Differential reactivity of the inner and outer positions of Au25(SCH2CH2Ph)18 dimeric staples under place exchange conditions

The kinetic anal. of the place exchange reaction on the neutral Au25(SCH2CH2Ph)\u200b18 cluster by using 4-\u200bfluorobenzylthiol and a series of substituted arylthiols allowed us to establish, for the first time, that the selectivity for the inner and outer positions of the dimeric staples of the cluster can be modulated by using incoming thiols with different structures

Stereoselective Solvolysis in the Synthesis of Dorzolamide Intermediates

The key intermediate in the synthesis of dorzolamide,(4S,6S)-methyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-4-ol-7,7-dioxide,can beobtained in the diastereoisomerically pure form in two straightforwardsteps starting from diastereoisomeric mixtures of cis/trans-(6S)-6-methyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-4-yl acetate,regardless of their ratio. The reaction of crucial importance in thisscheme is a remarkably stereoselective solvolysis of the acetate esterin an acetone/phosphate buffer mixture as the solvent system. Investigationof this so far unrecognized stereoselective reaction reveals thatit proceeds via an S(N)1-like pathway as indicated by thecorrelation of the solvolysis rate constants with the Y (OTs) values of different solvent mixtures and by trappingof the reaction intermediate with sodium azide. The structure of (4S,6S)-methyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-4-ol-7,7-dioxide was confirmedby single-crystal X-ray analysis

Causa prima: cosmology meets causal discovery for the first time

In astrophysics, experiments are impossible. We thus must rely exclusively on observational data. Other observational sciences increasingly leverage causal inference methods, but this is not yet the case in astrophysics. Here we attempt causal discovery for the first time to address an important open problem in astrophysics: the (co)evolution of supermassive black holes (SMBHs) and their host galaxies. We apply the Peter-Clark (PC) algorithm to a comprehensive catalog of galaxy properties to obtain a completed partially directed acyclic graph (CPDAG), representing a Markov equivalence class over directed acyclic graphs (DAGs). Central density and velocity dispersion are found to cause SMBH mass. We test the robustness of our analysis by random sub-sampling, recovering similar results. We also apply the Fast Causal Inference (FCI) algorithm to our dataset to relax the hypothesis of causal sufficiency, admitting unobserved confounds. Hierarchical SMBH assembly may provide a physical explanation for our findings.Comment: ML4PS NeurIPS workshop 2023 accepte

The extended halo of NGC 2682 (M 67) from Gaia DR2

Context: NGC 2682 is a nearby open cluster, approximately 3.5 Gyr old. Dynamically, most open clusters should dissolve on shorter timescales, of ~ 1 Gyr. Having survived until now, NGC 2682 was likely much more massive in the past, and is bound to have an interesting dynamical history. Aims: We investigate the spatial distribution of NGC 2682 stars to constrain its dynamical evolution, especially focusing on the marginally bound stars in the cluster outskirts. Methods: We use Gaia DR2 data to identify NGC 2682 members up to a distance of ~150 pc (10 degrees). Two methods (Clusterix and UPMASK) are applied to this end. We estimate distances to obtain three-dimensional stellar positions using a Bayesian approach to parallax inversion, with an appropriate prior for star clusters. We calculate the orbit of NGC 2682 using the GRAVPOT16 software. Results: The cluster extends up to 200 arcmin (50 pc) which implies that its size is at least twice as previously believed. This exceeds the cluster Hill sphere based on the Galactic potential at the distance of NGC 2682. Conclusions: The extra-tidal stars in NGC 2682 may originate from external perturbations such as disk shocking or dynamical evaporation from two-body relaxation. The former origin is plausible given the orbit of NGC 2682, which crossed the Galactic disk ~40 Myr ago.Comment: 9 pages, 5 figures, accepted for publication on A&

