Neutral and Cationic Rare Earth Metal Alkyl and Benzyl Compounds with the 1,4,6-Trimethyl-6-pyrrolidin-1-yl-1,4-diazepane Ligand and Their Performance in the Catalytic Hydroamination/Cyclization of Aminoalkenes

A new neutral tridentate 1,4,6-trimethyl-6-pyrrolidin-1-yl-1,4-diazepane (L) was prepared. Reacting L with trialkyls M(CH2SiMe3)3(THF)2 (M = Sc, Y) and tribenzyls M(CH2Ph)3(THF)3 (M = Sc, La) yielded trialkyl complexes (L)M(CH2SiMe3)3 (M = Sc, 1; M = Y, 2) and tribenzyl complexes (L)M(CH2Ph)3 (M = Sc, 3; M = La, 4). Complexes 1 and 2 can be converted to their corresponding ionic compounds [(L)M(CH2SiMe3)2(THF)][B(C6H5)4] (M = Sc, Y) by reaction with [PhNMe2H][B(C6H5)4] in THF. Complexes 3 and 4 can be converted to cationic species [(L)M(CH2Ph)2]+ by reaction with [PhNMe2H][B(C6F5)4] in C6D5Br in the absence of THF. The neutral complexes 1-4 and their cationic derivatives were studied as catalysts for the hydroamination/cyclization of 2,2-diphenylpent-4-en-1-amine and N-methylpent-4-en-1-amine reference substrates and compared with ligand-free Sc, Y, and La neutral and cationic catalysts. The most effective catalysts in the series were the cationic L-yttrium catalyst (for 2,2-diphenylpent-4-en-1-amine) and the cationic lanthanum systems (for N-methylpent-4-en-1-amine). For the La catalysts, evidence was obtained for release of L from the metal during catalysis.

The upgraded ISOLDE yield database - A new tool to predict beam intensities

At the CERN-ISOLDE facility a variety of radioactive ion beams are available to users of the facility. The number of extractable isotopes estimated from yield database data exceeds 1000 and is still increasing. Due to high demand and scarcity of available beam time, precise experiment planning is required. The yield database stores information about radioactive beam yields and the combination of target material and ion source needed to extract a certain beam along with their respective operating conditions. It allows to investigate the feasibility of an experiment and the estimation of required beamtime. With the increasing demand for ever more exotic beams, needs arise to extend the functionality of the database and website not only to provide information about yields determined experimentally, but also to predict yields of isotopes, which can only be measured with sophisticated setups. For the prediction of yields, in-target production and information about release properties of target materials must be known. While the former were estimated in a simulation campaign using FLUKA and ABRABLA codes, the latter is available from measurement data as already stored in the database. We have compiled the information necessary to predict yields, and made available a yield prediction tool as web application. This currently undergoes extensive testing and will be available as powerful tool to the ISOLDE user community.Peer reviewe

Relationship of faecal calprotectin and long-term outcomes in Finnish patients with Crohn's disease : retrospective multi-centre chart review study

Background and Aims: A retrospective non-interventional, multi-centre patient chart review study was conducted to investigate the association of faecal calprotectin (FC) 1 year (+/- 2 months) after biological therapy initiation with composite event-free survival (CEFS) consisting of surgical procedures, corticosteroid initiation, treatment failure or dose increase in patients with Crohn's disease (CD). In addition, the correlations of FC and other tests of disease activity were assessed. Materials and methods: Data on Finnish CD patients initiating a biological therapy between 2010 and 2016, were collected. The association of FC and CEFS was analysed with Kaplan-Meier and Cox proportional hazard modelling. The correlations were tested with Pearson's test. Results: Biological therapy was initiated in 186 patients, of which 87 (46.8%) had FC results available at 1 year and 80 had follow-up exceeding 14 months. The characteristics of patients with and without FC results were similar. Patients with elevated FC (>250 mu g/g) had a significantly increased risk of experiencing composite event (HR 3.4, 95% CI: 1.3-8.9; p = .013) when compared to patients with normal FC (FCPeer reviewe

Atropselective syntheses of (-) and (+) rugulotrosin A utilizing point-to-axial chirality transfer

Chiral, dimeric natural products containing complex structures and interesting biological properties have inspired chemists and biologists for decades. A seven-step total synthesis of the axially chiral, dimeric tetrahydroxanthone natural product rugulotrosin A is described. The synthesis employs a one-pot Suzuki coupling/dimerization to generate the requisite 2,2'-biaryl linkage. Highly selective point-to-axial chirality transfer was achieved using palladium catalysis with achiral phosphine ligands. Single X-ray crystal diffraction data were obtained to confirm both the atropisomeric configuration and absolute stereochemistry of rugulotrosin A. Computational studies are described to rationalize the atropselectivity observed in the key dimerization step. Comparison of the crude fungal extract with synthetic rugulotrosin A and its atropisomer verified that nature generates a single atropisomer of the natural product.P50 GM067041 - NIGMS NIH HHS; R01 GM099920 - NIGMS NIH HHS; GM-067041 - NIGMS NIH HHS; GM-099920 - NIGMS NIH HH

