NMR Hyperpolarization Techniques for Biomedicine

Recent developments in NMR hyperpolarization have enabled a wide array of new in vivo molecular imaging modalities, ranging from functional imaging of the lungs to metabolic imaging of cancer. This Concept article explores selected advances in methods for the preparation and use of hyperpolarized contrast agents, many of which are already at or near the phase of their clinical validation in patients.     

Reaction of 3,4,4,5-tetrachloro-4H-1,2,6-thiadiazine with benzyltriethylammonium chloride

3,4,4,5-Tetrachloro-4H-1,2,6-thiadiazine was reacted with BnEt₃NCl (10?mol%) to give perchloro-9-thia-1,5,8,10-tetraazaspiro[5.5]undeca-1,4,7,10-tetraene (up to 18% yield), 4,5,6-trichloropyrimidine-2-carbonitrile (up to 44% yield) and four minor side products: 2,7-dichlorothiazolo[5,4-d]pyrimidine-5-carbonitrile, 2-(4-chloro-6H-thiazolo[5,4-c][1,2,6]thia-diazin-6-ylidene)malononitrile, 4,8-dichloropyrrolo[2′,1′:2,3]imidazo[4,5-c][1,2,6]thiadiazine-6,7-dicarbonitrile and 4,7-dichloro-[1,2,6]thiadiazino[3,4-b]thiazolo[5,4-e][1,4]diazepin-9(10H)-one. Single crystal X-ray studies support the structures of the minor products. Tentative rationale for the formation of these minor products and the synthesis of 8-bromo-4-chloropyrrolo[2′,1′:2,3]imidazo[4,5-c][1,2,6]thiadiazine-6,7-dicarbonitrile are presented.     

Comparison of PD BLADE with fat saturation (FS), PD FS and T2 3D DESS with water excitation (WE) in detecting articular knee cartilage defects

The purpose of this study, is to compare the sequences: 1) proton density (PD) BLADE (BLADE is a PROPELLER-equivalent implementation of the Siemens Medical System) with fat saturation (FS) coronal (COR), 2) PD FS COR, 3) multi-planar reconstruction (MPR) with 3 mm slice thickness and 4) multi-planar reconstruction (MPR) with 1.5 mm slice thickness, both from the T2 3D-double-echo steady state (DESS) with water excitation (WE) sagittal (SAG), regarding their abilities to identify changes in the femorotibial condyle cartilage in knee MRI examinations. Thirty three consecutive patients with osteoarthritis (18 females, 15 males; mean age 56 years, range 37–71 years), who had been routinely scanned for knee examination using the previously mentioned image acquisition techniques, participated in the study. A quantitative analysis was performed based on the relative contrast (ReCON) measurements, which were taken both on normal tissues as well as on pathologies. Additionally, a qualitative analysis was performed by two radiologists. Motion and pulsatile flow artifacts were evaluated. The PD BLADE FS COR sequence produced images of higher contrast between Menisci and Cartilage, Fluid and Cartilage, Pathologies and Cartilage as well as of the Conspicuousness Superficial Cartilage and it was found to be superior to the other sequences (p < 0.001). The sequences T2 3D DESS 1.5 mm and T2 3D DESS 3 mm were significantly superior to the PD BLADE FS COR and the PD FS COR sequences in the visualization of Bone and Cartilage and the Conspicuousness Deep Surface Cartilage. This pattern of results is also confirmed by the quantitative analysis. PD FS BLADE sequences are ideal for the depiction of the cartilage pathologies compared to the conventional PD FS and T2 3D DESS sequences.     

Elimination of motion,pulsatile flow and cross-talk artifacts using blade sequences in lumbar spine MR imaging

The purpose of this study is to evaluate the ability of T2 turbo spin echo (TSE) axial and sagittal BLADE sequences in reducing or even eliminating motion, pulsatile flow and cross-talk artifacts in lumbar spine MRI examinations. Forty four patients, who had routinely undergone a lumbar spine examination, participated in the study. The following pairs of sequences with and without BLADE were compared: a) T2 TSE Sagittal (SAG) in thirty two cases, and b) T2 TSE Axial (AX) also in thirty two cases. Both quantitative and qualitative analyses were performed based on measurements in different normal anatomical structures and examination of seven characteristics, respectively. The qualitative analysis was performed by experienced radiologists. Also, the presence of image motion, pulsatile flow and cross-talk artifacts was evaluated. Based on the results of the qualitative analysis for the different sequences and anatomical structures, the BLADE sequences were found to be significantly superior to the conventional ones in all the cases. The BLADE sequences eliminated the motion artifacts in all the cases. In our results, it was found that in the examined sequences (sagittal and axial) the differences between the BLADE and conventional sequences regarding the elimination of motion, pulsatile flow and cross-talk artifacts were statistically significant. In all the comparisons, the T2 TSE BLADE sequences were significantly superior to the corresponding conventional sequences regarding the classification of their image quality. In conclusion, this technique appears to be capable of potentially eliminating motion, pulsatile flow and cross-talk artifacts in lumbar spine MR images and producing high quality images in collaborative and non-collaborative patients.     

Referential Doyle-Ericksen formulae for the Eshelby tensor in non-linear elasticity

This article introduces referential Doyle-Ericksen formulae for the various Eshelby tensors in the context of the covariant theory of non-linear elasticity. In light of these formulae, reciprocal equilibrium equations involving stress and energy-momentum are discussed for material bodies embedded in smooth manifolds.     

