Bacteria-laden microgels as autonomous three-dimensional environments for stem cell engineering

A one-step microfluidic system is developed in this study which enables the encapsulation of stem cells and genetically engineered non-pathogenic bacteria into a so-called three-dimensional (3D) pearl lace–like microgel of alginate with high level of monodispersity and cell viability. The alginate-based microgel constitutes living materials that control stem cell differentiation in either an autonomous or heteronomous manner. The bacteria (Lactococcus lactis) encapsulated within the construct surface display adhesion fragments (III7-10 fragment of human fibronectin) for integrin binding while secreting growth factors (recombinant human bone morphogenetic protein-2) to induce osteogenic differentiation of human bone marrow–derived mesenchymal stem cells. We concentrate on interlinked pearl lace microgels that enabled us to prototype a low-cost 3D bioprinting platform with highly tunable properties

Scanning tunneling spectroscopy of layers of superconducting 2H-TaSe2_\textbf{2}: Evidence for a zero bias anomaly in single layers

We report a characterization of surfaces of the dichalcogenide TaSe$_2$ using scanning tunneling microscopy and spectroscopy (STM/S) at 150 mK. When the top layer has the 2H structure and the layer immediately below the 1T structure, we find a singular spatial dependence of the tunneling conductance below 1 K, changing from a zero bias peak on top of Se atoms to a gap in between Se atoms. The zero bias peak is additionally modulated by the commensurate $3a_0 \times 3a_0$ charge density wave of 2H-TaSe$_2$. Multilayers of 2H-TaSe$_2$ show a spatially homogeneous superconducting gap with a critical temperature also of 1 K. We discuss possible origins for the peculiar tunneling conductance in single layers.Comment: 10 pages, 10 figure

Meisenheimer complexes as hidden intermediates in the aza-S_NAr mechanism

In this work we report a computational study about the aza-S_NAr mechanism in fluorine- and chlorine-containing azines with the aim to unravel the physical factors that determine the reactivity patterns in these heterocycles towards propylamine. The nature of the reaction intermediate was analyzed in terms of its electronic structure based on a topological analysis framework in some non-stationary points along the reaction coordinate. The mechanistic dichotomy of a concerted or a stepwise pathway is interpreted in terms of the qualitative Diabatic Model of Intermediate Stabilization (DMIS) approach, providing a general mechanistic picture for the S_NAr process involving both activated benzenes and nitrogen-containing heterocycles. With the information collected, a unified vision of the Meisenheimer complexes as transition state, hidden intermediate or real intermediate was proposed

Meisenheimer complexes as hidden intermediates in the aza-S_NAr mechanism

In this work we report a computational study about the aza-S_NAr mechanism in fluorine- and chlorine-containing azines with the aim to unravel the physical factors that determine the reactivity patterns in these heterocycles towards propylamine. The nature of the reaction intermediate was analyzed in terms of its electronic structure based on a topological analysis framework in some non-stationary points along the reaction coordinate. The mechanistic dichotomy of a concerted or a stepwise pathway is interpreted in terms of the qualitative Diabatic Model of Intermediate Stabilization (DMIS) approach, providing a general mechanistic picture for the S_NAr process involving both activated benzenes and nitrogen-containing heterocycles. With the information collected, a unified vision of the Meisenheimer complexes as transition state, hidden intermediate or real intermediate was proposed

Density Variations in the NW Star Stream of M31

The Pan Andromeda Archeological Survey (PAndAS) CFHT Megaprime survey of the M31-M33 system has found a star stream which extends about 120 kpc NW from the center of M31. The great length of the stream, and the likelihood that it does not significantly intersect the disk of M31, means that it is unusually well suited for a measurement of stream gaps and clumps along its length as a test for the predicted thousands of dark matter sub-halos. The main result of this paper is that the density of the stream varies between zero and about three times the mean along its length on scales of 2 to 20 kpc. The probability that the variations are random fluctuations in the star density is less than 10^-5. As a control sample we search for density variations at precisely the same location in stars with metallicity higher than the stream, [Fe/H]=[0, -0.5] and find no variations above the expected shot noise. The lumpiness of the stream is not compatible with a low mass star stream in a smooth galactic potential, nor is it readily compatible with the disturbance caused by the visible M31 satellite galaxies. The stream's density variations appear to be consistent with the effects of a large population of steep mass function dark matter sub-halos, such as found in LCDM simulations, acting on an approximately 10Gyr old star stream. The effects of a single set of halo substructure realizations are shown for illustration, reserving a statistical comparison for another study.Comment: ApJ revised version submitte

The Carbonation of Wollastonite: A Model Reaction to Test Natural and Biomimetic Catalysts for Enhanced CO2 Sequestration

