Peptidic "Molecular Beacon" for Collagen.

Collagen-mimetic peptides (CMP) have been invaluable tools for understanding the structure and function of collagen, which is the most abundant protein in animals. CMPs have also been developed as probes that detect damaged collagen because of the specificity required to form a collagen triple helix. These probes are not, however, ratiometric. Here, we used EPR spectroscopy to determine the end-to-end distances of CMPs that do not form stable homotrimeric helices. We found that those distances are shorter than the distances in the context of a collagen triple helix, suggesting their potential utility as a "molecular beacon" and guiding the choice and location of a pendant fluorophore-quencher pair. We then showed that a molecular beacon based on a glycine-(2S,4S)-4-fluoroproline-(2S,4R)-4-hydroxyproline tripeptide repeat and EDANS-DABCYL pair enabled the ratiometric detection of its binding to both other CMPs and natural mammalian collagen. These results provide guidance for the development of a new modality for detecting damaged collagen in physiological settings.

Long-Lived, Transportable Reservoir of Nuclear Polarization Used to Strongly Enhance Solution-State NMR Signals.

There is a fundamental issue with the use of dynamic nuclear polarization (DNP) to enhance nuclear spin polarization: the same polarizing agent (PA) needed for DNP is also responsible for shortening the lifetime of the hyperpolarization. As a result, long-term storage and transport of hyperpolarized samples is severely restricted and the apparatus for DNP is necessarily located near or integrated with the apparatus using the hyperpolarized spins. In this paper, we demonstrate that naphthalene single crystals can serve as a long-lived reservoir of proton polarization that can be exploited to enhance signals in benchtop and high-field NMR of target molecules in solution at a site 300 km away by a factor of several thousand. The naphthalene protons are polarized using short-lived optically excited triplet states of pentacene instead of stable radicals. In the absence of optical excitation, the electron spins remain in a singlet ground state, eliminating the major pathway of nuclear spin-lattice relaxation. The polarization decays with a time constant of about 50 h at 80 K and 0.5 T or above 800 h at 5 K and 20 mT. A module based on a Halbach array yielding a field of 0.75 T and a conventional cryogenic dry shipper, operating at liquid nitrogen temperature, allows storage and long distance transport of the polarization to a remote laboratory, where the polarization of the crystal is transferred after dissolution to a target molecule of choice by intermolecular cross-relaxation. The procedure has been executed repeatedly and has proven to be reliable and robust.

Hyperpolarized Solution-State NMR Spectroscopy with Optically Polarized Crystals.

Nuclear spin hyperpolarization provides a promising route to overcome the challenges imposed by the limited sensitivity of nuclear magnetic resonance. Here we demonstrate that dissolution of spin-polarized pentacene-doped naphthalene crystals enables transfer of polarization to target molecules via intermolecular cross-relaxation at room temperature and moderate magnetic fields (1.45 T). This makes it possible to exploit the high spin polarization of optically polarized crystals, while mitigating the challenges of its transfer to external nuclei. With this method, we inject the highly polarized mixture into a benchtop NMR spectrometer and observe the polarization dynamics for target 1H nuclei. Although the spectra are radiation damped due to the high naphthalene magnetization, we describe a procedure to process the data to obtain more conventional NMR spectra and extract the target nuclei polarization. With the entire process occurring on a time scale of 1 min, we observe NMR signals enhanced by factors between -200 and -1730 at 1.45 T for a range of small molecules.

Dynamic nuclear polarization with trityl radicals.

