Comparison of C═C bond hydrogenation in C-4 unsaturated nitriles over Pt/alumina

The hydrogenation of allyl cyanide (but-1-ene-4-nitrile, AC), trans- and cis-crotononitrile (E- and Z-but-2-ene nitrile, TCN and CCN), and methacrylonitrile (2-cyano-1-propene, MCN) were studied, both singly and competitively, over a Pt/alumina catalyst in the liquid phase. Each unsaturated nitrile only underwent C═C bond hydrogenation: no evidence was found for the formation of the saturated or unsaturated amine. The nonconjugated allyl cyanide was found to be the most reactive unsaturated nitrile. Activation energies for the hydrogenation of the C═C bond in AC and MCN were determined giving values of 64 ± 7 kJ mol–1 for AC and 37 ± 4 kJ mol–1 for MCN. The reaction was zero order for both nitriles. Competitive hydrogenations revealed that not only does allyl cyanide react preferentially over the other isomers but also it inhibits the hydrogenation of the other isomers. When all four nitriles were simultaneously hydrogenated, inhibition effects were easily seen suggesting that in terms of strength of bonding to the surface an order of AC > CCN > TCN ∼ MN can be generated

The Negative Halo Effect of Oppositional Defiant Behaviors on Teacher Ratings of ADHD: Impact of Child Gender

This study explored one potential reason for differences in diagnostic rates of attention-deficit hyperactivity disorder (ADHD) between genders: teacher-based rating bias. Abikoff, Courtney and Pelham (1993) showed elementary teachers two tapes of a male child in a fourth grade classroom, then had the teachers complete ADHD and ODD rating scales. One tape depicted a normal child; another depicted a child exhibiting either ADHD or ODD behaviors. Rating comparisons from the ADHD v. ODD tapes showed biases: the ADHD tape was rated higher than the ODD tape on ADHD rating scales and lower on ODD rating scales; while the ODD tape was rated higher than the ADHD tape on ODD rating scales but equal on ADHD rating scales. It was hypothesized that ODD behaviors exerted a halo effect on ADHD ratings. The present study replicated and extended Abikoff et. al\u27s study with new tapes including female actresses, hypothesizing that bias existed with the male, but not the female tapes. Following the procedures of Abikoff et al., this study showed new tapes to 80, rural Midwestern teachers. Though the tapes followed Abikoff\u27s scripts, objective behavioral rating scales found crucial differences between his tapes and the present study tapes. ADHD v. ODD tape comparisons showed no bias. Yet, comparisons of ADHD/ODD vs. normal tape ratings showed a bidirectional bias: ADHD behaviors inflated ODD ratings, with females rated significantly higher on ODD behaviors than males, and ODD behaviors inflated ADHD ratings, with males rated significantly higher than females on ADHD behaviors. Results indicate that teachers may not differentiate between ADHD and ODD behaviors on rating scales, and that gender of the child exhibiting disruptive behaviors influences teacher ratings. Since diagnosticians and prevalence rate studies rely upon teacher ratings, these findings imply: (a) compared to females, the male prevalence rate for ADHD may be artificially inflated by the presence of ODD behaviors; (b) compared to males, the female prevalence rate for ODD may be artificially inflated by the presence ADHD behaviors; and (c) the comorbidity rate between ADHD and ODD may be artificially inflated by teacher failure to differentiate between ADHD and ODD behaviors

The design of aircraft using the decision support problem technique

The Decision Support Problem Technique for unified design, manufacturing and maintenance is being developed at the Systems Design Laboratory at the University of Houston. This involves the development of a domain-independent method (and the associated software) that can be used to process domain-dependent information and thereby provide support for human judgment. In a computer assisted environment, this support is provided in the form of optimal solutions to Decision Support Problems

Modification of Coulomb's law in closed spaces

We obtain a modified version of Coulomb's law in two- and three-dimensional closed spaces. We demonstrate that in a closed space the total electric charge must be zero. We also discuss the relation between total charge neutrality of a isotropic and homogenous universe to whether or not its spatial sector is closed.Comment: 11 pages, 3 figure

Interaction energies of monosubstituted benzene dimers via nonlocal density functional theory

