Radical reactions enabled by polyfluoroaryl fragments: photocatalysis and beyond.

Polyfluoroarenes have been known for a long time, but they are most often used as fluorinated building blocks for the synthesis of aromatic compounds. At the same time, due to peculiar fluorine effect, they have unique properties that provide applications in various fields ranging from synthesis to materials science. This review summarizes advances in the radical chemistry of polyfluoroarenes, which have become possible mainly with the advent of photocatalysis. Transformations of the fluorinated ring via the C-F bond activation, as well as use of fluoroaryl fragments as activating groups and hydrogen atom transfer agents are discussed. The ability of fluoroarenes to serve as catalysts is also considred.

Direct conversion of carboxylic acids to free thiols via radical relay acridine photocatalysis enabled by N-O bond cleavage.

Carboxylic acids and thiols are basic chemical compounds with diverse utility and widespread reactivity. However, the direct conversion of unprotected acids to thiols is hampered due to a fundamental problem - free thiols are incompatible with the alkyl radicals formed on decarboxylation of carboxylic acids. Herein, we describe a concept for the direct photocatalytic thiolation of unprotected acids allowing unprotected thiols and their derivatives to be obtained. The method is based on the application of a thionocarbonate reagent featuring the N-O bond. The reagent serves both for the rapid trapping of alkyl radicals and for the facile regeneration of the acridine-type photocatalyst.

Clinical Value and Reliability of Quantitative Assessments of Lumbosacral Nerve Root Using Diffusion Tensor and Diffusion Weighted MR Imaging: A Systematic Review.

BACKGROUND: Lumbosacral radicular pain diagnosis remains challenging. Diffusion tensor imaging (DTI) and diffusion weighted imaging (DWI) have potential to quantitatively evaluate symptomatic nerve root, which may facilitate diagnosis. PURPOSE: To determine the ability of DTI and DWI metrics, namely fractional anisotropy (FA) and apparent diffusion coefficient (ADC), to discriminate between healthy and symptomatic lumbosacral nerve roots, to evaluate the association between FA and ADC values and patient symptoms, and to determine FA and ADC reliability. STUDY TYPE: Systematic review. SUBJECTS: Eight hundred twelve patients with radicular pain with or without radiculopathy caused by musculoskeletal-related compression or inflammation of a single, unilateral lumbosacral nerve root and 244 healthy controls from 29 studies. FIELD STRENGTH/SEQUENCE: Diffusion weighted echo planar imaging sequence at 1.5 T or 3 T. ASSESSMENT: An extensive systematic review of the literature was conducted in Embase, Scopus, and Medline databases. FA and ADC values in symptomatic and contralateral lumbosacral nerve roots were extracted and summarized, together with intra- and inter-rater agreements. Where available, associations between DWI or DTI parameters and patient symptoms or symptom duration were extracted. STATISTICAL TESTS: The main results of the included studies are summarized. No additional statistical analyses were performed. RESULTS: The DTI studies systematically found significant differences in FA values between the symptomatic and contralateral lumbosacral nerve root of patients suffering from radicular pain with or without radiculopathy. In contrast, identification of the symptomatic nerve root with ADC values was inconsistent for both DTI and DWI studies. FA values were moderately to strongly correlated with several symptoms (eg, disability, nerve dysfunction, and symptom duration). The inter- and intra-rater reliability of DTI parameters were moderate to excellent. The methodological quality of included studies was very heterogeneous. DATA CONCLUSION: This systematic review showed that DTI was a reliable and discriminative imaging technique for the assessment of symptomatic lumbosacral nerve root, which more consistently identified the symptomatic nerve root than DWI. Further studies of high quality are needed to confirm these results. EVIDENCE LEVEL: N/A TECHNICAL EFFICACY: Stage 2.

A Deep Learning Framework for Cardiac MR Under-Sampled Image Reconstruction with a Hybrid Spatial and k-Space Loss Function.