Photophysics,electrochemical properties,and electroluminescence of poly(p‐phenylenevinylene) derivatives with 1,3,5‐triphenylbenzene or 2,4,6‐triphenylpyridine segments along the backbone

The steady‐state and time‐resolved photoluminescence (PL), electrochemical behavior, and electroluminescence (EL) of didodecyloxy poly(p‐phenylenevinylene)‐based polymers that contained along the backbone structure 1,3,5‐triphenylbenzene (PC) or 2,4,6‐triphenylpyridine (PN) were studied. An intensive green PL broad‐band emission with maxima at 516 and 527 nm was observed from thin films of PC and PN polymers, respectively, redshifted in comparison with the PL emission spectra measured in tetrahydrofuran solutions. The PL decay dynamics revealed the existence of more than one excited species, and the decay curves were best described by three‐term exponential functions with a dominant lifetime of about 1 ns. The results of time‐resolved PL and steady‐state PL studies indicated excimer or aggregate formation. Both polymers oxidized irreversibly. A quasireversible reduction was observed in the PN polymer, whereas the PC polymer reduced irreversibly. For PC, slightly higher values of the ionization potential (E_IP) and electron affinity (E_A) were found (E_IP = 5.52 eV, E_A = 2.85 eV) than those for PN (E_IP = 5.37 eV, E_A = 2.77 eV). Light‐emitting devices with indium tin oxide hole‐injecting and aluminum electron‐injecting electrodes were prepared and studied. They emitted green light, and their EL spectra were similar to those of PL thin films. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 524–533, 2006     

The Reaction of Diethylthiophosphinyl Iodide,Et2P(S)I,with Nucleophiles

The compound Me₂AsSI can exist in two different forms, either as dimethylarsinosulfenyl iodide [or (iodothio)dimethylarsane)], Me₂As–S–I ( A ), or as dimethylthioarsinyl iodide (or dimethylarsinothioic iodide), Me₂As(S)–I ( B ). To confirm that the structure of the product of the reaction between Bunsen's cacodyl disulfide Me₂As(S)–S–AsMe₂ and iodine is A and not B , the known diethylthiophosphinyl iodide (or diethylphosphinothioic iodide), Et₂P(S)–I ( 2 ) was prepared and its hydrolytic stability and reactivity towards a variety of nitrogen, phosphorus(III), arsenic(III), oxygen, and sulfur(II) nucleophiles were studied. The results indicated that only a few reactions of 2 resembled those of A , thus strengthening the proposal that the reaction of Bunsen's cacodyl disulfide with iodine produced A and not B . A series of ³¹P NMR chemical shifts of diethylthiophosphinyl moiety is also reported. Et₂P(S)–DMAP, synthesized and isolated during the presented study, is the ethyl analogue of Me₂P(S)–DMAP, previously described as an important molecule. In our case, Et₂P(S)–DMAP was found to be a good intermediate for the synthesis of phosphoryl or thiophosphoryl derivatives since it was more reactive than 2 towards nucleophiles.     

Low‐frequency electromagnetic scattering by a metal torus in a lossless medium with magnetic dipolar illumination

The present contribution is concerned with an analytical presentation of the low‐frequency electromagnetic fields, which are scattered off a highly conductive ring torus that is embedded within an otherwise lossless ambient and interacting with a time‐harmonic magnetic dipole of arbitrary orientation, located nearby in the three‐dimensional space. Therein, the particular 3‐D scattering boundary value problem is modeled with respect to the solid impenetrable torus‐shaped body, where the toroidal geometry fits perfectly. The incident, the scattered, and the total non‐axisymmetric magnetic and electric fields are expanded in terms of positive integral powers of the real‐valued wave number of the exterior medium at the low‐frequency regime, whereas the static Rayleigh approximation and the first three dynamic terms provide the most significant part of the solution, because all the additional terms are small contributors and, hence, they are neglected. Consequently, the typical Maxwell‐type physical problem is transformed into intertwined either Laplace's or Poisson's potential‐type boundary value problems with the proper conditions, attached to the metallic surface of the torus. The fields of interest assume representations via infinite series expansions in terms of standard toroidal eigenfunctions, obtaining in that way analytical closed‐form solutions in a compact fashion. Although this mathematical procedure leads to infinite linear systems for every single case, these can be readily and approximately solved at a certain level of desired accuracy through standard cut‐off techniques. Copyright © 2016 John Wiley & Sons, Ltd.     

Theoretical and experimental investigation of the semiquinone forms of protocatechuic acid. The effect of manganese

Ten oxidized, oxygenated and dimeric forms of protocatechuic acid (PCA, 3,4-dihydroxybenzoic acid, 3,4-DHBA) have been studied using DFT calculations (at the B3LYP/TZVP level of theory) and their structural and spectroscopic parameters (electronic transitions, NMR resonances) have been calculated. Combination with experimental results (under anaerobic or aerobic environment) determines the conditions for the existence of protonated, fully deprotonate and/or oxygenated semiquinones of PCA. Several energy optimized conformers containing manganese–(PCA–semiquinones) and water or/and peroxo-groups have been drawn (species 11–16) and their structural and spectroscopic properties have been calculated at the same level of theory. Experimental parallel to the theoretical results provide evidence for the existence of Mn(II)– and Mn(III)–[PCA–semiquinone] as well the conditions of dioxygen activation. Two of the blue solids (17 and 18) isolated from these solutions, have been characterized. Elemental analyzes, TGA, IR and ESR spectra support the formulation Mn₂(PCA)₂(O₂)(OH)₂(AcO)(ClO₄)₂(H₂O)₃ (17), and Mn₂(PCA)₂(O₂)₂(OH)₂(AcO)H₂O (18). Their ESR spectra, in solution (blue solutions), are almost identical and indicative of Mn(IV) existence. From the whole investigation, the activation of dioxygen by the PCA, its relocation on manganese and the oxidation of the metal ion have been provided.