Despite the expanding applications of dynamic nuclear polarization (DNP) to problems in biological and materials science, there remain unresolved questions concerning DNP mechanisms. In this paper, we investigate the Zeeman DNP frequency profiles obtained with trityl radicals, OX063 and its partially deuterated analog OX071, in two commonly used glassing matrices based on glycerol and dimethyl sulfoxide (DMSO). When microwave irradiation is applied in the neighborhood of the narrow EPR transition, we observe a dispersive shape in the 1H Zeeman field and the effects are larger in DMSO than in glycerol. With the help of direct DNP observations on 13C and 2H nuclei, we investigate the origin of this dispersive field profile. In particular, we observe a weak nuclear Overhauser effect between 1H and 13C in the sample, which, when irradiating at the positive 1H solid effect (SE) condition, results in a negative enhancement of 13C spins. This observation is not consistent with thermal mixing (TM) being the mechanism responsible for the dispersive shape in the 1H DNP Zeeman frequency profile. Instead, we propose a new mechanism, resonant mixing, involving mixing of nuclear and electron spin states in a simple two-spin system without invoking electron-electron dipolar interactions.

Net Dzyaloshinskii-Moriya interaction in defect-enriched ferromagnet.

The Dzyaloshinskii-Moriya interaction (DMI), which typically occurs in lattices without space inversion symmetry, can also be induced in a highly symmetric lattice by local symmetry breaking due to any lattice defect. We recently presented an experimental study of polarized small angle neutron scattering (SANS) on the nanocrystalline soft magnet Vitroperm (Fe73Si16B7Nb3Cu1), where the interface between the FeSi nanoparticles and the amorphous magnetic matrix serves as such a defect. The SANS cross sections exhibited the polarization-dependent asymmetric term originating from the DMI. One would naturally expect the defects characterized by a positive and a negative DMI constantDto be randomly distributed and this DMI-induced asymmetry to disappear. Thus, the observation of such an asymmetry indicates that there exists an extra symmetry breaking. In the present work we experimentally explore the possible causes by measuring the DMI-induced asymmetry in the SANS cross sections of the Vitroperm sample tilted in different directions with respect to the external magnetic field. Furthermore, we analyzed the scattered neutron beam using a spin filter based on polarized protons and confirm that the asymmetric DMI signal originates from the difference between the two spin-flip scattering cross-sections.

Resonant Mixing Dynamic Nuclear Polarization.

We propose a mechanism for dynamic nuclear polarization that is different from the well-known Overhauser effect, solid effect, cross effect, and thermal mixing processes. We term it Resonant Mixing (RM), and we show that it arises from the evolution of the density matrix for a simple electron-nucleus coupled spin pair subject to weak microwave irradiation, the same interactions as the solid effect. However, the SE is optimal when the microwave field is off-resonance, whereas RM is optimal when the microwave field is on-resonance and involves the mixing of states by the microwave field together with the electron-nuclear coupling. Finally, we argue that this mechanism is responsible for the observed dispersive-shaped DNP field profile for trityl samples near the electron paramagnetic resonance center.

Coherent Dynamic Nuclear Polarization using Chirped Pulses.

This paper presents a study of coherent dynamic nuclear polarization (DNP) using frequency swept pulses at 94 GHz which optimize the polarization transfer efficiency. Accordingly, an enhancement ε ∼ 496 was observed using 10 mM trityl-OX063 as the polarizing agent in a standard 6:3:1 d8-glycerol/D2O/H2O glassing matrix at 70 K. At present, this is the largest DNP enhancement reported at this microwave frequency and temperature. Furthermore, the frequency swept pulses enhance the nuclear magnetic resonance (NMR) signal and reduce the recycle delay, accelerating the NMR signal acquisition.

Integrated, Stretched, and Adiabatic Solid Effects.

This paper presents a theory describing the dynamic nuclear polarization (DNP) process associated with an arbitrary frequency swept microwave pulse. The theory is utilized to explain the integrated solid effect (ISE) as well as the newly discovered stretched solid effect (SSE) and adiabatic solid effect (ASE). It is verified with experiments performed at 9.4 GHz (0.34 T) on single crystals of naphthalene doped with pentacene-d14. It is shown that the SSE and ASE can be more efficient than the ISE. Furthermore, the theory predicts that the efficiency of the SSE improves at high magnetic fields, where the EPR line width is small compared to the nuclear Larmor frequency. In addition, we show that the ISE, SSE, and ASE are based on similar physical principles and we suggest definitions to distinguish among them.