Magnetic resonance imaging (MRI) is an efficient, non-invasive diagnostic imaging tool for a variety of disorders. In modern MRI systems, the scanning procedure is time-consuming, which leads to problems with patient comfort and causes motion artifacts. Accelerated or parallel MRI has the potential to minimize patient stress as well as reduce scanning time and medical costs. In this paper, a new deep learning MR image reconstruction framework is proposed to provide more accurate reconstructed MR images when under-sampled or aliased images are generated. The proposed reconstruction model is designed based on the conditional generative adversarial networks (CGANs) where the generator network is designed in a form of an encoder-decoder U-Net network. A hybrid spatial and k-space loss function is also proposed to improve the reconstructed image quality by minimizing the L1-distance considering both spatial and frequency domains simultaneously. The proposed reconstruction framework is directly compared when CGAN and U-Net are adopted and used individually based on the proposed hybrid loss function against the conventional L1-norm. Finally, the proposed reconstruction framework with the extended loss function is evaluated and compared against the traditional SENSE reconstruction technique using the evaluation metrics of structural similarity (SSIM) and peak signal to noise ratio (PSNR). To fine-tune and evaluate the proposed methodology, the public Multi-Coil k-Space OCMR dataset for cardiovascular MR imaging is used. The proposed framework achieves a better image reconstruction quality compared to SENSE in terms of PSNR by 6.84 and 9.57 when U-Net and CGAN are used, respectively. Similarly, it demonstrates SSIM of the reconstructed MR images comparable to the one provided by the SENSE algorithm when U-Net and CGAN are used. Comparing cases where the proposed hybrid loss function is used against the cases with the simple L1-norm, the reconstruction performance can be noticed to improve by 6.84 and 9.57 for U-Net and CGAN, respectively. To conclude this, the proposed framework using CGAN provides the best reconstruction performance compared with U-Net or the conventional SENSE reconstruction techniques. The proposed framework seems to be useful for the practical reconstruction of cardiac images since it can provide better image quality in terms of SSIM and PSNR.

Improving detection of fMRI activation at 1.5 T using high permittivity ceramics.

In this work, we propose an application of high permittivity materials (HPMs) to improve functional magnetic resonance imaging (fMRI) at 1.5 T, increasing the receive (Rx) sensitivity of a commercial multi-channel head coil. To evaluate the transmit efficiency, specific absorption rate (SAR), and the signal-to-noise ratio (SNR) changes introduced by the HPMs with relative permittivity of 4500, we considered the following configurations in simulation: a whole-body birdcage coil and an Rx-only multi-channel head coil with and without the HPM blocks in the presence of a homogeneous head phantom or a human body model. Experimental studies were also performed with a phantom and with volunteers. Seven healthy volunteers enrolled in a prospective study of fMRI activation in the motor cortex with and without HPMs. fMRI data were analyzed using group-level paired T-tests between acquisitions with and without HPM blocks. Both electromagnetic simulations and experimental measurements showed ∼25% improvement in the Rx sensitivity of a commercial head coil in the areas of interest when HPM blocks were placed in close proximity. It increased the detected motor cortex fMRI activation volume by an average of 56%, thus resulting in more sensitive functional imaging at 1.5 T.

Light-Promoted Dearylation of Perfluorinated Aryl Sulfides with N-Heterocyclic Carbene-Borane.

The removal of the tetrafluoropyridinyl group tethered to a sulfur atom using a complex of N-heterocyclic carbene (NHC) with borane is described. The reaction is performed under blue light irradiation with a disulfide as radical initiator. The selective cleavage of S-Ar in preference to the weaker S-Alk bond is achieved as a result of aromatic radical substitution of the thiyl group by a NHC-stabilized boron-centered radical. Alkyl thiols, which are the primary products of the dearylation, are in situ oxidized or alkylated, affording disulfides or sulfides, respectively.

Flow cytometric sorting of loricate choanoflagellates from the oligotrophic ocean.

