SABRE Hyperpolarization with up to 200 bar Parahydrogen in Standard and Quickly Removable Solvents.

Parahydrogen (p-H2)-based techniques are known to drastically enhance NMR signals but are usually limited by p-H2 supply. This work reports p-H2-based SABRE hyperpolarization at p-H2 pressures of hundreds of bar, far beyond the typical ten bar currently reported in the literature. A recently designed high-pressure setup was utilized to compress p-H2 gas up to 200 bar. The measurements were conducted using a sapphire high-pressure NMR tube and a 43 MHz benchtop NMR spectrometer. In standard methanol solutions, it could be shown that the signal intensities increased with pressure until they eventually reached a plateau. A polarization of about 2%, equal to a molar polarization of 1.2 mmol L-1, could be achieved for the sample with the highest substrate concentration. While the signal plateaued, the H2 solubility increased linearly with pressure from 1 to 200 bar, indicating that p-H2 availability is not the limiting factor in signal enhancement beyond a certain pressure, depending on sample composition. Furthermore, the possibility of using liquefied ethane and compressed CO2 as removable solvents for hyperpolarization was demonstrated. The use of high pressures together with quickly removable organic/non-organic solvents represents an important breakthrough in the field of hyperpolarization, advancing SABRE as a promising tool for materials science, biophysics, and molecular imaging.

Refined high-pressure tube design for improved resolution in high-pressure NMR spectroscopy.

High-pressure NMR spectroscopy has become a valuable analytical tool in many activities, including the energy sector, chemical research, and biophysics. Many pressure-based applications could benefit from low-field NMR. In this context, a novel, simple, and low-cost high-pressure tube design improving the signal-to-noise ratio by more than 80% is presented.

Compact NMR Spectroscopy for Low-Cost Identification and Quantification of PVC Plasticizers.

Polyvinyl chloride (PVC), one of the most important polymer materials nowadays, has a large variety of formulations through the addition of various plasticizers to meet the property requirements of the different fields of applications. Routine analytical methods able to identify plasticizers and quantify their amount inside a PVC product with a high analysis throughput would promote an improved understanding of their impact on the macroscopic properties and the possible health and environmental risks associated with plasticizer leaching. In this context, a new approach to identify and quantify plasticizers employed in PVC commodities using low-field NMR spectroscopy and an appropriate non-deuterated solvent is introduced. The proposed method allows a low-cost, fast, and simple identification of the different plasticizers, even in the presence of a strong solvent signal. Plasticizer concentrations below 2 mg mL-1 in solution corresponding to 3 wt% in a PVC product can be quantified in just 1 min. The reliability of the proposed method is tested by comparison with results obtained under the same experimental conditions but using deuterated solvents. Additionally, the type and content of plasticizer in plasticized PVC samples were determined following an extraction procedure. Furthermore, possible ways to further decrease the quantification limit are discussed.

Analysis of Aging Products from Biofuels in Long-Term Storage.

The long-term aging processes during storage of different heating oils and their blends with biofuels including fatty acid methyl ester, hydrogenated vegetable oil, and power-to-liquids products were followed by different analytical techniques, and the aging products were analyzed. While most standard techniques are time-consuming and labor-intensive and specify only a single property, analyses by benchtop nuclear magnetic resonance spectroscopy proved to be effortless and fast. Moreover, only 0.4 mL of the sample is required for nondestructive NMR measurements. White and waxlike precipitates were found in FAME stored at a cold temperature and identified as esters of glycerol with saturated side chains by chromatographic, thermal, and spectroscopic analyses. At colder temperatures, they reversibly precipitate and can lead to system failure.

Quantification of PVC plasticizer mixtures by compact proton NMR spectroscopy and indirect hard modeling.

A novel approach is introduced for the fast, reliable, and low-cost recognition and quantification of plasticizers in plasticizers mixtures. It uses benchtop 1H NMR spectroscopy and indirect hard modeling, a mechanistic multivariate regression technique. The approach is demonstrated on five different PVC plasticizers having similar spectral signatures in proton NMR spectra. With only 16 scans per spectrum, i.e., 2 min 40 s measurement time, quantification limits down to 0.14 mg mL-1, or 0.35 wt% plasticizer in PVC, were achieved. Apart from the rapid data acquisition, the use of spectral hard modeling enabled the quantification of plasticizer mixtures while using only 4 to 6 training samples per component. Despite strongly overlapping signals in the NMR spectra, various plasticizers were differentiated and quantified, as exemplarily demonstrated for binary mixtures. A commercial PVC specimen with three different layers was also examined, confirming the applicability of benchtop NMR spectroscopy. Additionally, the use of the proposed method to validate official regulations concerning the plasticizer content in PVC is assessed. The presented results demonstrate that the combination of benchtop NMR and spectral hard modeling is a very promising analytical tool for rapid PVC plasticizer recognition and quantification with high analytical throughput. Moreover, the results indicate a high potential for benchtop NMR and spectral hard modeling for microchemical analysis, even for complex samples.

Versatile high-pressure gas apparatus for benchtop NMR: Design and selected applications.

A simple, yet highly versatile setup is presented for benchtop NMR analyses of gases at high-pressure. It consists mostly of commercial parts and includes multiple safety features while maintaining a small size to fit into a 1.20 m wide fume hood. Pressures up to 200 bar can be adjusted independently of the sample gas-bottle pressure in a matter of seconds. Mixtures of multiple gases can be produced in situ in a mixing chamber, which also serves to adjust the pressure. The high-pressure hardware and benchtop NMR spectrometer have been tested for long-term stability and repeatability of the measurements. The versatility of the setup is demonstrated by analyzing hydrocarbon-gas with attention to linewidths as well as their 1H relaxation times, by improving the resolution of 1H NMR spectra from solid polymers with pressurized CO2, and by visualizing the ingress of gaseous and supercritical methane into liquid benzene.