Understanding the acceleration in the ring-opening of lactones delivered by microwave heating

This paper reports the first detailed study focussed upon identifying the influence that microwave heating (MWH) has upon the mechanic steps involved in the tin catalysed ring-opening of lactones such as ?-caprolactone (CL). Direct comparison of conventional (CH) and microwave (MWH) heated kinetic studies showed that a key factor in the reduction of the polymerisation cycle time with MWH was the elimination of the induction period associated with in situ catalyst manufacture and initiation. NMR studies demonstrated that the most significant mechanistic change contributing to the observed induction time reduction/elimination was faster initiation (i.e., reaction of the initiatior/catalyst complex with the first monomer unit). Consequently, analysis of the dielectric properties of the reaction components predicted that this MWH induced change was related to the selective volumetric heating of both the catalyst and the monomer. Furthermore, this indication of the greater significance of the initiation step in defining the length of the induction period suggests that this is the rate determining step of the process, whether conducted by CH or MWH. Increasing the catalyst concentration was demonstrated to produce significant reductions in reaction heat-up time and to induce a significant (up to 30 °C) overshoot in reaction mixture bulk temperature in with MWH only. Thus supporting the conclusion that selective heating of the organometallic species in the system contributes directly to differences in the reaction conditions and which need to be taken into account when drawing comparisons with CH systems. Consequently, both effects were concluded to be thermally generated from selective volumetric heating.     

Formation of protein-metal oxide nanostructures by the sonochemical method: observation of nanofibers and nanoneedles

The sonochemical reaction of iron pentacarbonyl is explored in water and in water with the protein BSA (bovine serum albumen). In water, the reaction is found to produce spherical nanoparticles of magnetite (Fe3O4) with a particle size distribution of <10 to approximately 60 nm. In water with BSA, the reaction produces either nanofibers or nanoneedles, depending on the concentration of BSA. The nanofiber and nanoneedle samples are found to be mixtures of goethite, lepidocrocite, and hematite (alpha-FeOOH, gamma-FeOOH, and alpha-Fe2O3, respectively). The sonochemical reaction of iron pentacarbonyl with BSA in water is thought to proceed through the thermal decomposition mechanism for iron pentacarbonyl with BSA acting as a templating agent.     

Tetra-CMPO-derivatives of calix[4]arenes fixed in the 1,3-alternate conformation

Calix[4]arene derivatives fixed in the 1,3-alternate conformation and substituted at one side by four carbamoylmethylphosphine oxide (CMPO) residues were synthesised. Two CMPO groups are directly attached to the wide rim, while the second pair is bound to the narrow rim via a tri- or tetramethylene spacer. Similar compounds, in which two CMPO groups at the wide rim are combined with two picolinamide groups or two ionisable carboxylic groups at the narrow rim, were also prepared. Some of these calixarene derivatives were studied as extractants for lanthanides (La³⁺, Eu³⁺, Yb³⁺) and thorium (Th⁴⁺) from acidic solution into methylene chloride. For selected samples, stability constants in methanol were determined by spectrophotometric titrations. Three compounds (1b′, 13, 17) in the 1,3-alternate conformation and one intermediate in the cone conformation (18) were confirmed by a crystal structure.     

Validation of Monte Carlo simulation of 6 MV photon beam produced by Varian Clinac 2100 linear accelerator using BEAMnrc code and DOSXYZnrc code

The Monte Carlo model for the photon-beam output from the Varian Clinac 2100 linear accelerator was validated to compare the calculated to measured PDD and beam dose profiles The Monte Carlo calculation method is considered to be the most accurate method for dose calculation in radiotherapy. The objective of this study is to build a Monte Carlo geometry of Varian Clinac 2100 linear accelerator as realistically as possible. The Monte Carlo codes used in this work were the BEAMnrc code to simulate the photons beam and the DOSXYZnrc code to examinate the absorbed dose in the water phantom. We have calculated percentage depth dose (PDD) and beam profiles of the 6 MV photon beam for the 6 × 6 cm², 10 × 10 cm² and 15 × 15 cm² field sizes. We have used the gamma index technique for the quantitative evaluation to compare the measured and calculated distributions. Good agreement was found between calculated PDD and beam profile compared to measured data. The comparison was evaluated using the gamma index method and the criterions were 3% for dose difference and 3 mm for distance to agreement. The gamma index acceptance rate was more than 97% of both distribution comparisons PDDs and dose profiles and our results were more developed and accurate. The Varian Clinac 2100 linear accelerator was accurately modeled using Monte Carlo codes: BEAMnrc and DOSXYZnrc codes package.     

