Design, Optimization, and Application of a 3D-Printed Polymer Sample Introduction System for the ICP-MS Analysis of Nanoparticles and Cells.

Commonly used sample introduction systems for inductively coupled plasma mass spectrometry (ICP-MS) are generally not well-suited for single particle ICP-MS (spICP-MS) applications due to their high sample requirements and low efficiency. In this study, the first completely 3D-printed, polymer SIS was developed to facilitate spICP-MS analysis. The system is based on a microconcentric pneumatic nebulizer and a single-pass spray chamber with an additional sheath gas flow to further facilitate the transport of larger droplets or particles. The geometry of the system was optimized using numerical simulations. Its aerosol characteristics and operational conditions were studied via optical particle counting and a course of spICP-MS measurements, involving nanodispersions and cell suspensions. In a comparison of the performance of the new and the standard (quartz microconcentric nebulizer plus a double-pass spray chamber) systems, it was found that the new sample introduction system has four times higher particle detection efficiency, significantly better signal-to-noise ratio, provides ca. 20% lower size detection limit, and allows an extension of the upper limit of transportable particle diameters to about 25 µm.

Continuous spark plasma synthesis of Au/Co binary nanoparticles with tunable properties.

We present here a scalable and environmentally friendly gas phase technique employing atmospheric pressure electrical spark discharge plasmas for the production of Au/Co binaries, an effective catalyst system for the decomposition of hydrogen-rich compounds, such as ammonium borane. We demonstrate that Au/Co alloy nanoparticles can be produced via the spark plasma-based technique. The possibility of varying the morphology and phase structure via real time heat treatment of the generated aerosol to form Au/Co/CoO particles with continuous control over a wide particle compositional range (from 24 to 64 at.% [Co]/([Co] + [Au]) content) is also demonstrated. Since our spark-based approach is proven to be capable of providing reasonable particle yields, these results may contribute to the transition of lab-scale, nanocatalyst-based hydrogen storage systems to real world applications.

Multifunctional microfluidic chips for the single particle inductively coupled plasma mass spectrometry analysis of inorganic nanoparticles.

This study aimed at exploiting the so far unexploited potential of carrying out on-line sample pretreatment steps on microfluidic chips for single particle inductively coupled plasma mass spectrometry (spICP-MS) measurements, and demonstrating their ability to practically facilitate most of the simpler tasks involved in the spICP-MS analysis of nanoparticles. For this purpose, polydimethylsiloxane microfluidic chips, capable of high-range dilution and sample injection were made by casting, using high-precision, 3D-printed molds. Optimization of their geometry and functions was done by running several hydrodynamic simulations and by gravimetric, fluorescence enhanced microscope imaging and solution-based ICP-MS experiments. On the optimized microfluidic chips, several experiments were done, demonstrating the benefits of the approach and these devices, such as the determination of nanoparticle concentration using only a few tens of microliters of sample, elimination of solute interferences by dilution, solution-based size calibration and characterisation of binary nanoparticles. Due to the unique design of the chips, they can be linked together to extend the dilution range of the system by more than a magnitude per chip. This feature was also demonstrated in applications requiring multiple-magnitude dilution rates, when two chips were sequentially coupled.

Full range tuning of the composition of Au/Ag binary nanoparticles by spark discharge generation.

Gold/silver bimetallic nanoparticles still attract extensive interest due to their favorable properties e.g. in plasmonics or catalysis. We present here a facile and robust way for the production of clean Au/Ag binary nanoparticles (BNPs) with a total control over the composition via the spark discharge nanoparticle generation technique. With the application of pure Ag and Au electrodes, a tuning range of 55 to 90% Au content was achieved, but this can be further extended to the full 0 to 100% range by using a couple of alloyed electrodes. An added benefit of the approach is that either the concentration or the mean particle size can be kept constant at every composition by adjusting the generator parameters. Based on the systematic experimental data collected, a semi-empirical model for the prediction of the Au/Ag BNP composition was also developed. This model was used to calculate the theoretically achievable Au/Ag composition at a given spark parameter set in the parameter range most commonly used in the literature.

Determination of the structure and composition of Au-Ag bimetallic spherical nanoparticles using single particle ICP-MS measurements performed with normal and high temporal resolution.

In this study, the information that can be obtained by combining normal and high resolution single particle ICP-MS (spICP-MS) measurements for spherical bimetallic nanoparticles (BNPs) was assessed. One commercial certified core-shell Au-Ag nanoparticle and three newly synthesized and fully characterized homogenous alloy Au-Ag nanoparticle batches of different composition were used in the experiments as BNP samples. By scrutinizing the high resolution spICP-MS signal time profiles, it was revealed that the width of the signal peak linearly correlates with the diameter of nanoparticles. It was also observed that the width of the peak for same-size nanoparticles is always significantly larger for Au than for Ag. It was also found that it can be reliably determined whether a BNP is of homogeneus alloy or core-shell structure and that, in the case of the latter, the core comprises of which element. We also assessed the performance of several ICP-MS based analytical methods in the analysis of the quantitative composition of bimetallic nanoparticles. Out of the three methods (normal resolution spICP-MS, direct NP nebulization with solution-mode ICP-MS, and solution-mode ICP-MS after the acid dissolution of the nanoparticles), the best accuracy and precision was achieved by spICP-MS. This method allows the determination of the composition with less than 10% relative inaccuracy and better than 3% precision. The analysis is fast and only requires the usual standard colloids for size calibration. Combining the results from both quantitative and structural analyses, the core diameter and shell thickness of core-shell particles can also be calculated.