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Electrocatalytic hydrogen evolution reaction (eHER) is crucial in addressing the growing global energy demand. Although nickel-pincer-based molecular complexes, varying in donor atoms, were studied previously for eHER, the impact of variations in the substituents attached to the donor atoms was not investigated. Herein, three air-stable R1PN3PR2-based NiII-pincer complexes [R1=R2=Ph2 (7); R1=R2=tBu2 (9); R1= tBu2, R2=Ph2 (10)], varying solely in P-substituents, were studied in acetonitrile. While the redox potentials for NiII/I and NiI/0 couples underwent anodic shifts by ~100 mV upon progressively substituting tert-butyl by phenyl groups on each P-atom, the corresponding eHER reactivity with organic acids (acetic acid,  p-toluenesulfonic acid and trifluoromethanesulfonic acid) of different strengths followed different trends; likely influenced by the pKa of intermediate metal-hydride (M-H) species [pKa(M-H9) > pKa(M-H10) > pKa(M-H7)]. Depending on the acid strength, different oxidation states of the metal were activated to promote eHER. The catalytic rates for 9, 10, and 7 were calculated to be 85 s-1, 77 s-1 and 95 s-1 with Faradaic efficiencies of 88.5 ± 2%, 66.1 ± 1.4%, and 91.7 ± 1.5% respectively, in acetic acid. Electrochemical data supported by theoretical results reinforce a significant electronic influence of the anchoring P-substituents on the activity of these complexes., (© 2024 Wiley‐VCH GmbH.)

The growing emphasis on sustainable chemistry has driven research into utilizing carbon dioxide (CO2) as a nontoxic, abundant, and cost-effective C1 building block. CO2 offers a promising avenue for direct conversion into valuable chemicals ranging from fuels to pharmaceuticals. This review focuses on the utilization of CO2 for reductive N-formylation/N-methylation reactions of various amines, providing advantages over conventional methods involving toxic CO and other methylating reagents. The approach employs readily available reductants such as silane, borane reagents, and hydrogen (H2). The discussion encompasses recent developments in transition metal and organocatalyst systems for these reactions, highlighting mechanistic interpretations and factors influencing product selectivity., (© 2024 Wiley‐VCH GmbH.)

The highly efficient reductive amination of aldehydes with ammonia (NH 3 ) and hydrogen (H 2 ) to form secondary imines is described, as well as the dehydrogenative homocoupling of benzyl amines. Using an air-stable, well-defined PN 3 -manganese(II) pincer complex as a catalyst precursor, various aldehydes are easily converted directly into secondary imines using NH 3 as a nitrogen source under H 2 in a one-pot reaction. Importantly, the same catalyst facilitates the dehydrogenative homocoupling of various benzylamines, exclusively forming imine products. These reactions are conducted under very mild conditions, without the addition of any additives, yielding excellent selectivities and high yields of secondary imines in a green manner by minimizing wastes.

Well-defined and air-stable PN 3 -pincer manganese(II) complexes were synthesized and used for the hydrogenation of aldehydes into alcohols under mild conditions using MeOH as a solvent. This protocol is applicable for a wide range of aldehydes containing various functional groups. Importantly, α,β-unsaturated aldehydes, including ynals, are hydrogenated with the CC double bond/CC triple bond intact. Our methodology was demonstrated for the conversion of biomass derived feedstocks such as furfural and 5-formylfurfural to furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol respectively.

Water oxidation is a primary step in natural as well as artificial photosynthesis to convert renewable solar energy into chemical energy/fuels. Electrocatalytic water oxidation to evolve O 2 , utilizing suitable low-cost catalysts and renewable electricity, is of fundamental importance considering contemporary energy and environmental issues, yet it is kinetically challenging owing to the complex multiproton/electron transfer processes. Herein, we report the first cobalt-based pincer catalyst for catalytic water oxidation at neutral pH with high efficiency under electrochemical conditions. Most importantly, ligand (pseudo)aromaticity is identified to play an important role during electrocatalysis. A significant potential jump (∼300 mV) was achieved toward a lower positive value when the aromatized cobalt complex was transformed into a (pseudo)dearomatized cobalt species. The dearomatized species catalyzes the water oxidation reaction to evolve oxygen at a much lower overpotential (∼340 mV) on the basis of the onset potential (at a current density of 0.5 mA/cm 2 ) of catalysis at pH 10.5, outperforming other Co-based molecular catalysts reported to date. These observations may provide a new strategy for the judicious design of earth-abundant transition-metal-based water oxidation catalysts.

