Disorder in Ho2Ti2−xZrxO7: pyrochlore to defect fluorite solid solution series

Pyrochlore (A₂B₂O₇) is an important, isometric structure-type because of its large variety of compositions and structural derivatives that are generally related to different disordering mechanisms at various spatial scales. The disordering is key to understanding variations in properties, such as magnetic behavior or ionic conduction. Neutron and X-ray total scattering methods were used to investigate the degree of structural disorder in the Ho₂Ti_2−xZr_xO₇ (x = 0.0–2.0, Δx = 0.25) solid solution series as a function of the Zr-content, x. Ordered pyrochlores (Fd$\bar{3}$m) disorder to defect fluorite (Fm$\bar{3}$m) via cation and anion disordering. Total scattering experiments with sensitivity to the cation and anion sublattices provide unique insight into the underlying atomic processes. Using simultaneous Rietveld refinement (long-range structure) and small-box refinement PDF analysis (short-range structure), we show that the series undergoes a rapid transformation from pyrochlore to defect fluorite at x ≈ 1.2, while the short-range structure exhibits a linear increase in a local weberite-type phase, C222₁, over the entire composition range. Enthalpies of formation from the oxides determined using high temperature oxide melt solution calorimetry support the structural data and provide insight into the effect of local ordering on the energetics of disorder. The measured enthalpies of mixing are negative and are fit by a regular solution parameter of W = −31.8 ± 3.7 kJ mol⁻¹. However, the extensive short-range ordering determined from the structural analysis strongly suggests that the entropies of mixing must be far less positive than implied by the random mixing of a regular solution. We propose a local disordering scheme involving the pyrochlore 48f to 8a site oxygen Frenkel defect that creates 7-coordinated Zr sites contained within local weberite-type coherent nanodomains. Thus, the solid solution is best described as a mixture of two phases, with the weberite-type nanodomains triggering the long-range structural transformation to defect fluorite after accumulation above a critical concentration (50% Ti replaced by Zr).

Combined neutron and X-ray total scattering with calorimetric measurements of the solid solution series Ho₂Ti_2−xZr_xO₇ reveals a complex order–disorder transition across short, intermediate, and long length scales induced by chemical substitution.     

Iodine-mediated synthesis of benzo[a]fluorenones from yne-enones

The chalcones derived from o-alkynylacetophenones and aromatic aldehydes (yne-enones) when heated under reflux with iodine in acetic acid gave a range of benzo[a]fluorenone derivatives in moderate to good yields. The transformation involves the formation of a vinyl indenone intermediate through regioselective alkyne hydration and intramolecular aldol condensation followed by electrocyclic ring closure and aromatization.

An iodine mediated synthesis of benzo[a]fluorenone derivatives from the chalcones derived from o-alkynylacetophenones and aromatic aldehydes is described.     

Thalidomide attenuates nitric oxide-driven angiogenesis by interacting with soluble guanylyl cyclase

Background and purpose:

Nitric oxide (NO) promotes angiogenesis by activating endothelial cells. Thalidomide arrests angiogenesis by interacting with the NO pathway, but its putative targets are not known. Here, we have attempted to identify these targets.

Experimental approach:

Cell-based angiogenesis assays (wound healing of monolayers and tube formation in ECV304, EAhy926 and bovine arterial endothelial cells), along with ex vivo and in vivo angiogenesis assays, were used to explore interactions between thalidomide and NO. We also carried out in silico homology modelling and docking studies to elucidate possible molecular interactions of thalidomide and soluble guanylyl cyclase (sGC).

Key results:

Thalidomide inhibited pro-angiogenic functions in endothelial cell cultures, whereas 8-bromo-cGMP, sildenafil (a phosphodiesterase inhibitor) or a NO donor [sodium nitroprusside (SNP)] increased these functions. The inhibitory effects of thalidomide were reversed by adding 8-bromo-cGMP or sildenafil, but not by SNP. Immunoassays showed a concentration-dependent decrease of cGMP in endothelial cells with thalidomide, without affecting the expression level of sGC protein. These results suggested that thalidomide inhibited the activity of sGC. Molecular modelling and docking experiments revealed that thalidomide could interact with the catalytic domain of sGC, which would explain the inhibitory effects of thalidomide on NO-dependent angiogenesis.

