Use of titanocalix[4]arenes in the ring opening polymerization of cyclic esters

The known dichloride complexes [TiCl2L(O)2(OR)2] (type I: R = Me (1), n-Pr (2) and n-pentyl (3); L(OH)2(OR)2 = 1,3-dialkyloxy-p-tert-butylcalix[4]arene), together with the new complexes {[TiL(O)3(OR)]2(μ-Cl)2}·6MeCN (R = n-decyl (4·6MeCN)), and [Ti(NCMe)Cl(L(O)3(OR))]·MeCN (type II: R = Me, 5·MeCN) are reported. Attempts to prepare type II for R = n-Pr and n-pentyl using [TiCl4] resulted in the complexes {[TiL(O)3(On-propyl)]2(μ-Cl)(μ-OH)} 6·7MeCN and {[TiL(O)3(On-pentyl)]2(μ-Cl)(μ-OH)}·7.5MeCN (7·7.5MeCN), respectively; use of [TiCl4(THF)2] resulted in a co-crystallized THF ring-opened product [Ti(NCMe)(μ3-O)L(O)4TiCl(O(CH2)4Cl)]2-2[TiCl(NCMe)(L(O)3(On-Pr))]·11MeCN (8·11MeCN). The molecular structures of 2·2MeCN, 4·6MeCN, and 5·MeCN together with the hydrolysis products {[TiL(O)3(OR)]2(μ-Cl)(μ-OH)} (R = n-Pr 6·7MeCN; n-pentyl, 7·7.5MeCN, 9·9MeCN); R = n-decyl 10·8.5MeCN) and that of the ring opened product 8·11MeCN and the co-crystallized species [Ti2(OH)Cl(L(O)3(OR))][L(OH)2(OR)2]·2.85(C2H3N)·0.43(H2O) (R = n-pentyl, 11·2.85(C2H3N)·0.43(H2O)) are reported. Type I and II complexes have been screened for their ability to act as catalysts in the ring opening polymerization (ROP) of ϵ-caprolactone (ϵ-CL), δ-valerolactone (δ-VL), ω-pentadecalactone (ω-PDL) and rac-lactide (r-LA), both with and without benzyl alcohol present and either under N2 or in air. The copolymerization of ϵ-CL with δ-VL and with r-LA has also been investigated. For the ROP of ϵ-CL, all performed efficiently (>99% conversion) at 130 °C over 24 h both under N2 and in air, whilst over 1 h, for the type I complexes the trend was 3 > 2 > 1 but all were poor (≤12% conversion). By contrast, 5 over 1 h at 130 °C was highly active (85% conversion). At 80 °C, the activity trend followed the order 5 ≈ 4 > 3 > 2 > 1. For δ-VL, at 80 °C the activity trend 5 ≈ 4 > 1 > 2 > 3 was observed. ROP of the larger ω-PDL was only possible using 5 at 130 °C over 24 h with moderate activity (48% conversion). For r-LA, only low molecular weight products were obtained, whilst for the co-polymerization of ϵ-CL with δ-VL using 5, high activity was observed at 80 °C affording a polymer of molecular weight >23,000 Da and with equal incorporation of each monomer. In the case of ϵ-CL/r-LA co-polymerization using 5 either under N2 or air, the polymerization was more sluggish and only 65% conversion of CL was observed and the resultant co-polymer had 65:35 incorporation. Complex 5 could also be supported on silica, however this system was not as active as its homogeneous counterpart. Finally, the activity of these complexes is compared with that of three benchmark species: a di-phenolate Ti compound {TiCl2(2,2′-CH3CH[4,6-(t-Bu)2C6H2O]2)} (12) and a previously reported NO2-containing titanocalix[4]arene catalyst, namely cone-5,17-bis-tert-butyl-11,23-dinitro-25,27-dipropyloxy-26,28-dioxo-calix[4]arene titanium dichloride (13), as well as [Ti(Oi-Pr)4]; the parent calixarenes were also screened

Rapid destruction of protoplanetary discs due to external photoevaporation in star-forming regions