We present density-functional calculations for the interaction energy of monosubstituted benzene dimers. Our approach utilizes a recently developed fully nonlocal correlation energy functional, which has been applied to the pure benzene dimer and several other systems with promising results. The interaction energy as a function of monomer distance was calculated for four different substituents in a sandwich and two T-shaped configurations. In addition, we considered two methods for dealing with exchange, namely using the revPBE generalized gradient functional as well as full Hartree-Fock. Our results are compared with other methods, such as Moller-Plesset and coupled-cluster calculations, thereby establishing the usefulness of our approach. Since our density-functional based method is considerably faster than other standard methods, it provides a computational inexpensive alternative, which is of particular interest for larger systems where standard calculations are too expensive or infeasible.Comment: submitted to J. Chem. Phy

An X-ray absorption spectroscopic study at the mercury LIII edge on phenylmercury(II) oxygen species

The X-ray absorption spectra of the reference and model compounds HgCl2, PhHgCl, PhHgOAc and [(PhHg)2OH][BF4].H2O have been analysed in both the XANES and EXAFS regions, and the technique was extended to determine the structures of (PhHg)2O, PhHgOH, and the basic salts PhHgOH.PhHgNO3 and PhHgOH.(PhHg)2SO4, which were previously structurally uncharacterised. Results indicate that (PhHg)2O is a molecular species with Hg-O-Hg 135°, while PhHgOH contains the [(PhHg)2OH]+ cation and is better formulated as [(PhHg)2OH]OH. The same cation is also featured in the two basic salts. Electrospray mass spectral studies of PhHgOH in aqueous solutions show that [PhHgOH2]+, [(PhHg)2OH]+ and [(PhHg)3O]+ co-exist in solution in a pH-dependent equilibrium

Factors Regulating Immunoglobulin Production by Normal and Disease-Associated Plasma Cells

mmunoglobulins are molecules produced by activated B cells and plasma cells in response to exposure to antigens. Upon antigen exposure, these molecules are secreted allowing the immune system to recognize and effectively respond to a myriad of pathogens. Immunoglobulin or antibody secreting cells are the mature form of B lymphocytes, which during their development undergo gene rearrangements and selection in the bone marrow ultimately leading to the generation of B cells, each expressing a single antigen-specific receptor/immunoglobulin molecule. Each individual immunoglobulin molecule has an affinity for a unique motif, or epitope, found on a given antigen. When presented with an antigen, activated B cells differentiate into either plasma cells (which secrete large amounts of antibody that is specific for the inducing antigen), or memory B cells (which are long-lived and elicit a stronger and faster response if the host is re-exposed to the same antigen). The secreted form of immunoglobulin, when bound to an antigen, serves as an effector molecule that directs other cells of the immune system to facilitate the neutralization of soluble antigen or the eradication of the antigen-expressing pathogen. This review will focus on the regulation of secreted immunoglobulin by long-lived normal or disease-associated plasma cells. Specifically, the focus will be on signaling and transcriptional events that regulate the development and homeostasis of long-lived immunoglobulin secreting plasma cells.This article is made openly accessible in part by an award from the Northern Illinois University Libraries’ Open Access Publishing Fund

Chk1 requirement for high global rates of replication fork progression during normal vertebrate S phase

Chk1 protein kinase maintains replication fork stability in metazoan cells in response to DNA damage and DNA replication inhibitors. Here, we have employed DNA fiber labeling to quantify, for the first time, the extent to which Chk1 maintains global replication fork rates during normal vertebrate S phase. We report that replication fork rates in Chk1¿/¿ chicken DT40 cells are on average half of those observed with wild-type cells. Similar results were observed if Chk1 was inhibited or depleted in wild-type DT40 cells or HeLa cells by incubation with Chk1 inhibitor or small interfering RNA. In addition, reduced rates of fork extension were observed with permeabilized Chk1¿/¿ cells in vitro. The requirement for Chk1 for high fork rates during normal S phase was not to suppress promiscuous homologous recombination at replication forks, because inhibition of Chk1 similarly slowed fork progression in XRCC3¿/¿ DT40 cells. Rather, we observed an increased number of replication fibers in Chk1¿/¿ cells in which the nascent strand is single-stranded, supporting the idea that slow global fork rates in unperturbed Chk1¿/¿ cells are associated with the accumulation of aberrant replication fork structure