Conclusion and implications:

Our results showed that thalidomide interacted with sGC, suppressing cGMP levels in endothelial cells, thus exerting its anti-angiogenic effects. These results could lead to the formulation of thalidomide-based drugs to curb angiogenesis by targeting sGC.     

Relationship between posttetanic count and response to carinal stimulation during vecuronium-induced neuromuscular blockade

The correlation between degree of peripheral neuromuscular blockade and response to carinal stimulation was evaluated in two groups of 25 patients: one group was anaesthetized with thiopental, N2O and halothane, and the other group received thiopental, N2O and fentanyl. The degree of peripheral blockade was evaluated using train-of-four (TOF) and posttetanic twitch (PTC) stimulation of the ulnar nerve. The degree of diaphragmatic paralysis was evaluated indirectly by stimulating the carina and observing the corresponding muscular response, which was graded as severe, mild or absent. During halothane anaesthesia a PTC of 0 always indicated that no response to carinal stimulation could be elicited. On the appearance of the first response to posttetanic twitch stimulation (PTC = 1), 2% of the patients showed a mild response to carinal stimulation. At the first response to TOF stimulation, 48% of the patients reacted with a mild response. During thiopental, N2O, fentanyl anaesthesia one of 25 patients showed a mild response to carinal stimulation at a PTC of 0. When PTC was 1, 20% of the patients reacted mildly to the stimulation. At the first response to TOF stimulation, 92% showed a response to carinal stimulation; 24% of these responses were severe, necessitating intervention. It is concluded that the TOF response elicited peripherally is a late sign of neuromuscular recovery of the diaphragm, and that the method of counting posttetanic twitches is superior to the TOF response in evaluating early recovery of this muscle. Further, to ensure total diaphragmatic paralysis, the neuromuscular blockade of the peripheral muscles should be so intense that no response to posttetanic twitch stimulation (PTC = 0) can be elicited.     

Fazio-Londe syndrome in siblings from India with different phenotypes

Background

Fazio-Londe syndrome also called progressive bulbar palsy of childhood is a very rare motor neuron disease of pediatric age group characterized by progressive paralysis of lower cranial nerves.

Studies on Fundamental Interaction Parameters for Stainless Steel and Titanium Biomaterials Using Flattened and Un-Flattened Megavoltage X-Ray Beams

Purpose: This work presents the measure of fundamental interaction parameters like mass attenuation coefficient(μ/ρ), mean energy, total atomic (σa) and electronic (σe) cross section, effective atomic number (Zeff), electron density(Nel) and mean free path (mfp) using FF and UF megavoltage x-ray beam for high Z implants. Methods: Narrow beamgeometry is used to find out mass attenuation coefficient (μ/ρ) (MAC) which is then used to calculate mean energy (usingNIST data), total atomic (σa) and electronic cross section (σe) for different energies. The effective atomic number (Zeff),Electron density (Nel), mean free path (mfp) for both flattened and unflattened x-ray beams for high Z material stainlesssteel (SS316) and titanium alloy (Grade 5) are studied. Results: The mean energies calculated from NIST data againstmass attenuation coefficient were in good agreement with Monte Carlo value. It shows that spectral weighted effectiveatomic number is independent of megavoltage energies in the Compton region. Effective electron density calculatedusing Zeff and MAC method is lesser compared to direct method for both high Z materials. The mean free path (mfp)is higher along the central axis than off-axis for flattened beam in comparison to unflattened beam for both of the highZ materials studied because of the variation in energy spectrum for both FF and UF x-ray beams. Conclusion: Thisstudy elaborated the fundamental interaction parameters of different energies of flattened and unflattened x-ray beaminteractions with high Z materials such as Stainless Steel (SS316) and Titanium (Grade5) relevant in a clinical scenario.     

