The reductive metalation of 1,2-dihalobenzocyclobutenes by NaFe(CO)2Cp and HFe(CO)2Cp

The reactions between cis- and trans-1,2-dibromo- or 1,2-diidobenzocyclobutene and NaFe(CO)₂Cp (NaFp) were investigated. The mechanism of formation of 1,2-bis(cyclopentadienyldicarbonyliron)benzocyclobutene (I) and 1-(cyclopentadienyldicarbonyliron)benzocyclobutene (II) is thought to involve initial formation of benzocyclobutadiene, addition of a Fp radical to benzocyclobutadiene and subsequent addition of a second Fp radical to form I, or hydrogen abstraction from FpH to form II.     

Development of an on-line automated sample clean-up method and liquid chromatography–tandem mass spectrometry analysis: application in an in vitro proteolytic assay

Fluorescence detection has been a method of choice in industry for screening assays, including identification of enzyme inhibitors, owing to its high-throughput capabilities, excellent reproducibility, and sensitivity. Occasionally, inhibitors are identified that challenge the fluorescence assay limit, necessitating the development of more sensitive detection methods to assess these compounds. For data mining purposes, however, original assay conditions may be required. A direct method transfer to highly sensitive and specific LC-MS-based methods has not always been possible due to the presence of MS-incompatible neutral detergents and non-volatile salts in the assay matrix. Utilizing an in vitro proteolytic screening assay for the serine protease hepatitis C virus (HCV) nonstructural (NS) 3 protease as a test case, we report the development of an automated sample clean-up procedure implemented on-line with liquid chromatography–tandem mass spectrometry (LC-MS/MS) analysis to complement fluorescence detection. Ion exchange and peptide microtraps were employed to remove MS-incompatible assay matrix components. Three protease inhibitors were used to validate the MS/MS method. Comparable potencies were achieved for these compounds when assessed by fluorescence and MS/MS detection. Furthermore, four-fold less enzyme could be utilized when employing the MS/MS method compared to fluorescence detection. The longer analysis time, however, resulted in reduced sample capacity. The potency of our designed HCV NS3 protease inhibitors are thus routinely evaluated using a continuous fluorescence-based assay. Only pertinent inhibitors approaching the fluorescence assay sensitivity limit are subsequently analyzed further by LC-MS/MS. This methodology allows us to maintain a database and to compare results independent of the detection method. Despite the relatively slow sample turnaround time of this LC-MS approach, the versatility of the automated on-line clean-up procedure and sample analysis can be applied to assays containing reagents which were historically considered to be MS incompatible.     

Migratory insertion of [B(C6F5)2] into C-H bonds: CO promoted transfer of the boryl fragment

The reaction of (eta(5)-C5H5)Fe(CO)2B(C6F5)2 with CO has been shown to proceed via ligand substitution at the metal with accompanying transfer of the boryl fragment (via C-H insertion) to the Cp ring, thereby generating the zwitterion [eta(5)-C5H4B(C6F5)2H]Fe(CO)3 in quantitative yield.     

Conceptualizations of slope in Mexican intended curriculum

Slope is a fundamental mathematics concept in middle and high school that transcends to the university level. An understanding of slope is needed at the university level since slope plays an important role in understanding problems involving variation and change. In this study Mexican curricula documents were examined to determine which conceptualizations of slope are addressed in the intended mathematics curriculum. To explain the results, we use conceptualizations of slope identified in previous research. Our findings reveal that, to a certain extent, the conceptualizations proposed in the Mexican intended mathematics curriculum differ slightly in terms of the emphasis and timing of instruction from what others have identified in the U.S., with slope as a geometric ratio receiving less emphasis in the Mexican curriculum. There was also noted discontinuity within the Mexican curriculum in introducing slope in grade 9 and subsequently introducing of linear functions in grade 10 without explicit mention of slope. Suggestions are made for future studies, both to consider the conceptualizations of slope promoted in the Mexican textbooks and the impact they have in classroom instruction and student learning of slope.     

