One-electron oxidation chemistry and subsequent reactivity of diiron imido complexes.

The chemical oxidation and subsequent group transfer activity of the unusual diiron imido complexes Fe((i)PrNPPh2)3Fe≡NR (R = tert-butyl ((t)Bu), 1; adamantyl, 2) was examined. Bulk chemical oxidation of 1 and 2 with Fc[PF6] (Fc = ferrocene) is accompanied by fluoride ion abstraction from PF6(-) by the iron center trans to the Fe≡NR functionality, forming F-Fe((i)PrNPPh2)3Fe≡NR ((i)Pr = isopropyl) (R = (t)Bu, 3; adamantyl, 4). Axial halide ligation in 3 and 4 significantly disrupts the Fe-Fe interaction in these complexes, as is evident by the >0.

Testing for 'threads' and leucocyte esterase in first-void urine to exclude the diagnosis of non-specific urethritis in asymptomatic men.

Recent evidence suggests that asymptomatic nonspecific urethritis (NSU), which is not routinely tested for, is a clinically significant pathology.The aim of this pilot study was to determine if testing for urinary threads, leucocyte esterase (LE) or both in asymptomatic men is a good screening tool for NSU. Of the126 asymptomatic men, 8% met microscopic criteria for the diagnosis of NSU.

Specific recommendations for accurate and direct use of PET-CT in PET guided radiotherapy for head and neck sites.

Purpose: To provide specific experience-based guidance and recommendations for centers wishing to develop, validate, and implement an accurate and efficient process for directly using positron emission tomography-computed tomography (PET-CT) for the radiotherapy planning of head and neck cancer patients.

Methods: A PET-CT system was modified with hard-top couch, external lasers and radiotherapy immobilization and indexing devices and was subject to a commissioning and quality assurance program. PET-CT imaging protocols were developed specifically for radiotherapy planning and the image quality and pathway tested using phantoms and five patients recruited into an in-house study.

Method Issues in Epidemiological Studies of Medically Unexplained Symptom-based Conditions in Veterans.

Symptom-based conditions such as chronic fatigue syndrome (CFS) and medically unexplained multi-symptom illness (MSI) are fairly common in the general population and are also important veteran's health concerns due to their higher frequency among U.S. veterans who served during the 1990-1991 Gulf War.

Identification of patients with persistent trophoblastic disease after complete hydatidiform mole by using a normal 24-hour urine hCG regression curve.

Objective: The aim of this study was to establish a reference 24-hour urine human chorionic gonadotropin (hCG) regression curve in patients with complete hydatidiform mole (CHM) as diagnostic tool in the prediction of persistent trophoblastic disease (PTD).

Methods: From 2004 to 2011, 312 cases suitable for this study were registered at the Hydatidiform Mole Registry of the Royal Women's Hospital Melbourne, Australia. hCG levels of 61 patients diagnosed as having PTD according to FIGO 2000 criteria were compared with the 95th-percentile (p95) of the normal regression curve derived from hCG levels of 251 cases of uneventful CHM.

Biosynthesis of mupirocin by Pseudomonas fluorescens NCIMB 10586 involves parallel pathways.

Mupirocin, a clinically important antibiotic produced via a trans-AT Type I polyketide synthase (PKS) in Pseudomonas fluorescens, consists of a mixture of mainly pseudomonic acids A, B, and C. Detailed metabolic profiling of mutant strains produced by systematic inactivation of PKS and tailoring genes, along with re-feeding of isolated metabolites to mutant stains, has allowed the isolation of a large number of novel metabolites, identification of the 10,11-epoxidase, and full characterization of the mupirocin biosynthetic pathway, which proceeds via major (10,11-epoxide) and minor (10,11-alkene) parallel pathways.

Zinc and cobalt complexes based on tripodal ligands: synthesis, structure and reactivity toward lactide.

The coordination chemistry of a series of pro-ligands ([L¹]-[L⁶]) with cobalt and zinc derivatives has been studied. All complexes have been characterized by multinuclear NMR, elemental analysis, and by single-crystal X-ray diffraction studies. Polymerization of rac-lactide takes place at 130 °C in the presence of cobalt and zinc complexes to yield polymers under solvent free conditions with controlled molecular masses and narrow polydispersities.

Metal-metal multiple bonding in C3-symmetric bimetallic complexes of the first row transition metals.

Metal-metal multiple bonds have been an intense area of focus in inorganic chemistry for many decades as a result of their fundamentally interesting bonding properties, as well as their potential applications in multielectron transfer and small molecule activation processes. Much of what is known in this field revolves around 2nd and 3rd row transition metals, with fundamental knowledge lacking in the area of bonds between elements of the first transition series. The smaller size and tendency of first row ions to adopt high-spin electron configurations weaken metal-metal interactions and serve to complicate the interpretation of the electronic structure and bonding in bimetallic species containing first row transition metals.

