The influence of iodide on glass transition temperature of high-pressure nuclear waste glasses

The glass transition temperature (T_g) is a key parameter to investigate for application in nuclear waste immobilization in borosilicate glasses. T_g for several glasses containing iodine (I) has been measured in order to determine the I effect on T_g. Two series of glass composition (ISG and NH) containing up to 2.5 mol% I and synthesized under high pressure (0.5 to 1.5 GPa) have been investigated using differential scanning calorimetry (DSC). The I local environment in glasses has been determined using X-ray photoelectron spectroscopy and revealed that I is dissolved under its iodide form (I⁻). Results show that T_g is decreased with the I addition in the glass in agreement with previous results. We also observed that this T_g decrease is a strong function of glass composition. For NH, 2.5 mol% I induces a decrease of 24°C in T_g, whereas for ISG, 1.2 mol% decreases the T_g by 64°C. We interpret this difference as the result of the I dissolution mechanism and its effect on the polymerization of the boron network. The I dissolution in ISG is accompanied by a depolymerization of the boron network, whereas it is the opposite in NH. Although ISG corresponds to a standardized glass, for the particular case of I immobilization it appears less adequate than NH considering that the decrease in T_g for NH is small in comparison to ISG.     

Development and characterisation of microporous biomimetic scaffolds loaded with magnetic nanoparticles as bone repairing material

Fine-tuning of the scaffolds structural features for bone tissue engineering can be an efficient approach to regulate the specific response of the osteoblasts. Here, we loaded magnetic nanoparticles aka superparamagnetic iron oxide nanoparticles (SPIONs) into 3D composite scaffolds based on biological macromolecules (chitosan, collagen, hyaluronic acid) and calcium phosphates for potential applications in bone regeneration, using a biomimetic approach. We assessed the effects of organic (chitosan/collagen/hyaluronic acid) and inorganic (calcium phosphates, SPIONs) phase over the final features of the magnetic scaffolds (MS). Mechanical properties, magnetic susceptibility and biological fluids retention are strongly dependent on the final composition of MS and within the recommended range for application in bone regeneration. The MS architecture/pore size can be made bespoken through changes of the final organic/inorganic ratio. The scaffolds undertake mild degradation as the presence of inorganic components hinders the enzyme catalytic activity. In vitro studies indicated that osteoblasts (SaOS-2) on MS9 had similar cell behaviour activity in comparison with the TCP control. In vivo data showed an evident development of integration and resorption of the MS composites with low inflammation activity. Current findings suggest that the combination of SPIONs into 3D composite scaffolds can be a promising toolkit for bone regeneration.     

Design and Characterization of a New pVII Combinatorial Phage Display Peptide Library for Protease Substrate Mining Using Factor VII Activating Protease (FSAP) as Model

We describe a novel, easy and efficient combinatorial phage display peptide substrate-mining method to map the substrate specificity of proteases. The peptide library is displayed on the pVII capsid of the M13 bacteriophage, which renders pIII necessary for infectivity and efficient retrieval, in an unmodified state. As capture module, the 3XFLAG was chosen due to its very high binding efficiency to anti-FLAG mAbs and its independency of any post-translational modification. This library was tested with Factor-VII activating protease (WT-FSAP) and its single-nucleotide polymorphism variant Marburg-I (MI)-FSAP. The WT-FSAP results confirmed the previously reported Arg/Lys centered FSAP cleavage site consensus as dominant, as well as reinforcing MI-FSAP as a loss-of-function mutant. Surprisingly, rare substrate clones devoid of basic amino acids were also identified. Indeed one of these peptides was cleaved as free peptide, thus suggesting a broader range of WT-FSAP substrates than previously anticipated.     

