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.

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.

"Pomacytosis"-Semi-extracellular phagocytosis of cyanobacteria by the smallest marine algae.

The smallest algae, less than 3 µm in diameter, are the most abundant eukaryotes of the World Ocean. Their feeding on planktonic bacteria of similar size is globally important but physically enigmatic. Tiny algal cells tightly packed with the voluminous chloroplasts, nucleus, and mitochondria appear to have insufficient organelle-free space for prey internalization. Here, we present the first direct observations of how the 1.3-µm algae, which are only 1.6 times bigger in diameter than their prey, hold individual Prochlorococcus cells in their open hemispheric cytostomes. We explain this semi-extracellular phagocytosis by the cell size limitation of the predatory alga, identified as the Braarudosphaera haptophyte with a nitrogen (N2)-fixing endosymbiont. Because the observed semi-extracellular phagocytosis differs from all other types of protistan phagocytosis, we propose to name it "pomacytosis" (from the Greek πώµα for "plug").

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.

Reconciliation of the carbon budget in the ocean's twilight zone.

Photosynthesis in the surface ocean produces approximately 100 gigatonnes of organic carbon per year, of which 5 to 15 per cent is exported to the deep ocean. The rate at which the sinking carbon is converted into carbon dioxide by heterotrophic organisms at depth is important in controlling oceanic carbon storage. It remains uncertain, however, to what extent surface ocean carbon supply meets the demand of water-column biota; the discrepancy between known carbon sources and sinks is as much as two orders of magnitude. Here we present field measurements, respiration rate estimates and a steady-state model that allow us to balance carbon sources and sinks to within observational uncertainties at the Porcupine Abyssal Plain site in the eastern North Atlantic Ocean. We find that prokaryotes are responsible for 70 to 92 per cent of the estimated remineralization in the twilight zone (depths of 50 to 1,000 metres) despite the fact that much of the organic carbon is exported in the form of large, fast-sinking particles accessible to larger zooplankton. We suggest that this occurs because zooplankton fragment and ingest half of the fast-sinking particles, of which more than 30 per cent may be released as suspended and slowly sinking matter, stimulating the deep-ocean microbial loop. The synergy between microbes and zooplankton in the twilight zone is important to our understanding of the processes controlling the oceanic carbon sink.

On-Site Analysis of Bacterial Communities of the Ultraoligotrophic South Pacific Gyre.

The South Pacific Gyre (SPG) covers 10% of the ocean's surface and is often regarded as a marine biological desert. To gain an on-site overview of the remote, ultraoligotrophic microbial community of the SPG, we developed a novel onboard analysis pipeline, which combines next-generation sequencing with fluorescence in situ hybridization and automated cell enumeration. We tested the pipeline during the SO-245 "UltraPac" cruise from Chile to New Zealand and found that the overall microbial community of the SPG was highly similar to those of other oceanic gyres. The SPG was dominated by 20 major bacterial clades, including SAR11, SAR116, the AEGEAN-169 marine group, SAR86, Prochlorococcus, SAR324, SAR406, and SAR202. Most of the bacterial clades showed a strong vertical (20 m to 5,000 m), but only a weak longitudinal (80°W to 160°W), distribution pattern. Surprisingly, in the central gyre, Prochlorococcus, the dominant photosynthetic organism, had only low cellular abundances in the upper waters (20 to 80 m) and was more frequent around the 1% irradiance zone (100 to 150 m). Instead, the surface waters of the central gyre were dominated by the SAR11, SAR86, and SAR116 clades known to harbor light-driven proton pumps. The alphaproteobacterial AEGEAN-169 marine group was particularly abundant in the surface waters of the central gyre, indicating a potentially interesting adaptation to ultraoligotrophic waters and high solar irradiance. In the future, the newly developed community analysis pipeline will allow for on-site insights into a microbial community within 35 h of sampling, which will permit more targeted sampling efforts and hypothesis-driven research.IMPORTANCE The South Pacific Gyre, due to its vast size and remoteness, is one of the least-studied oceanic regions on earth. However, both remote sensing and in situ measurements indicated that the activity of its microbial community contributes significantly to global biogeochemical cycles. Presented here is an unparalleled investigation of the microbial community of the SPG from 20- to 5,000-m depths covering a geographic distance of ∼7,000 km. This insight was achieved through the development of a novel onboard analysis pipeline, which combines next-generation sequencing with fluorescence in situ hybridization and automated cell enumeration. The pipeline is well comparable to onshore systems based on the Illumina platforms and yields microbial community data in less than 35 h after sampling. Going forward, the ability to gain on-site knowledge of a remote microbial community will permit hypothesis-driven research, through the generation of novel scientific questions and subsequent additional targeted sampling efforts.