An Assessment of Dosimetric Characteristics of Inline 2.5 Mega Voltage Unflattened Imaging X-Ray Beam

Purpose: The aim of this work is to study the dosimetric parameters of newly introduced 2.5 MV imaging x-ray beam used as inline imaging to do setup verification of the patient undergoing radiation therapy. As this x-ray beam is in megavoltage range but comprises of a lower energy spectrum. It is essential to study the pros and cons of 2.5 MV imaging x-ray beam for clinical use.Methods: The mean energy was calculated using the NIST XCOM table through MAC. Profile analysis was done using RFA to understand the percentage depth dose, degree of unflatteness, symmetry, penumbra and out of field dose. Dose to skin for the 2.5 MV x-ray beam was analysed for field sizes 10x10 cm2, 20x20 cm2, 30x30 cm2. Leakage measurements for treatment head and at the patient plane were done using IEC 819/98 protocol. Finally, the spatial resolution and contrast were analyzed with and without patient scatter medium. Results: The MAC at 15 cm off-axis was found to be lower than that at the CAX. Similarly, there was a decrease in mean energy from 0.47 MV to 0.37 MV at 15 cm off-axis. The reduction of mean energy towards off-axis is lower than the other high energy MV x-ray beams. The tuned absolute dose of 1 cGy/MU is consistent and within < ±1 %. The relative output factors were found to be in correlation with Co-60. The beam quality of 2.5 MV x-ray beam was found to be 0.4771. The profile parameters like the degree of unflatness of the 2.5 x-ray beam were studied at 85 %, 90 %, 95 % lateral distances, and the penumbra at different depth and field sizes are higher than the 6 MV treatment beam. In addition, out of field dose also drastically increases to a maximum of up to 30 % laterally at 5cm at deeper depths. The skin dose increases from 48.51 % to 88.15 % from 6 MV to 2.5 MV x-ray beam for the field size 10x10 cm2. Also, the skin dose increases from 88.15 % to 91.78 % from the field size 10x10 cm2 to 30x30 cm2. Although the measured leakage radiation for 2.5 MV x-ray beam at the patient plane and other than patient planes are with the tolerance limit, an increase in exposure towards gantry side compared to other areas around treatment head and the patient plane may lead to more skin dose to head and chest while imaging pelvis region. The MLC transmission of 2.5 MV x-ray beam such as inter, intra and edge effect are 0.40 %, 0.37 % and 11% respectively. The spatial resolution of 2.0, 1.25 and 0.9 LP/mm was observed for KV, 2.5MV, and 6 MV x-ray beams. The spatial resolution and contrast of 2.5 MV x-ray beam are superior to 6 MV x-ray beam and inferior to KV x-rays. Conclusions: The 2.5 MV x-ray imaging beam is analysed in view of beam characteristics and radiation safety to understand the above-studied concepts while using this imaging beam in a clinical situation. In future, if 2.5MV x-ray beam is used for treatment purpose with increased dose rate, the above-studied notions can be incorporated prior to implementation.     

Thermochemistry of cation disordered Li ion battery cathode materials, (M′ = Nb and Ta,M′′ = Mn and Fe)

High temperature oxide melt solution calorimetry studies on (M′ = Nb⁵⁺, M′′ = Mn³⁺ and Fe³⁺ and x = 0.20, 0.30 and 0.40) oxides and a new family of Ta containing Li excess disordered cathode materials, (M′ = Ta⁵⁺, M′′ = Fe³⁺ and x = 0.20, 0.30 and 0.40), synthesized by a rapid quenching method, are reported in this study. The enthalpies of formation determined from high temperature calorimetry studies reveal that the stability of compounds increases with the increasing Li content per formula unit. The reaction between more basic Li₂O and acidic transition metal oxides results in the more negative enthalpies of formation for these compounds. The work reveals that the formation enthalpy term plays a more important role in the stabilization of such disordered Li ion materials at room temperature whereas configurational entropy along with lattice entropy (vibrational and magnetic) contributes to the stabilization at high temperature from which the samples are quenched.

Enthalpies of formation from oxides (ΔH_f,ox) of novel disordered Li_1+xTa_xFe_1−2xO₂ and reported (M′′ = Mn³⁺ and Fe³⁺).