Charge compensation and the luminescence of Cr3+ in KMgF3

Studies of the photoluminescence spectra of Cr³⁺ ions in KMgF₃ crystals co-doped with Cr³⁺ and Ni²⁺ ions are reported. Several crystal field sites are identified by the different R-line spectra due to the ² E⁴ A ₂ transition and broadband luminescences associated with the ⁴ T ₂⁴ A ₂ transitions. Cr³⁺ ions substituting without local charge compensation on the octahedral Mg²⁺ site give rise to a low temperature R line in photoluminescence at =702.3 nm with a radiative decaytime of 3 ms at T=14 K. At T=300 K this isotropic centre gives rise to an unpolarized broadband ⁴ T ₂⁴ A ₂ emission, which results from the thermal occupancy of an excited ⁴ T ₂ state just above the ² E level which, at lower temperature, gives rise to emission in the R-line. Other crystal field sites are due to some Cr³⁺ ions having Mg²⁺ or K⁺ vacancies in nearest-neighbour positions, these vacancies being required to maintain charge neutrality in doped fluoride perovskites. The Cr³⁺–K⁺ vacancy complex results in the centre having trigonal symmetry, and low temperature, photoluminescence via R ₁ and R ₂ lines at 716.8 nm and 716.0 nm, respectively. Finally, Cr³⁺ ions having a nearest neighbour Mg²⁺ vacancy have tetragonal symmetry, experiencing weak crystal fields. In consequence, the ⁴ T ₂ level lies below ² E and the photoluminescence spectrum at low temperature takes the form of a polarized broad ⁴ T ₂⁴ A ₂ band with peak at 760 nm and radiative decaytime of 54 s.     

Bridged ring systems—VIII A novel ring expansion reaction

Acid treatment of 2-(β-Benzoylethyl)-cyclopentanone (III) leads directly to a phenylcycloheptene carboxylic acid (VII) and the related lactone (XI), via a bicyclic intermediate.     

Peptide structural analysis using continuous Ar cluster and C60 ion beams

A novel application of time-of-flight secondary ion mass spectrometry (ToF-SIMS) with continuous Ar cluster beams to peptide analysis was investigated. In order to evaluate peptide structures, it is necessary to detect fragment ions related to multiple neighbouring amino acid residues. It is, however, difficult to detect these using conventional ToF-SIMS primary ion beams such as Bi cluster beams. Recently, C₆₀ and Ar cluster ion beams have been introduced to ToF-SIMS as primary ion beams and are expected to generate larger secondary ions than conventional ones. In this study, two sets of model peptides have been studied: (des-Tyr)-Leu-enkephalin and (des-Tyr)-Met-enkephalin (molecular weights are approximately 400 Da), and [Asn¹ Val⁵]-angiotensin II and [Val⁵]-angiotensin I (molecular weights are approximately 1,000 Da) in order to evaluate the usefulness of the large cluster ion beams for peptide structural analysis. As a result, by using the Ar cluster beams, peptide molecular ions and large fragment ions, which are not easily detected using conventional ToF-SIMS primary ion beams such as Bi₃ ⁺, are clearly detected. Since the large fragment ions indicating amino acid sequences of the peptides are detected by the large cluster beams, it is suggested that the Ar cluster and C₆₀ ion beams are useful for peptide structural analysis.     

A Robust Algorithm for Roots Selection and Saturation Pressure Calculation for Cubic Equations of State

Journal of Solution Chemistry - In this work, a robust and rigorous procedure for roots calculation and selection for a Cubic Equation of State is presented. Roundoff errors are detected and...     

β-Ketoiminato Iridium(III) Organometallic Complexes: Selective Cytotoxicity towards Colorectal Cancer Cells HCT116 p53-/-

This report presents a new library of organometallic iridium(III) compounds of the type [Cp*IrCl(L)] (Cp*=pentamethylcyclopentadienyl and L=a functionalized β-ketoiminato ligand) showing moderate to high cytotoxicity against a range of cancer cell lines. All compounds show increased activity towards colorectal cancer, with preferential activity observed against the immortalized p53-null colorectal cell line, HCT116 p53-/-, with sensitivity factors (SF) up to 26.7. Additionally, the compounds have excellent selectivity for cancerous cells when tested against normal cell types, with selectivity ratios (SR) up to 35.6, contrary to that of cisplatin, which is neither selective nor specific for cancerous cells (SF=0.43 and SR=0.7–2.3). This work provides a preliminary understanding of the cytotoxicity of iridium compounds in the absence of p53 and has potential applications in treatment of cancers for which the p53 gene is absent or mutant.     

Test of the Duh-Haymet-Henderson theory for mixtures: cavity correlation functions and excess volumes

The accuracy of the Duh-Haymet-Henderson (DHH) integral equation theory for predicting the cavity correlation functions of mixtures has been tested by comparison with molecular simulations. We have compared the cavity correlation functions, internal energies, and pressures computed for Lennard-Jones model mixtures of Ar/Kr, Ar/Ne, and Ar/Xe with these same quantities computed from the DHH theory and also, for reference, the Percus-Yevick (PY) integral equation theory. We found that DHH gave much better accuracy than PY at high densities. At low densities DHH and PY give essentially identical predictions. We have computed excess volumes for Ar/Kr mixtures at two pressures (10 and 20?MPa) at 132.32?K, for which experimentally derived data are available. The DHH theory predicts the correct trends and is quantitatively more accurate than the PY theory for predicting the excess volumes. We have tested the local optimality of the DHH theory for pure fluids by adding two adjustable parameters to the DHH bridge function expression to see if it is possible to improve the DHH predictions of the cavity correlation function empirically, holding the form of the bridge function constant. We found that no single set of adjustable parameter values could improve the accuracy of DHH over multiple different isotherms. Furthermore, perturbing DHH leads to a decrease in accuracy of the predictions of both the pressure and energy, although small improvements in the cavity correlation functions were achieved. Thus, the DHH theory is locally optimal, given the form of the bridge function.     

Separation of intact pyruvate dehydrogenase complex using blue native agarose gel electrophoresis

We show that the blue native gel polyacrylamide electrophoresis system (BN-PAGE) can be applied to pyruvate dehydrogenase complex (PDC). BN-PAGE has been used extensively to study the multisubunit enzymes of oxidative phosphorylation, as nondenaturing separation in the first dimension maintains holoenzyme integrity. However, the standard protocol was inappropriate for PDC as, at 10 MDa, it is approximately ten times larger than the largest respiratory chain enzyme complex. Therefore, agarose was substituted for polyacrylamide. Moreover, a substantial decrease in salt concentration was necessary to prevent dissociation of PDC. As with standard BN-PAGE, immunoblots of second-dimensional sodium dodecyl sulfate-PAGE (SDS-PAGE) provided more detailed information on specific subunits and subcomplexes. The method was applied to human heart mitochondrial fragments, control cultured human cells, rho0 cells that lack mitochondrial DNA, and two cell lines derived from patients with PDC deficiency. The PDC deficient cell lines showed a clear correlation between amount of PDC holoenzyme and disease severity. In cells lacking mitochondrial DNA, synthesis and assembly of all PDC subunits (all nuclearly encoded) appeared normal, suggesting that respiratory function has no regulatory role in PDC biogenesis. Blue native agarose gel electrophoresis coupled with standard second-dimensional SDS-PAGE provides a new tool to be used in conjunction with biochemical assays and immunoblots of one-dimensional SDS-PAGE to further elucidate the nature of PDC in normal and disease states. Furthermore, other cellular protein complexes of 1 MDa or more can be analysed by this method.