Redox-Transmetalation Reactions: Easy Access to Homo- and Heterodimetallic d8,d10 Complexes.

The ability of the imine PyCH═N-CH2Py (Py = 2-pyridyl, bpi) to behave as a heteroditopic ligand, which is suitable for creating two separate compartments to host metals in different oxidation states, has been developed by studying the reactions of the mixed-valence complexes [(cod)M-Ι(µ-bpi)MΙ(cod)] (M = Rh, Ir) with [M'(Cl)2(PPh3)2] (M' = Pd, Ni). The results depend on the molar ratio of the reagents used (1:1 or 1:2) to give the heterometallic complexes {d10-M',d8-M}-[(PPh3)(Cl)M'0(µ-bpi)MΙ(cod)] (Pd,Rh, 4; Pd,Ir, 5; Ni,Rh, 8; Ni,Ir, 9) and the two-electron mixed-valent compounds [(PPh3)(Cl)M'0(µ-bpi)M'ΙΙ(Cl)] (M' = Ni, 10; Pd, 11), respectively. A redox process occurs in the replacement of the low-valent [(cod)M-I] fragment, whereas the exchange of the [(cod)MI] fragment is redox-neutral. The metal with a d8 configuration in the products exhibits a square-planar geometry coordinated to two (Rh/Ir) or three (Ni/Pd) nitrogen atoms of the bridging bpi ligand. Conversely, the metal with a d10 configuration adopts trigonal-planar geometries, π-bonded to the imine C═N bond. The isolated complexes 4/5 and 10/11, along with the hypothetical heterometallic Pd,Ni compound (12), were studied by DFT methods. Additionally, the T-shaped moiety 'M'ΙΙ(PPh3)(Cl)(η1-CH-N(bpi))', stabilized by a secondary γ-agostic interaction, and the 'M'II(Cl)(κ3N-bpi)' fragment was found to be accessible redoxomers of complexes 10 and 11 by DFT calculations.

Delabelling beta-lactam allergy.

Background: Hypersensitivity to beta-lactam (BL) antibiotics is one of the most frequent reported drug allergies. In our population, it is common to find labels of BL allergy in electronic medical records (EMRs) that have not been assessed. The objective of our study was to detect patients with beta-lactam allergy labels in their EMRs and to assess how many of them are false after a correct diagnostic evaluation. Methods: A multicentre prospective study was performed with patients labelled as allergic to BLs in their EMRs in the previous 5 years. Demographical and clinical data, as well as variables regarding the BL allergy label and the characteristics of the index reaction from clinical history and EMRs, were recorded. Then, diagnostic assessments including clinical history, skin tests (STs), and drug provocation tests (DPTs) were conducted in order to confirm or exclude the diagnosis of BL allergy. Results: A total of 249 patients completed the study, of which 160 (64.3%) were women with a median age of 57 years (interquartile range [IQR], 45-68). The most frequent BL allergy labels detected were for penicillin (124), amoxicillin/clavulanic acid (61), and amoxicillin (54). Of the 204 patients who underwent STs, 20.1% were positive. DPTs were performed in 224 patients, showing good tolerance in 87.1% of cases. After the allergy diagnosis work-up, 186 patients (74.7%) were diagnosed as non-allergic to BL antibiotics. Conclusion: In our study population, the number of patients labelled as allergic to BLs in their EMRs was similar to that in previously published studies, with proportions near to 75%-80% being falsely labelled as allergic to BLs.

Iridium-Catalyzed Regio- and Diastereoselective Synthesis of C-Substituted Piperazines.

Piperazine rings are essential motifs frequently found in commercial drugs. However, synthetic methodologies are mainly limited to N-substituted piperazines, preventing structural diversity. Disclosed herein is a straightforward catalytic method for the synthesis of complex C-substituted piperazines based on an uncommon head-to-head coupling of easily prepared imines. This 100% atom-economic process allows the selective formation of a sole diastereoisomer, a broad substrate scope, and a good functional group tolerance employing a bench-stable iridium catalyst under mild reaction conditions. Key to the success is the addition of N-oxides to the reaction mixture, as they notably enhance the catalytic activity and selectivity.

Sonographic cervical length as a predictor of type of delivery after induced labor.

PURPOSE: This study was undertaken to evaluate the comparative value of sonographic cervical length and the Bishop score in predicting the type of delivery after induced labor. METHODS: The Bishop score was determined by digital examination and cervical length by transvaginal sonography in 177 women. RESULTS: The best cut-off points for predicting type of delivery found with ROC curves were 25.2 mm for cervical length and 5 for the Bishop score. The Bishop score was not predictive of type of delivery. Cervical length was related to type of delivery in women with Bishop score ≤5. A logistic regression model showed that only cervical length ≥25.2 mm, parity, and body mass index significantly predicted the likelihood of cesarean delivery. CONCLUSIONS: Our study suggests that both Bishop score and sonographic cervical length can contribute to predicting type of delivery after labor induction, but cervical length is a better predictor of the risk of cesarean delivery.

