Long-lived enhanced magnetization-A practical metabolic MRI contrast material.

Noninvasive tracking of biochemical processes in the body is paramount in diagnostic medicine. Among the leading techniques is spectroscopic magnetic resonance imaging (MRI), which tracks metabolites with an amplified (hyperpolarized) magnetization signal injected into the subject just before scanning. Traditionally, the brief enhanced magnetization period of these agents limited clinical imaging. We propose a solution based on amalgamating two materials-one having diagnostic-metabolic activity and the other characterized by robust magnetization retention. This combination slows the magnetization decay in the diagnostic metabolic probe, which receives continuously replenished magnetization from the companion material. Thus, it extends the magnetization lifetime in some of our measurements to beyond 4 min, with net magnetization enhanced by more than four orders of magnitude. This could allow the metabolic probes to remain magnetized from injection until they reach the targeted organ, improving tissue signatures in clinical imaging. Upon validation, this metabolic MRI technique promises wide-ranging clinical applications, including diagnostic imaging, therapeutic monitoring, and posttreatment surveillance.

Biphasic NMR of Hyperpolarized Suspensions-Real-Time Monitoring of Solute-to-Solid Conversion to Watch Materials Grow.

Nuclear magnetic resonance (NMR) spectroscopy is a key method for the determination of molecular structures. Due to its intrinsically high (i.e., atomistic) resolution and versatility, it has found numerous applications for investigating gases, liquids, and solids. However, liquid-state NMR has found little application for suspensions of solid particles as the resonances of such systems are excessively broadened, typically beyond the detection threshold. Herein, we propose a route to overcoming this critical limitation by enhancing the signals of particle suspensions by >3.000-fold using dissolution dynamic nuclear polarization (d-DNP) coupled with rapid solid precipitation. For the proof-of-concept series of experiments, we employed calcium phosphate (CaP) as a model system. By d-DNP, we boosted the signals of phosphate 31P spins before rapid CaP precipitation inside the NMR spectrometer, leading to the inclusion of the hyperpolarized phosphate into CaP-nucleated solid particles within milliseconds. With our approach, within only 1 s of acquisition time, we obtained spectra of biphasic systems, i.e., micrometer-sized dilute solid CaP particles coexisting with their solution-state precursors. Thus, this work is a step toward real-time characterization of the solid-solution equilibrium. Finally, integrating the hyperpolarized data with molecular dynamics simulations and electron microscopy enabled us to shed light on the CaP formation mechanism in atomistic detail.

Processing of Bimetallic Inconel 625-16Mo3 Steel Tube via Supercritical Bend: Study of the Mechanical Properties and Structure.

Incineration is currently the standard way of disposing of municipal waste. It uses components protected by high-temperature-resistant layers of materials, such as Inconel alloys. Therefore, the objective of the current paper is to study the mechanical properties and structure of a bimetallic Inconel 625-16Mo3 steel tube. The Inconel 625 layer was 3.5 mm thick and was applied to the surface of the tube with a wall thickness of 7 mm via the cold metal transfer method. The bimetallic tube was bent using a supercritical bend (d ≤ 0.7D). This paper is focused on the investigation of the material changes in the Inconel 625 layer areas influenced by the maximum tensile and compressive stresses after the bend. The change in layer thickness after the bend was evaluated and compared to the non-deformed tube. In addition, the local mechanical properties (nanohardness, Young modulus) across the indicated interfacial areas using quasistatic nanoindentation were investigated. Subsequently, a thorough microstructure observation was carried out in areas with maximum tensile and compressive stresses to determine changes in the morphology and size of dendrites related to the effect of tensile or compressive stresses induced by bending. It was found that the grain featured a stretched secondary dendrite axis in the area of tensile stress, but compressive stress imparted a prolongation of the primary dendrite axis.

Effect of Cryo-Treated Cutting Tool End Milling on Custom 450 Stainless Steel.

