Supramolecular and Biomacromolecular Enhancement of Metal-Free Magnetic Resonance Imaging Contrast Agents

Many contrast agents for magnetic resonance imaging are based on gadolinium, however side effects limit their use in some patients. Organic radical contrast agents (ORCAs) are potential alternatives, but are reduced rapidly in physiological conditions and have low relaxivities as single molecule contrast agents. Herein, we use a supramolecular strategy where cucurbit[8]uril binds with nanomolar affinities to ORCAs and protects them against biological reductants to create a stable radical in vivo. We further over came the weak contrast by conjugating this complex on the surface of a self-assembled biomacromolecule derived from the tobacco mosaic virus.</div

Influence of ¹³C Isotopic Labeling Location on Dynamic Nuclear Polarization of Acetate

Dynamic nuclear polarization (DNP) via the dissolution method has alleviated the insensitivity problem in liquid-state nuclear magnetic resonance (NMR) spectroscopy by amplifying the signals by several thousand-fold. This NMR signal amplification process emanates from the microwave-mediated transfer of high electron spin alignment to the nuclear spins at high magnetic field and cryogenic temperature. Since the interplay between the electrons and nuclei is crucial, the chemical composition of a DNP sample such as the type of free radical used, glassing solvents, or the nature of the target nuclei can significantly affect the NMR signal enhancement levels that can be attained with DNP. Herein, we have investigated the influence of ¹³C isotopic labeling location on the DNP of a model ¹³C compound, sodium acetate, at 3.35 T and 1.4 K using the narrow electron spin resonance (ESR) line width free radical trityl OX063. Our results show that the carboxyl ¹³C spins yielded about twice the polarization produced in methyl ¹³C spins. Deuteration of the methyl ¹³C group, while proven beneficial in the liquid-state, did not produce an improvement in the ¹³C polarization level at cryogenic conditions. In fact, a slight reduction of the solid-state ¹³C polarization was observed when ²H spins are present in the methyl group. Furthermore, our data reveal that there is a close correlation between the solid-state ¹³C <i>T</i>₁ relaxation times of these samples and the relative ¹³C polarization levels. The overall results suggest the achievable solid-state polarization of ¹³C acetate is directly affected by the location of the ¹³C isotopic labeling via the possible interplay of nuclear relaxation leakage factor and cross-talks between nuclear Zeeman reservoirs in DNP

1H and 195Pt NMR Study of the Parallel Two-Chain Compound Per2[Pt(mnt)2]

1H and 195Pt NMR are used to probe the spin ½ anion chain in the quasi-one-dimensional conductor Per2[Pt(mnt)2], which exhibits nearly simultaneous charge density wave (CDW) and spin-Peierls (SP) transitions at low temperatures (Tc ~ 8 K). Below Tc the [Pt(mnt)2] chain forms a spin-singlet state that is evident in 1H NMR spectra and spin relaxation (1/T1) rates; however minority unpaired Pt spins may remain in the SP ground state. With increasing magnetic field, the SP and CDW order parameters decrease in unison, indicating they are coupled up to a critical field Bc ~ 20 T. Above Bc, the spin singlet evolves into a spin-polarized configuration. The 195Pt NMR signals vanish as either Tc or Bc are approached from within the SP ground state, suggesting the hyperfine field of the Pt nucleus is significantly stronger than at the proton sites. Simulations yield a consistent picture of the angular, temperature, and magnetic field-dependent spectral features

Single-walled carbon nanotube buckypaper and mesophase pitch carbon/carbon composites

Carbon/carbon composites consisting of single-walled carbon nanotube (SWCNT) buckypaper (BP) and mesophase pitch resin have been produced through impregnation of BP with pitch using toluene as a solvent. Drying, stabilization and carbonization processes were performed sequentially, and repeated to increase the pitch content. Voids in the carbon/carbon composite samples decreased with increasing impregnation process cycles. Electrical conductivity and density of the composites increased with carbonization by two to three times that of pristine BP. These results indicate that discontinuity and intertube contact barriers of SWCNTs in the BP are partially overcome by the carbonization process of pitch. The temperature dependence of the Raman shift shows that mechanical strain is increased since carbonized pitch matrix surrounds the nanotubes.close

Enhanced Efficiency of ¹³C Dynamic Nuclear Polarization by Superparamagnetic Iron Oxide Nanoparticle Doping

The attainment of high NMR signal enhancements is crucial to the success of in vitro or in vivo hyperpolarized NMR or imaging (MRI) experiments. In this work, we report on the use of a superparamagnetic iron oxide nanoparticle (SPION) MRI contrast agent Feraheme (ferumoxytol) as a beneficial additive in ¹³C samples for dissolution dynamic nuclear polarization (DNP). Our DNP data at 3.35 T and 1.2 K reveal that the addition of 11 mM elemental iron concentration of Feraheme in trityl OX063-doped 3 M [1-¹³C] acetate samples resulted in a substantial improvement of ¹³C DNP signal by a factor of almost three-fold. Concomitant with the large DNP signal increase is the narrowing of the ¹³C microwave DNP spectra for samples doped with SPION. W-band electron paramagnetic resonance (EPR) spectroscopy data suggest that these two prominent effects of SPION doping on ¹³C DNP can be ascribed to the shortening of trityl OX063 electron <i>T</i>₁, as explained within the thermal mixing DNP model. Liquid-state ¹³C NMR signal enhancements as high as 20,000-fold for SPION-doped samples were recorded after dissolution at 9.4 T and 297 K, which is about three times the liquid-state NMR signal enhancement of the control sample. While the presence of SPION in hyperpolarized solution drastically reduces ¹³C <i>T</i>₁, this can be mitigated by polarizing smaller aliquots of DNP samples. Moreover, we have shown that Feraheme nanoparticles (∼30 nm in size) can be easily and effectively removed from the hyperpolarized liquid by simple mechanical filtration, and thus one can potentially incorporate an in-line filtration for these SPIONS along the dissolution pathway of the hyperpolarizer, a significant advantage over other DNP enhancers such as the lanthanide complexes. The overall results suggest that the commercially available and FDA-approved Feraheme is a highly efficient DNP enhancer that could be readily translated for use in clinical applications of dissolution DNP