It is challenging to study protists with extensive, loosely-associated extracellular structures because of the problems with keeping specimens intact. Here we have tested the suitability of high-speed flow cytometric sorting as a tool for studying such protists using oceanic loricate choanoflagellates as a model. We chose choanoflagellates because their lorica-to-cell volume ratio is > 10 and the voluminous loricae, i.e., the siliceous cell baskets essential for taxonomic identification, only loosely enclose the cells. Besides, owing to low concentrations, choanoflagellates are grossly under-sampled in the oligotrophic ocean. On four research cruises the small heterotrophic protists from samples collected in the photic layer of the South Atlantic and South Pacific oligotrophic (sub)tropical gyres and adjacent mesotrophic waters were flow sorted at sea for electron microscopy ashore. Among the flow-sorted protozoa we were able to select loricate choanoflagellates to assess their species diversity and concentrations. The well-preserved loricae of flow-sorted choanoflagellates made identification of 29 species from 14 genera possible. In the oligotrophic waters, we found neither endemic species nor evident morphological adaptations other than a tendency for lighter silicification of loricae. Common sightings of specimens storing extra costae in preparation for division, indicate choanoflagellates thriving in oligotrophic waters rather than enduring them. Thus, this case study demonstrates that high-speed flow sorting can assist in studying protists with extracellular structures 16-78× bigger than the enclosed cell.

Notable predominant morphology of the smallest most abundant protozoa of the open ocean revealed by electron microscopy.

In the microbe-driven ecosystems of the open ocean, the small heterotrophic flagellates (sHF) are the chief microbial predators and recyclers of essential nutrients to phototrophic microbes. Even with intensive molecular phylogenetic studies of the sHF, the origins of their feeding success remain obscure because of limited understanding of their morphological adaptations to feeding. Here, we examined the sHF morphologies in the largest, most oligotrophic South Pacific and Atlantic (sub)tropical gyres and adjacent mesotrophic waters. On four research cruises, the sHF cells were flow cytometrically sorted from bacterioplankton and phytoplankton for electron microscopy. The sorted sHF comprised chiefly heterokont (HK) biflagellates and unikont choanoflagellates numerically at around 10-to-1 ratio. Of the four differentiated morphological types of HK omnipresent in the open ocean, the short-tinsel heterokont (stHK), whose tinsel flagellum is too short to propagate a complete wave, is predominant and a likely candidate to be the most abundant predator on Earth. Modeling shows that the described stHK propulsion is effective in feeding on bacterioplankton cells at low concentrations; however, owing to general prey scarcity in the oligotrophic ocean, selective feeding is unsustainable and omnivory is equally obligatory for the seven examined sHF types irrespective of their mode of propulsion.

Evaluation of new MR invisible silicon carbide based dielectric pads for 7 T MRI.

PURPOSE: The use of dielectric pads to redistribute the radiofrequency fields is currently a popular solution for 7 T MRI practical applications, especially in brain imaging. In this work, we tackle several downsides of the previous generation of dielectric pads. This new silicon carbide recipe makes them MR invisible and greatly extends the performance lifespan. METHOD: We produce a set of two 10x10x1cm3 dielectric pads based on silicon carbide (SiC) powder dispersed in 4-Fluoro 1, 3-dioxalan-2-one (FEC) and polyethylene Glycol (PEG). The stability of the complex permittivity and the invisibility of the pads are characterized experimentally. Numerical simulations are done to evaluate global and local SAR over the head in presence of the pads. B0, B1+ and standard imaging sequences are performed on healthy volunteers. RESULTS: SiC pads are compared to state-of-the-art perovskite based dielectric pads with similar dielectric properties (barium titanate). Numerical simulations confirm that head and local SAR are similar. MRI measurements confirm that the pads do not induce susceptibility artefacts and improve B1+ amplitude in the temporal lobe regions by 25% on average. CONCLUSION: We demonstrate the long-term performance and invisibility of these new pads in order to increase the contrast in the brain temporal lobes in a commercial 7 T MRI head coil.

Photocatalyzed Decarboxylative Thiolation of Carboxylic Acids Enabled by Fluorinated Disulfide.

