Dynamic Nuclear Polarization of Silicon Carbide Micro- and Nanoparticles

[Image: see text] Two dominant crystalline phases of silicon carbide (SiC): α-SiC and β-SiC, differing in size and chemical composition, were investigated regarding their potential for dynamic nuclear polarization (DNP). (29)Si nuclei in α-SiC micro- and nanoparticles with sizes ranging from 650 nm to 2.2 μm and minimal oxidation were successfully hyperpolarized without the use of free radicals, while β-SiC samples did not display appreciable degrees of polarization under the same polarization conditions. Long T(1) relaxation times in α-SiC of up to 1600 s (∼27 min) were recorded for the (29)Si nuclei after 1 h of polarization at a temperature of 4 K. Interestingly, these promising α-SiC particles allowed for direct hyperpolarization of both (29)Si and (13)C nuclei, resulting in comparably strong signal amplifications. Moreover, the T(1) relaxation time of (13)C nuclei in 750 nm-sized α-SiC particles was over 33 min, which far exceeds T(1) times of conventional (13)C DNP probes with values in the order of 1–2 min. The present work demonstrates the feasibility of DNP on SiC micro- and nanoparticles and highlights their potential as hyperpolarized magnetic resonance imaging agents

Study of the properties of hyperpolarized xenon-129 for magnetic resonance imaging

Produkce hyperpolarizovaných plynů, především helia (3He) nebo xenonu (129Xe), nachází stále rostoucí rozsah aplikací v zobrazování magnetickou rezonancí (MRI). Helium ani xenon nejsou obyčejně obsaženy v těle a experimenty tedy nejsou ovlivněny nechtěným signálem z okolních tkání. Ukázalo se, že několika hyperpolarizačními technikami může být magnetická polarizace (magnetizace) jader vzácných plynů zvýšena na hladinu, se kterou jsou praktické aplikace proveditelné. Hyperpolarizované plyny mohou tedy být užitečným nástrojem pro neinvazivní zkoumání lidského dýchání, dovolující statické zobrazování během zadržení dechu nebo zkoumání dynamiky výdechu nebo nádechu, nebo funkčního zobrazování. V neživé přírodě, mohou být hyperpolarizovaný plyny využity jako kontrastní látka při studiu mikroporézních materiálů, jako jsou zeolity, stavební látky a hmoty, atd. V této doktorské práci je popsán vývoj a konstrukce aparatury pro hyperpolarizaci xenonu (izotopu 129Xe). Nákup hyperpolarizovaného xenonu od jiných výzkumných center v zahraničí a jeho dovážení by ovšem nebylo efektivní a to zejména z důvodu náročnosti zajištění potřebných fyzikálních podmínek pro přepravu hyperpolarizovaného plynu. Toto bylo hlavní motivací k vývoji vlastní technologie pro přípravu hyperpolarizovaného xenonu. Se zvládnutou technologií by bylo možné navázat spolupráci s medicínskými zařízeními, nebo s týmy zabývající se živou nebo neživou přírodou (např. při studiu mikroporézních materiálů, gelů, v zemědělských aplikacích nebo při výzkumu využívajících zvířat, atd.). Cílem této práce je studium teorie hyperpolarizovaných vzácných plynů se zaměřením na 129Xe a experimentální ověření a změření relaxačních časů pomocí jaderné magnetické rezonance. Vzhledem k tomu, že je možné hyperpolarizované vzácné plyny skladovat pro pozdější využití, se tato práce také zabývá možnostmi zásobníku hyperpolarizovaného vzácného plynu a jeho teoretickým a experimentálním řešením. V této práci jsou popsány především dva základní typy experimentů přípravy hyperpolarizovaného xenonu. V obou jsou využity zatavené válcové skleněné vzorky naplněné xenonem a doplňujícím plynem – dusíkem, heliem. První z experimentů se zabývá měřením vlastností termálně polarizovaného xenonu a druhý měřením vlastností hyperpolarizovaného xenonu. Pro hyperpolarizaci 129Xe bylo použito výkonového laseru a experimentálně byla zkoumána jednak míra polarizace na základě změny spektrální hustoty čerpacího laserového svazku a dále pak optimální doba optického čerpání 129Xe a relaxační časy xenonu.The production of hyperpolarized gases (HpG), predominantly helium (3He) or xenon (129Xe), have found a steadily increasing range of applications in magnetic resonance imaging (MRI). Neither helium nor xenon are normally present in the body, thus the magnetic resonance experiments do not suffer from unwanted background signals. It has been demonstrated by several techniques of hyperpolarization that the magnetic polarization (magnetization) of the noble gas nuclei can be increased to levels that make practical application feasible. Hence, hyperpolarized gases may become a useful tool for non-invasive investigation of human lung ventilation, permitting static imaging during breathhold or probing the dynamics of inhalation/exhalation, or functional imaging. In inanimate nature, hyperpolarized gas can be used as a contrast medium for microporous materials, such zeolites, constructive materials in civil engineering, etc. This thesis describes the development and construction of a xenon (129Xe) hyperpolarization (Hp) device. Buying hyperpolarized xenon from other research centres abroad is inefficient mainly because of a need of a fast transport of HpXe under specific conditions. That was the main motivation for developing of our own technology for production of HpXe. Well-handled technology could allow a medical cooperation or cooperation with teams dealing with in/animate nature (microporous material, gels, agriculture, animals, etc.). The aim of this work is to study the hyperpolarized noble gases theory with concern to 129Xe and to experimentally prove and measure xenon relaxation times by the NMR. Since it is possible to store hyperpolarized noble gases for later use, this doctoral thesis also explores the potentials of hyperpolarized noble gas storage system and its theoretical and experimental solution. Mainly two types of experiments are described in the thesis. In both experiments, sealed cylindrical Simax sample filled with xenon and supplement gas – nitrogen, helium were used. The first type of experiment is based on thermally polarized xenon and the second on hyperpolarized xenon. For hyperpolarization of 129Xe a high-power laser was used. In this experiment, the relation between power spectral density of optical pumping beam and efficiency of HpXe production process was investigated. The optimal duration of optical pumping and relaxation times of HpXe were investigated too.