We analyse N-body simulations of star-forming regions to investigate the effects of external far- and extreme-ultraviolet photoevaporation from massive stars on protoplanetary discs. By varying the initial conditions of simulated star-forming regions, such as the spatial distribution, net bulk motion (virial ratio), and density, we investigate which parameters most affect the rate at which discs are dispersed due to external photoevaporation. We find that disc dispersal due to external photoevaporation is faster in highly substructured star-forming regions than in smooth and centrally concentrated regions. Subvirial star-forming regions undergoing collapse also show higher rates of disc dispersal than regions that are in virial equilibrium or are expanding. In moderately dense (∼100 M⊙ pc−3) regions, half of all protoplanetary discs with radii ≥100 au are photoevaporated within 1 Myr, three times faster than is currently suggested by observational studies. Discs in lower density star-forming regions (∼10 M⊙ pc−3) survive for longer, but half are still dispersed on short time-scales (∼2 Myr). This demonstrates that the initial conditions of the star-forming regions will greatly impact the evolution and lifetime of protoplanetary discs. These results also imply that either gas giant planet formation is extremely rapid and occurs before the gas component of discs is  evaporated, or gas giants only form in low-density star-forming regions where no massive stars are present to photoevaporate gas from protoplanetary discs

Unilateral interactions in granular packings: A model for the anisotropy modulus

Unilateral interparticle interactions have an effect on the elastic response of granular materials due to the opening and closing of contacts during quasi-static shear deformations. A simplified model is presented, for which constitutive relations can be derived. For biaxial deformations the elastic behavior in this model involves three independent elastic moduli: bulk, shear, and anisotropy modulus. The bulk and the shear modulus, when scaled by the contact density, are independent of the deformation. However, the magnitude of the anisotropy modulus is proportional to the ratio between shear and volumetric strain. Sufficiently far from the jamming transition, when corrections due to non-affine motion become weak, the theoretical predictions are qualitatively in agreement with simulation results.Comment: 6 pages, 5 figure

Partially fluidized shear granular flows: Continuum theory and MD simulations

The continuum theory of partially fluidized shear granular flows is tested and calibrated using two dimensional soft particle molecular dynamics simulations. The theory is based on the relaxational dynamics of the order parameter that describes the transition between static and flowing regimes of granular material. We define the order parameter as a fraction of static contacts among all contacts between particles. We also propose and verify by direct simulations the constitutive relation based on the splitting of the shear stress tensor into a``fluid part'' proportional to the strain rate tensor, and a remaining ``solid part''. The ratio of these two parts is a function of the order parameter. The rheology of the fluid component agrees well with the kinetic theory of granular fluids even in the dense regime. Based on the hysteretic bifurcation diagram for a thin shear granular layer obtained in simulations, we construct the ``free energy'' for the order parameter. The theory calibrated using numerical experiments with the thin granular layer is applied to the surface-driven stationary two dimensional granular flows in a thick granular layer under gravity.Comment: 20 pages, 19 figures, submitted to Phys. Rev.

The NuSTAR Serendipitous Survey: Hunting for the Most Extreme Obscured AGN at >10 keV

We identify sources with extremely hard X-ray spectra (i.e., with photon indices of ${\rm{\Gamma }}\lesssim 0.6$) in the 13 deg2 NuSTAR serendipitous survey, to search for the most highly obscured active galactic nuclei (AGNs) detected at $\gt 10\,\mathrm{keV}$. Eight extreme NuSTAR sources are identified, and we use the NuSTAR data in combination with lower-energy X-ray observations (from Chandra, Swift XRT, and XMM-Newton) to characterize the broadband (0.5–24 keV) X-ray spectra. We find that all of the extreme sources are highly obscured AGNs, including three robust Compton-thick (CT; ${N}_{{\rm{H}}}\gt 1.5\times {10}^{24}$ cm−2) AGNs at low redshift ($z\lt 0.1$) and a likely CT AGN at higher redshift (z = 0.16). Most of the extreme sources would not have been identified as highly obscured based on the low-energy ($\lt 10$ keV) X-ray coverage alone. The multiwavelength properties (e.g., optical spectra and X-ray–mid-IR luminosity ratios) provide further support for the eight sources being significantly obscured. Correcting for absorption, the intrinsic rest-frame 10–40 keV luminosities of the extreme sources cover a broad range, from $\approx 5\times {10}^{42}$ to 1045 erg s−1. The estimated number counts of CT AGNs in the NuSTAR serendipitous survey are in broad agreement with model expectations based on previous X-ray surveys, except for the lowest redshifts ($z\lt 0.07$), where we measure a high CT fraction of ${f}_{\mathrm{CT}}^{\mathrm{obs}}={30}_{-12}^{+16} \%$. For the small sample of CT AGNs, we find a high fraction of galaxy major mergers (50% ± 33%) compared to control samples of "normal" AGNs

Model-based analyses: Promises, pitfalls, and example applications to the study of cognitive control

