Molecular structure in correlation with electrochemical properties of mixed-ligand cobalt(III) complexes

Four mixed-ligand cobalt(III) complexes (1–4) of the general formula [Co(Rdtc)cyclam](ClO4)2 and [Co(Rac)cyclam](ClO4)2 (cyclam = 1,4,8,11-tetraazacyclotetradecane; Rdtc = thiomorpholine-(Timdtc) or 2-methylpiperidine-(2-Mepipdtc) dithiocarbamates; Rac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionato (Hfac) or 2,2,6,6-tetramethyl-3,5-heptanedionato (Tmhd), respectively) were electro­chemically examined on a glassy carbon and an iron electrode in perchloric acid solution. The obtained results showed the influence of these complexes on hydrogen evolution, the oxygen reduction reaction and iron dissolution. The exhibited effects of the complexes on these reactions depend on structure related to the bidentate dithiocarbamato or b-diketonato ligand. The electrochemical properties of the complexes were correlated with molecular structure and parameters derived from spectral analysis and molecular modeling

Accuracy assessment of CBCT-based volumetric brain shift field

The displacement of the brain parenchyma during open brain surgery, known as ‘brain shift’, affects the applicability of pre-operative planning and affects the outcome of the surgery. In this article we investigated the accuracy of a novel method to intra-operatively determine the brain shift displacement field throughout the whole brain volume. The brain shift displacement was determined by acquiring contrast enhanced cone-beam CT before and during the surgery. The respective datasets were pre-processed, landmark enhanced, and elastically registered to find the displacement field. The accuracy of this method was evaluated by artificially creating post-operative data with a known ground truth deformation. The artificial post-operative data was obtained by applying the deformation field from one patient on the pre-operative data of another patient, which was repeated for three patients. The mean error that was found with this method ranged from 1 to 2 mm, while the standard deviation was about 1 mm

Volumetric measurements of brain shift using intraoperative cone-beam computed tomography: preliminary study

BACKGROUND: Cerebrospinal fluid leakage and ventricular compression during open surgery may lead to brain deformation called brain shift. Brain shift may affect intraoperative navigation that is based on image-based preoperative planning. Tools to correct or predict these anatomic modifications can be important to maintain precision during open guided neurosurgery. OBJECTIVE: To obtain a reliable intraoperative volumetric deformation vector field describing brain shift during intracranial neurosurgical procedures. METHODS: We acquired preoperative and intraoperative cone-beam computed tomography enhanced with intravenous injection of iodine contrast. These data sets were preprocessed and elastically registered to obtain the volumetric brain shift deformation vector fields. RESULTS: We obtained the brain shift deformation vector field in 9 cases. The deformation fields proved to be highly nonlinear, particularly around the ventricles. Interpatient variability was considerable, with a maximum deformation ranging from 8.1 to 26.6 mm and a standard deviation ranging from 0.9 to 4.9 mm. CONCLUSION: Contrast-enhanced cone-beam computed tomography provides a feasible technique for intraoperatively determining brain shift deformation vector fields. This technique can be used perioperatively to adjust preoperative planning and coregistration during neurosurgical procedures

Multi-messenger characterization of Mrk 501 during historically low X-ray and γ\gamma-ray activity

We study the broadband emission of the TeV blazar Mrk501 using multi-wavelength (MWL) observations from 2017 to 2020 performed with a multitude of instruments, involving, among others, MAGIC, Fermi-LAT, NuSTAR, Swift, GASP-WEBT, and OVRO. During this period, Mrk501 showed an extremely low broadband activity, which may help to unravel its baseline emission. Despite the low activity, significant flux variations are detected at all wavebands, with the highest variations occurring at X-rays and VHE $\gamma$-rays. A significant correlation (>3$\sigma$) between X-rays and VHE $\gamma$-rays is measured, supporting leptonic scenarios to explain the variable parts of the spectral energy distribution (SED), also during low activity states. Extending our data set to 12-years (from 2008 to 2020), we find significant correlations between X-rays and HE $\gamma$-rays, indicating, for the first time, a common physical origin driving the variability between these two bands. We additionally find a correlation between HE $\gamma$-rays and radio, with the radio emission lagging the HE $\gamma$-ray emission by more than 100 days. This is consistent with the $\gamma$-ray emission zone being located upstream of the radio-bright regions of the Mrk501 jet. Furthermore, Mrk501 showed a historically low activity in both X-rays and VHE $\gamma$-rays from mid-2017 to mid-2019 with a stable VHE flux (>2TeV) of 5% the emission of the Crab Nebula. The broadband SED of this 2-year long low-state, the potential baseline emission of Mrk501, can be adequately characterized with a one-zone leptonic model, and with (lepto)-hadronic models that fulfill the neutrino flux constraints from IceCube. We explore the time evolution of the SED towards the historically low-state, revealing that the stable baseline emission may be ascribed to a standing shock, and the variable emission to an additional expanding or traveling shock

Multi-messenger characterization of Mrk 501 during historically low X-ray and γ\gamma-ray activity

International audienceWe study the broadband emission of the TeV blazar Mrk501 using multi-wavelength (MWL) observations from 2017 to 2020 performed with a multitude of instruments, involving, among others, MAGIC, Fermi-LAT, NuSTAR, Swift, GASP-WEBT, and OVRO. During this period, Mrk501 showed an extremely low broadband activity, which may help to unravel its baseline emission. Despite the low activity, significant flux variations are detected at all wavebands, with the highest variations occurring at X-rays and VHE $\gamma$-rays. A significant correlation (>3$\sigma$) between X-rays and VHE $\gamma$-rays is measured, supporting leptonic scenarios to explain the variable parts of the spectral energy distribution (SED), also during low activity states. Extending our data set to 12-years (from 2008 to 2020), we find significant correlations between X-rays and HE $\gamma$-rays, indicating, for the first time, a common physical origin driving the variability between these two bands. We additionally find a correlation between HE $\gamma$-rays and radio, with the radio emission lagging the HE $\gamma$-ray emission by more than 100 days. This is consistent with the $\gamma$-ray emission zone being located upstream of the radio-bright regions of the Mrk501 jet. Furthermore, Mrk501 showed a historically low activity in both X-rays and VHE $\gamma$-rays from mid-2017 to mid-2019 with a stable VHE flux (>2TeV) of 5% the emission of the Crab Nebula. The broadband SED of this 2-year long low-state, the potential baseline emission of Mrk501, can be adequately characterized with a one-zone leptonic model, and with (lepto)-hadronic models that fulfill the neutrino flux constraints from IceCube. We explore the time evolution of the SED towards the historically low-state, revealing that the stable baseline emission may be ascribed to a standing shock, and the variable emission to an additional expanding or traveling shock