Monte Carlo study of the spin-spin interactions between radicals used for dynamic nuclear polarization.

The spectrum of the electron spin-spin interactions largely determines which mechanism is responsible for the growth of the nuclear spin polarization in dynamic nuclear polarization (DNP). When electron spin-spin interactions are weak and their spectrum is narrow, the solid effect (SE) dominates the process. When they are stronger, the cross effect (CE) and thermal mixing (TM) come into play. Then a narrow spectrum favours the CE-that is an exchange of electron Zeeman energy with the nuclear spins-and a broad spectrum also TM-that is an exchange of electron spin-spin interaction energy with the nuclear spins. Moreover, the spectrum of the electron spin-spin interactions critically determines the rate of spectral diffusion of electron spin polarization across the electron spin resonance (ESR) line, and the associated conversion of electron Zeeman energy into electron spin-spin interaction energy. This way electron spin-spin interactions indirectly influence the DNP process. The present work describes Monte Carlo simulations of the spectrum of these interactions for approximately spherical radicals in glasses and analytical approximations of the simulation results. As an example application expressions for the relative strengths of the energy flows due to the CE and TM are derived.

Impact of the neutron-depolarization effect on polarized neutron scattering in ferromagnets.

It has been known for decades that a ferromagnetic sample can depolarize a transmitted neutron beam. This effect was used and developed into the neutron-depolarization technique to investigate the magnetic structure of ferromagnetic materials. Since the polarization evolves continuously as the neutrons move through the sample, the initial spin states on scattering will be different at different depths within the sample. This leads to a contamination of the measured spin-dependent neutron-scattering intensities by the other spin-dependent cross sections. The effect has rarely been considered in polarized neutron-scattering experiments even though it has a crucial impact on the observable signal. A model is proposed to describe the depolarization of a neutron beam traversing a ferromagnetic sample, provide the procedure for data correction and give guidelines to choose the optimum sample thickness. It is experimentally verified for a small-angle neutron-scattering geometry with samples of the nanocristalline soft-magnet Vitroperm (Fe73Si16B7Nb3Cu1). The model is general enough to be adapted to other types of neutron-diffraction experiments and sample geometries.

Defect-induced Dzyaloshinskii-Moriya interaction in a nanocrystalline two-phase alloy.

The Dzyaloshinskii-Moriya interaction (DMI) is believed to be operative in low-symmetry crystal structures lacking space-inversion symmetry. However, already in 1963, Arrott pointed out that even in a high-symmetry lattice, where the DMI would normally vanish, this interaction is present in the vicinity of any lattice defect. Based on these considerations and recent theoretical work, first experimental studies of the impact of the DMI on the spin-polarized magnetic small-angle neutron scattering (SANS) of polycrystalline magnets exhibiting a large density of microstructural defects have been performed. They demonstrated that an asymmetry in the difference between the two polarized SANS cross sections is induced by the DMI in nanocrystalline terbium and holmium as well as in mechanically-deformed microcrystalline cobalt. Here, we present a more complicated case, the nanocrystalline magnetically-textured soft magnet Vitroperm (Fe73Si16B7Nb3Cu1), where the interface between the FeSi nanoparticles and the amorphous magnetic matrix serves as the defect. The SANS cross section exhibits the polarization-dependent asymmetric term originating from the DMI. The effect has a magnetic field dependence and is less pronounced at higher fields until it eventually vanishes at full saturation. The result supports the generic relevance of the DMI for the magnetic structure of defect-rich ferromagnets. Furthermore, it shows that polarized SANS is a particularly powerful tool for investigating defect-induced DMI, which is a consequence of the unique dependence of the SANS cross section on the chiral interactions.