Volumetric wireless coil based on periodically coupled split-loop resonators for clinical wrist imaging.

PURPOSE: Design and characterization of a new inductively driven wireless coil (WLC) for wrist imaging at 1.5 T with high homogeneity operating due to focusing the B1 field of a birdcage body coil. METHODS: The WLC design has been proposed based on a volumetric self-resonant periodic structure of inductively coupled split-loop resonators with structural capacitance. The WLC was optimized and studied regarding radiofrequency fields and interaction to the birdcage coil (BC) by electromagnetic simulations. The manufactured WLC was characterized by on-bench measurements and in vivo and phantom study in comparison to a standard cable-connected receive-only coil. RESULTS: The WLC placed into BC gave the measured B1+ increase of the latter by 8.6 times for the same accepted power. The phantom and in vivo wrist imaging showed that the BC in receiving with the WLC inside reached equal or higher signal-to-noise ratio than the conventional clinical setup comprising the transmit-only BC and a commercial receive-only flex-coil and created no artifacts. Simulations and on-bench measurements proved safety in terms of specific absorption rate and reflected transmit power. CONCLUSIONS: The results showed that the proposed WLC could be an alternative to standard cable-connected receive coils in clinical magnetic resonance imaging. As an example, with no cable connection, the WLC allowed wrist imaging on a 1.5 T clinical machine using a full-body BC for transmitting and receive with the desired signal-to-noise ratio, image quality, and safety.

Small-animal, whole-body imaging with metamaterial-inspired RF coil.

Particular applications in preclinical magnetic resonance imaging require the entire body of an animal to be imaged with sufficient quality. This is usually performed by combining regions scanned with small coils with high sensitivity or long scans using large coils with low sensitivity. Here, a metamaterial-inspired design employing a parallel array of wires operating on the principle of eigenmode hybridization was used to produce a small-animal imaging coil. The coil field distribution responsible for the coil field of view and sensitivity was simulated in an electromagnetic simulation package and the coil geometrical parameters were optimized for whole-body imaging. A prototype coil was then manufactured and assembled using brass telescopic tubes with copper plates as distributed capacitance. Its field distribution was measured experimentally using the B1+ mapping technique and was found to be in close correspondence with the simulated results. The coil field distribution was found to be suitable for large field of view small-animal imaging and the coil image quality was compared with a commercially available coil by whole-body scanning of living mice. Signal-to-noise measurements in living mice showed higher values than those of a commercially available coil with large receptive fields, and rivalled the performance of small receptive field and high-sensitivity coils. The coil was deemed to be suitable for some whole-body, small-animal preclinical applications.

Low-bandwidth space/frequency component separation for quantitative imaging.