Rheology of polyacrylate binders produced via catalytic chain transfer polymerization as an alternative to bitumen in road pavement materials

Catalytic chain transfer polymerization has been successfully used to produce a range of methyl acrylate (MA) and butyl acrylate (BA) synthetic polymers of specific, targeted molecular weights, with polydispersity index values in the range of 2–4.5. The rheological properties of a subgroup of these synthetic binders consisting of four MA homo-polymers and one MA–BA co-polymer were then determined by means of oscillatory testing using a dynamic shear rheometer (DSR). The rheological tests consisted of a combination of stress/strain amplitude and frequency sweeps using a standard 8 mm diameter parallel plate testing geometry. The rheological parameters of phase angle and complex, storage and loss moduli were then shifted to form master curves at a reference temperature of 25 °C and isochronal plots at 0.1, 1 and 10 Hz. The rheological properties of the synthetic polymers were also compared to those of standard road pavement bitumens. The results show that it is possible to produce a range of synthetic polyacrylates with different rheological responses by altering the reactant type, reactant concentration and polymerization conditions to match the rheological properties of road bitumens. All the polyacrylate binders showed a similar rheological profile with a unique viscoelastic response as represented by the phase angle master curves together with an upper limiting stiffness and intermediate temperature/frequency ‘plateau’ region as shown in the complex modulus master curves. The results of the rheological examination of the binders showed that the key material property that influenced the performance of the polyacrylates in these specific application tests was glass transition temperature rather than molecular weight. Over this range of investigated molecular weights, it is the ratio between the two polymers which determines the glass transition and as such determines the material properties. These findings suggest that such sustainably sourced polyacrylate binders may allow for a move from petrochemical feed stocks to be made and allow for targeted road pavement design based on local climates, offering improved mechanical robustness.     

Photon beam softening coefficients evaluation for a 6 MeV photon beam for an aluminum slab: Monte Carlo study using BEAMnrc Code,DOSXYZnrc Code,and BEAMDP code

Determination and understanding the photon beam attenuation by the photon beam modifier and the radiation beam softening for clinical use is more important part of material study for the beam modifier enhancements and the linac improvements. A Monte Carlo model was used to simulate 6 MeV photon beams from a Varian Clinac 2100 accelerator with the flattening filter and the later was replaced by the aluminum slab with variable thickness. The Monte Carlo geometry was validated by a gamma index acceptance rate of 99% in PDD and 98% in dose profiles, the gamma criteria was 3% for dose difference and 3 mm for distance to agreement. The purpose was to investigate aluminum material attenuation and beam softening coefficients as a function of the inserted aluminum slab thickness and of off-axis distance. The attenuation and beam softening coefficients were not identical for the same off-axis distance and they varied as a function of aluminum slab thickness. The results of our study were shown that the beam softening coefficients were varied with thickness beam modifier material used for beam softening and the off-axis distance inside the irradiation field. Thereafter, the softening coefficient a ₁ have a maximum of 2.5 × 10^–1 cm^–1 for the aluminum slab thickness of 1 mm, 1.4 × 10^–1 cm^–1 for the aluminum slab thickness of 1.5 mm and 4.47 × 10^–2 cm^–1 for the aluminum slab thickness of 2 mm. The maximum of the second softening coefficient a ₂ was 1.02 × 10^–2 cm^–2 for the aluminum slab thickness of 1 mm, was 1.92 × 10^–2 cm^–2 for the aluminum slab thickness of 1.5 mm and was 1.93 × 10^–2 cm^–2 for the aluminum slab thickness of 2 mm. Our study can be a basic investigation of photon beam softening material that will be used in the future linac configuration and also in the photon beam modifiers.     

Lanthanide complexation with CMPO and CMPO-calix[4]arenes in solution: spectrophotometric and electrospray mass spectrometric approaches

The binding of lanthanide(III) cations with organophosphorous ligands like CMPO and related calix[4]arene-based derivatives have been investigated using two experimental methods. The stability constants of the lanthanum, europium and ytterbium complexes were first determined in methanol by UV absorption spectrophotometry in the presence of nitrate or chloride anions. The results showed that the stoichiometry and the stability of the complexes formed depend on the position of the CMPO moieties either on the wide or the narrow rim of the calixarene scaffold, the nature of the medium, the conformational mobility of the ligands. Complexation of lanthanum was also followed by ESI-mass spectrometry in the same solvent. This method confirmed the stoichiometry of the complexes, giving also structural information, like coordination of anion or solvent molecules to the complexes, and allowed the calculation of distribution curves in good agreement with those derived from the spectrophotometric results. This is an important result showing that ESI-MS can be used to provide with quantitative information when absorption spectrophotometry is not applicable, i.e. for systems where complexation leads to weak spectral changes.