Condensed-phase relaxation of multilevel quantum systems. II. Comparison of path integral calculations and second-order relaxation theory for a nondegenerate three-level system

An exactly solvable model of multisite condensed-phase vibrational relaxation was studied in Paper I (Peter, S.; Evans, D. G.; Coalson, R. D. J. Phys. Chem. B 2006, 110, 18758.), where it was shown that long-time steady-state site populations of a degenerate N-level system are not equal (hence, they are non-Boltzmann) and depend on the initial preparation of the system and the number of sites that it comprises. Here we consider a generalization of the model to the case of a nondegenerate three-level system coupled to a high-dimensional bath: such a model system has direct relevance to a large class of donor-bridge-acceptor electron transfer processes. Because the quantum dynamics of this system cannot be computed analytically, we compare numerically exact path integral calculations to the predictions of second-order time-local relaxation theory. For modest system-bath coupling strengths, the two sets of results are in excellent agreement. They show that non-Boltzmann long-time steady-state site populations are obtained when the level splitting is small but nonzero, whereas at larger values of the system bias (asymmetry) these populations become Boltzmann distributed.     

Capturing two elements in unavoidable minors of 3-connected binary matroids

Let M be a 3-connected binary matroid and let n   be an integer exceeding 2. Ding, Oporowski, Oxley, and Vertigan proved that there is an integer f(n)$f(n)$ so that if |E(M)|>f(n)$|E(M)|>f(n)$, then M has a minor isomorphic to one of the rank-n wheel, the rank-n   tipless binary spike, or the cycle or bond matroid of _K3,n$K_{3,n}$. This result was recently extended by Chun, Oxley, and Whittle to show that there is an integer g(n)$g(n)$ so that if |E(M)|>g(n)$|E(M)|>g(n)$ and x∈E(M)$x\in E(M)$, then x is an element of a minor of M isomorphic to one of the rank-n wheel, the rank-n   binary spike with a tip and a cotip, or the cycle or bond matroid of _K1,1,1,n$K_{1,1,1,n}$. In this paper, we prove that, for each i   in {2,3}$\{2,3\}$, there is an integer _hi(n)$h_i(n)$ so that if |E(M)|>_hi(n)$|E(M)|>h_i(n)$ and Z is an i-element rank-2 subset of M, then M has a minor from the last list whose ground set contains Z.     

Production and extraction of astaxanthin from Phaffia rhodozyma and its biological effect on alcohol-induced renal hypoxia in Carassius auratus

The effect of astaxanthin (3,3′-dihydroxy-s-carotene-4,4′-dione) on alcohol-induced morphological changes in Carassius auratus, as an experimental model, was determined. The yeast Phaffia rhodozyma was used as a source of astaxanthin. The animals were divided into three groups for 30 days: one group was treated with ethanol at a dose of 1.5% mixed in water, the second one with EtOH 1.5% and food enriched with astaxanthin from P. rhodozyma, and the third was a control group. After a sufficient experimental period, the samples were processed using light microscopy and evaluated by histomorphological and histochemical staining, and the data were supported by immunohistochemical analysis, using a wide range of antibodies, such as calbindin, vimentin and alpha-smooth muscle actin. The results show that the alcoholic damage in the kidney led to hypoxia. In contrast, the group fed with astaxanthin from P. rhodozyma showed a normal morphological picture, with better glomeruli organisation and the presence of the area of filtration. Furthermore, the immunohistochemistry has confirmed these results.     

Synthesis of High χ–Low N Diblock Copolymers by Polymerization-Induced Self-Assembly

Polymerization-induced self-assembly (PISA) enables the scalable synthesis of functional block copolymer nanoparticles with various morphologies. Herein we exploit this versatile technique to produce so-called “high χ–low N” diblock copolymers that undergo nanoscale phase separation in the solid state to produce sub-10 nm surface features. By varying the degree of polymerization of the stabilizer and core-forming blocks, PISA provides rapid access to a wide range of diblock copolymers, and enables fundamental thermodynamic parameters to be determined. In addition, the pre-organization of copolymer chains within sterically-stabilized nanoparticles that occurs during PISA leads to enhanced phase separation relative to that achieved using solution-cast molecularly-dissolved copolymer chains.