Custom 450 stainless steel is the most desirable material across industries due to its widespread application in the aerospace, defense and marine industries. Stainless-steel materials are challenging to deal with and fall into the list of hard-to-process materials due to their low heat conduction coefficient and high mechanical properties. In this research work, end milling was carried out on Custom 450 stainless steel machined using TiAlN coated with tungsten carbide inserts that have been cryo-treated (CT) for 24 h (24 h) and 36 h (36 h), as well as untreated (UT) inserts. The inserts were evaluated in terms of feed force, feed rate and consistent depth of cut (ap) at various spindle speeds (S). Also examined were the tool morphology, chip anatomy and surface morphology of cryo-treated material compared to untreated inserts at various responses to cutting force (Fx, Fy, Fz), cutting temperature (Tc), vibration and surface abrasion. For inserts that have been cryo-treated for 36 h, the feed force (Fx) value was 44% and 5% less compared to inserts treated for 24 h and in UT inserts, respectively. Furthermore, for 24-h and 36-h CT inserts, feed force (Fx) was 12% and 20% less compared to a UT insert. Using 24-h cryo-treated inserts as opposed to UT inserts significantly reduced the surface roughness by 20%. Cutting inserts that have undergone cryogenic treatment have been observed to exhibit longer cutting tool life due to less wear and friction on the cutting edges.

Radical-induced hetero-nuclear mixing and low-field 13C relaxation in solid pyruvic acid.

Radicals serve as a source of polarization in dynamic nuclear polarization, but may also act as polarization sink, in particular at low field. Additionally, if the couplings between the electron spins and different nuclear reservoirs are stronger than any of the reservoirs' couplings to the lattice, radicals can mediate hetero-nuclear polarization transfer. Here, we report radical-enhanced 13C relaxation in pyruvic acid doped with trityl. Up to 40 K, we find a linear carbon T1 field dependence between 5 mT and 2 T. We model the dependence quantitatively, and find that the presence of trityl accelerates direct hetero-nuclear polarization transfer at low fields, while at higher fields 13C relaxation is diffusion limited. Measurements of hetero-nuclear polarization transfer up to 600 mT confirm the predicted radical-mediated proton-carbon mixing.

Radical-Induced Low-Field 1H Relaxation in Solid Pyruvic Acid Doped with Trityl-OX063.

In dynamic nuclear polarization (DNP), radicals such as trityl provide a source for high nuclear spin polarization. Conversely, during the low-field transfer of hyperpolarized solids, the radicals' dipolar or Non-Zeeman reservoir may act as a powerful nuclear polarization sink. Here, we report the low-temperature proton spin relaxation in pyruvic acid doped with trityl, for fields from 5 mT to 2 T. We estimate the heat capacity of the radical Non-Zeeman reservoir experimentally and show that a recent formalism by Wenckebach yields a parameter-free, yet quantitative model for the entire field range.

Activated Sintering of Cr2O3-Based Composites by Hot Pressing.

The paper presents and discusses questions on structure formation during the sintering process of Cr2O3-based composites using the hot pressing method, when a chemical reaction between the components takes place. The task was difficult because Cr2O3 decomposes when sintered at temperatures above 1300 °C. The proposed novel method allowed for interaction between aluminum and chromia, thus avoiding the decomposition of the latter. Here, ultrafine aluminum powder played the role of the active agent forming a liquid phase and reacting with Cr2O3. The appearance of the solid solutions of (Cr,Al)2O3 with different stoichiometry of Cr and Al depended on the aluminum content in the initial mixture. The solid solution significantly strengthened boundaries between composite phases, resulting in the composite material of high fracture toughness between 5 and 7 MPa m½ and bending strength of ca. 500 MPa. The best mechanical properties exhibited the cermet with 22 wt.% of the restored chromium.

Optimizing Friction Stir Welding of Dissimilar Grades of Aluminum Alloy Using WASPAS.

Aluminum is a widely popular material due to its low cost, low weight, good formability and capability to be machined easily. When a non-metal such as ceramic is added to aluminum alloy, it forms a composite. Metal Matrix Composites (MMCs) are emerging as alternatives to conventional metals due to their ability to withstand heavy load, excellent resistance to corrosion and wear, and comparatively high hardness and toughness. Aluminum Matrix Composites (AMCs), the most popular category in MMCs, have innumerable applications in various fields such as scientific research, structural, automobile, marine, aerospace, domestic and construction. Their attractive properties such as high strength-to-weight ratio, high hardness, high impact strength and superior tribological behavior enable them to be used in automobile components, aviation structures and parts of ships. Thus, in this research work an attempt has been made to fabricate Aluminum Alloys and Aluminum Matrix Composites (AMCs) using the popular synthesis technique called stir casting and join them by friction stir welding (FSW). Dissimilar grades of aluminum alloy, i.e., Al 6061 and Al 1100, are used for the experimental work. Alumina and Silicon Carbide are used as reinforcement with the aluminum matrix. Mechanical and corrosion properties are experimentally evaluated. The FSW process is analyzed by experimentally comparing the welded alloys and welded composites. Finally, the best suitable FSW combination is selected with the help of a Multi-Attribute Decision Making (MADM)-based numerical optimization technique called Weighted Aggregated Sum Product Assessment (WASPAS).

