Eclipsing binaries and fast rotators in the Kepler sample. Characterization via radial velocity analysis from Calar Alto

The Kepler mission has provided high-accurate photometric data in a long time span for more than two hundred thousands stars, looking for planetary transits. Among the detected candidates, the planetary nature of around 15% has been established or validated by different techniques. But additional data is needed to characterize the rest of the candidates and reject other possible configurations. We started a follow-up program to validate, confirm, and characterize some of the planet candidates. In this paper we present the radial velocity analysis (RV) of those presenting large variations, compatible with being eclipsing binaries. We also study those showing large rotational velocities, which prevents us from obtaining the necessary precision to detect planetary-like objects. We present new RV results for 13 Kepler objects of interest (KOIs) obtained with the CAFE spectrograph at the Calar Alto Observatory, and analyze their high-spatial resolution images and the Kepler light curves of some interesting cases. We have found five spectroscopic and eclipsing binaries. Among them, the case of KOI-3853 is of particular interest. This system is a new example of the so-called heartbeat stars, showing dynamic tidal distortions in the Kepler light curve. We have also detected duration and depth variations of the eclipse. We suggest possible scenarios to explain such effect, including the presence of a third substellar body possibly detected in our RV analysis. We also provide upper mass limits to the transiting companions of other six KOIs with large rotational velocities. This property prevents the RV method to obtain the necessary precision to detect planetary-like masses. Finally, we analyze the large RV variations of other two KOIs, incompatible with the presence of planetary-mass objects. These objects are likely to be stellar binaries but a longer timespan is still needed.Comment: Accepted for publication in A&A. 18 pages, 9 figures, 17 tables. This version fixes an error affecting the values of tables A.1-A.13. The text remains unaltere

Kepler-447b: a hot-Jupiter with an extremely grazing transit

We present the radial velocity confirmation of the extrasolar planet Kepler-447b, initially detected as a candidate by the Kepler mission. In this work, we analyze its transit signal and the radial velocity data obtained with the Calar Alto Fiber-fed Echelle spectrograph (CAFE). By simultaneously modeling both datasets, we obtain the orbital and physical properties of the system. According to our results, Kepler-447b is a Jupiter-mass planet ($M_p=1.37^{+0.48}_{-0.46}~M_{\rm Jup}$), with an estimated radius of $R_p=1.65^{+0.59}_{-0.56}~R_{\rm Jup}$ (uncertainties provided in this work are $3\sigma$ unless specified). This translates into a sub-Jupiter density. The planet revolves every $\sim7.8$ days in a slightly eccentric orbit ($e=0.123^{+0.037}_{-0.036}$) around a G8V star with detected activity in the Kepler light curve. Kepler-447b transits its host with a large impact parameter ($b=1.076^{+0.112}_{-0.086}$), being one of the few planetary grazing transits confirmed so far and the first in the Kepler large crop of exoplanets. We estimate that only around 20% of the projected planet disk occults the stellar disk. The relatively large uncertainties in the planet radius are due to the large impact parameter and short duration of the transit. Planets with such an extremely large impact parameter can be used to detect and analyze interesting configurations such as additional perturbing bodies, stellar pulsations, rotation of a non-spherical planet, or polar spot-crossing events. All these scenarios would periodically modify the transit properties (depth, duration, and time of mid-transit), what could be detectable with sufficient accurate photometry. Short-cadence photometric data (at the 1 minute level) would help in the search for these exotic configurations in grazing planetary transits like that of Kepler-447b.Comment: Accepted for publication in A&A. 13 pages, 8 figures, 4 tables. This version replaces an earlier version of the pape

Crystallographic and spectroscopic study on a known orally active progestin

6,17a-dimethyl-4,6-pregnadiene-3,20-dione (medrogestone, 2) is for a long time known steroid endowed with progestational activity. In order to study its crystallographic and NMR spectroscopic properties with the aim to fill the literature gap, we prepared medrogestone following a traditional procedure. A careful NMR study allowed the complete assignement of the 1H and 13C NMR signals not only of medrogestone but also of its synthetic intermediates. The structural and stereochemical characterizations of medrogestone togheter with its precursor 17a-methyl-3-ethoxy-pregna-3,5- dien-20-one were described by means of X-ray analysis, allowing a deepened conformational investigation

Effects of a medium cut-off (Theranova®) dialyser on haemodialysis patients: a prospective, cross-over study

