Facile O-atom insertion into C-C and C-H bonds by a trinuclear copper complex designed to harness a singlet oxene

Two trinuclear copper [CuICuICuI(L)]1+ complexes have been prepared with the multidentate ligands (L) 3,3'-(1,4-diazepane-1,4-diyl)bis(1-((2-(dimethylamino)ethyl)(methyl)amino)propan-2-ol) (7-Me) and (3,3'-(1,4-diazepane-1,4-diyl)bis(1-((2-(diethylamino) ethyl)(ethyl) amino)propan-2-ol) (7-Et) as models for the active site of the particulate methane monooxygenase (pMMO). The ligands were designed to form the proper spatial and electronic geometry to harness a "singlet oxene," according to the mechanism previously suggested by our laboratory. Consistent with the design strategy, both [CuICuICuI(L)]1+ reacted with dioxygen to form a putative bis(µ3-oxo)CuIICuIICuIII species, capable of facile O-atom insertion across the central C-C bond of benzil and 2,3-butanedione at ambient temperature and pressure. These complexes also catalyze facile O-atom transfer to the C-H bond of CH3CN to form glycolonitrile. These results, together with our recent biochemical studies on pMMO, provide support for our hypothesis that the hydroxylation site of pMMO contains a trinuclear copper cluster that mediates C-H bond activation by a singlet oxene mechanism

Mass Hierarchy, Mixing, CP-Violation and Higgs Decay---or Why Rotation is Good for Us

The idea of a rank-one rotating mass matrix (R2M2) is reviewed detailing how it leads to ready explanations both for the fermion mass hierarchy and for the distinctive mixing patterns between up and down fermion states, which can be and have been tested against experiment and shown to be fully consistent with existing data. Further, R2M2 is seen to offer, as by-products: (i) a new solution of the strong CP problem in QCD by linking the theta-angle there to the Kobayashi-Maskawa CP-violating phase in the CKM matrix, and (ii) some novel predictions of possible anomalies in Higgs decay observable in principle at the LHC. A special effort is made to answer some questions raised.Comment: 47 pages, 9 figure

A computer-assisted motivational social network intervention to reduce alcohol, drug and HIV risk behaviors among Housing First residents.

BackgroundIndividuals transitioning from homelessness to housing face challenges to reducing alcohol, drug and HIV risk behaviors. To aid in this transition, this study developed and will test a computer-assisted intervention that delivers personalized social network feedback by an intervention facilitator trained in motivational interviewing (MI). The intervention goal is to enhance motivation to reduce high risk alcohol and other drug (AOD) use and reduce HIV risk behaviors.Methods/designIn this Stage 1b pilot trial, 60 individuals that are transitioning from homelessness to housing will be randomly assigned to the intervention or control condition. The intervention condition consists of four biweekly social network sessions conducted using MI. AOD use and HIV risk behaviors will be monitored prior to and immediately following the intervention and compared to control participants' behaviors to explore whether the intervention was associated with any systematic changes in AOD use or HIV risk behaviors.DiscussionSocial network health interventions are an innovative approach for reducing future AOD use and HIV risk problems, but little is known about their feasibility, acceptability, and efficacy. The current study develops and pilot-tests a computer-assisted intervention that incorporates social network visualizations and MI techniques to reduce high risk AOD use and HIV behaviors among the formerly homeless. CLINICALTRIALS.Gov identifierNCT02140359

Effects of aging and links removal on epidemic dynamics in scale-free networks

We study the combined effects of aging and links removal on epidemic dynamics in the Barab\'{a}si-Albert scale-free networks. The epidemic is described by a susceptible-infected-refractory (SIR) model. The aging effect of a node introduced at time $t_{i}$ is described by an aging factor of the form $(t-t_{i})^{-\beta}$ in the probability of being connected to newly added nodes in a growing network under the preferential attachment scheme based on popularity of the existing nodes. SIR dynamics is studied in networks with a fraction $1-p$ of the links removed. Extensive numerical simulations reveal that there exists a threshold $p_{c}$ such that for $p \geq p_{c}$, epidemic breaks out in the network. For $p < p_{c}$, only a local spread results. The dependence of $p_{c}$ on $\beta$ is studied in detail. The function $p_{c}(\beta)$ separates the space formed by $\beta$ and $p$ into regions corresponding to local and global spreads, respectively.Comment: 8 pages, 3 figures, revtex, corrected Ref.[11

Constitutive modeling for isotropic materials (HOST)