One of the most promising strategies for the safe and permanent disposal of anthropogenic CO2 is its conversion into carbonate minerals via the carbonation of calcium and magnesium silicates. However, the mechanism of such a reaction is not well constrained, and its slow kinetics is a handicap for the implementation of silicate mineral carbonation as an effective method for CO2 capture and storage (CCS). Here, we studied the different steps of wollastonite (CaSiO3) carbonation (silicate dissolution -> carbonate precipitation) as a model CCS system for the screening of natural and biomimetic catalysts for this reaction. Tested catalysts included carbonic anhydrase (CA), a natural enzyme that catalyzes the reversible hydration of CO2(aq), and biomimetic metal-organic frameworks (MOFs). Our results show that dissolution is the rate-limiting step for wollastonite carbonation. The overall reaction progresses anisotropically along different [hkl] directions via a pseudomorphic interface-coupled dissolution–precipitation mechanism, leading to partial passivation via secondary surface precipitation of amorphous silica and calcite, which in both cases is anisotropic (i.e., (hkl)-specific). CA accelerates the final carbonate precipitation step but hinders the overall carbonation of wollastonite. Remarkably, one of the tested Zr-based MOFs accelerates the dissolution of the silicate. The use of MOFs for enhanced silicate dissolution alone or in combination with other natural or biomimetic catalysts for accelerated carbonation could represent a potentially effective strategy for enhanced mineral CCS.This research was funded by the Spanish Government (grants CGL2015-70642-R, CGL2015-73103-EXP, CTQ2017-84692-R), EU FEDER funding, the University of Granada (“Unidad Científica de Excelencia” UCE-PP2016-05) and the Junta de Andalucía (grant P11-RNM-7550 and Research Group RNM-179). We thank the personnel of the Centro de Instrumentación Científica (CIC) of the University of Granada for their help during TG-DSC, FESEM, -XRD, and ICP-OES analyses

PAndAS' cubs: discovery of two new dwarf galaxies in the surroundings of the Andromeda and Triangulum galaxies

We present the discovery of two new dwarf galaxies, Andromeda XXI and Andromeda XXII, located in the surroundings of the Andromeda and Triangulum galaxies (M31 and M33). These discoveries stem from the first year data of the Pan-Andromeda Archaeological Survey (PAndAS), a photometric survey of the M31/M33 group conducted with the Megaprime/MegaCam wide-field camera mounted on the Canada-France-Hawaii Telescope. Both satellites appear as spatial overdensities of stars which, when plotted in a color-magnitude diagram, follow metal-poor, [Fe/H]=-1.8, red giant branches at the distance of M31/M33. Andromeda XXI is a moderately bright dwarf galaxy (M_V=-9.9+/-0.6), albeit with low surface brightness, emphasizing again that many relatively luminous M31 satellites still remain to be discovered. It is also a large satellite, with a half-light radius close to 1 kpc, making it the fourth largest Local Group dwarf spheroidal galaxy after the recently discovered Andromeda XIX, Andromeda II and Sagittarius around the Milky Way, and supports the trend that M31 satellites are larger than their Milky Way counterparts. Andromeda XXII is much fainter (M_V=-6.5+/-0.8) and lies a lot closer in projection to M33 than it does to M31 (42 vs. 224 kpc), suggesting that it could be the first Triangulum satellite to be discovered. Although this is a very exciting possibility in the context of a past interaction of M33 with M31 and the fate of its satellite system, a confirmation will have to await a good distance estimate to confirm its physical proximity to M33. Along with the dwarf galaxies found in previous surveys of the M31 surroundings, these two new satellites bring the number of dwarf spheroidal galaxies in this region to 20.Comment: 10 pages, 6 figures, accepted for publication in ApJ; v2: minor typographical correction

The PAndAS Field of Streams: stellar structures in the Milky Way halo toward Andromeda and Triangulum

We reveal the highly structured nature of the Milky Way stellar halo within the footprint of the PAndAS photometric survey from blue main sequence and main sequence turn-off stars. We map no fewer than five stellar structures within a heliocentric range of ~5 to 30 kpc. Some of these are known (the Monoceros Ring, the Pisces/Triangulum globular cluster stream), but we also uncover three well-defined stellar structures that could be, at least partly, responsible for the so-called Triangulum/Andromeda and Triangulum/Andromeda 2 features. In particular, we trace a new faint stellar stream located at a heliocentric distance of ~17 kpc. With a surface brightness of \Sigma_V ~ 32-32.5 mag/arcsec^2, it follows an orbit that is almost parallel to the Galactic plane north of M31 and has so far eluded surveys of the Milky Way halo as these tend to steer away from regions dominated by the Galactic disk. Investigating our follow-up spectroscopic observations of PAndAS, we serendipitously uncover a radial velocity signature from stars that have colors and magnitudes compatible with the stream. From the velocity of eight likely member stars, we show that this stellar structure is dynamically cold, with an unresolved velocity dispersion that is lower than 7.1 km/s at the 90-percent confidence level. Along with the width of the stream (300-650 pc), its dynamics points to a dwarf-galaxy-accretion origin. The numerous stellar structures we can map in the Milky Way stellar halo between 5 and 30 kpc and their varying morphology is a testament to the complex nature of the stellar halo at these intermediate distances.Comment: 11 pages, 8 figures, accepted for publication in the ApJ, Figure 3 is the money plo