Cultural adaptation of birthing services in rural Ayacucho, Peru.

PROBLEM: Maternal mortality is particularly high among poor, indigenous women in rural Peru, and the use of facility care is low, partly due to cultural insensitivities of the health care system. APPROACH: A culturally appropriate delivery care model was developed in poor and isolated rural communities, and implemented between 1999 and 2001 in cooperation with the Quechua indigenous communities and health professionals. Data on birth location and attendance in one health centre have been collected up to 2007. LOCAL SETTING: The international nongovernmental organization, Health Unlimited, and its Peruvian partner organization, Salud Sín Límites Perú, conducted the project in Santillana district in Ayacucho. RELEVANT CHANGES: The model involves features such as a rope and bench for vertical delivery position, inclusion of family and traditional birth attendants in the delivery process and use of the Quechua language. The proportion of births delivered in the health facility increased from 6% in 1999 to 83% in 2007 with high satisfaction levels. LESSONS LEARNED: Implementing a model of skilled delivery attendance that integrates modern medical and traditional Andean elements is feasible and sustainable. Indigenous women with little formal education do use delivery services if their needs are met. This contradicts common victim-blaming attitudes that ascribe high levels of home births to 'cultural preferences' or 'ignorance'

Effect of Kramecyne on the Inflammatory Response in Lipopolysaccharide-Stimulated Peritoneal Macrophages

Kramecyne is a new peroxide, it was isolated from Krameria cytisoides, methanol extract, and this plant was mostly found in North and South America. This compound showed potent anti-inflammatory activity; however, the mechanisms by which this compound exerts its anti-inflammatory effect are not well understood. In this study, we examined the effects of kramecyne on inflammatory responses in mouse lipopolysaccharide- (LPS-) induced peritoneal macrophages. Our findings indicate that kramecyne inhibits LPS-induced production of tumor necrosis factor (TNF-α) and interleukin- (IL-) 6. During the inflammatory process, levels of cyclooxygenase- (COX-) 2, nitric oxide synthase (iNOS), and nitric oxide (NO) increased in mouse peritoneal macrophages; however, kramecyne suppressed them significantly. These results provide novel insights into the anti-inflammatory actions and support its potential use in the treatment of inflammatory diseases

Bis(hydrosulfido)-bridged dinuclear rhodium(I) complexes as a platform for the synthesis of trinuclear sulfido aggregates with the core [MRh2(μ3-S2)] (M = Rh, Ir, Pd, Pt, Ru)

The reaction of [Rh(μ-SH)(CO)(PPh3)]2 or [Rh(μ-SH){P(OPh)3}2]2 with [Cp*MCl2]2 (M = Rh, Ir) in the presence of NEt3 afforded the Rh3 and IrRh2 sulfido-bridged compounds [Cp*M(μ3-S)2Rh2(CO)2(PPh3)2] (M = Rh, 1; Ir, 2) and [Cp*Rh(μ3-S)2Rh2{P(OPh)3}4] (3). The reaction with [MCl2(cod)] (M = Pd, Pt), cis-[PtCl2(PPh3)2] or [(η6-C6H6)RuCl2]2 under the same experimental conditions gave [(cod)M(μ3-S)2Rh2{P(OPh)3}4] (M = Pd, 6; Pt, 7), [(cod)M(μ3-S)2Rh2(CO)2(PPh3)2] (M = Pd, 8; Pt, 9), [(PPh3)2Pt(μ3-S)2Rh2(CO)2(PPh3)2] (10) and [(η6-C6H6)Ru(μ3-S)2Rh2(CO)2(PPh3)2] (12), with PdRh2, PtRh2 and RuRh2 trimetallic cores. The aggregates derived from [Rh(μ-SH)(CO)(PPh3)]2 were isolated as a mixture of trans and cis isomers in which the trans isomer predominates. The reaction of [Rh(μ-SH){P(OPh)3}2]2 with 2 equiv. of n-BuLi at 253 K followed by addition of [Cp*IrCl2]2 gave [Cp*Ir(μ3-S)2Rh2{P(OPh)3}4] (4) and [Cp*2ClIr2(μ3-S)2Rh{P(OPh)3}2] (5) in a 3:2 ratio. The RuRh2 compound [(η6-C6H6)Ru(μ3-S)2Rh2{P(OPh)3}4] (11) was prepared similarly from [Rh(μ-SH){P(OPh)3}2]2 and [(η6-C6H6)RuCl2]2 using n-BuLi as a deprotonating agent. The molecular structures of compounds 3, 6, 7, 9 and 11 have been determined by X-ray analysis. The trinuclear complexes exhibit an asymmetric triangular metal core with two triply bridging sulfido ligands resulting in a distorted trigonal-bipyramidal M3(μ3-S)2 heterometallic metal–sulfur core.Financial support from the Ministerio de Ciencia e Innovación (MICINN/FEDER) of Spain (Project CTQ2010-15221), the Diputación General de Aragón (E07), and CONSOLIDER INGENIO-2010, Projects MULTICAT (CSD2009-00050) and Factoría de Cristalización (CSD2006-0015) is gratefully acknowledged.Peer Reviewe

