Electrophotocatalytic perfluoroalkylation by LMCT excitation of Ag(II) perfluoroalkyl carboxylates.

Molecular Ag(II) complexes are superoxidizing photoredox catalysts capable of generating radicals from redox-reticent substrates. In this work, we exploited the electrophilicity of Ag(II) centers in [Ag(bpy)(TFA)][OTf] and Ag(bpy)(TFA) (bpy, 2,2'-bipyridine; OTf, CFSO) complexes to activate trifluoroacetate (TFA) by visible light-induced homolysis. The resulting trifluoromethyl radicals may react with a variety of arenes to forge C(sp)-CF bonds.

Lewis Acid Supported Nickel Nitrenoids.

Metalation of the polynucleating ligand LH (1,3,5-C H (NC H -4-F-2-NSiMe Bu) ) with two equivalents of Zn(N(SiMe ) ) affords the dinuclear product ( LH )Zn (1), which can be further deprotonated to yield ( L)Zn Li (OEt ) (2). Transmetalation of 2 with NiCl (py) yields the heterometallic, trinuclear cluster ( L)Zn Ni(py) (3). Reduction of 3 with KC affords [KC ][( L)Zn Ni] (4) which features a monovalent Ni centre.

Crystal structure of a methyl benzoate quadruple-bonded dimolybdenum complex.

Quadruple-bond dimolybdenum complexes provide invaluable insight into the two-electron bond, with structural chemistry providing a foundation for examination of bond properties. The synthesis and solid-state structure of the quadruple-bonded dimolybdenum(II) complex tetra-kis-(-4-methyl-benzoato- :')bis[(tetra-hydro-furan-κ)molybdenum(II)] tetra-hydro-furan disolvate, [Mo(CHO)(CHO)]·2CHO, are presented. This complex crystallizes in a triclinic cell with low-symmetry space group .

Probing the Halide Effect in the δ-Bond with One- and Two-Photon Spectroscopy.

Two electrons in two orbitals give rise to four states. When the orbitals are weakly coupled as in the case for the d orbitals of quadruple bond species, two of the states are diradical in character with electrons residing in separate orbitals and two of the states are zwitterionic with electrons paired in one orbital or the other. By measuring one-and two-photon spectra, the one-electron (ΔW) and two-electron (K) energies may be calculated, which are the determinants of the state energies of the four-state model for the two-electron bond.

Pig Brains Have Homologous Resting-State Networks with Human Brains.

Many neurological and psychiatric diseases in humans are caused by disruptions to large-scale functional properties of the brain, including functional connectivity. There has been growing interest in discovering the functional organization of brain networks in larger animal models. As a result, the use of translational pig models in neuroscience has significantly increased in the past decades.

Synthesis of a new disulfide Fmoc monomer for creating biologically susceptible linkages in peptide nucleic acid oligomers.

Peptide nucleic acids (PNA) are one of many synthetic mimics of DNA and RNA that have found applications as biological probes, as nano-scaffold components, and in diagnostics. In an effort to use PNA as constructs for cellular delivery we investigated the possibility of installing a biologically susceptible disulfide bond in the backbone of a PNA oligomer. Here we report the synthesis of a new abasic Fmoc monomer containing a disulfide bond that can be incorporated into a PNA oligomer (DS-PNA) using standard solid phase peptide synthesis.

All-optical regenerator of multi-channel signals.

One of the main reasons why nonlinear-optical signal processing (regeneration, logic, etc.) has not yet become a practical alternative to electronic processing is that the all-optical elements with nonlinear input-output relationship have remained inherently single-channel devices (just like their electronic counterparts) and, hence, cannot fully utilise the parallel processing potential of optical fibres and amplifiers. The nonlinear input-output transfer function requires strong optical nonlinearity, e.

On the electrostatic properties of homodimeric proteins.

A large fraction of proteins function as homodimers, but it is not always clear why the dimerization is important for functionality since frequently each monomer possesses a distinctive active site. Recent work (PLoS Computational Biology, 9(2), e1002924) indicates that homodimerization may be important for forming an electrostatic funnel in the spermine synthase homodimer which guides changed substrates toward the active centers. This prompted us to investigate the electrostatic properties of a large set of homodimeric proteins and resulted in an observation that in a vast majority of the cases the dimerization indeed results in specific electrostatic features, although not necessarily in an electrostatic funnel.