Analysis of Surface State after Turning of High Tempered Bearing Steel.

This paper investigates surface state after turning of the high tempered bearing steel 100Cr6 with a hardness of 40 HRC. White layer (WL) thickness and its microhardness, as well as surface roughness, are investigated as a function of tool flank wear VB as well as cutting speed vc. The mechanical and thermal load of the machined surface were analysed in order to provide a deeper insight into their superimposing contribution. Cutting energy expressed in terms of cutting force was analyses as that consumed for chip formation Fγ and consumed in the flank wear land Fα. It was found that the mechanical energy expressed in terms of the shear components of the Fα grows with VB, converts to the heat and strongly affects the thickness of the re-hardened layer. Furthermore, the superimposing contribution of the heat generation and its duration in the VB region should also be taken into account. It was also found that the influence of VB predominates over the variable cutting speed.

A cryogen-free, semi-automated apparatus for bullet-dynamic nuclear polarization with improved resolution.

In dissolution-dynamic nuclear polarization, a hyperpolarized solid is dissolved with a jet of hot solvent. The solution is then transferred to a secondary magnet, where spectra can be recorded with improved sensitivity. In bullet-dynamic nuclear polarization this order is reversed. Pressurized gas is used to rapidly transfer the hyperpolarized solid to the secondary magnet, and the hyperpolarized solid is dissolved only upon arrival. A potential advantage of this approach is that it may avoid excessive dilution and the associated signal loss, in particular for small sample quantities. Previously, we have shown that liquid-state NMR spectra with polarization levels of up to 30 % may be recorded within less than 1 s after the departure of the hyperpolarized solid from the polarizing magnet. The resolution of the recorded spectra however was limited. The system consumed significant amounts of liquid helium, and substantial manual work was required in between experiments to prepare for the next shot. Here, we present a new bullet-DNP (dynamic nuclear polarization) system that addresses these limitations.

Scalable dissolution-dynamic nuclear polarization with rapid transfer of a polarized solid.

In dissolution-dynamic nuclear polarization, nuclear spins are hyperpolarized at cryogenic temperatures using radicals and microwave irradiation. The hyperpolarized solid is dissolved with hot solvent and the solution is transferred to a secondary magnet where strongly enhanced magnetic resonance signals are observed. Here we present a method for transferring the hyperpolarized solid. A bullet containing the frozen, hyperpolarized sample is ejected using pressurized helium gas, and shot into a receiving structure in the secondary magnet, where the bullet is retained and the polarized solid is dissolved rapidly. The transfer takes approximately 70 ms. A solenoid, wound along the entire transfer path ensures adiabatic transfer and limits radical-induced low-field relaxation. The method is fast and scalable towards small volumes suitable for high-resolution nuclear magnetic resonance spectroscopy while maintaining high concentrations of the target molecule. Polarization levels of approximately 30% have been observed for 1-13C-labelled pyruvic acid in solution.

Alignment of 17O-enriched water-endofullerene H2O@C60 in a liquid crystal matrix.

We present a 17O and 1H NMR study of molecular endofullerene H2O@C60 dissolved in the nematic liquid crystal N-(4-methoxybenzylidene)-4-butylaniline (MBBA). The 17O NMR peak is split into five components by the 17O residual quadrupolar coupling, each of which is split into a triplet by the 1H-17O residual dipolar coupling and scalar coupling. The splittings are analysed in terms of the partial alignment of the encapsulated water molecules. Order parameters describing the alignment are estimated. It is found that the preferential orientation of the endohedral water molecule has the molecular plane perpendicular to the liquid crystal director.

Spin-Isomer Conversion of Water at Room Temperature and Quantum-Rotor-Induced Nuclear Polarization in the Water-Endofullerene H_{2}O@C_{60}.