Dinuclear pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture

A series of dinuclear pyridine-4-thiolate (4-Spy)-bridged rhodium and iridium compounds [M(μ-4-Spy)(diolef)]2 [diolef = 1,5-cyclooctadiene (cod), M = Rh (1), Ir (2); diolef = 2,5-norbornadiene (nbd), M = Rh (3)] were prepared by the reaction of Li(4-Spy) with the appropriate compound [M(μ-Cl)(diolef)]2 (M = Rh, Ir). The dinuclear compound [Rh(μ-4-Spy)(CO)(PPh3)]2 (4) was obtained by the reaction of [Rh(acac)(CO)(PPh3)] (acac = acetylacetonate) with 4-pySH. Compounds 1-4 were assessed as metalloligands in self-assembly reactions with the cis-blocked acceptors [M(cod)(NCCH3)2](BF 4) [M = Rh (a), Ir (b)] and [M(H2O)2(dppp)] (OTf)2 [M = Pd (c), Pt (d); dppp = 1,3-bis(diphenylphosphino)propane] . The homometallic hexanuclear metallomacrocycles [{M2(μ-4-Spy) 2(cod)2}2{M(cod)}2](BF 4)2 (M = Rh [(1a)2], Ir [(2b)2]) and the heterometallic hexanuclear metallomacrocycles [{Rh2(μ-4-Spy) 2(cod)2}2{Ir(cod)}2](BF 4)2 [(1b)2], [{Rh2(μ-4-Spy) 2(cod)2}2{M′(dppp)}2](OTf) 4 (M′ = Pd [(1c)2], Pt [(1d)2]), and [{Ir2(μ-4-Spy)2(cod)2}2{M′ (dppp)}2](OTf)4 (M′ = Pd [(2c)2], Pt [(2d)2]) were obtained. NMR spectroscopy in combination with electrospray ionization mass spectrometry was used to elucidate the nature of the metalloligands and their respective supramolecular assemblies. Most of the synthesized species were found to be nonrigid in solution, and their fluxional behavior was studied by variable-temperature 1H NMR spectroscopy. An X-ray diffraction study of the assemblies (1a)2 and (1d)2 revealed the formation of rectangular (9.6 Å × 6.6 Å) hexanuclear metallomacrocycles with alternating dinuclear (Rh2) and mononuclear (Rh or Pt) corners. The hexanuclear core is supported by four pyridine-4-thiolate linkers, which are bonded through the thiolate moieties to the dinuclear rhodium units, exhibiting a bent-anti arrangement, and through the peripheral pyridinic nitrogen atoms to the mononuclear corners.Financial support for this work was provided by the Ministerio de Economía y Competitividad (MINECO/FEDER) of Spain (Projects CTQ2010-15221 and CTQ2012-31335), Diputación General de Aragón (Group E07), and Fondo Social Europeo.Peer Reviewe

Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture

A series of dinuclear pyridine-4-thiolate rhodium and iridium compounds [M(μ-4-Spy)(diolef)]2 (diolef = 1,5-cyclooctadiene, cod; M = Rh (1), Ir (2); 2,5-norbornadiene, nbd; M = Rh (3)) have been prepared by reaction of Li(4-Spy) with the appropriate compound [M(μ-Cl)(diolef)]2 (M = Rh, Ir). The dinuclear compound [Rh(μ-4-Spy)(CO)(PPh3)]2 (4) has been obtained by reaction of [Rh(acac)(CO)(PPh3] with 4-pySH. Compounds 1-4 have been assessed as metalloligands in self-assembly reactions with the cis-blocked [M(cod)(NCCH3)2](BF4) (M = Rh (a) and M = Ir (b)) and [M(H2O)2(dppp)](OTf)2 (M = Pd (c), Pt (d)) (dppp = 1,3-bis(diphenylphosphino)propane) acceptors. Homo [{M2(μ-4-Spy)2(cod)2}2{M(cod)}2](BF4)2 (M = Rh (1a)2, and M = Ir (2b)2), and hetero [{Rh2(μ-4-Spy)2(cod)2}2{Ir(cod)}2](BF4)2 (1b)2, [{Rh2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 ( M' = Pd (1c)2 and M'= Pt (1d)2) and [{Ir2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 ( M' = Pd (2c)2 and M'= Pt (2d)2) hexanuclear metallomacrocycles have been obtained. NMR spectroscopy, in combination with ESI mass spectrometry has been used to elucidate the nature of the metalloligands and their respective supramolecular assemblies. Most of synthesized species have shown to be non-rigid in solution and their fluxional behavior has been studied by VT 1H NMR spectroscopy. An X-ray diffraction study on the assemblies (1a)2 and (1d)2 revealed the formation of rectangular (9.6 x 6.6 Å) hexanuclear metallomacrocycles with alternating dinuclear (Rh2) and mononuclear (Rh or Pt) corners. The hexanuclear core is supported by four pyridine-4-thiolate linkers, which are bonded through the thiolate moiety to the dinuclear rhodium units, exhibiting a bent-anti arrangement, and through the peripheral pyridinic nitrogen atoms to the mononuclear corners

Observation of the Crab Nebula with the HAWC Gamma-Ray Observatory

The Crab Nebula is the brightest TeV gamma-ray source in the sky and has been used for the past 25 years as a reference source in TeV astronomy, for calibration and verification of new TeV instruments. The High Altitude Water Cherenkov Observatory (HAWC), completed in early 2015, has been used to observe the Crab Nebula at high significance across nearly the full spectrum of energies to which HAWC is sensitive. HAWC is unique for its wide field-of-view, nearly 2 sr at any instant, and its high-energy reach, up to 100 TeV. HAWC's sensitivity improves with the gamma-ray energy. Above $\sim$1 TeV the sensitivity is driven by the best background rejection and angular resolution ever achieved for a wide-field ground array. We present a time-integrated analysis of the Crab using 507 live days of HAWC data from 2014 November to 2016 June. The spectrum of the Crab is fit to a function of the form $\phi(E) = \phi_0 (E/E_{0})^{-\alpha -\beta\cdot{\rm{ln}}(E/E_{0})}$. The data is well-fit with values of $\alpha=2.63\pm0.03$, $\beta=0.15\pm0.03$, and log$_{10}(\phi_0~{\rm{cm}^2}~{\rm{s}}~{\rm{TeV}})=-12.60\pm0.02$ when $E_{0}$ is fixed at 7 TeV and the fit applies between 1 and 37 TeV. Study of the systematic errors in this HAWC measurement is discussed and estimated to be $\pm$50\% in the photon flux between 1 and 37 TeV. Confirmation of the Crab flux serves to establish the HAWC instrument's sensitivity for surveys of the sky. The HAWC survey will exceed sensitivity of current-generation observatories and open a new view of 2/3 of the sky above 10 TeV.Comment: Submitted 2017/01/06 to the Astrophysical Journa

The 2HWC HAWC Observatory Gamma Ray Catalog

We present the first catalog of TeV gamma-ray sources realized with the recently completed High Altitude Water Cherenkov Observatory (HAWC). It is the most sensitive wide field-of-view TeV telescope currently in operation, with a 1-year survey sensitivity of ~5-10% of the flux of the Crab Nebula. With an instantaneous field of view >1.5 sr and >90% duty cycle, it continuously surveys and monitors the sky for gamma ray energies between hundreds GeV and tens of TeV. HAWC is located in Mexico at a latitude of 19 degree North and was completed in March 2015. Here, we present the 2HWC catalog, which is the result of the first source search realized with the complete HAWC detector. Realized with 507 days of data and represents the most sensitive TeV survey to date for such a large fraction of the sky. A total of 39 sources were detected, with an expected contamination of 0.5 due to background fluctuation. Out of these sources, 16 are more than one degree away from any previously reported TeV source. The source list, including the position measurement, spectrum measurement, and uncertainties, is reported. Seven of the detected sources may be associated with pulsar wind nebulae, two with supernova remnants, two with blazars, and the remaining 23 have no firm identification yet.Comment: Submitted 2017/02/09 to the Astrophysical Journa