Thermo-Mechanical Properties of Poly ε-Caprolactone/Poly L-Lactic Acid Blends: Addition of Nalidixic Acid and Polyethylene Glycol Additives Journal of the Mechanical Behavior of Biomedical Materials

The search for ideal biomaterials is still on-going for tissue regeneration. In this study, blends of Poly ε-caprolactone (PCL) with Poly l-lactic acid (PLLA), Nalidixic Acid (NA) and Polyethylene glycol (PEG) were prepared. Mechanical and thermal properties of the blends were investigated by tensile and flexural analysis, DSC, TGA, WXRD, MFI, BET, SEM and hot stage optical microscopy. Results showed that the loading of PLLA caused a significant decrease in tensile strength and almost total eradication of the elongation at break of PCL matrix, especially after PEG and NA addition. Increased stiffness was also noted with additional NA, PEG and PLLA, resulting in an increase in the flexural modulus of the blends.
Isothermal degradation indicated that bulk PCL, PLLA and the blends were thermally stable at 200°C for the duration of 2h making extrusion of the blends at this temperature viable. Morphological study showed that increasing the PLLA content and addition of the very low viscosity PEG and powder NA decreased the Melt Flow Indexer and increased the viscosity.
At the higher temperature the PLLA begins to soften and eventually melts allowing for increased flow and, coupling this with, the natural increase in MFI caused by temperature is enhanced further. The PEG and NA addition increased dramatically the pore volume which is important for cell growth and flow transport of nutrients and metabolic waste.

Lack of genetic structure and evidence for long-distance dispersal in ash (Fraxinus excelsior) populations under threat from an emergent fungal pathogen: implications for restorative planting

Genetic analysis on populations of European ash (Fraxinus excelsior) throughout Ireland was carried out to determine the levels and patterns of genetic diversity in naturally seeded trees in ash woodlands and hedgerows, with the aim of informing conservation and replanting strategies in the face of potential loss of trees as a result of ash dieback. Samples from 33 sites across Northern Ireland and three sites in the Republic of Ireland were genotyped for eight nuclear and ten chloroplast microsatellites. Levels of diversity were high (mean A R = 10.53; mean H O = 0.709; mean H E = 0.765) and were similar to those in Great Britain and continental Europe, whilst levels of population genetic differentiation based on nuclear microsatellites were extremely low (Φ ST = 0.0131). Levels of inbreeding (mean F IS = 0.067) were significantly lower than those reported for populations from Great Britain. Fine-scale analysis of seed dispersal indicated potential for dispersal over hundreds of metres. Our results suggest that ash woodlands across Ireland could be treated as a single management unit, and thus native material from anywhere in Ireland could be used as a source for replanting. In addition, high potential for dispersal has implications for recolonization processes post-ash dieback (Chalara fraxinea) infection, and could aid in our assessment of the capacity of ash to shift its range in response to global climate change.

Catalyst-Free Photoredox Addition-Cyclisations: Exploitation of Natural Synergy between Aryl Acetic Acids and Maleimide

Suitably functionalised carboxylic acids undergo a previously unknown photoredox reaction when irradiated with UVA in the presence of maleimide. Maleimide was found to synergistically act as a radical generating photoxidant and as a radical acceptor, negating the need for an extrinsic photoredox catalyst. Modest to excellent yields of the product chromenopyrroledione, thiochromenopyrroledione and pyrroloquinolinedione derivatives were obtained in thirteen preparative photolyses. In situ NMR spectroscopy was used to study each reaction. Reactant decay and product build-up were monitored, enabling reaction profiles to be plotted. A plausible mechanism, whereby photo-excited maleimide acts as an oxidant to generate a radical ion pair, has been postulated and is supported by UV/Vis. spectroscopy and DFT computations. The radical-cation reactive intermediates were also characterised in solution by EPR spectroscopy.

Effect of nanosilica addition on the fresh properties and shrinkage of mortars with fly ash and superplasticizer

The ongoing use of various mineral additions along with chemical admixtures such as superplasticizers justifies the need for further research. Understanding and quantifying their effects and possible synergies on the fresh and hardened properties of cement-based materials is necessary, especially if some of these components are known to have a pozzolanic effect. This paper describes and models the fresh and hardened properties of cement mortars including nanosilica and fly ash, and relates their properties to the proportioning of these materials and the superplasticizer dosage. Mini-slump, Marsh cone and Lombardi cone tests were used to examine the properties of the fresh mortars, and to assess density, plastic shrinkage, and drying shrinkage up to 20 days. The equations presented in this paper make it possible to optimize mortar proportionings to the required levels of performance in both fresh and hardened states.