The Ni II complex 1 containing pyridyl- and hydroxy-functionalized N-heterocyclic carbenes (NHCs) is synthesized and its catalytic utility for the selective nitrile hydration to the corresponding amide under base-free conditions is evaluated. The title compound exploits a hemilabile pyridyl unit to interact with a catalytically relevant water molecule through hydrogen-bonding and promotes a nucleophilic water attack to the nitrile. A wide variety of nitriles is hydrated to the corresponding amides including the pharmaceutical drugs rufinamide, Rifater, and piracetam. Synthetically challenging α-hydroxyamides are accessed from cyanohydrins under neutral conditions. Related catalysts that lack the pyridyl unit (i.e., compounds 2 and 4) are not active whereas those containing both the pyridyl and the hydroxy or only the pyridyl pendant (i.e., compounds 1 and 3) show substantial activity. The linkage isomer 1' where the hydroxy group is bound to the metal instead of the pyridyl group was isolated under different crystallization conditions insinuating a ligand hemilabile behavior. Additional pK a measurements reveal an accessible pyridyl unit under the catalytic conditions. Kinetic studies support a ligand-promoted nucleophilic water addition to a metal-bound nitrile group. This work reports a Ni-based catalyst that exhibits functional hemilability for hydration chemistry., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

To find out the safety, effectiveness and tolerability of using desogestrel (75 microg/day), a progesterone only pill on lactating mother, a prospective clinical study was undertaken among 200 lactating women during the period from 1st January 2010 to 13th June 2011 at Gice Clinic, Kalyani, Nadia, West Bengal. The same number of cases were taken as placebo for comparison. Desogestrel was started after six weeks of delivery for six months. Patients were reviewed at 8th, 12th, 16th, 24th weeks and one year. The very interesting results were found from the follow-up study that desogestrel (75 microg/day) did not alter the amount and composition of breast milk, pregnancy was not reported as compared to placebo. The drug had good tolerability, less side-effects and did not affect the growth and development of breastfed babies. Due to the safety, good efficacy, tolerability and less side-effects it is concluded that desogestrel (75 microg/day) was well accepted in majority of women (97.5%) and provided good contraceptive efficacy during the lactating period. This treatment does not have any effect on the growth and development of breastfed baby.

This is a review on the transition from our empirical approach to treat ovarian cancer to a specific treatment based on molecular signature. We have reviewed not only the evidence-based medicine focused on the origin and tumor morphology of ovarian cancer but also the molecular signature era based on molecular phenotyping of the tumor and its microenvironment, which influences the direct targeted therapy. Evidence-based medicine has shown that the targeted therapy studies are mainly biomarker driven, more focused, and hence treat only those patients who have the underlying molecular abnormality. This molecular abnormality is the target of the drug, leading to higher rates of response. These findings will carry important implications for screening, detection, and treatment of ovarian cancer in the future.

In a recent paper in this journal Abasolo and Tsuchiya [Abasolo, I., Tsuchiya, A., 2004. Exploring social welfare functions and violation of monotonicity: an example from inequalities in health. Journal of Health Economics 23, 313-329] have strongly argued for the use of a non-monotonic health related social welfare function. This note discusses both the limitations of the measure proposed by Abasolo and Tsuchiya [Abasolo, I., Tsuchiya, A., 2004. Exploring social welfare functions and violation of monotonicity: an example from inequalities in health. Journal of Health Economics 23, 313-329] and the problems associated with their empirics. We are able to show how non-monotonicity may lead to paradoxical results and policies. Further we examine the empirics of Abasolo and Tsuchiya [Abasolo, I., Tsuchiya, A., 2004. Exploring social welfare functions and violation of monotonicity: an example from inequalities in health. Journal of Health Economics 23, 313-329] and provide an alternative explanation to the observed patterns in the data that do not violate monotonicity. Finally we briefly mention why the Atkinson-Sen framework may be more appropriate as a way forward.