The results of the first year of work on a program to validate unified constitutive models for isotropic materials utilized in high temperature regions of gas turbine engines and to demonstrate their usefulness in computing stress-strain-time-temperature histories in complex three-dimensional structural components. The unified theories combine all inelastic strain-rate components in a single term avoiding, for example, treating plasticity and creep as separate response phenomena. An extensive review of existing unified theories is given and numerical methods for integrating these stiff time-temperature-dependent constitutive equations are discussed. Two particular models, those developed by Bodner and Partom and by Walker, were selected for more detailed development and evaluation against experimental tensile, creep and cyclic strain tests on specimens of a cast nickel base alloy, B19000+Hf. Initial results comparing computed and test results for tensile and cyclic straining for temperature from ambient to 982 C and strain rates from 10(exp-7) 10(exp-3) s(exp-1) are given. Some preliminary date correlations are presented also for highly non-proportional biaxial loading which demonstrate an increase in biaxial cyclic hardening rate over uniaxial or proportional loading conditions. Initial work has begun on the implementation of both constitutive models in the MARC finite element computer code

Mapping of serotype-specific, immunodominant epitopes in the NS-4 region of hepatitis C virus (HCV):use of type-specific peptides to serologically differentiate infections with HCV types 1, 2, and 3

The effect of sequence variability between different types of hepatitis C virus (HCV) on the antigenicity of the NS-4 protein was investigated by epitope mapping and by enzyme-linked immunosorbent assay with branched oligopeptides. Epitope mapping of the region between amino acid residues 1679 and 1768 in the HCV polyprotein revealed two major antigenic regions (1961 to 1708 and 1710 to 1728) that were recognized by antibody elicited upon natural infection of HCV. The antigenic regions were highly variable between variants of HCV, with only 50 to 60% amino acid sequence similarity between types 1, 2, and 3. Although limited serological cross-reactivity between HCV types was detected between peptides, particularly in the first antigenic region of NS-4, type-specific reactivity formed the principal component of the natural humoral immune response to NS-4. Type-specific antibody to particular HCV types was detected in 89% of the samples from anti-HCV-positive blood donors and correlated almost exactly with genotypic analysis of HCV sequences amplified from the samples by polymerase chain reaction. Whereas almost all blood donors appeared to be infected with a single virus type (97%), a higher proportion of samples (40%) from hemophiliacs infected from transfusion of non-heat-inactivated clotting factor contained antibody to two or even all three HCV types, providing evidence that long-term exposure may lead to multiple infection with different variants of HCV

Exact Black Hole and Cosmological Solutions in a Two-Dimensional Dilaton-Spectator Theory of Gravity

Exact black hole and cosmological solutions are obtained for a special two-dimensional dilaton-spectator ($\phi-\psi$) theory of gravity. We show how in this context any desired spacetime behaviour can be determined by an appropriate choice of a dilaton potential function $V(\phi)$ and a ``coupling function'' $l(\phi)$ in the action. We illustrate several black hole solutions as examples. In particular, asymptotically flat double- and multiple- horizon black hole solutions are obtained. One solution bears an interesting resemblance to the $2D$ string-theoretic black hole and contains the same thermodynamic properties; another resembles the $4D$ Reissner-Nordstrom solution. We find two characteristic features of all the black hole solutions. First the coupling constants in $l(\phi)$ must be set equal to constants of integration (typically the mass). Second, the spectator field $\psi$ and its derivative $\psi^{'}$ both diverge at any event horizon. A test particle with ``spectator charge" ({\it i.e.} one coupled either to $\psi$ or $\psi^{'}$), will therefore encounter an infinite tidal force at the horizon or an ``infinite potential barrier'' located outside the horizon respectively. We also compute the Hawking temperature and entropy for our solutions. In $2D$ $FRW$ cosmology, two non-singular solutions which resemble two exact solutions in $4D$ string-motivated cosmology are obtained. In addition, we construct a singular model which describes the $4D$ standard non-inflationary big bang cosmology ($big-bang\rightarrow radiation\rightarrow dust$). Motivated by the similaritiesbetween $2D$ and $4D$ gravitational field equations in $FRW$ cosmology, we briefly discuss a special $4D$ dilaton-spectator action constructed from the bosonic part of the low energy heterotic string action andComment: 34 pgs. Plain Tex, revised version contains some clarifying comments concerning the relationship between the constants of integration and the coupling constants

EHR-Based Care Coordination Performance Measures in Ambulatory Care

Describes electronic health record-based measures for assessing coordination in referrals, including information communicated with referral, communication to patient, and specialist report to primary care physician. Offers preliminary evaluation findings