Thiolation of carboxylic acids using a disulfide reagent having tetrafluoropyridinyl groups is described. The light-mediated process is performed using an acridine-type photocatalyst. Primary, secondary, tertiary, and heteroatom-substituted carboxylic acids can be thiolated, and the method can be applied to the late-stage modification of a range of naturally occurring compounds and drugs. The fluorinated pyridine fragment is believed to enable the C-S bond formation. The resulting sulfides were used as redox-active radical precursors.

Imaging Capabilities of the ¹H-X-Nucleus Metamaterial-Inspired Multinuclear RF-Coil.

In this paper, we present the initial experimental investigation of a two-coil receive/transmit design for small animals imaging at 7T MRI. The system uses a butterfly-type coil tuned to 300 MHz for scanning the 1H nuclei and a non-resonant loop antenna with a metamaterial-inspired resonator with the ability to tune over a wide frequency range for X-nuclei. 1H, 31P, 23Na and 13C, which are of particular interest in biomedical MRI, were selected as test nuclei in this work. Coil simulations show the two parts of the radiofrequency (RF) assembly to be decoupled and operating independently due to the orthogonality of the excited RF transverse magnetic fields. Simulations and phantom experimental imaging show sufficiently homogeneous transverse transmit RF fields and tuning capabilities for the pilot multiheteronuclear experiments.

Using the Thiyl Radical for Aliphatic Hydrogen-Atom Transfer: Thiolation of Unactivated C-H Bonds.

A metal- and catalyst-free thiyl-radical-mediated activation of alkanes is described. Tetrafluoropyridinyl disulfide is used to perform thiolation of the C-H bonds under irradiation with 400 nm light-emitting diodes. The key C-H activation step is believed to proceed via hydrogen-atom abstraction effected by the fluorinated thiyl radical. Secondary, tertiary, and heteroatom-substituted C-H bonds can be involved in the thiolation reaction. The resulting sulfides have wide potential as photoredox-active radical precursors in reactions with alkenes and heteroarenes.

Radiometric approach for the detection of picophytoplankton assemblages across oceanic fronts.

Cell abundances of Prochlorococcus, Synechococcus, and autotrophic picoeukaryotes were estimated in surface waters using principal component analysis (PCA) of hyperspectral and multispectral remote-sensing reflectance data. This involved the development of models that employed multilinear correlations between cell abundances across the Atlantic Ocean and a combination of PCA scores and sea surface temperatures. The models retrieve high Prochlorococcus abundances in the Equatorial Convergence Zone and show their numerical dominance in oceanic gyres, with decreases in Prochlorococcus abundances towards temperate waters where Synechococcus flourishes, and an emergence of picoeukaryotes in temperate waters. Fine-scale in-situ sampling across ocean fronts provided a large dynamic range of measurements for the training dataset, which resulted in the successful detection of fine-scale Synechococcus patches. Satellite implementation of the models showed good performance (R2 > 0.50) when validated against in-situ data from six Atlantic Meridional Transect cruises. The improved relative performance of the hyperspectral models highlights the importance of future high spectral resolution satellite instruments, such as the NASA PACE mission's Ocean Color Instrument, to extend our spatiotemporal knowledge about ecologically relevant phytoplankton assemblages.

Fluoroalkyl sulfides as photoredox-active coupling reagents for alkene difunctionalization.

A visible-light-promoted fluoroalkylation-thiolation of alkenes is described. A 4-tetrafluoropyridinylthio fragment serves as a photoredox-active group in the initiation step and undergoes a radical group transfer, which is important for the reaction efficiency. In the primary products, the pyridinylthio substituent may be further functionalized via radical processes or an aromatic substitution reaction.

Loricate choanoflagellates (Acanthoecida) from warm water seas. VII. Calotheca Thomsen and Moestrup, Stephanacantha Thomsen and Syndetophyllum Thomsen and Moestrup.