Cooperative double deprotonation of bis(2-picolyl)amine leading to unexpected bimetallic mixed valence (M(-I), M(I)) rhodium and iridium complexes.

Cooperative reductive double deprotonation of the complex [Rh(I)(bpa)(cod)](+) ([4](+), bpa = PyCH(2)NHCH(2)Py) with one molar equivalent of base produces the bimetallic species [(cod)Rh(bpa-2H)Rh(cod)] (7), which displays a large Rh(-I),Rh(I) contribution to its electronic structure. The doubly deprotonated ligand in 7 hosts the two "Rh(cod)" fragments in two distinct compartments: a "square planar compartment" consisting of one of the Py donors and the central nitrogen donor and a "tetrahedral π-imine compartment" consisting of the other pyridine and an "imine C═N" donor. The formation of an "imine donor" in this process is the result of substantial electron transfer from the {bpa-2H}(2-) ligand to one of the rhodium centers to form the neutral imine ligand bpi (bpi = PyCH(2)N═CHPy). Hence, deprotonation of [Rh(I)(bpa)(cod)](+) represents a reductive process, effectively leading to a reduction of the metal oxidation state from Rh(I) to Rh(-I). The dinuclear iridium counterpart, complex 8, can also be prepared, but it is unstable in the presence of 1 mol equiv of the free bpa ligand, leading to quantitative formation of the neutral amido mononuclear compound [Ir(I)(bpa-H)(cod)] (2). All attempts to prepare the rhodium analog of 2 failed and led to the spontaneous formation of 7. The thermodynamic differences are readily explained by a lower stability of the M(-I) oxidation state for iridium as compared to rhodium. The observed reductive double deprotonation leads to the formation of unusual structures and unexpected reactivity, which underlines the general importance of "redox noninnocent ligands" and their substantial effect on the electronic structure of transition metals.

Sexual and reproductive health of incarcerated women in French Guiana: a qualitative approach.

PURPOSE: Incarcerated women are a vulnerable population in terms of sexual and reproductive health. In French Guiana, most incarcerated women come from unsafe environments and are incarcerated because of drug trafficking. Medical follow-up processes used in prison (medical assessment on arrival, and then two half-days per week upon request but without an obstetrician-gynecologist) does not allow for a thorough assessment of the impact of incarceration on women prisoners' health to take place. In the absence of data, the purpose of this study was to describe incarcerated women's experiences in relation to sexual and reproductive health. DESIGN/METHODOLOGY/APPROACH: Semi-structured interviews were conducted among French-speaking adult women who had been incarcerated for at least four months in a French Guianan prison. Menstruation, contraception, pregnancy, abortion, sexually transmitted infections and sexuality were described by means of interpretative phenomenological analysis. FINDINGS: A total of 14 women were interviewed. They suffered from menstrual cycle disorders, poor hygiene and menstrual insecurity. They appeared to have emotionally disinvested sexuality. However, intra-prison sexual activity existed for some (masturbation, conjugal prison visits, homosexual intercourse between fellow prisoners). Homosexual relations were a source of discrimination. Being pregnant while incarcerated was viewed negatively. A lack of knowledge about sexual and reproductive health and high-risk behaviors such as piercing and tattooing practices were widespread. ORIGINALITY/VALUE: Incarceration is a vulnerable time for women's sexual and reproductive health. Sexual activity exposes women to risks and discrimination that should be taken into account in a multidisciplinary approach adapted to the prison environment.

Role of Overweight and Obesity in Gastrointestinal Disease.

The prevalence of obesity is increasing worldwide, leading to a severe impairment of overall health. Actually, obesity has been associated with several pathological conditions, causing an excess overall mortality. In particular, overweight and obesity are well known risk factors for a variety of gastrointestinal (GI) disorders i.e., functional GI disorders as well as, inflammatory bowel disease (IBD), pancreatitis, and GI cancer. The aim of the present review is to summarize the potential role of overweight and obesity in GI disease with particular focus on plausible biological mechanisms that could explain the association between obesity and GI disease based on the most recent evidence in the literature.

Intake of fruits and vegetables in relation to 10-year weight gain among Spanish adults.