Can we reduce costs and prevent more unintended pregnancies? A cost of illness and cost-effectiveness study comparing two methods of EHC.

Objectives: To calculate the cost of an unintended pregnancy in 2011 and use this cost in a cost-effectiveness model comparing ulipristal acetate (UPA) with levonorgestrel (LNG) for emergency hormonal contraception (EHC).

Design: Retrospective analysis of published data sources and published cost-effectiveness model.

Setting: Women presenting in primary care in England for EHC within 24 or 72 h of unprotected sexual intercourse (UPSI).

How do providers prioritize prevention? A qualitative study.

Background: Preventive care is an essential element of comprehensive primary care medicine, yet many providers do not address the full range of recommended preventive care services. There is little understanding of how, during time-constrained clinical encounters, providers prioritize preventive care services.

Objectives: To identify and compare how Department of Veterans Affairs (VA) primary care providers (PCPs) prioritized general preventive care services, including HIV testing.

Replacing tin in lactide polymerization: design of highly active germanium-based catalysts.

Most germane: Hexacoordinate germanium(IV) species exhibit unprecedented activities, yet controlled behavior, as initiators for the ring-opening polymerization of rac-lactide to form polylactide polymers.

Effect of ligand modification on the reactivity of phosphinoamide-bridged heterobimetallic Zr/Co complexes.

The effect of modifying the N-aryl substituent (aryl = mesityl vs. m-xylyl) of the phosphinoamide ligands linking Zr and Co in tris(phosphinoamide)-linked heterobimetallic complexes has been investigated. Treatment of the metalloligand ((i)Pr2PNXyl)3ZrCl (2) (Xyl = m-xylyl) with CoI2 affords the iodide-bridged product ICo((i)Pr2PNXyl)2(μ-I)Zr(η(2-i)Pr2PNXyl) (3) rather than the C3-symmetric isomer observed using the N-mesityl derivative, ICo((i)Pr2PNMes)3ZrCl.

Angiotensin type 1a receptor-deficient mice develop diabetes-induced cardiac dysfunction, which is prevented by renin-angiotensin system inhibitors.

Background: Diabetes-induced organ damage is significantly associated with the activation of the renin-angiotensin system (RAS). Recently, several studies have demonstrated a change in the RAS from an extracellular to an intracellular system, in several cell types, in response to high ambient glucose levels. In cardiac myocytes, intracellular angiotensin (ANG) II synthesis and actions are ACE and AT1 independent, respectively.

Noninnocent behavior of bidentate amidophosphido [NP]2- ligands upon coordination to copper.

The synthesis and preliminary coordination chemistry of two new redox-active bidentate ligands containing amido and phosphido donors are described. Treatment of the [(R)NP](2-) (R = Ph, 2,4,6-trimethylphenyl) ligands with CuCl2 and PMe3 results in a dimeric copper(I) P-P coupled product via ligand oxidation. The intermediate of this reaction is proposed to involve a ligand radical generated via oxidation of the [(R)NP](2-) ligand by copper(II), and the existence of such an intermediate is probed using computational methods.

Lactobacillus reuteri-specific immunoregulatory gene rsiR modulates histamine production and immunomodulation by Lactobacillus reuteri.

Human microbiome-derived strains of Lactobacillus reuteri potently suppress proinflammatory cytokines like human tumor necrosis factor (TNF) by converting the amino acid l-histidine to the biogenic amine histamine. Histamine suppresses mitogen-activated protein (MAP) kinase activation and cytokine production by signaling via histamine receptor type 2 (H2) on myeloid cells. Investigations of the gene expression profiles of immunomodulatory L.

Tris(phosphinoamide)-supported uranium-cobalt heterobimetallic complexes featuring Co → U dative interactions.

A series of tris- and tetrakis(phosphinoamide) U/Co complexes has been synthesized. The uranium precursors, (η(2)-Ph2PN(i)Pr)4U (1), (η(2)-(i)Pr2PNMes)4U (2), (η(2)-Ph2PN(i)Pr)3UCl (3), and (η(2)-(i)Pr2PNMes)3UI (4), were easily accessed via addition of the appropriate stoichiometric equivalents of [Ph2PN(i)Pr]K or [(i)Pr2PNMes]K to UCl4 or UI4(dioxane)2. Although the phosphinoamide ligands in 1 and 4 have been shown to coordinate to U in an η(2)-fashion in the solid state, the phosphines are sufficiently labile in solution to coordinate cobalt upon addition of CoI2, generating the heterobimetallic Co/U complexes ICo(Ph2PN(i)Pr)3U[η(2)-Ph2PN(i)Pr] (5), ICo((i)Pr2PNMes)3U[η(2)-((i)Pr2PNMes)] (6), ICo(Ph2PN(i)Pr)3UI (7), and ICo((i)Pr2PNMes)3UI (8).