Merging black holes in young star clusters

Searching for distinctive signatures, which characterize different formation channels of binary black holes (BBHs), is a crucial step towards the interpretation of current and future gravitationalwave detections.Here, we investigate the demography ofmerging BBHs in young star clusters (SCs), which are the nursery of massive stars. We performed 4 7 103 N-body simulations of SCs with metallicity Z = 0.002, initial binary fraction 0.4, and fractal initial conditions, to mimic the clumpiness of star-forming regions. Our simulations include a novel population-synthesis approach based on the code MOBSE. We find that SC dynamics does not affect the merger rate significantly, but leaves a strong fingerprint on the properties of merging BBHs. More than 50 per cent of merging BBHs in young SCs form by dynamical exchanges in the first few Myr. Dynamically formed merging BBHs are significantly heavier than merging BBHs in isolated binaries: merging BBHs with total mass up to ~120M 99 form in young SCs, while the maximum total mass of merging BBHs in isolated binaries with the same metallicity is only ~70 M 99. Merging BBHs born via dynamical exchanges tend to have smaller mass ratios than BBHs in isolated binaries. Furthermore, SC dynamics speeds up the merger: the delay time between star formation and coalescence is significantly shorter in young SCs. In our simulations, massive systems such as GW170729 form only via dynamical exchanges. Finally ~2 per cent of merging BBHs in young SCs have mass in the pair-instability mass gap (~60-120 M 99). This represents a unique fingerprint of merging BBHs in SCs

Proteolytically Resistant Bioactive Peptide-Grafted Sr/Mg-Doped Hardystonite Foams: Comparison of Two Covalent Functionalization Strategies

Hardystonite-based (HT) bioceramic foams were easily obtained via thermal treatment of silicone resins and reactive oxide fillers in air. By using a commercial silicone, incorporating strontium oxide and magnesium oxide precursors (as well as CaO and ZnO), and treating it at 1100 °C, a complex solid solution (Ca1.4Sr0.6Zn0.85Mg0.15Si2O7) that has superior biocompatibility and bioactivity properties compared to pure hardystonite (Ca2ZnSi2O7) can be obtained. Proteolytic-resistant adhesive peptide mapped on vitronectin (D2HVP), was selectively grafted to Sr/Mg-doped HT foams using two different strategies. Unfortunately, the first method (via protected peptide) was unsuitable for acid-sensitive materials such as Sr/Mg-doped HT, resulting in the release of cytotoxic levels of Zinc over time, with consequent negative cellular response. To overcome this unexpected result, a novel functionalization strategy requiring aqueous solution and mild conditions was designed. Sr/Mg-doped HT functionalized with this second strategy (via aldehyde peptide) showed a dramatic increase in human osteoblast proliferation at 6 days compared to only silanized or non-functionalized samples. Furthermore, we demonstrated that the functionalization treatment does not induce any cytotoxicity. Functionalized foams enhanced mRNA-specific transcript levels coding IBSP, VTN, RUNX2, and SPP1 at 2 days post-seeding. In conclusion, the second functionalization strategy proved to be appropriate for this specific biomaterial and was effective at enhancing the material’s bioactivity

Mn-Containing Bioactive Glass-Ceramics: BMP-2-Mimetic Peptide Covalent Grafting Boosts Human-Osteoblast Proliferation and Mineral Deposition

The addition of Mn in bioceramic formulation is gaining interest in the field of bone implants. Mn activates human osteoblast (h-osteoblast) integrins, enhancing cell proliferation with a dose-dependent effect, whereas Mn-enriched glasses induce inhibition of Gram-negative or Gram-positive bacteria and fungi. In an effort to further optimize Mn-containing scaffolds' beneficial interaction with h-osteoblasts, a selective and specific covalent functionalization with a bioactive peptide was carried out. The anchoring of a peptide, mapped on the BMP-2 wrist epitope, to the scaffold was performed by a reaction between an aldehyde group of the peptide and the aminic groups of silanized Mn-containing bioceramic. SEM-EDX, FT-IR, and Raman studies confirmed the presence of the peptide grafted onto the scaffold. In in vitro assays, a significant improvement in h-osteoblast proliferation, gene expression, and calcium salt deposition after 7 days was detected in the functionalized Mn-containing bioceramic compared to the controls

Extrapolating SMBH correlations down the mass scale: the case for IMBHs in globular clusters