Background. Despite significant advances in haemodialysis (HD) in recent decades, current dialysis techniques are limited by inadequate removal of uraemic solutes such as middle molecules and protein-bound uraemic toxins. Novel medium cut-off (MCO) membrane or \u2018expanded haemodialysis\u2019 (HDx) provides diffusive removal of conventional and large middle molecular weight uraemic toxins, with marginal albumin leak. Methods. This prospective, open-label, controlled, cross-over pilot study compared HDx (novel MCO membrane TheranovaVR 400) and conventional HD in 20 prevalent HD patients. Biochemical, dialysis adequacy and safety measures (adverse events, infections and hospitalization frequency) were recorded. Ten patients underwent conventional HD high-flux dialyser and 10 patients underwent HDx for 3 months, and the patients then switched and received the other treatment for a further 3 months. Results. Treatment with HDx was associated with a significant reduction in serum albumin concentration [median (interquartile range) reduction 0.45 g/dL (0.575 to 0.05); P \ubc 0.025]. However, median albumin levels were 3.5 g/dL and no patients had clinical symptoms of hypoalbuminaemia or needed intravenous albumin administration. The number of infections was lower in patients treated with HDx (n \ubc 7/19) compared with patients treated with HD (n \ubc 14/20; P \ubc 0.03). Patients treated with HDx had reduced levels of interleukin (IL)-1b (from 0.06 6 0.02 pg/mL versus 0.28 6 0.18 pg/mL with HD) and IL-6 (6.45 6 1.57 pg/mL versus 9.48 6 2.15 pg/mL), while tumour necrosis factor-a levels remain unchanged. Conclusions. This study demonstrates that the chronic use of the novel MCO dialyser TheranovaVR appears to be safe and well-tolerated, without serious side effects or hypoalbuminaemia, as well as fewer infections. These results need to be confirmed in larger randomized clinical trials

Crystallographic and NMR Investigation of Ergometrine and Methylergometrine, Two Alkaloids from Claviceps purpurea

Ergometrine and methylergometrine are two alkaloids that are used as maleate salts for the prevention and control of postpartum hemorrhage. Although the two molecules have been known for a long time, few and discordant crystallographic and NMR spectroscopic data are available in the literature. With the aim of providing more conclusive data, we performed a careful NMR study for the complete assignment of the 1H, 13C, and 15N NMR signals of ergometrine, methylergometrine, and their maleate salts. This information allowed for a better definition of their conformational equilibria. In addition, the stereochemistry and the intermolecular interactions in the solid state of the two maleate salts were deeply investigated by means of single-crystal X-ray diffraction, showing the capability of these derivatives to act as both hydrogen-bond donors and acceptors, and evidencing a correlation between the number of intermolecular interactions and their different solubility

A Cross-Flow Ultrasound-Assisted Extraction of Curcuminoids from Curcuma longa L.: Process Design to Avoid Degradation

Rhizomes of Curcuma longa L. are well known for their content of curcuminoids, which are compounds with interesting biological activity against various inflammatory states and diseases. Curcuminoids can degrade during processing. This piece of work investigates fast, efficient and cost-effective metabolite recovery from turmeric under ultrasound-assisted extraction (UAE). An analytical evaluation of curcuminoid stability under sonication in different solvents is reported for the first time. HPLC and quantitative 1H-NMR were used. Under the applied conditions, EtOAc was found to be the optimal extraction medium, rather than EtOH, due to its lower radical generation, which facilitates better curcuminoid stability. Kinetic characterization, by means of the Peleg equation, was applied for single-step UAE on two different rhizome granulometries. Over a time of 90 min, maximum extraction yields were 25.63% and 47.56% for 6 and 2 mm matrix powders, respectively. However, it was observed that the largest portion of curcuminoid recovery was achieved in the first 30 min. Model outcomes were used as the basis for the design of a suitable multi-step cross-flow approach that supports and emphasizes the disruptive role of cavitation. The maximum curcuminoid yield was achieved over three steps (92.10%) and four steps (80.04%), for lower and higher granulometries, respectively. Finally, the central role of the solvent was further confirmed by turmeric oleoresin purification. The EtOAc extract was purified via crystallization, and a 95% pure curcuminoid product was isolated without any chromatographic procedure. No suitable crystallization was observed for the EtOH extract

(S)-Pramipexole and Its Enantiomer, Dexpramipexole : a New Chemoenzymatic Synthesis and Crystallographic Investigation of Key Enantiomeric Intermediates