Influence of phosphate addition on the arsenic uptake by wheat (Triticum Durum) grown in arsenic polluted soils

Arsenic (As) uptake and distribution in the roots, shoots, and grain of wheat (Triticum durum) grown in 2 As polluted soils (192 and 304 mg kg ^-1 respectively), and an uncontaminated soil (14 mg kg^-1 ), collected from Scarlino plain (Tuscany, Italy), was investigated with respect with phosphorus fertilization. Three different level of phosphorus (P) fertilization: PO [0 kg ha^-1], Pl [75 kg ha^-1], and P2 [150 kg ha^-1], as KH₂PO₄ of P, were applied. The presence of high concentrations of As in soils reduced plants growth, decreased grain yield and increased root, shoot and grain As concentrations, especially in the absence of P fertilization. The P fertilization decreased the As concentration in all the tissues as well as the translocation of As to the shoot and grain. This observation may be useful in certain areas of the world with high levels of As in soils, to reduce the potential risk posed to human health by As entering the food-chain. © by PSP.

Response of soil microbial biomass to 1,2-dichlorobenzene addition in the presence of plant residues

The impact of 1,2-dichlorobenzene on soil microbial biomass in the presence and absence of fresh plant residues (roots) was investigated by assaying total vital bacterial counts, vital fungel hyphal length, total culturable bacterial counts, and culturable fluorescent pseudomonads. Diversity of the fluorescent pseudomonads was investigated using fatty acid methyl ester (FAME) characterization in conjunction with metabolic profiling of the sampled culturable community (Biolog). Mineralization of [¹⁴C]1,2- dichlorobenzene was also assayed. Addition of fresh roots stimulated 1,2- dichlorobenzene mineralization by over 100%, with nearly 20% of the label mineralized in root-amended treatments by the termination of the experiment. Presence of roots also buffered any impacts of 1,2-dichlorobenzene on microbial numbers. In the absence of roots, 1,2-dichlorobenzene greatly stimulated total culturable bacteria and culturable pseudomonads in a concentration-dependent manner. 1,2-Dichlorobenzene, up to concentrations of 50 μg/g soil dry weight had little or no deleterious effects on microbial counts. The phenotypic diversity of the fluorescent pseudomonad population was unaffected by the treatments, even though fluorescent pseudomonad numbers were greatly stimulated by both roots and 1,2-dichlorobenzene. The presence of roots had no detectable impact on the bacterial community composition. No phenotypic shifts in the natural population were required to benefit from the presence of roots and 1,2-dichlorobenzene. The metabolic capacity of the culturable bacterial community was altered in the presence of roots but not in the presence of 1,2-dichlorobenzene. It is argued that the increased microbial biomass and shifts in metabolic capacity of the microbial biomass are responsible for enhanced degradation of 1,2-dichlorobenzene in the presence of decaying plant roots.

The addition of CO2 to four superbase ionic liquids: a DFT study

The addition of carbon dioxide to four superbase ionic liquids, [P3333][Benzim], [P3333][124Triz], [P3333][123Triz] and [P3333][Bentriz] was studied using a molecular DFT approach involving anions alone and individual ion pairs. Intermolecular bonding within the individual ion pairs is characterised by a number of weak hydrogen bonds, with the superbase anion geometrically arranged so as to maximize interactions between the heterocyclic N atoms and the cation. The pairing energies show no correlation to the observed CO2 adsorption capacity. Addition of CO2 to the anion alone clearly resulted in the formation of a covalently-bound carbamate function with the strength of binding correlated to experimental capacity. In the ion pair however the cation significantly alters the nature of the bonding such that the overall cohesive energy is reduced. Formation of a strong carbamate function occurs at the expense of weakening the interaction between anion and cation. In the more weakly absorbing ion pairs which contain [123Triz]- and [Bentriz]-, the carbamate-functionalised systems are very close in energy to adducts in which CO2 is more weakly bound, suggesting an equilibrium between the chemi- and physisorbed CO2.