The tectiform loricate choanoflagellate genera Calotheca, Stephanacantha and Syndetophyllum have all been first described from warm water habitats and share the presence of flattened and often elaborate costal strips in the lorica. The current reinvestigation does confirm both the widespread occurrence of these taxa within the global warm water belt, and largely corroborates the established genus and species matrix. We describe here Stephanacantha oceanica sp. nov. which closely resembles S. campaniformis, and transfer Parvicorbicula zigzag to the genus Stephanacantha, despite differences in costal strip morphology, but based on a complete agreement in lorica constructional details.

Loricate choanoflagellates (Acanthoecida) from warm water seas. VI. Pleurasiga Schiller and Parvicorbicula Deflandre.

The loricate choanoflagellate genera Pleurasiga and Parvicorbicula are taxonomically ambiguous. Pleurasiga because of the uncertainty that relates to the true identity of the type species, and Parvicorbicula because too many newly described species over time have been dumped here in lack of better options. While all species currently allocated to the genus Pleurasiga (with the exception of the type species) are observed in our samples from the global warm water belt, the genus Parvicorbicula is represented by just a few and mostly infrequently recorded taxa. Two new species, viz. Pl. quadrangiella sp. nov. and Pl. minutissima sp. nov., are described here. While the former is closely related to Pl. echinocostata, the latter is reminiscent of Pl. minima. Core species of Pleurasiga and Parvicorbicula deviate from the vast majority of loricate choanoflagellates in having both the anterior and the mid-lorica transverse costae located exterior to the longitudinal costae. In Pl. quadrangiella there is no mid-lorica transverse costa but rather a small posterior transverse costa located inside the longitudinal costae. In Pl. minutissima the mid-lorica transverse costa has extensive costal strip overlaps which reveal patterns of costal strip junctions that deviate from the norm.

Design of a RF-resonant set improving locally the B1+ efficiency. Applications for clinical MRI in andrology and urology.

Modern diagnostic imaging methods for andrology and urology fall behind other well-developed applications such as cardiology or neurology. Particularly, MRI despite its superior soft tissue contrast is hardly used for MR-imaging of the penis, primarily due to the lack of the corresponding receive or transmit coils. In order to fix this, a new radio frequency resonator, based on the birdcage operating principles has been designed, simulated, fabricated, tested and compared experimentally to existing RF coils. In order to provide high transmit efficiency and high sensitivity, while maintaining the coil safety, the resonator spatially separates alternating magnetic and electric fields. The transmitted magnetic field (B1+) is concentrated in the centre of the imaging volume, while the electric field remains on its edge and does not lead to tissue heating. The resonator design was optimised for human MRI in 1.5 T scanners. Both simulations and experiment showed the resonator to provide around 100-fold specific absorption rate reduction, around 10-fold improvement of the transmit efficiency and more than 10-fold enhancement of the signal to noise ratio (SNR) in a phantom compared to the body coil, around 2-fold SNR enhancement in a phantom compared to the commercial flexible 4-element coil, and up to 1.5-fold enhancement compared to the same coil in-vivo.

Accumulation of ambient phosphate into the periplasm of marine bacteria is proton motive force dependent.

Bacteria acquire phosphate (Pi) by maintaining a periplasmic concentration below environmental levels. We recently described an extracellular Pi buffer which appears to counteract the gradient required for Pi diffusion. Here, we demonstrate that various treatments to outer membrane (OM) constituents do not affect the buffered Pi because bacteria accumulate Pi in the periplasm, from which it can be removed hypo-osmotically. The periplasmic Pi can be gradually imported into the cytoplasm by ATP-powered transport, however, the proton motive force (PMF) is not required to keep Pi in the periplasm. In contrast, the accumulation of Pi into the periplasm across the OM is PMF-dependent and can be enhanced by light energy. Because the conventional mechanism of Pi-specific transport cannot explain Pi accumulation in the periplasm we propose that periplasmic Pi anions pair with chemiosmotic cations of the PMF and millions of accumulated Pi pairs could influence the periplasmic osmolarity of marine bacteria.