Quantitative MRI is often used to analyse multicomponent systems. The analysis requires the contributions from different species to be isolated. Species with distinct chemical shifts can be separated by using a low acquisition bandwidth, which is easy to achieve in common quantitative imaging protocols. The bandwidth reduction leads to separation of NMR contributions from different species in the image space. This new method was implemented and tested on two multicomponent systems containing several spectrally and spatially unresolved components with both distinctly different and similar diffusion coefficients and relaxation times. Separation was achieved with routine MRI diffusion and relaxation measurement pulse sequences in a microimaging environment for water/polyethylene glycol solution and for chloroform/TMS/polyethylene glycol solution. Conventional monoexponential fitting was used to determine diffusion coefficients and relaxation times from the spectrally separated data, whereas biexponential or triexponential fitting was required in the unseparated reference experiments. In the two-component sample, the variation in the determined fast diffusing components was on the same order of magnitude for all experiments, while the variation in the slow diffusing polyethylene glycol was larger when no separation was present. The separation technique provided lower variability for all the determined diffusion coefficients and relaxation times in the three-component sample. The low-bandwidth separation method can provide separation of multicomponent systems based on the chemical shift difference between the species. The accuracy of the technique is comparable with the commonly used methods for bicomponent system analysis and surpasses those when there are more than two components in the sample. Copyright © 2016 John Wiley & Sons, Ltd.

Physical characterization using diffusion NMR spectroscopy.

NMR diffusion measurements (or dNMR) provide a powerful tool for analysis of solution organization and microgeometry of the environment by probing random molecular motion. Being a very versatile method, dNMR can be applied to a large variety of samples and systems. Here, a brief introduction into dNMR and a summary of recent advances in the field are presented. The research topics include restricted diffusion, anisotropic diffusion, polymer dynamics, solution structuring and dNMR method development. The dNMR studied systems include plants, cells (cell models), liquid crystals, polymer solutions, ionic liquids, supercooled solutions, untreated water, amino acid solutions and more. It is demonstrated how a variety of dNMR methods can be applied to a system to extract the data on particular structures present among, formed by or surrounding the diffusing particles. It is also demonstrated how dNMR methods can be developed to allow probing larger geometries, low sample concentrations and faster processes. Copyright © 2016 John Wiley & Sons, Ltd.

Prochlorococcus can use the Pro1404 transporter to take up glucose at nanomolar concentrations in the Atlantic Ocean.

Prochlorococcus is responsible for a significant part of CO2 fixation in the ocean. Although it was long considered an autotrophic cyanobacterium, the uptake of organic compounds has been reported, assuming they were sources of limited biogenic elements. We have shown in laboratory experiments that Prochlorococcus can take up glucose. However, the mechanisms of glucose uptake and its occurrence in the ocean have not been shown. Here, we report that the gene Pro1404 confers capability for glucose uptake in Prochlorococcus marinus SS120. We used a cyanobacterium unable to take up glucose to engineer strains that express the Pro1404 gene. These recombinant strains were capable of specific glucose uptake over a wide range of glucose concentrations, showing multiphasic transport kinetics. The Ks constant of the high affinity phase was in the nanomolar range, consistent with the average concentration of glucose in the ocean. Furthermore, we were able to observe glucose uptake by Prochlorococcus in the central Atlantic Ocean, where glucose concentrations were 0.5-2.7 nM. Our results suggest that Prochlorococcus are primary producers capable of tuning their metabolism to energetically benefit from environmental conditions, taking up not only organic compounds with key limiting elements in the ocean, but also molecules devoid of such elements, like glucose.

Steady state effects in a two-pulse diffusion-weighted sequence.

In conventional nuclear magnetic resonance (NMR) diffusion measurements a significant amount of experimental time is used up by magnetization recovery, serving to prevent the formation of the steady state, as in the latter case the manifestation of diffusion is modulated by multiple applications of the pulse sequence and conventional diffusion coefficient inference procedures are generally not applicable. Here, an analytical expression for diffusion-related effects in a two-pulse NMR experiment (e.g., pulsed-gradient spin echo) in the steady state mode (with repetition times less than the longitudinal relaxation time of the sample) is derived by employing a Fourier series expansion within the solution of the Bloch-Torrey equations. Considerations are given for the transition conditions between the full relaxation and the steady state experiment description. The diffusion coefficient of a polymer solution (polyethylene glycol) is measured by a two-pulse sequence in the full relaxation mode and for a range of repetition times, approaching the rapid steady state experiment. The precision of the fitting employing the presented steady state solution by far exceeds that of the conventional fitting. Additionally, numerical simulations are performed yielding results strongly supporting the proposed description of the NMR diffusion measurements in the steady state.