A new chemoenzymatic method has been developed for the synthesis of (S)- and (R)-N-(6-hydroxy-4,5,6,7-tetrahydrobenzo[d]thiazol-2-yl) acetamide, two key synthons for the preparation of (S)-pramipexole, an anti-Parkinson drug, and its enantiomer dexpramipexole, which is currently under investigation for the treatment of eosinophil-associated disorders. These two building blocks have been obtained in good yields and high enantiomeric excess (30% and >98% ee for the R-enantiomer, and 31% and >99% ee for the S- one) through a careful optimization of the reaction conditions, starting from the corresponding racemic mixture and using two consecutive irreversible transesterifications, catalyzed by Candida antarctica lipase type A. Single crystal X-ray analysis has been carried out to unambiguously define the stereochemistry of the two enantiomers, and to explore in depth their three-dimensional features

Current Therapy in CKD Patients Can Affect Vitamin K Status

Chronic kidney disease (CKD) patients have a higher risk of cardiovascular (CVD) morbidity and mortality compared to the general population. The links between CKD and CVD are not fully elucidated but encompass both traditional and uremic-related risk factors. The term CKD-mineral and bone disorder (CKD-MBD) indicates a systemic disorder characterized by abnormal levels of calcium, phosphate, PTH and FGF-23, along with vitamin D deficiency, decreased bone mineral density or altered bone turnover and vascular calcification. A growing body of evidence shows that CKD patients can be affected by subclinical vitamin K deficiency; this has led to identifying such a condition as a potential therapeutic target given the specific role of Vitamin K in metabolism of several proteins involved in bone and vascular health. In other words, we can hypothesize that vitamin K deficiency is the common pathogenetic link between impaired bone mineralization and vascular calcification. However, some of the most common approaches to CKD, such as (1) low vitamin K intake due to nutritional restrictions, (2) warfarin treatment, (3) VDRA and calcimimetics, and (4) phosphate binders, may instead have the opposite effects on vitamin K metabolism and storage in CKD patients

A New Chemoenzymatic Synthesis of the Chiral Key Intermediate of the Antiepileptic Brivaracetam

Brivaracetam is a new anticonvulsant compound, recently approved as an antiepileptic drug. This drug substance presents a 4-substituted pyrrolidone structure: the (4R)-configuration of the stereocenter present on the heterocyclic ring is the main target of the synthesis. The described method allows to prepare the suitable optically pure 2-substituted primary alcohol by means of a Pseudomonas fluorescens lipase-catalyzed transesterification. The obtained (2R)-alcohol was easily transformed into the (3R)-3-propylbutyrolactone, an advanced intermediate of brivaracetam. The described synthetic pathway is completed with the chromatographic methods and the NMR analyses necessary to establish the chemical and the optical purity of the intermediates and of the final lactone

Qatar Exoplanet Survey : Qatar-3b, Qatar-4b and Qatar-5b

We report the discovery of Qatar-3b, Qatar-4b, and Qatar-5b, three new transiting planets identified by the Qatar Exoplanet Survey (QES). The three planets belong to the hot Jupiter family, with orbital periods of $P_{Q3b}$=2.50792 days, $P_{Q4b}$=1.80539 days, and $P_{Q5b}$=2.87923 days. Follow-up spectroscopic observations reveal the masses of the planets to be $M_{Q3b}$=4.31$\pm0.47$ $M_{\rm J}$, $M_{Q4b}$=6.10$\pm0.54$ $M_{\rm J}$, and $M_{Q5b}$ = 4.32$\pm0.18$ $M_{\rm J}$, while model fits to the transit light curves yield radii of $R_{Q3b}$ = 1.096$\pm0.14$ $R_{\rm J}$, $R_{Q4b}$ = 1.135$\pm0.11$ $R_{\rm J}$, and $R_{Q5b}$ = 1.107$\pm0.064$ $R_{\rm J}$. The host stars are low-mass main sequence stars with masses and radii $M_{Q3}$ = 1.145$\pm0.064$ $M_{\odot}$, $M_{Q4}$ = 0.896$\pm0.048$ $M_{\odot}$, $M_{Q5}$ = 1.128$\pm0.056$ $M_{\odot}$ and $R_{Q3}$ = 1.272$\pm0.14$ $R_{\odot}$, $R_{Q4}$ = 0.849$\pm0.063$ $R_{\odot}$ and $R_{Q5}$ = 1.076$\pm0.051$ $R_{\odot}$ for Qatar-3, 4 and 5 respectively. The V magnitudes of the three host stars are $V_{Q3}$=12.88, $V_{Q4}$=13.60, and $V_{Q5}$=12.82. All three new planets can be classified as heavy hot Jupiters (M > 4 $M_{J}$).Comment: 13Pages, 8Figure