Thermomechanical relaxation and different water states in cottonseed protein derived bioplastics

Thermomechanical relaxation events and different water states in cottonseed protein bioplastics are presented whilst investigating the effects of aldehyde cross-linking agents. Thermomechanical relaxation of cottonseed protein bioplastics associated with protein denaturation, moisture absorption and broad glass transitions (Tg) were observed from DSC and DMA measurements. It was shown that variation of the aldehyde influences the storage modulus at very low temperature (below Tg). From measurements of the water fusion point, enthalpy, vaporisation, and weight loss, three water states in the water-absorbed bioplastics are suggested; namely strongly-bound-to-polymer, weakly-bound-to-polymer and bulk-like water. The water content and unreacted cross-linking agents are influential factors in controlling formation of the different water states, whilst the selection of different aldehydes was found to be negligible. These results could be valuable for adjusting the thermomechanical relaxations of protein based bioplastics, and tailoring their properties in wet environments

Macroscopic CNT fibres inducing non-epitaxial nucleation and orientation of semicrystalline polymers

In the presence of macroscopic fibres of carbon nanotubes (CNT), various semicrystalline polymers are shown to present accelerated crystallisation through the formation of a transcrystalline (TC) layer perpendicular to the fibre axis. From differential scanning calorimetry, polarized optical microscopy and X-ray diffraction we establish this to be due to much faster nucleation rates at the fibre surface. The formation of a TC layers is demonstrated for polyvinyldene fluoride, isotactic polypropylene and poly(lactic acid) in spite of the large differences in their chemistry and structure unit cells, suggesting that epitaxy in terms of lattice type or size matching is not a prerequisite. For the three polymers as well as poly(ether ether ketone), the TC layer is identically oriented with the chain axis in the lamella parallel to the CNTs, as observed by wide and small angle X-ray scattering. These results point to polymer chain orientation at the point of adsorption and the formation of a mesomorphic layer as possible steps in the fast nucleation of oriented lamella, with wetting of the CNT fibre surface by the molten semi-crystalline polymer a key condition for heterogeneous nucleation to take place

Threading Through Macrocycles Enhances the Performance of Carbon Nanotubes as Polymer Fillers

In this work we study the reinforcement of polymers by mechanically interlocked derivatives of single-walled carbon nanotubes (SWNTs). We compare the mechanical properties of fibers made of polymers and of composites with pristine single-walled carbon nanotubes (SWNTs), mechanically interlocked derivatives of SWNTs (MINTs) and the corresponding supramolecular models. Improvements of both Young's modulus and tensile strength of up to 200 % were observed for the polystyrene-MINTs samples with an optimized loading of just 0.01 wt.%, while the supramolecular models with identical chemical composition and loading showed negligible or even detrimental influence. This behavior is found for three different types of SWNTs and two types of macrocycles. Molecular dynamics simulations show that the polymer adopts an elongated conformation parallel to the SWNT when interacting with MINT fillers, irrespective of the macrocycle chemical nature, whereas a more globular structure is taken upon facing with either pristine SWNTs or supramolecular models. The MINT composite architecture thus leads to a more efficient exploitation of the axial properties of the SWNTs and of the polymer chain at the interface, in agreement with experimental results. Our findings demonstrate that the mechanical bond imparts distinctive advantageous properties to SWNT derivatives as polymer fillers.Comment: 39 pages, 19 figure

The cosmic evolution of the spatially-resolved star formation rate and stellar mass of the CALIFA survey

We investigate the cosmic evolution of the absolute and specific star formation rate (SFR, sSFR) of galaxies as derived from a spatially-resolved study of the stellar populations in a set of 366 nearby galaxies from the CALIFA survey. The analysis combines GALEX and SDSS images with the 4000 break, H_beta, and [MgFe] indices measured from the datacubes, to constrain parametric models for the SFH, which are then used to study the cosmic evolution of the star formation rate density (SFRD), the sSFR, the main sequence of star formation (MSSF), and the stellar mass density (SMD). A delayed-tau model, provides the best results, in good agreement with those obtained from cosmological surveys. Our main results from this model are: a) The time since the onset of the star formation is larger in the inner regions than in the outer ones, while tau is similar or smaller in the inner than in the outer regions. b) The sSFR declines rapidly as the Universe evolves, and faster for early than for late type galaxies, and for the inner than for the outer regions of galaxies. c) SFRD and SMD agree well with results from cosmological surveys. At z< 0.5, most star formation takes place in the outer regions of late spiral galaxies, while at z>2 the inner regions of the progenitors of the current E and S0 are the major contributors to SFRD. d) The inner regions of galaxies are the major contributor to SMD at z> 0.5, growing their mass faster than the outer regions, with a lookback time at 50% SMD of 9 and 6 Gyr for the inner and outer regions. e) The MSSF follows a power-law at high redshift, with the slope evolving with time, but always being sub-linear. f) In agreement with galaxy surveys at different redshifts, the average SFH of CALIFA galaxies indicates that galaxies grow their mass mainly in a mode that is well represented by a delayed-tau model, with the peak at z~2 and an e-folding time of 3.9 Gyr.Comment: 23 pages, 16 figures, 6 tables, accepted for publication in Astronomy & Astrophysics. *Abridged abstract