Automation of an interferon-γ release assay and comparison to the tuberculin skin test for screening basic military trainees for Mycobacterium tuberculosis infection.

We automated portions of the QuantiFERON-TB Gold In-Tube test (QFT-GIT) and assessed its quality when performed concurrently with the tuberculin skin test (TST) among U.S. Air Force basic military trainees (BMTs).

Variability of the QuantiFERON®-TB gold in-tube test using automated and manual methods.

Background: The QuantiFERON®-TB Gold In-Tube test (QFT-GIT) detects Mycobacterium tuberculosis (Mtb) infection by measuring release of interferon gamma (IFN-γ) when T-cells (in heparinized whole blood) are stimulated with specific Mtb antigens. The amount of IFN-γ is determined by enzyme-linked immunosorbent assay (ELISA). Automation of the ELISA method may reduce variability.

Protein Nano-Object Integrator (ProNOI) for generating atomic style objects for molecular modeling.

Background: With the progress of nanotechnology, one frequently has to model biological macromolecules simultaneously with nano-objects. However, the atomic structures of the nano objects are typically not available or they are solid state entities. Because of that, the researchers have to investigate such nano systems by generating models of the nano objects in a manner that the existing software be able to carry the simulations.

Within-subject interlaboratory variability of QuantiFERON-TB gold in-tube tests.

Background: The QuantiFERON®-TB Gold In-Tube test (QFT-GIT) is a viable alternative to the tuberculin skin test (TST) for detecting Mycobacterium tuberculosis infection. However, within-subject variability may limit test utility. To assess variability, we compared results from the same subjects when QFT-GIT enzyme-linked immunosorbent assays (ELISAs) were performed in different laboratories.

Multiple cytokines are released when blood from patients with tuberculosis is stimulated with Mycobacterium tuberculosis antigens.

Background: Mycobacterium tuberculosis (Mtb) infection may cause overt disease or remain latent. Interferon gamma release assays (IGRAs) detect Mtb infection, both latent infection and infection manifesting as overt disease, by measuring whole-blood interferon gamma (IFN-γ) responses to Mtb antigens such as early secreted antigenic target-6 (ESAT-6), culture filtrate protein 10 (CFP-10), and TB7.7.

Synthesis and evaluation of azabicyclo[3.2.1]octane derivatives as potent mixed vasopressin antagonists.

A series of biaryl amides containing an azabicyclooctane amine headpiece were synthesized and evaluated as mixed arginine vasopressin (AVP) receptor antagonists. Several analogues, including 8g, 12g, 13d, and 13g, were shown to have excellent V(1a)- and good V(2)-receptor binding affinities. Compound 13d was further profiled for drug-like properties and for an in vitro comparison with conivaptan, the program's mixed V(1a)/V(2)-receptor antagonist standard.

Unexpected rearrangement of enantiomerically pure 3-aminoquinuclidine as a simple way of preparing diastereomeric octahydropyrrolo[2,3-c]pyridine derivatives.

Reaction of (S)- or (R)-3-aminoquinuclidine with 2-chloropyrimidine or 2-bromopyrimidine led to an unexpected formation of both cis- and trans-octahydropyrrolo [2,3]pyridine derivatives. A single-step synthesis of two of the four stereoisomers of these octahydropyrrolo[2,3]pyridine derivatives provides a convenient way of generating stereochemically defined isomers. Optimization of reaction conditions was carried out by (1)H NMR monitoring.

Two classes of p38alpha MAP kinase inhibitors having a common diphenylether core but exhibiting divergent binding modes.

Two new classes of diphenylether inhibitors of p38alpha MAP kinase are described. Both chemical classes are based on a common diphenylether core that is identified by simulated fragment annealing as one of the most favored chemotypes within a prominent hydrophobic pocket of the p38alpha ATP-binding site. In the fully elaborated molecules, the diphenylether moiety acts as an anchor occupying the deep pocket, while polar extensions make specific interactions with either the adenine binding site or the phosphate binding site of ATP.