Nitrogen Bridged Diazocines: Photochromes Switching within the Near-Infrared Region with High Quantum Yields in Organic Solvents and in Water.

Diazocines are bridged azobenzenes with superior photophysical properties. In contrast to azobenzenes the Z configuration is thermodynamically stable and the E isomer is metastable. We present a new class of nitrogen bridged diazocines with bathochromically shifted switching wavelengths and remarkably high quantum yields (-NH-CH2- bridged diazocine: ΦZ→E = 0.57, ΦE→Z = 0.8). Z to E isomerization is induced by irradiation with blue light, whereas switching back to the Z isomer is accomplished with light in the near-infrared window (up to 740 nm), which is important for medical applications like photopharmacology (deep tissue penetration). Furthermore, substitution at the bridging nitrogen should provide access to widely applicable tricyclic, photoswitchable pharmacophores. The -NAc-CH2- bridged derivative is soluble in water, and all photophysical properties (conversion rates, quantum yields, and thermal half-lives) are largely retained. Hence, this diazocine is an ideal photoswitch for applications in biochemical systems and in photopharmacology.

Dendronised Ni(ii) porphyrins as photoswitchable contrast agents for MRI.

Light-responsive contrast agents for magnetic resonance imaging (MRI) based on Ni(ii) porphyrin molecular spin switches have recently been introduced. We present their implementation in water and methanol based gels leading to the first soft materials that are rewritable with light and readable with MRI. Light of two different wavelengths as non-invasive stimuli can be applied to switch MRI contrast on and off, with a high spatiotemporal resolution and without fatigue.

Optimized Schlieren imaging for real-time visualization of high-intensity focused ultrasound waves.

OBJECTIVES: This article presents an low-cost experimental setup for visualizing refraction anomalies caused by high-intensity focused ultrasound (HIFU). The technique is based on Schlieren imaging, commonly used to visualize temperature and pressure differences in a medium. With this setup, double images of the Schlieren or their shadows to be investigated occur, so that the experimental setup is modified to avoid these double image artifacts. METHODS: The optical setup mainly consists of a point light source, a parabolic mirror, and a camera. Birefringence artifacts are avoided by placing the point light source at a certain vertical distance to the camera, so that the light beam passes through the medium only once. The soundfield is generated by a HIFU transducer in a water tank placed in the beam path of the optical setup. RESULTS: The experimental setup is capable of capturing Schlieren or shadow images. These images show the soundfield without disturbing double images and enable further analysis and qualitative assessment of the soundfield. CONCLUSIONS: The presented setup provides a reliable and efficient method for visualizing refraction anomalies caused by the sonic field of a HIFU transducer and allows for accurate depiction of the refraction anomalies. The double images that usually occur are avoided.

Cognition and sensation in very high static magnetic fields: a randomized case-crossover study with different field strengths.

PURPOSE: To establish the extent to which representative cognitive functions in subjects undergoing magnetic resonance (MR) imaging are acutely impaired by static magnetic fields of varying field strengths. MATERIALS AND METHODS: This study was approved by the local ethics committee, and informed consent was obtained from all subjects. In this single-blind case-crossover study, 41 healthy subjects underwent an extensive neuropsychologic examination while in MR units of differing field strengths (1.5, 3.0, and 7.0 T), including a mock imager with no magnetic field as a control condition. Subjects were blinded to field strength. Tests were performed while subjects were lying still in the MR unit and while the examination table was moved. The tests covered a representative set of cognitive functions, such as memory, eye-hand coordination, attention, reaction time, and visual discrimination. Subjective sensory perceptions were also assessed. Effects were analyzed with a repeated-measures analysis of variance; the within-subject factors were field strength (0, 1.5, 3.0, and 7.0 T) and state (static, dynamic). RESULTS: Static magnetic fields were not found to have a significant effect on cognitive function at any field strength. However, sensory perceptions did vary according to field strength. Dizziness, nystagmus, phosphenes, and head ringing were related to the strength of the static magnetic field. CONCLUSION: Static magnetic fields as high as 7.0 T did not have a significant effect on cognition.

A cross-over study of effects on the hypothalamus-pituitary-adrenal (HPA) axis and the sympathoadrenergic system in magnetic field strength exposure from 0 to 7 T.

The concept of stress is relevant to magnetic resonance imaging (MRI) examination in various ways. First, levels of stress to staff and patients have not been quantified in ultra-high magnetic fields. Second, research is increasingly interested in experimentally defining regional brain activity during stress. It is therefore important to know whether exposure to the ultra-high static magnetic fields per se might also lead to neurohormonal responses in the hypothalamus-pituitary-adrenal axis and the sympathoadrenal systems. In the present blinded case cross-over study with 41 healthy participants, we measured cortisol not only before and after but also during static magnetic field exposure in MRI scanners. Measures of catecholamines before and after exposure were also part of the study protocol. Using three different field strengths (1.5, 3 and 7 T) and a mock scanner (0 T), we examined whether not only the MRI procedure but also the static magnetic field per se has an influence on the neuroendocrine responses. We found no significant differences in the course of cortisol or catecholamine concentrations between the different static magnetic fields. Our study suggests that the results of MRI studies using stress-paradigms are not influenced by the static magnetic field itself.