OBJECTIVE: Despite the alarming increase in the prevalence of obesity, epidemiologic studies that prospectively examine the fruit and vegetable consumption and other lifestyle factors in relation to weight gain (WG) are still insufficient. We explored the associations between fruit and vegetable intake and WG over a 10-year period in an adult Mediterranean population. METHODS AND PROCEDURES: We performed a 10-year follow-up study with healthy participants (n = 206) aged 15-80 years at baseline in 1994, who participated in a nutrition survey in Valencia, Spain. Data on diet, lifestyle factors, and body weight were obtained in 1994 and 2004 using a food frequency questionnaire (FFQ) and direct measurements. RESULTS: The average WG over the study period was 3.41 (s.d. 6.9) kg. In multivariate analyses, participants in the third quartile of fruit intake at baseline in 1994 had lower risk of WG> or =3.41 kg compared to those in the lowest quartile (oddsratio (OR) = 0.31, 95% confidence interval (CI), 0.11-0.85; P trend = 0.044). Regarding vegetable intake, the risk of WG was lowest in participants of the fourth quartile (>333 g/day), which had an 84% reduced risk of gaining 3.41 kg weight (OR = 0.18, 95% CI, 0.05-0.66; P trend = 0.017). When the intake of fruits and vegetables was combined, the risk of WG decreased across quartiles, with the lowest risk among those in the fourth quartile (OR = 0.22, 95% CI, 0.06-0.81; P trend = 0.022). Further adjustment for an increased intake of fruits and vegetables over the past 10 years reported by participants in 2004 did not appreciably alter the observed ORs. DISCUSSION: Dietary patterns associated with a high intake of fruits and vegetables in Mediterranean populations may reduce long-term risk of subsequent WG and obesity among adults.

Plasma concentrations of carotenoids and vitamin C are better correlated with dietary intake in normal weight than overweight and obese elderly subjects.

Carotenoid and vitamin C intakes, assessed by FFQ, have been positively associated with plasma concentrations in different populations. However, the influence of BMI on these associations has not been explored in detail. We explored in a cross-sectional study the relation between dietary carotenoid and vitamin C intakes, using a 135-item FFQ, with their plasma concentrations by BMI categories in 252 men and 293 women, 65 years and older. For men and women combined, significant (P < 0.05) Pearson correlations were observed between energy-adjusted dietary intakes and plasma concentrations (carotenoids adjusted for cholesterol) for: alpha-carotene 0.21, beta-carotene 0.19, lycopene 0.18, beta-cryptoxanthin 0.20 and vitamin C 0.36. Multiple linear regression analyses showed that the intake of carotenoids and vitamin C were significant predictors of their respective plasma concentration (P<0.01), and that BMI was inversely associated with plasma concentration of carotenoids (P< or =0.01) but not with plasma vitamin C. In addition, we observed significant interactions between BMI and the intakes of alpha-carotene and lutein + zeaxanthin, and to a lower extent beta-carotene, suggesting that these intakes in subjects with high BMI were not good predictors of their plasma concentration. The present data suggest that plasma carotenoids and vitamin C may be good markers of dietary intake in elderly subjects, but not so for alpha-carotene, beta-carotene and lutein + zeaxanthin in obese subjects.

Estimation of height and body mass index from demi-span in elderly individuals.

BACKGROUND: Obtaining accurate height and, consequently, body mass index (BMI) measurements in elderly subjects can be difficult due to changes in posture and loss of height during ageing. Measurements of other body segments can be used as an alternative to estimate standing height, but population- and age-specific equations are necessary. OBJECTIVE: Our objectives were to validate existing equations, to develop new simple equations to predict height in an elderly Spanish population and to assess the accuracy of the BMI calculated by estimated height from the new equations. METHODS: We measured height and demi-span in a representative sample of 592 individuals, 271 men and 321 women, 65 years and older (mean +/- SD, 73.8 +/- 6.3 years). We suggested equations to predict height from demi-span by multiple regression analyses and performed an agreement analysis between measured and estimated indices. RESULTS: Height estimated from demi-span correlated significantly (p < 0.001) with measured height (men: r = 0.708, women: r = 0.625). The best prediction equations were as follows: men, height (in cm) = 77.821 + (1.132 x demi-span in cm) + (-0.215 x 5-year age category); women: height (in cm) = 88.854 + (0.899 x demi-span in cm) + (-0.692 x 5-year age category). No significant differences between the mean values of estimated and measured heights were found for men (-0.03 +/- 4.6 cm) or women (-0.02 +/- 4.1 cm). The BMI derived from measured height did not differ significantly from the BMI derived from estimated height either. CONCLUSION: Predicted height values from equations based on demi-span and age may be acceptable surrogates to derive accurate nutritional indices such as the BMI, particularly in elderly populations, where height may be difficult to measure accurately.