Synthesis, structural studies, and redox chemistry of bimetallic [Mn(CO)₃] and [Re(CO)₃] complexes

Manganese ([Mn(CO)₃]) and rhenium tricarbonyl ([Re(CO)₃]) complexes represent a workhorse family of compounds with applications in a variety of fields. Here, the coordination, structural, and electrochemical properties of a family of mono- and bimetallic [Mn(CO)₃] and [Re(CO)₃] complexes are explored. In particular, a novel heterobimetallic complex featuring both [Mn(CO)₃] and [Re(CO)₃] units supported by 2,2′-bipyrimidine (bpm) has been synthesized, structurally characterized, and compared to the analogous monomeric and homobimetallic complexes. To enable a comprehensive structural analysis for the series of complexes, we have carried out new single crystal X-ray diffraction studies of seven compounds: Re(CO)₃Cl(bpm), anti-[{Re(CO₃)Cl}₂(bpm)], Mn(CO)₃Br(bpz) (bpz = 2,2′-bipyrazine), Mn(CO)₃Br(bpm), syn- and anti-[{Mn(CO3)Br}₂(bpm)], and syn-[Mn(CO₃)Br(bpm)Re(CO)₃Br]. Electrochemical studies reveal that the bimetallic complexes are reduced at much more positive potentials (ΔE ≥ 380 mV) compared to their monometallic analogues. This redox behavior is consistent with introduction of the second tricarbonyl unit which inductively withdraws electron density from the bridging, redox-active bpm ligand, resulting in more positive reduction potentials. [Re(CO₃)Cl]₂(bpm) was reduced with cobaltocene; the electron paramagnetic resonance spectrum of the product exhibits an isotropic signal (near g = 2) characteristic of a ligand-centered bpm radical. Our findings highlight the facile synthesis as well as the structural characteristics and unique electrochemical behavior of this family of complexes

Eosinophils Are Important for Protection, Immunoregulation and Pathology during Infection with Nematode Microfilariae

Eosinophil responses typify both allergic and parasitic helminth disease. In helminthic disease, the role of eosinophils can be both protective in immune responses and destructive in pathological responses. To investigate whether eosinophils are involved in both protection and pathology during filarial nematode infection, we explored the role of eosinophils and their granule proteins, eosinophil peroxidase (EPO) and major basic protein-1 (MBP-1), during infection with Brugia malayi microfilariae. Using eosinophil-deficient mice (PHIL), we further clarify the role of eosinophils in clearance of microfilariae during primary, but not challenge infection in vivo. Deletion of EPO or MBP-1 alone was insufficient to abrogate parasite clearance suggesting that either these molecules are redundant or eosinophils act indirectly in parasite clearance via augmentation of other protective responses. Absence of eosinophils increased mast cell recruitment, but not other cell types, into the broncho-alveolar lavage fluid during challenge infection. In addition absence of eosinophils or EPO alone, augmented parasite-induced IgE responses, as measured by ELISA, demonstrating that eosinophils are involved in regulation of IgE. Whole body plethysmography indicated that nematode-induced changes in airway physiology were reduced in challenge infection in the absence of eosinophils and also during primary infection in the absence of EPO alone. However lack of eosinophils or MBP-1 actually increased goblet cell mucus production. We did not find any major differences in cytokine responses in the absence of eosinophils, EPO or MBP-1. These results reveal that eosinophils actively participate in regulation of IgE and goblet cell mucus production via granule secretion during nematode-induced pathology and highlight their importance both as effector cells, as damage-inducing cells and as supervisory cells that shape both innate and adaptive immunity

Framing Male Circumcision to Promote its Adoption in Different Settings

The effectiveness of male circumcision in preventing transmission of HIV from females to males has been established. Those who are now advocating its widespread use face many challenges in convincing policy-makers and the public of circumcision’s value. We suggest that frames are a useful lens for communicating public health messages that may help promote adoption of circumcision. Frames relate to how individuals and societies perceive and understand the world. Existing frames are often hard to shift, and should be borne in mind by advocates and program implementers as they attempt to promote male circumcision by invoking new frames. Frames differ across and within societies, and advocates must find ways of delivering resonant messages that take into account prior perceptions and use the most appropriate means of communicating the benefits and value of male circumcision to different audiences

Prognostic Value of Tumor-Infiltrating Lymphocytes in Triple-Negative Breast Cancers From Two Phase III Randomized Adjuvant Breast Cancer Trials: ECOG 2197 and ECOG 1199

Purpose Recent studies suggest that tumor-infiltrating lymphocytes (TILs) are associated with disease-free (DFS) and overall survival (OS) in operable triple-negative breast cancer (TNBC). We seek to validate the prognostic impact of TILs in primary TNBCs in two adjuvant phase III trials conducted by the Eastern Cooperative Oncology Group (ECOG). Patients and Methods Full-face hematoxylin and eosin–stained sections of 506 tumors from ECOG trials E2197 and E1199 were evaluated for density of TILs in intraepithelial (iTILs) and stromal compartments (sTILs). Patient cases of TNBC from E2197 and E1199 were randomly selected based on availability of sections. For the primary end point of DFS, association with TIL scores was determined by fitting proportional hazards models stratified on study. Secondary end points were OS and distant recurrence–free interval (DRFI). Reporting recommendations for tumor marker prognostic studies criteria were followed, and all analyses were prespecified. Results The majority of 481 evaluable cancers had TILs (sTILs, 80%; iTILs, 15%). With a median follow-up of 10.6 years, higher sTIL scores were associated with better prognosis; for every 10% increase in sTILs, a 14% reduction of risk of recurrence or death (P = .02), 18% reduction of risk of distant recurrence (P = .04), and 19% reduction of risk of death (P = .01) were observed. Multivariable analysis confirmed sTILs to be an independent prognostic marker of DFS, DRFI, and OS. Conclusion In two national randomized clinical trials using contemporary adjuvant chemotherapy, we confirm that stromal lymphocytic infiltration constitutes a robust prognostic factor in TNBCs. Studies assessing outcomes and therapeutic efficacies should consider stratification for this parameter

Quiver Structure of Heterotic Moduli

We analyse the vector bundle moduli arising from generic heterotic compactifications from the point of view of quiver representations. Phenomena such as stability walls, crossing between chambers of supersymmetry, splitting of non-Abelian bundles and dynamic generation of D-terms are succinctly encoded into finite quivers. By studying the Poincar\'e polynomial of the quiver moduli space using the Reineke formula, we can learn about such useful concepts as Donaldson-Thomas invariants, instanton transitions and supersymmetry breaking.Comment: 38 pages, 5 figures, 1 tabl

Bad governance:How privatization increases corruption in the developing world

International organizations have become key actors in the fight against corruption. Among these organizations, the International Monetary Fund (IMF) maintains a powerful position over borrowing countries in its ability to mandate far‐ranging policy reforms – so‐called “conditionalities” – in exchange for access to financial assistance. While IMF pressure can force the implementation of anti‐corruption policies, potentially reducing corruption, other IMF policy measures, such as the privatization of state‐owned enterprises, can create rent‐extraction opportunities and limit the capacity of state institutions to limit corrupt behavior. To test these mechanisms, we conduct instrumental‐variable regression analysis using an original dataset on IMF conditionality for up to 141 developing countries from 1982 to 2014. We find that conditions to privatize state‐owned enterprises exert significant detrimental effects on corruption control. Conversely, other areas of IMF intervention are not consistently related to corruption abatement. These findings offer policy lessons regarding the design of conditionality, which should avoid large‐scale privatization, especially under conditions of weak accountability