Processing and mechanical properties of novel biodegradable poly-lactic acid/Zn 3D printed scaffolds for application in tissue regeneration

The feasibility to manufacture scaffolds of poly-lactic acid reinforced with Zn particles by fused filament fabrication is demonstrated for the first time. Filaments of 2.85 mm in diameter of PLA reinforced with different weight fractions of $\mu$m-sized Zn - 1 wt. \% Mg alloy particles (in the range 3.5 to 17.5 wt. \%) were manufactured by a double extrusion in method in which standard extrusion is followed by a precision extrusion in a filament-maker machine. Filaments with constant diameter, negligible porosity and a homogeneous reinforcement distribution were obtained for Zn weight fractions of up to 10.5\%. It was found that the presence of Zn particles led to limited changes in the physico-chemical properties of the PLA that did not affect the window temperature for 3D printing nor the melt flow index. Thus, porous scaffolds could be manufactured by fused filament fabrication at 190\textdegree C with poly-lactic acid/Zn composites containing 3.5 and 7 wt. \% of Zn and at 170\textdegree C when the Zn content was 10.5 wt. \% with excellent dimensional accuracy and mechanical properties

Stellar populations of bulges at low redshift

This chapter summarizes our current understanding of the stellar population properties of bulges and outlines important future research directions.Comment: Review article to appear in "Galactic Bulges", Editors: Laurikainen E., Peletier R., Gadotti D., Springer Publishing. 34 pages, 12 figure

Bio-based carbonaceous composite materials from epoxidised linseed oil, bio-derived curing agent and starch with controllable functionality

Development of biomass-derived materials using sustainable practices has been one of the major scientific aims over the last few decades. A new class of bio-derived nanocomposite derived from epoxidised linseed oil, a bio-derived crosslinker and a starch based carbonaceous mesoporous material (Starbon®) has been developed. The use of Starbons® technology enables the incorporation of carbonaceous materials with tuneable surface functionality (from hydrophilic to hydrophobic). The resulting composite demonstrated good thermal stability up to 300 °C, good low temperature modulus, flexibility and uniformity, as demonstrated by TGA, DMA and SEM studies, respectively. Furthermore, the thermoset composites' swelling behaviour in solvents with a high polar index through to non-polar ones was investigated, revealing initially that non polar solvents have a greater impact on swelling than polar solvents and that in all cases the addition of filler reduces the extent of swelling. The inclusion of this carbonaceous material with hierarchical pore structure and high BET surface area may further aid the use of such composites in membrane separation applications

Cytokine profile and anti-inflammatory activity of a standardized conditioned medium obtained by coculture of monocytes and mesenchymal stromal cells (PRS CK STORM)

Intercellular communication between monocytes/macrophages and cells involved in tissue regeneration, such as mesenchymal stromal cells (MSCs) and primary tissue cells, is essential for tissue regeneration and recovery of homeostasis. Typically, in the final phase of the inflammation-resolving process, this intercellular communication drives an anti-inflammatory immunomodulatory response. To obtain a safe and effective treatment to counteract the cytokine storm associated with a disproportionate immune response to severe infections, including that associated with COVID-19, by means of naturally balanced immunomodulation, our group has standardized the production under GMP-like conditions of a secretome by coculture of macrophages and MSCs. To characterize this proteome, we determined the expression of molecules related to cellular immune response and tissue regeneration, as well as its possible toxicity and anti-inflammatory potency. The results show a specific molecular pattern of interaction between the two cell types studied, with an anti-inflammatory and regenerative profile. In addition, the secretome is not toxic by itself on human PBMC or on THP-1 monocytes and prevents lipopolysaccharide (LPS)-induced growth effects on those cell types. Finally, PRS CK STORM prevents LPS-induced TNF-A and IL-1B secretion from PBMC and from THP-1 cells at the same level as hydrocortisone, demonstrating its anti-inflammatory potency. © 2022 by the authors. Licensee MDPI, Basel, Switzerland

What Does It Drive the Relationship Between Suicides and Economic Conditions? New Evidence from Spain

In this paper we analyse suicides across the 17 Spanish regions over the period 2002?2013. In doing so, we estimate count panel data models considering gender differences taking into account before and during economic crisis periods. A range of aggregate socioeconomic regional-level factors have been considered. Our empirical results show that: (1) a socioeconomic urban?rural suicide differentials exist, (2) there exists a Mediterranean suicide pattern; and (3) unemployment levels have a marked importance during the crisis period. The results of this study may have usefulness for suicide prevention in Spain