Tandem catalysis: a new approach to polymers.

The creation of polymers by tandem catalysis represents an exciting frontier in materials science. Tandem catalysis is one of the strategies used by Nature for building macromolecules. Living organisms generally synthesize macromolecules by in vivo enzyme-catalyzed chain growth polymerization reactions using activated monomers that have been formed within cells during complex metabolic processes.

A conserved motif flags acyl carrier proteins for β-branching in polyketide synthesis.

Type I polyketide synthases often use programmed β-branching, via enzymes of a 'hydroxymethylglutaryl-CoA synthase (HCS) cassette', to incorporate various side chains at the second carbon from the terminal carboxylic acid of growing polyketide backbones. We identified a strong sequence motif in acyl carrier proteins (ACPs) where β-branching is known to occur. Substituting ACPs confirmed a correlation of ACP type with β-branching specificity.

Multimetallic complexes featuring a bridging N-heterocyclic phosphido/phosphenium ligand: synthesis, structure, and theoretical investigation.

By incorporating an N-heterocyclic phosphenium/phosphide (NHP) ligand into a chelating pincer ligand framework (PPP(+)/PPP(-)), we have elucidated several different and unprecedented binding modes of NHP ligands in homobimetallic, heterobimetallic, and trimetallic metal complexes. One-electron reduction of the previously reported (PPP)(-)/M(II) complexes (PPP)M-Cl (M = Pd (1), Pt (2)) results in clean formation of the symmetric homobimetallic M(I)/M(I) complexes [(μ-PPP)Pd]2 (5) and [(μ-PPP)Pt]2 (6). The tridentate NHP ligand has also been utilized as a bridging linker in the M/Co heterobimetallic compounds (OC)3Co(u-PPP)M(CO) (M = Pd (7), Pt (8)), synthesized via salt elimination from mixtures of 1 and 2 and Na[Co(CO)4].

Rebuilding a statewide network of community health centers for the medically underserved: a longitudinal assessment.

The Strategic Facility Improvement (SFI) initiative, has resulted in the replacement of 44 outpatient clinics and 28 clinic renovation capital improvement projects across Louisiana's 64 parishes. A total of $67.3 million has been invested in this effort to date.

Long-term outcome of placental site trophoblastic tumor in The Netherlands.

Objective: To evaluate the outcome of 16 cases of placental site trophoblastic tumors (PSTTs) treated throughout The Netherlands.

Study Design: Patients with PSTT between 1991 and 2009 were identified using the nationwide network and registry of histopathology and cytopathology in The Netherlands (PALGA) and medical records.

Results: Data for 16 patients could be retrieved.

Linear regression of postevacuation serum human chorionic gonadotropin concentrations predicts postmolar gestational trophoblastic neoplasia.

Objective: Currently, human chorionic gonadotropin (hCG) follow-up after evacuation of hydatidiform moles is essential to identify patients requiring chemotherapeutic treatment for gestational trophoblastic neoplasia (GTN). We propose a model based on linear regression of postevacuation serum hCG concentrations for the prediction of GTN.

Methods: One hundred thirteen patients with at least 3 serum samples from days 7 to 28 after evacuation were selected from the Dutch Central Registry for Hydatidiform Moles (1994-2009).

Stoichiometric C═O bond oxidative addition of benzophenone by a discrete radical intermediate to form a cobalt(I) carbene.

Single electron transfer from the Zr(III)Co(0) heterobimetallic complex (THF)Zr(MesNP(i)Pr2)3Co-N2 (1) to benzophenone was previously shown to result in the isobenzopinacol product [(Ph2CO)Zr(MesNP(i)Pr2)3Co-N2]2 (2) via coupling of two ketyl radicals. In this work, thermolysis of 2 in an attempt to favor a monomeric ketyl radical species unexpectedly led to cleavage of the C-O bond to generate a Zr/Co μ-oxo species featuring an unusual terminal Co═CPh2 carbene linkage, (η(2)-MesNP(i)Pr2)Zr(μ-O)(MesNP(i)Pr2)2Co═CPh2 (3). This complex was characterized structurally and spectroscopically, and its electronic structure is discussed in the context of density functional theory calculations.

Acute stimulation of transplanted neurons improves motoneuron survival, axon growth, and muscle reinnervation.

Few options exist for treatment of pervasive motoneuron death after spinal cord injury or in neurodegenerative diseases such as amyotrophic lateral sclerosis. Local transplantation of embryonic motoneurons into an axotomized peripheral nerve is a promising approach to arrest the atrophy of denervated muscles; however, muscle reinnervation is limited by poor motoneuron survival. The aim of the present study was to test whether acute electrical stimulation of transplanted embryonic neurons promotes motoneuron survival, axon growth, and muscle reinnervation.