Empirical evidence for both stellar mass black holes M_bh<10^2 M_sun) and supermassive black holes (SMBHs, M_bh>10^5 M_sun) is well established. Moreover, every galaxy with a bulge appears to host a SMBH, whose mass is correlated with the bulge mass, and even more strongly with the central stellar velocity dispersion sigma_c, the `M-sigma' relation. On the other hand, evidence for "intermediate-mass" black holes (IMBHs, with masses in the range 1^2 - 10^5 M_sun) is relatively sparse, with only a few mass measurements reported in globular clusters (GCs), dwarf galaxies and low-mass AGNs. We explore the question of whether globular clusters extend the M-sigma relationship for galaxies to lower black hole masses and find that available data for globular clusters are consistent with the extrapolation of this relationship. We use this extrapolated M-sigma relationship to predict the putative black hole masses of those globular clusters where existence of central IMBH was proposed. We discuss how globular clusters can be used as a constraint on theories making specific predictions for the low-mass end of the M-sigma relation.Comment: 14 pages, 3 figures, accepted for publication in Astrophysics and Space Science; fixed typos and a quote in Sec.

Bioconjugates of Glucose Oxidase and Gold Nanorods Based on Electrostatic Interaction with Enhanced Thermostability

Bioconjugates made up of an enzyme and gold nanorods (GNRs) were fabricated by electrostatic interactions (layer-by-layer method, LBL) between anionic glucose oxidase (GOD) and positively charged GNRs. The assembled processes were monitored by UV–Vis spectra, zeta potential measurements, and transmission electron microscopy. The enzyme activity assays of the obtained bioconjugates display a relatively enhanced thermostability behavior in contrast with that of free enzyme. Free GOD in solution only retains about 22% of its relative activity at 90 °C. Unexpectedly, the immobilized GOD on GNRs still retains about 39.3% activity after the same treatment. This work will be of significance for the biologic enhancement using other kinds of anisotropic nanostructure and suggests a new way of enhancing enzyme thermostability using anisotropic metal nanomaterials

<i>Gaia</i> Data Release 1. Summary of the astrometric, photometric, and survey properties

Context. At about 1000 days after the launch of Gaia we present the first Gaia data release, Gaia DR1, consisting of astrometry and photometry for over 1 billion sources brighter than magnitude 20.7. Aims. A summary of Gaia DR1 is presented along with illustrations of the scientific quality of the data, followed by a discussion of the limitations due to the preliminary nature of this release. Methods. The raw data collected by Gaia during the first 14 months of the mission have been processed by the Gaia Data Processing and Analysis Consortium (DPAC) and turned into an astrometric and photometric catalogue. Results. Gaia DR1 consists of three components: a primary astrometric data set which contains the positions, parallaxes, and mean proper motions for about 2 million of the brightest stars in common with the HIPPARCOS and Tycho-2 catalogues – a realisation of the Tycho-Gaia Astrometric Solution (TGAS) – and a secondary astrometric data set containing the positions for an additional 1.1 billion sources. The second component is the photometric data set, consisting of mean G-band magnitudes for all sources. The G-band light curves and the characteristics of ∼3000 Cepheid and RR-Lyrae stars, observed at high cadence around the south ecliptic pole, form the third component. For the primary astrometric data set the typical uncertainty is about 0.3 mas for the positions and parallaxes, and about 1 mas yr−1 for the proper motions. A systematic component of ∼0.3 mas should be added to the parallax uncertainties. For the subset of ∼94 000 HIPPARCOS stars in the primary data set, the proper motions are much more precise at about 0.06 mas yr−1. For the secondary astrometric data set, the typical uncertainty of the positions is ∼10 mas. The median uncertainties on the mean G-band magnitudes range from the mmag level to ∼0.03 mag over the magnitude range 5 to 20.7. Conclusions. Gaia DR1 is an important milestone ahead of the next Gaia data release, which will feature five-parameter astrometry for all sources. Extensive validation shows that Gaia DR1 represents a major advance in the mapping of the heavens and the availability of basic stellar data that underpin observational astrophysics. Nevertheless, the very preliminary nature of this first Gaia data release does lead to a number of important limitations to the data quality which should be carefully considered before drawing conclusions from the data