Carbon Dioxide Utilisation -The Formate Route

UIDB/50006/2020 CEEC-Individual 2017 Program Contract.The relentless rise of atmospheric CO2 is causing large and unpredictable impacts on the Earth climate, due to the CO2 significant greenhouse effect, besides being responsible for the ocean acidification, with consequent huge impacts in our daily lives and in all forms of life. To stop spiral of destruction, we must actively reduce the CO2 emissions and develop new and more efficient “CO2 sinks”. We should be focused on the opportunities provided by exploiting this novel and huge carbon feedstock to produce de novo fuels and added-value compounds. The conversion of CO2 into formate offers key advantages for carbon recycling, and formate dehydrogenase (FDH) enzymes are at the centre of intense research, due to the “green” advantages the bioconversion can offer, namely substrate and product selectivity and specificity, in reactions run at ambient temperature and pressure and neutral pH. In this chapter, we describe the remarkable recent progress towards efficient and selective FDH-catalysed CO2 reduction to formate. We focus on the enzymes, discussing their structure and mechanism of action. Selected promising studies and successful proof of concepts of FDH-dependent CO2 reduction to formate and beyond are discussed, to highlight the power of FDHs and the challenges this CO2 bioconversion still faces.publishersversionpublishe

The role of maternal obesity in infant outcomes in polycystic ovary syndrome—a systematic review, meta-analysis, and meta-regression

Polycystic ovary syndrome (PCOS) is associated with worsened pregnancy and infant outcomes, higher body mass index (BMI), and longitudinal weight gain. Despite most of the clinical features of PCOS being risk factors for worsened infant outcomes in the general population, their impact on infant outcomes in PCOS is unknown. We aimed to investigate the association of PCOS with infant outcomes considering maternal adiposity, other known risk factors, and potential confounders. The meta-analyses included 42 studies in 7041 women with PCOS and 63 722 women without PCOS. PCOS was associated with higher gestational weight gain (GWG) and with higher preterm birth and large for gestational age and with lower birth weight with this association varying by geographic continent, PCOS phenotypes, and study quality. However, PCOS was associated with none of these outcomes on BMI-matched studies. Gestational diabetes was significantly associated with an increased preterm birth on meta-regression. We report for the first time that GWG is higher in PCOS. Infant outcomes vary by geographic continent and study quality but are similar in BMI-matched women with and without PCOS. This suggests that infant outcomes in PCOS may be related to maternal obesity. These novel findings warrant future studies in PCOS investigating screening and management of infant outcomes with consideration of maternal obesity.Mahnaz Bahri Khomami, Anju E. Joham, Jacqueline A. Boyle, Terhi Piltonen, Chavy Arora, Michael Silagy, Marie L. Misso, Helena J. Teede, Lisa J. Mora

Increased maternal pregnancy complications in polycystic ovary syndrome appear to be independent of obesity—a systematic review, meta-analysis, and meta-regression

Polycystic ovary syndrome (PCOS) is associated with an increased risk of maternal pregnancy and delivery complications. However, the impact of clinical features of PCOS and other potential risk factors in PCOS is still unknown. We aimed to investigate the association of PCOS with maternal pregnancy and delivery complications with consideration of risk factors and potential confounders. The meta-analysis included 63 studies. PCOS was associated with higher miscarriage, gestational diabetes mellitus, gestational hypertension, pre-eclampsia, induction of labour, and caesarean section. The association of PCOS with these outcomes varied by geographic continent, PCOS phenotypes, and study quality. Pre-eclampsia and induction of labour were not associated with PCOS on body mass index-matched studies. No outcome was associated with PCOS on assisted pregnancies. Age was significantly associated with higher miscarriage on meta-regression. There were no studies assessing perinatal depression. We confirm that PCOS is associated with an increased risk of maternal pregnancy and delivery complications. The association of PCOS with the outcomes is worsened in hyperandrogenic PCOS phenotypes, in specific geographic continents, and in the highest quality studies but disappears in assisted pregnancies. Future studies in PCOS are warranted to investigate proper timing for screening and prevention of maternal pregnancy and delivery complications with consideration of clinical features of PCOS.Mahnaz Bahri Khomami, Anju E. Joham, Jacqueline A. Boyle, Terhi Piltonen, Michael Silagy, Chavy Arora, Marie L. Misso, Helena J. Teede, Lisa J. Mora

Preparation, characterization, and reactivity of an osmium-alkenyl dihydrogen complex

Treatment of OsCl2(PPh3)(PNP) (PNP = 2,6-(Ph2PCH2)(2)C5H3N) with LiC=CPh produced OsCl(PPh3)(2-Ph2PCH(CPh=CH)-6-Ph2PCH2C5H The structure of the latter; unusual complex has been confirmed by an X-ray diffraction study. Reaction of OsCl(PPh3)(2-Ph-2-PCH(CPh=CH)-6-Ph2PCH2C5H3N) With H-2 and K2CO3 in the presence of NaBF4 in methanol produced OsH(PPh3)(2-Ph2PCH(CPh=CH)-6-Ph2PCH2C5H3N). Protonation of OsH(PPh3)(2-Ph2PCH(CPh=CH)-6-Ph2PCH2C5H3N) with HEF4 gave [Os(H-2)(PPh3)(2-Ph2PCH(CPh-CH)-6-Ph2PCH2C5H3N)]BF4. which reacted with H-2 to give [OsH(B-2)(PPh3)(2-Ph2PCH(CPh=CH2)-6-Ph2PCH2C5H3N)]BF4