Quantum Sensing in a Physiological‐Like Cell Niche Using Fluorescent Nanodiamonds Embedded in Electrospun Polymer Nanofibers

Fluorescent nanodiamonds (fNDs) containing nitrogen vacancy (NV) centers are promising candidates for quantum sensing in biological environments. This work describes the fabrication and implementation of electrospun poly lactic‐co‐glycolic acid (PLGA) nanofibers embedded with fNDs for optical quantum sensing in an environment, which recapitulates the nanoscale architecture and topography of the cell niche. A protocol that produces uniformly dispersed fNDs within electrospun nanofibers is demonstrated and the resulting fibers are characterized using fluorescent microscopy and scanning electron microscopy (SEM). Optically detected magnetic resonance (ODMR) and longitudinal spin relaxometry results for fNDs and embedded fNDs are compared. A new approach for fast detection of time varying magnetic fields external to the fND embedded nanofibers is demonstrated. ODMR spectra are successfully acquired from a culture of live differentiated neural stem cells functioning as a connected neural network grown on fND embedded nanofibers. This work advances the current state of the art in quantum sensing by providing a versatile sensing platform that can be tailored to produce physiological‐like cell niches to replicate biologically relevant growth environments and fast measurement protocols for the detection of co‐ordinated endogenous signals from clinically relevant populations of electrically active neuronal circuits.     

Mechanics-aided digital image correlation for the investigation of piezoelectric and ferroelectric behaviour of a soft PZT

The strain response of a polarised PZT was characterised using Digital Image Correlation (DIC). The DIC algorithm is based on a global approach and regularises the displacement field using the balance equations of solid mechanics. The measurement error is reduced by correcting the displacements that are mechanically not admissible. A ferroelectric test showed that the standard deviations of strain fields remain mostly under 1.2 × 10^?4 for an element size of 64 px. The standard deviation on the average value is 3 × 10^?6. The strain field is homogeneous and its average value is consistent with the strain obtained from a CCD laser measurement device. The longitudinal strain, transverse strain and polarisation response of the PZT were measured for bipolar and unipolar loadings ranging from 50 to 5000 V/mm. Material properties were extracted from these measurements. This work shows the advantages of a novel 2D-DIC algorithm for piezoelectric strain characterisation.     

A Logic for Conditional Local Strategic Reasoning

Journal of Logic, Language and Information - We consider systems of rational agents who act and interact in pursuit of their individual and collective objectives. We study and formalise the...     

Synthesis of Spiro[piperidine‐3,3′‐oxindoles] via Gold(I)‐Catalyzed Dearomatization of N‐Propargyl‐ and N‐Homoallenyl‐2‐bromotryptamines

N‐Propargyl‐ and N‐homoallenyl‐2‐bromo‐β‐tryptamines undergo gold(I)‐catalyzed dearomatizing cyclizations to afford 2‐bromospiroindolenines that are in situ hydrolyzed to furnish spirooxindoles in a one‐pot process. Tryptophane derivatives (R²=CO₂Et) led upon cyclization to chiral spirooxindoles in excellent diastereoselectivities.

     

Ru-Containing Polymeric Catalysts for Cellulose Conversion to Polyols

In this paper Ru-containing catalysts based on hypercrosslinked polystyrene (MN-270) and its functional analogues (MN-100 and MN-500) were studied for the first time in cellulose hydrolytic hydrogenation. The catalysts were characterized using transmission electron microscopy (TEM), high resolution TEM, and porosity measurements. Catalytic studies demonstrated that the catalyst containing 1.0 % Ru and based on MN-270 is the most active. The total yield of sorbitol and mannitol was 50 % on the average at 85 % cellulose conversion.     

Structural Analysis of Partial and Total Esters of Glycerol Undecenoate and Diglycerol Undecenoate

The direct esterification reaction between glycerol and undecylenic acid or between diglycerol and undecylenic acid generates all the possible types of glycerol or diglycerol esters. Purification by silica gel chromatography resulted in the isolation of each of these types of ester in a pure form. The molecular structures of the compounds isolated were characterized and identified by mass spectrometry, ¹H NMR, ¹³C NMR and DEPT‐135. We then studied the composition of esters of undecylenic acid formed with glycerol or diglycerol as a function of their reaction conditions, which constitute a highly complex system. We purified undecylenic acid esters from each polyol family to allow the structural identification of each ester of glycerol and each ester of diglycerol with undecylenic acid. We found that the polarity of these non‐ionic amphiphilic esters directly affected their affinity for organic and inorganic solvents and that these esters behaved very differently from anionic amphiphilic molecules, such as undecylenic acid.