reaction (urease-mediated hydrolysis of urea to decrease [H+]; glucose oxidase-mediated oxidization of glucose to increase [H+]), the bending of the needle allowed reliable quantification of urea or glucose when referencing pre-calibrated concentration scales. After method optimization, the method's detection limits for urea and glucose were 4.9 and 7.0 µM, respectively, within a working concentration range from 0.1 to 10 mM. We verified the reliability of this analytical method by determining the concentrations of urea and glucose in samples of human urine, fetal bovine serum, and rat plasma with spike analyses and comparing the results with those obtained using commercial assay kits. Our results confirm that 4DP technologies can allow the direct fabrication of stimuli-responsive devices for quantitative chemical analysis, and that they can advance the development and applicability of 3DP-enabling analytical methods.

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.

Post-administration labeling with Palladium(II) ions enables ICP-MS-based determination of the biodistribution of carbonized nanogels.

Carbonized nanogels (CNGs) are carbon-based nanomaterials possessing excellent antibacterial and antiviral activities for treating infectious diseases. Thus, investigations of the biodistribution of CNGs are crucial in ensuring their biosafety for in vivo applications. In this study, we combined a labeling scheme, employing tetrachloropalladate (PdCl42-) ions to selectively label the administered CNGs in solubilized tissue samples, and an automatic sample pretreatment scheme, using a knotted reactor to effectively separate the PdCl42--labeled CNGs from the free PdCl42- ions and the tissue matrices, to enable reliable and interference-free quantification of CNGs through measuring the signal intensities of Pd using inductively coupled plasma mass spectrometry (ICP-MS). After optimizing the labeling conditions and the separation scheme, we observed that the PdCl42- ions bound strongly to the CNGs (dissociation constant: 23.0 nM), with the method's detection limits reaching 1.6 fg L-1 and 0.9 µg L-1 within working ranges from 10-4 to 1 µg L-1 and from 1 to 1000 µg L-1, respectively. We verified the reliability and applicability of this analytical method through spike analyses of solubilized rat liver, spleen, kidney, lung, brain, and blood samples (recoveries ranging from 96 to 102%) and through analyses of these rat organ and tissue samples after giving rats an intravenous dose of CNGs (2.5 mg kg-1 body weight). The biodistribution data indicated that these administered CNGs deposited mainly in the liver, lung, and spleen at 10 min and 1 h post-administration. Our study revealed that this post-administration labeling scheme coupled with ICP-MS allows accurate determination of the biodistribution of carbonized nanomaterials.

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 pH sensing claw.

As an example of extending the functionality of analytical devices manufactured using four-dimensional printing (4DP), in this study we employed acrylonitrile butadiene styrene (ABS) thermoplastic filaments, poly(4-vinylpyridine) (P4VP)-incorporated ABS filaments, and multi-material fused deposition modeling three-dimensional printing (3DP) to fabricate a pH measurement device that underwent pH-dependent geometric changes. Upon immersion in a solution having a pH close to the value of pKa of P4VP (ca. 5.0), electrostatic repulsion among the protonated units of P4VP resulted in swelling only of the part printed using the P4VP-incorporated ABS filaments, leading to lifting of the whole device along the z-axis (ΔH) in a pH-dependent manner. After optimizing the device's design and fabrication, this 4D-printed pH sensing claw exhibited linearity between the value of ΔH and values of pH in the range from 5.0 to 8.6. We used this 4D-printed pH sensing claw to perform pH analyses of complicated real samples, verifying its analytical reliability for non-electrochemical and non-optical pH measurement and highlighting the capability of 4DP technologies in the direct fabrication of stimuli-responsive sensing devices. We envision that 4DP technologies will prompt the manufacture of smart sensing devices through the printing of stimuli-responsive materials, thereby diversifying the development of 3DP-enabling analytical chemistry.

In vivo monitoring of the transfer kinetics of trace elements in animal brains with hyphenated inductively coupled plasma mass spectrometry techniques.

The roles of metal ions to sustain normal function and to cause dysfunction of neurological systems have been confirmed by various studies. However, because of the lack of adequate analytical method to monitor the transfer kinetics of metal ions in the brain of a living animal, research on the physiopathological roles of metal ions in the CNS remains in its early stages and more analytical efforts are still needed. To explicitly model the possible links between metal ions and physiopathological alterations, it is essential to develop in vivo monitoring techniques that can bridge the gap between metalloneurochemistry and neurophysiopathology. Although inductively coupled plasma mass spectrometry (ICP-MS) is a very powerful technique for multiple trace element analyses, when dealing with chemically complex microdialysis samples, the detection capability is largely limited by instrumental sensitivity, selectivity, and contamination that arise from the experimental procedure. As a result, in recent years several high efficient and clean on-line sample pretreatment systems have been developed and combined with microdialysis and ICP-MS for the continuous and in vivo determination of the concentration-time profiles of metal ions in the extracellular space of rat brain. This article reviews the research relevant to the development of analytical techniques for the in vivo determination of dynamic variation in the concentration levels of metal ions in a living animal.