Water exists in two forms, para and ortho, that have nuclear spin states with different symmetries. Here we report the conversion of fullerene-encapsulated para water to ortho water. The enrichment of para water at low temperatures is monitored via changes in the electrical polarizability of the material. Upon rapid dissolution of the material in toluene the excess para water converts to ortho water. In H_{2}^{16}O@C_{60} the conversion leads to a slow increase in the NMR signal. In H_{2}^{17}O@C_{60} the conversion gives rise to weak signal enhancements attributed to quantum-rotor-induced nuclear spin polarization. The time constants for the para-to-ortho conversion of fullerene-encapsulated water in ambient temperature solution are estimated as 30±4 s for the ^{16}O isotopolog of water, and 16±3 s for the ^{17}O isotopolog.

Synthesis and Properties of Open Fullerenes Encapsulating Ammonia and Methane.

We describe the synthesis and characterisation of open fullerene (1) and its reduced form (2) in which CH4 and NH3 are encapsulated, respectively. The 1 H NMR resonance of endohedral NH3 is broadened by scalar coupling to the quadrupolar 14 N nucleus, which relaxes rapidly. This broadening is absent for small satellite peaks, which are attributed to natural abundance 15 N. The influence of the scalar relaxation mechanism on the linewidth of the 1 H ammonia resonance is probed by variable temperature NMR. A rotational correlation time of τc =1.5 ps. is determined for endohedral NH3 , and of τc =57±5 ps. for the open fullerene, indicating free rotation of the encapsulated molecule. IR spectroscopy of NH3 @2 at 5 K identifies three vibrations of NH3 (ν1 , ν3 and ν4 ) redshifted in comparison with free NH3 , and temperature dependence of the IR peak intensity indicates the presence of a large number of excited translational/ rotational states. Variable temperature 1 H NMR spectra indicate that endohedral CH4 is also able to rotate freely at 223 K, on the NMR timescale. Inelastic neutron scattering (INS) spectra of CH4 @1 show both rotational and translational modes of CH4 . Energy of the first excited rotational state (J=1) of CH4 @1 is significantly lower than that of free CH4 .

NMR Lineshapes and Scalar Relaxation of the Water-Endofullerene H217 O@C60.

The 17 O isotopomer of the water-endofullerene H2 O@C60 displays a remarkable proton NMR spectrum, with six well resolved peaks. These peaks are due to the J-coupling between the water protons and the 17 O nucleus, which has spin-5/2. The resolution of these peaks is enabled by the suppression of water proton exchange by the fullerene cage. The six peaks display an unusual pattern of linewidths, which we model by a Liouville-space treatment of scalar relaxation due to quadrupolar relaxation of the 17 O nuclei. The data are consistent with rotational diffusion of the water molecules on the sub-picosecond timescale.

NMR of molecular endofullerenes dissolved in a nematic liquid crystal.

We report the NMR of the molecular endofullerenes H2@C60, H2O@C60 and HF@C60 dissolved in the nematic liquid crystal N-(4-methoxybenzylidene)-4-butylaniline (MBBA). The 1H NMR lines of H2 and H2O display a doublet splitting due to residual dipole-dipole coupling. The dipolar splitting depends on temperature in the nematic phase and vanishes above the nematic-isotropic phase transition. The 19F spectrum of HF@C60 dissolved in MBBA displays a doublet splitting in the nematic phase, with contributions from the 1H-19F dipole-dipole coupling and J-coupling. The phenomena are analyzed using a model in which the fullerene cages acquire a geometrical distortion, either through interaction with the liquid crystal environment, or through their interaction with the endohedral molecules. The distorted cages become partially oriented with respect to the liquid crystal director, and the endohedral molecules become partially oriented with respect to the distorted cages.

The dipolar endofullerene HF@C60.

The cavity inside fullerenes provides a unique environment for the study of isolated atoms and molecules. We report the encapsulation of hydrogen fluoride inside C60 using molecular surgery to give the endohedral fullerene HF@C60. The key synthetic step is the closure of the open fullerene cage with the escape of HF minimized. The encapsulated HF molecule moves freely inside the cage and exhibits quantization of its translational and rotational degrees of freedom, as revealed by inelastic neutron scattering and infrared spectroscopy. The rotational and vibrational constants of the encapsulated HF molecules were found to be redshifted relative to free HF. The NMR spectra display a large (1)H-(19)F J coupling typical of an isolated species. The dipole moment of HF@C60 was estimated from the temperature dependence of the dielectric constant at cryogenic temperatures and showed that the cage shields around 75% of the HF dipole.