Ultrafast Laplace NMR

Project Information

UFLNMR

Grant agreement ID: 772110

DOI

10.3030/772110

Project closed

EC signature date 10 January 2018

Start date 1 April 2018

End date 31 March 2024

Funded under

• EXCELLENT SCIENCE - European Research Council (ERC)

Total cost

€ 2 625 000,00

EU contribution

€ 2 625 000,00

Coordinated by

OULUN YLIOPISTO
Finland

Periodic Reporting for period 4 - UFLNMR (Ultrafast Laplace NMR)

Reporting period: 2022-10-01 to 2024-03-31

Summary of the context and overall objectives of the project

Nuclear magnetic resonance (NMR) spectroscopy, is one of the most versatile methods of chemical analysis. Traditional NMR spectroscopy is based on the rich chemical information contained in spectra. The Laplace NMR (LNMR), which comprises diffusion and relaxation measurements, reveals detailed information on the movement of molecules, making it possible to observe the different kinds of physical or chemical environments of the molecules, even if they would not be visible in the spectra. As is the case with traditional NMR spectroscopy, LNMR resolution and information content can be improved through the use of multidimensional experiments. However, these experiments are very time-consuming, and consequently, they are not suitable for the study of fast processes.

This ERC project focuses on the development of new class of NMR experiments, called ultrafast Laplace NMR (UF-LNMR). The method is based on the spatial coding of multidimensional information, making it possible to read it with one measurement. The method shortens the experiment time by one to three orders of magnitude as compared to the conventional method, offering unprecedented opportunity to study fast processes in real time. Furthermore, it enables boosting the sensitivity by several orders of magnitude by using nuclear spin hyperpolarization, which allows investigation of low-concentration samples.

The method offers groundbreaking possibilities for chemical, biochemical, geological, archaeological, and medical analysis. It allows, for example, the study of the dynamics of cancer cell metabolism in real time. The method can also reveal completely new information on the structure and characteristics of ionic liquids, gels, polymers, catalysts, and proteins, and it can be utilized in the development of biosensors.

The method is also applicable to low-field NMR sensors which are much less expensive than high field devices, and are easy to move. Their geometry also allows the study of samples of all sizes. UF-LNMR combined with the use of hyperpolarized substances increases the sensitivity and resolution of low-field devices to previously unseen levels. This means significant possibilities for low-cost mobile chemical and medical analysis.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

The project was divided into three Work Packages (WPs). WP 1 concentrated on the development of the UF-LNMR experiments, WP 2 on application of the methods using standard, high-field NMR instruments and WP 3 on applications with mobile, low-field devices.

The progress of the project was very good. During the project, we published altogether 48 scientific articles in international peer reviewed journals. Six of the articles are related to WP 1; we introduced two novel UF-LNMR method for observing molecular exchange via relaxation and diffusion contrasts; one article focuses on optimizing the sampling schemes of the spatially encoded indirect dimension in UF-LNMR; one on improving Laplace inversion algorithm used for processing experimental data; one in which we introduced an ultrafast chemical shift – T2 relaxation correlation experiment; and one in which introduced a completely new contrast, T1 relaxation time in rotating frame of reference, for ultrafast Laplace NMR toolbox. There are 29 articles belonging to WP 2 and they concentrate on novel applications of UF-LNMR and developing hyperpolarization methods for boosting the sensitivity of the experiments. The applications include metabolites of cancer cells, exosomes, which are promising novel biomarkers for various diseases, novel energy storage materials, novel selective adsorbents of noble gases, various biomaterials produced according to principles of circular economy for replacing oil-based materials, sustainable cements, shales, wood and lignin. Seven of the articles are related to WP 3 and they introduce novel hyperpolarized UF-LNMR methods for low-field, mobile, single-sided NMR instruments as well as their applications in the investigation of curing process, reaction mechanisms and pore structure of metakaolin-based geopolymers, molecular exchange phenomena in cell suspensions, and ancient wood samples. Six of the articles are review articles or book chapter. Furthermore, one popular article was published.

In addition to the scientific articles, the results were disseminated in tens of international scientific conferences as well as science popularization events. Furthermore, application of the methods with industrial collaborators has been started.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

The project aimed at to accelerate multidimensional LNMR experiments by one to three orders of magnitude via spatial encoding and improve the sensitivity by several orders of magnitude through the use of modern hyperpolarization methods. We introduced seven new UF-LNMR experiments and implementation of several others are in progress. We showed that the single-scan approach makes it possible to exploit three major hyperpolarization techniques, dissolution dynamic nuclear polarization (dDNP), parahydrogen-induced polarization (PHIP) and spin exchange optical pumping (PHIP), to boost the sensitivity of the experiments. We applied the developed UF-LNMR methods in various disciplines. For example, we exploited them in the investigation of aggregation phenomena of surfactant relevant in aerosol research, novel solid electrolytes for battery applications, metabolites of cancer cells, porous materials, catalysts, wood, lignin, sustainable cement and shale. We showed that the UF-LNMR experiments are feasible also with low-field NMR instruments, which are much cheaper than the high-field instruments and easily portable for field studies, and the high sensitivity provided by hyperpolarized substances enables single-scan multidimensional experiments at low-field.