Mixotrophic basis of Atlantic oligotrophic ecosystems.

Oligotrophic subtropical gyres are the largest oceanic ecosystems, covering >40% of the Earth's surface. Unicellular cyanobacteria and the smallest algae (plastidic protists) dominate CO(2) fixation in these ecosystems, competing for dissolved inorganic nutrients. Here we present direct evidence from the surface mixed layer of the subtropical gyres and adjacent equatorial and temperate regions of the Atlantic Ocean, collected on three Atlantic Meridional Transect cruises on consecutive years, that bacterioplankton are fed on by plastidic and aplastidic protists at comparable rates. Rates of bacterivory were similar in the light and dark. Furthermore, because of their higher abundance, it is the plastidic protists, rather than the aplastidic forms, that control bacterivory in these waters. These findings change our basic understanding of food web function in the open ocean, because plastidic protists should now be considered as the main bacterivores as well as the main CO(2) fixers in the oligotrophic gyres.

High bacterivory by the smallest phytoplankton in the North Atlantic Ocean.

Planktonic algae <5 m in size are major fixers of inorganic carbon in the ocean. They dominate phytoplankton biomass in post-bloom, stratified oceanic temperate waters. Traditionally, large and small algae are viewed as having a critical growth dependence on inorganic nutrients, which the latter can better acquire at lower ambient concentrations owing to their higher surface area to volume ratios. Nonetheless, recent phosphate tracer experiments in the oligotrophic ocean have suggested that small algae obtain inorganic phosphate indirectly, possibly through feeding on bacterioplankton. There have been numerous microscopy-based studies of algae feeding mixotrophically in the laboratory and field as well as mathematical modelling of the ecological importance of mixotrophy. However, because of methodological limitations there has not been a direct comparison of obligate heterotrophic and mixotrophic bacterivory. Here we present direct evidence that small algae carry out 40-95% of the bacterivory in the euphotic layer of the temperate North Atlantic Ocean in summer. A similar range of 37-70% was determined in the surface waters of the tropical North-East Atlantic Ocean, suggesting the global significance of mixotrophy. This finding reveals that even the smallest algae have less dependence on dissolved inorganic nutrients than previously thought, obtaining a quarter of their biomass from bacterivory. This has important implications for how we perceive nutrient acquisition and limitation of carbon-fixing protists as well as control of bacterioplankton in the ocean.

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.

Elemental composition of natural populations of key microbial groups in Atlantic waters.

Intracellular carbon (C), nitrogen (N) and phosphorus (P) content of marine phytoplankton and bacterioplankton can vary according to cell requirements or physiological acclimation to growth under nutrient limited conditions. Although such variation in macronutrient content is well known for cultured organisms, there is a dearth of data from natural populations that reside under a range of environmental conditions. Here, we compare C, N and P content of Synechococcus, Prochlorococcus, low nucleic acid (LNA) content bacterioplankton and small plastidic protists inhabiting surface waters of the North and South subtropical gyres and the Equatorial Region of the Atlantic Ocean. While intracellular C:N ratios ranged between 3.5 and 6, i.e. below the Redfield ratio of 6.6, all the C:P and N:P ratios were up to 10 times higher than the corresponding Redfield ratio of 106 and 16, respectively, reaching and in some cases exceeding maximum values reported in the literature. Similar C:P or N:P ratios in areas with different concentrations of inorganic phosphorus suggests that this is not just a response to the prevailing environmental conditions but an indication of the extremely low P content of these oceanic microbes.

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.