Diamonds On The Inside: Imaging Nanodiamonds With Hyperpolarized MRI

Nontoxic nanodiamonds (NDs) have proven useful as a vector for therapeutic drug delivery to cancers and as optical bioprobes of subcellular processes. Despite their potential clinical relevance, an effective means of noninvasively imaging NDs in vivo is still lacking. Recent developments in hyperpolarized MRI leverage an over 10 000 times increase in the nuclear polarization of biomolecules, enabling new molecular imaging applications. This work explores hyperpolarization via intrinsic paramagnetic defects in nanodiamond. We present the results of MRI experiments that enable direct imaging of nanodiamond via hyperpolarized 13C MRI and indirect imaging of nanodiamonds via Overhauser-enhanced MRI. The construction of custom hardware for these experiments is detailed and the path to future in vivo experiments outlined. As nanodiamond has been established as a biocompatible platform for drug delivery, our results will motivate further research into hyperpolarized MRI for tracking nanoparticles in vivo

Hyperpolarized Nanodiamond for Magnetic Resonance Imaging

This thesis describes a new MRI contrast agent based on hyperpolarized 13C in nanodiamond. Nanodiamonds are readily available, non-toxic, can be surface functionalized, and have long T1 relaxation times. Electronic defects in the nanodiamonds are used to hyperpolarize the 13C nuclear spins through dynamic nuclear polarization, building up large nuclear magnetic resonance signals that persist for a long time. Enhancements are comparable to those used in liquid state hyperpolarization experiments, and can be detected in an MRI scan with low background signal. This imaging modality encompasses no ionizing radiation, and long imaging windows stemming from the long T1 relaxation times of solids

DNP-NMR of surface hydrogen on silicon microparticles

Dynamic nuclear polarization (DNP) enhanced nuclear magnetic resonance (NMR) offers a promising route to studying local atomic environments at the surface of both crystalline and amorphous materials. We take advantage of unpaired electrons due to defects close to the surface of the silicon microparticles to hyperpolarize adjacent 1H nuclei. At 3.3 T and 4.2 K, we observe the presence of two proton peaks, each with a linewidth on the order of 5 kHz. Echo experiments indicate a homogeneous linewidth of 150 - 300 Hz for both peaks, indicative of a sparse distribution of protons in both environments. The high frequency peak at 10 ppm lies within the typical chemical shift range for proton NMR, and was found to be relatively stable over repeated measurements. The low frequency peak was found to vary in position between −19 and −37 ppm, well outside the range of typical proton NMR shifts, and indicative of a high-degree of chemical shielding. The low frequency peak was also found to vary significantly in intensity across different experimental runs, suggesting a weakly-bound species. These results suggest that the hydrogen is located in two distinct microscopic environments on the surface of these Si particles

Nitrogen-Vacancy Centers in Diamond for Nanoscale Magnetic Resonance Imaging Applications

The nitrogen-vacancy (NV) center is a point defect in diamond with unique properties for use in ultra-sensitive, high-resolution magnetometry. One of the most interesting and challenging applications is nanoscale magnetic resonance imaging (nano-MRI). While many review papers have covered other NV centers in diamond applications, there is no survey targeting the specific development of nano-MRI devices based on NV centers in diamond. Several different nano-MRI methods based on NV centers have been proposed with the goal of improving the spatial and temporal resolution, but without any coordinated effort. After summarizing the main NV magnetic imaging methods, this review presents a survey of the latest advances in NV center nano-MRI