Unidentifed gamma-ray sources: hunting gamma-ray blazars

One of the main scientific objectives of the ongoing Fermi mission is unveiling the nature of the unidentified gamma-ray sources (UGSs). Despite the large improvements of Fermi in the localization of gamma-ray sources with respect to the past gamma-ray missions, about one third of the Fermi-detected objects are still not associated to low energy counterparts. Recently, using the Wide-Field Infrared Survey Explorer (WISE) survey, we discovered that blazars, the rarest class of Active Galactic Nuclei and the largest population of gamma-ray sources, can be recognized and separated from other extragalactic sources on the basis of their infrared (IR) colors. Based on this result, we designed an association method for the gamma-ray sources to reognize if there is a blazar candidate within the positional uncertainty region of a generic gamma-ray source. With this new IR diagnostic tool, we searched for gamma-ray blazar candidates associated to the UGS sample of the second Fermi gamma-ray catalog (2FGL). We found that our method associates at least one gamma-ray blazar candidate as a counterpart each of 156 out of 313 UGSs analyzed. These new low-energy candidates have the same IR properties as the blazars associated to gamma-ray sources in the 2FGL catalog.Comment: 24 pages, 4 figures, Accepted for publication on the Astrophysical Journa

Cannabis through the looking glass: chemo- and enantio-selective separation of phytocannabinoids by enantioselective ultra high performance supercritical fluid chromatography

By using the Inverted Chirality Columns Approach (ICCA) we have developed an enantioselective UHPSFC method to determine the enantiomeric excess (ee) of (-)-Δ(9)-THC in medicinal marijuana (Bedrocan®). The ee was high (99.73%), but the concentration of the (+)-enantiomer (0.135%) was not negligible, and it is worth a systematic evaluation of bioactivity

Chiral azole derivatives. 4. Enantiomers of bifonazole and related antifungal agents: synthesis, configuration assignment, and biological evaluation

The first synthesis, full stereochem. characterization and biol. evaluation of of both enantiomers of bifonazole (I) and the related II, III and IV are described

A penalized framework for distributed lag non-linear models.

: Distributed lag non-linear models (DLNMs) are a modelling tool for describing potentially non-linear and delayed dependencies. Here, we illustrate an extension of the DLNM framework through the use of penalized splines within generalized additive models (GAM). This extension offers built-in model selection procedures and the possibility of accommodating assumptions on the shape of the lag structure through specific penalties. In addition, this framework includes, as special cases, simpler models previously proposed for linear relationships (DLMs). Alternative versions of penalized DLNMs are compared with each other and with the standard unpenalized version in a simulation study. Results show that this penalized extension to the DLNM class provides greater flexibility and improved inferential properties. The framework exploits recent theoretical developments of GAMs and is implemented using efficient routines within freely available software. Real-data applications are illustrated through two reproducible examples in time series and survival analysis.<br/

Conformation, Stereodynamics, and Chiral Separation of the Rotational Enantiomers of Hindered Naphthyl Ketones.

A no. of α-naphthyl ketones bearing a Me group in the 2-position of the naphthalene ring adopt a twisted conformation, yielding a pair of rotational enantiomers owing to the restricted rotation about the naphthalene-carbonyl bond. NOE measurements indicate that the twisted conformation is almost exactly orthogonal. The enantiomerization barriers were detd. by variable-temp. dynamic NMR spectroscopy, with monitoring of either the anisochronous signals of prochiral substituents or the pairs of signals of the enantiomers themselves, made detectable at low temp. by the addn. of a chiral auxiliary agent. The free energies of activation cover a range of 8-20 kcal mol-1, depending on the steric hindrance of the various acyl groups. Mol. mechanics calcns. suggest that enantiomerization occurs through a pathway where the carbonyl function passes position 2, rather than position 8, of the naphthalene ring. In the case of a 1,5-disubstituted acyl deriv. contg. the tert-Bu moiety (I), the expected meso and racemic conformers were both obsd. in soln., whereas only the meso structure was present in the crystals (obtained by the usual slow crystn. procedure) as judged by CP MAS solid-state NMR spectra and by low-temp. soln. spectra in nonequil. conditions. Low-temp. (-15°) chiral high-performance liq. chromatog. (LT-ChirHPLC) was employed to sep., identify, and det. the yields of the two enantiomers of 2-methyl-1-naphthyl tert-Bu ketone (II) as well as the three conformers (meso, SS, and RR) of I. The low-temp. CD spectra of the rotational enantiomers of II and I were obtained and the abs. configurations assigned by connecting online a CD spectrometer to the LT-ChirHPLC app. Resp., the S and SS configurations were found to correspond to the conformational enantiomers with the shorter retention times [(R,R)-DAC-DNB column]

Dynamic HPLC on chiral stationary phases: a powerful tool for the investigation of stereomutation processes

Dynamic HPLC on enantioselective stationary phases has become a well-established technique to investigate chiral molecules with internal motions that result in stereoinversion and occur on the time scale of the separation process. Kinetic parameters for the on-column interconversion phenomena can be extracted from experimental peak profiles by computer simulation or by direct calculation methods. The technique has been used in a wide range of temperatures and is complementary in scope to dynamic NMR spectroscopy

Conformational Assignement, Absolute Configuration and Chiral Separation of all the Stereoisomers Created by the Combined Presence of Stereogenic Centers and Stereogenic Conformational Axes in a Highly Hindered 1,5-Naphthyl Sulfoxide.