Preparation of amino-substituted indenes and 1,4-dihydronaphthalenes using a one-pot multireaction approach: total synthesis of oxybenzo[c]phenanthridine alkaloids

Allylic trichloroacetimidates bearing a 2-vinyl or 2-allylaryl group have been designed as substrates for a one-pot, two-step multi-bond-forming process leading to the general preparation of aminoindenes and amino-substituted 1,4-dihydronaphthalenes. The synthetic utility of the privileged structures formed from this one-pot process was demonstrated with the total synthesis of four oxybenzo[c]phenanthridine alkaloids, oxychelerythrine, oxysanguinarine, oxynitidine, and oxyavicine. An intramolecular biaryl Heck coupling reaction, catalyzed using the Hermann–Beller palladacycle was used to effect the key step during the synthesis of the natural products

Superradiance from an ultrathin film of three-level V-type atoms: Interplay between splitting, quantum coherence and local-field effects

We carry out a theoretical study of the collective spontaneous emission (superradiance) from an ultrathin film comprised of three-level atoms with $V$-configuration of the operating transitions. As the thickness of the system is small compared to the emission wavelength inside the film, the local-field correction to the averaged Maxwell field is relevant. We show that the interplay between the low-frequency quantum coherence within the subspace of the upper doublet states and the local-field correction may drastically affect the branching ratio of the operating transitions. This effect may be used for controlling the emission process by varying the doublet splitting and the amount of low-frequency coherence.Comment: 15 pages, 5 figure

Inclusive J/psi production at midrapidity in pp collisions at root s=13 Tev

We report on the inclusive J/psi production cross section measured at the CERN Large Hadron Collider in proton-proton collisions at a center-of-mass energy root s = 13 TeV. The J/psi mesons are reconstructed in the e(+)e(-) decay channel and the measurements are performed at midrapidity (vertical bar y vertical bar < 0.9) in the transverse-momentum interval 0 < p(T) < 40 GeV/c, using a minimum-bias data sample corresponding to an integrated luminosity L-i(nt) = 32.2 nb(-1) and an Electromagnetic Calorimeter triggered data sample with L-i(nt) = 8.3 pb(-1). The p(T)-integrated J/psi production cross section at midrapidity, computed using the minimumbias data sample, is d sigma/dy vertical bar(y) =0 = 8.97 +/- 0.24 (stat) 0.48 (syst) +/- 0.15 (lumi) mu b. An approximate logarithmic dependence with the collision energy is suggested by these results and available world data, in agreement with model predictions. The integrated and p(T)-differential measurements are compared with measurements in pp collisions at lower energies and with several recent phenomenological calculations based on the non-relativistic QCD and Color Evaporation models.Peer reviewe

Measurement of the Groomed Jet Radius and Momentum Splitting Fraction in pp and Pb-Pb Collisions at root S-NN=5.02 TeV

This article presents groomed jet substructure measurements in pp and Pb-Pb collisions at root s(NN )= 5.02 TeV with the ALICE detector. The soft drop grooming algorithm provides access to the hard parton splittings inside a jet by removing soft wide-angle radiation. We report the groomed jet momentum splitting fraction, z(g), and the (scaled) groomed jet radius, theta(g). Charged-particle jets are reconstructed at midrapidity using the anti-k(T) algorithm with resolution parameters R = 0.2 and R = 0.4. In heavy-ion collisions, the large underlying event poses a challenge for the reconstruction of groomed jet observables, since fluctuations in the background can cause groomed parton splittings to be misidentified. By using strong grooming conditions to reduce this background, we report these observables fully corrected for detector effects and background fluctuations for the first time. A narrowing of the theta(g) distribution in Pb-Pb collisions compared to pp collisions is seen, which provides direct evidence of the modification of the angular structure of jets in the quark-gluon plasma. No significant modification of the z(g) distribution in Pb-Pb collisions compared to pp collisions is observed. These results are compared with a variety of theoretical models of jet quenching, and provide constraints on jet energy-loss mechanisms and coherence effects in the quark-gluon plasma.Peer reviewe

K-S(0)- and (anti-)Lambda-hadron correlations in pp collisions at root s=13 TeV

Two-particle Azimuthal correlations are measured with the ALICE apparatus in pp collisions at root s = 13 TeV to explore strangeness- and multiplicity-related effects in the fragmentation of jets and the transition regime between bulk and hard production, probed with the condition that a strange meson (K-S(0)) or baryon (Lambda) with transverse momentum p(T) > 3 GeV/c is produced. Azimuthal correlations between kaons or Lambda hyperons with other hadrons are presented at midrapidity for a broad range of the trigger (3 < p(T)(trigg) < 20 GeV/c) and associated particle p(T) (1 GeV/c < p(T)(assoc) < p(T)(trigg)), for minimum-bias events and as a function of the event multiplicity. The near- and away-side peak yields are compared for the case of either K-S(0) or Lambda((Lambda) over bar) being the trigger particle with that of inclusive hadrons (a sample dominated by pions). In addition, the measurements are compared with predictions from PYTHIA 8 and EPOS LHC event generators.Peer reviewe