Multi-contrast T2(⁎)-relaxometry upon visual stimulation at 3T and 7T.

This study aims to quantify the mean change of the effective transverse relaxation time T2(⁎) in active brain regions of human volunteers at field strengths of B0=3T and 7T. Besides the mono-exponential signal decay model an extended model is tested that considers mesoscopic field gradients across imaging voxels. Both models are checked for cross-talk and correlations between the parameters. A visual checkerboard-stimulation experiment with pause and stimulation periods of 50s and six repetitions was performed on healthy volunteers. Eleven contrasts were acquired in about 1.47s/1.43s at 3T/7T using a segmented multi-contrast echo-planar imaging (EPI) sequence. Average BOLD-signal time courses were calculated in a multi-step (non-)linear least-squares process. Baseline T2(⁎) values of 37.72ms/24.99ms (47.34ms/33.71ms) with stimulus-correlated changes ∆T2(⁎)of 1.32ms/0.74ms (1.99ms/1.43ms) resulted from the mono-exponential (extended) model for 3T/7T. A dependence of those values on the initial intensity S0 was observed. Stimulus-correlated changes of S0 in the order of 1% were measured at both field strengths. The mono-exponential model was found to be less prone to instabilities in the regression of both parameters. Signal alterations due to inflow were observed. Measured relaxation times agree with values from literature using repetitive stimulation. A strong dependence of the measured relaxation times on the inflow-related model parameter was found for both models. The extended model is applicable to dynamic neurofunctional measurements, but is currently limited due to the low number of contrasts acquired.

Azoimidazole functionalized Ni-porphyrins for molecular spin switching and light responsive MRI contrast agents.

Azo-N-methylimidazole functionalized Ni(ii)porphyrins were rationally designed and synthesized and their performance as molecular spin switches was investigated. They perform intramolecular light-driven coordination-induced spin state switching (LD-CISSS) in the presence of water and therefore are an important step towards spin switches for medicinal applications, particularly functional MRI contrast agents.

Modular Coils with Low Hydrogen Content Especially for MRI of Dry Solids.

INTRODUCTION: Recent advances have enabled fast magnetic resonance imaging (MRI) of solid materials. This development has opened up new applications for MRI, but, at the same time, uncovered new challenges. Previously, MRI-invisible materials like the housing of MRI detection coils are now readily depicted and either cause artifacts or lead to a decreased image resolution. In this contribution, we present versatile, multi-nuclear single and dual-tune MRI coils that stand out by (1) a low hydrogen content for high-resolution MRI of dry solids without artifacts; (2) a modular approach with exchangeable inductors of variable volumes to optimally enclose the given object; (3) low cost and low manufacturing effort that is associated with the modular approach; (4) accurate sample placement in the coil outside of the bore, and (5) a wide, single- or dual-tune frequency range that covers several nuclei and enables multinuclear MRI without moving the sample. MATERIALS AND METHODS: The inductors of the coils were constructed from self-supporting copper sheets to avoid all plastic materials within or around the resonator. The components that were mounted at a distance from the inductor, including the circuit board, coaxial cable and holder were manufactured from polytetrafluoroethylene. RESULTS AND CONCLUSION: Residual hydrogen signal was sufficiently well suppressed to allow 1H-MRI of dry solids with a minimum field of view that was smaller than the sensitive volume of the coil. The SNR was found to be comparable but somewhat lower with respect to commercial, proton-rich quadrature coils, and higher with respect to a linearly-polarized commercial coil. The potential of the setup presented was exemplified by 1H/23Na high-resolution zero echo time (ZTE) MRI of a model solution and a dried human molar at 9.4 T. A full 3D image dataset of the tooth was obtained, rich in contrast and similar to the resolution of standard cone-beam computed tomography.

Women are more strongly affected by dizziness in static magnetic fields of magnetic resonance imaging scanners.

Increasing field strengths in MRI necessitate the examination of potential side effects. Previously reported results have been contradictory, possibly caused by imbalanced samples. We aimed to examine whether special groups of people are more prone to develop side effects that might have led to contradictory results in previous studies. We examined the occurrence of sensory side effects in static magnetic fields of MRI scanners of 1.5, 3, and 7 T and a mock scanner in 41 healthy participants. The contribution of field strength, sex, age, and attention to bodily processes, and stress hormone levels to the sensation of dizziness was examined in separate univariate analyses and in a joint analysis that included all variables. Field strength and sex were significant factors in the joint analysis (P=0.001), with women being more strongly affected than men by dizziness in higher static magnetic fields. This effect was not mediated by the other variables such as attention to bodily symptoms or stress hormones. Further research needs to elucidate the underlying factors of increased dizziness in women in static magnetic fields in MRI. We hypothesize that imbalanced samples of earlier studies might be one reason for previous contradictory results on the side effects of static magnetic fields.