The presence of two stereogenic centers and of two stereogenic conformational axes in 2,6-dimethyl-1,5-bis(2-methyl-2-propylsulfinyl)naphthalene (1) entails the existence of 10 stereoisomers. In particular, both the meso form (1a) and the racemic form (1b) are constituted by three atropisomers; in the case of the latter (1b) each of them entails a pair of enantiomers (total of six species), whereas owing to the symmetry only one of the three atropisomers of the meso form (1a) yields a pair of enantiomers (a total of four species). Despite the low conformational interconversion barrier (18.5 kcal/mol) all of them have been separated by low temperature (-45°C) chiral HPLC. Their configurational and conformational assignment has been achieved by a combined use of NMR (both in solution and solid state) and on-line CD-detected chiral HPLC. The single crystal X-ray diffraction yielded the absolute configuration of one of the stereoisomers ((ZR,ER)-1b) from which all the others could be obtained by CD relationship

The WISE gamma-ray strip parametrization: the nature of the gamma-ray Active Galactic Nuclei of Uncertain type

Despite the large number of discoveries made recently by Fermi, the origins of the so called unidentified gamma-ray sources remain unknown. The large number of these sources suggests that among them there could be a population that significantly contributes to the isotropic gamma-ray background and is therefore crucial to understand their nature. The first step toward a complete comprehension of the unidentified gamma-ray source population is to identify those that can be associated with blazars, the most numerous class of extragalactic sources in the gamma-ray sky. Recently, we discovered that blazars can be recognized and separated from other extragalactic sources using the infrared (IR) WISE satellite colors. The blazar population delineates a remarkable and distinctive region of the IR color-color space, the WISE blazar strip. In particular, the subregion delineated by the gamma-ray emitting blazars is even narrower and we named it as the WISE Gamma-ray Strip (WGS). In this paper we parametrize the WGS on the basis of a single parameter s that we then use to determine if gamma-ray Active Galactic Nuclei of the uncertain type (AGUs) detected by Fermi are consistent with the WGS and so can be considered blazar candidates. We find that 54 AGUs out of a set 60 analyzed have IR colors consistent with the WGS; only 6 AGUs are outliers. This result implies that a very high percentage (i.e., in this sample about 90%) of the AGUs detected by Fermi are indeed blazar candidates.Comment: 22 pages, 13 figures, Astrophysical Journal in pres

Atropisomerism in Hindered Naphthyl Sulfoxides: Structure, Stereodynamics, and Chiral Resolution.

Barriers for the EZ interconversion of atropisomers of 1-naphthyl sulfoxides (ArSOR) having a methyl group at position 2 of the naphthalene moiety were measured by variable-temperature NMR. Their values were found to cover the range 10.6-18.4 kcal mol-1, the extreme values corresponding to derivatives 1 (R = Me) and 4 (R = Bu(t)), respectively. NOE and LIS measurements indicated that the Z atropisomer is more stable than the E but that the absence of the methyl group at position 2 of the naphthalene moiety reverses this trend, rendering E more stable than Z. Solid-state NMR and X-ray diffraction of 4 established that only the more stable atropisomer (Z) is present in the crystalline state. Molecular mechanics calculations suggest that the Z,E interconversion process might occur by a rotation pathway having an opposite direction in the case of the more hindered derivatives 3 and 4 (R = Pr(i) and Bu(t), respectively) with respect to the less hindered 1 and 2 (R = Me and Et, respectively). The enantiomers, which are due to the presence of the asymmetric sulfur atom, were resolved on a chiral stationary phase (DACH-DNB) having an SS configuration. Asymmetric oxidation reactions were employed to assign the absolute R configuration to the more retained enantiomers of alkyl aryl sulfoxides. The opposite trend (S being retained longer) was observed for diaryl sulfoxides such as 5 (R = Ph). In the case of the derivative with the largest interconversion barrier, sulfoxide 4, it was also possible to resolve (at -35-degrees-C) the two enantiomeric forms and their associated atropisomers. The use of on-line CD detection and the knowledge of the NMR assignments allowed us to unambiguously assign the elution order of the four species as ES, ER, ZS, ZR