We discuss a recent approach to investigating cognitive control, which has the potential to deal with some of the challenges inherent in this endeavour. In a model-based approach, the researcher defines a formal, computational model that performs the task at hand and whose performance matches that of a research participant. The internal variables in such a model might then be taken as proxies for latent variables computed in the brain. We discuss the potential advantages of such an approach for the study of the neural underpinnings of cognitive control and its pitfalls, and we make explicit the assumptions underlying the interpretation of data obtained using this approach

The Gaia-ESO Survey: Homogenisation of stellar parameters and elemental abundances

The Gaia-ESO Survey is a public spectroscopic survey that targeted ≳105 stars covering all major components of the Milky Way from the end of 2011 to 2018, delivering its final public release in May 2022. Unlike other spectroscopic surveys, Gaia-ESO is the only survey that observed stars across all spectral types with dedicated, specialised analyses: from O (Teff ~ 30 000–52 000 K) all the way to K-M (≳3500 K). The physics throughout these stellar regimes varies significantly, which has previously prohibited any detailed comparisons between stars of significantly different types. In the final data release (internal data release 6) of the Gaia-ESO Survey, we provide the final database containing a large number of products, such as radial velocities, stellar parameters and elemental abundances, rotational velocity, and also, for example, activity and accretion indicators in young stars and membership probability in star clusters for more than 114 000 stars. The spectral analysis is coordinated by a number of working groups (WGs) within the survey, each specialised in one or more of the various stellar samples. Common targets are analysed across WGs to allow for comparisons (and calibrations) amongst instrumental setups and spectral types. Here we describe the procedures employed to ensure all survey results are placed on a common scale in order to arrive at a single set of recommended results for use by all survey collaborators. We also present some general quality and consistency checks performed on the entirety of the survey results.This work was partly supported by the European Union FP7 programme through ERC grant number 320360 and by the Leverhulme Trust through grant RPG-2012-541. We acknowledge the support from INAF and Ministero dell’Istruzione, dell’Università e della Ricerca (MIUR) in the form of the grant “Premiale VLT 2012”. L. Magrini and M. Van der Swaelmen acknowledge support by the WEAVE Italian consortium, and by the INAF Grant “Checs”. A.J. Korn acknowledges support by the Swedish National Space Agency (SNSA). A. Lobel acknowledges support in part by the Belgian Federal Science Policy Office under contract no. BR/143/A2/BRASS and by the European Union Framework Programme for Research and Innovation Horizon 2020 (2014-2020) under the Marie Sklodowska-Curie grant Agreement No. 823734. D.K. Feuillet was partly supported by grant no. 2016-03412 from the Swedish Research Council. D. Montes acknowledges financial support from the Agencia Estatal de Investigacion of the Ministerio de Ciencia, Innovation through project PID2019-109522GB-C54 /AEI/10.13039/501100011033. E. Marfil acknowledges financial support from the European Regional Development Fund (ERDF) and the Gobierno de Canarias through project ProID2021010128. J.I. Gonzalez Hernandez acknowledges financial support from the Spanish Ministry of Science and Innovation (MICINN) project PID2020-117493GB-I00. M. Bergemann is supported through the Lise Meitner grant from the Max Planck Society and acknowledges support by the Collaborative Research centre SFB 881 (projects A5, A10), Heidelberg University, of the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation). This project has received funding from the European Research Council (ERC) under the European Union, Horizon 2020 research and innovation programme (Grant agreement No. 949173). P. Jofré acknowledges financial support of FONDECYT Regular 1200703 as well as Nucleo Mile-nio ERIS NCN2021_017. R. Smiljanic acknowledges support from the National Science Centre, Poland (2014/15/B/ST/03981). S.R. Berlanas acknowledges support by MCIN/AEI/10.13039/501100011033 (contract FJC 2020-045785-I) and NextGeneration EU/PRTR and MIU (UNI/551/2021) through grant Margarita Salas-ULL. T. Bensby acknowledges financial support by grant No. 2018-04857 from the Swedish Research Council. T. Merle is supported by a grant from the Foundation ULB. T. Morel are grateful to Belgian F.R.S.-FNRS for support, and are also indebted for an ESA/PRODEX Belspo contract related to the Gaia Data Processing and Analysis Consortium and for support through an ARC grant for Concerted Research Actions financed by the Federation Wallonie-Brussels. W. Santos acknowledges FAPERJ for a Ph.D. fellowship. H.M. Tabernero acknowledges financial support from the Agencia Estatal de Investigation of the Ministerio de Ciencia, Innovation through project PID2019-109522GB-C51/AEI/10.13039/501100011033