A Generally Applicable Method for Disentangling the Effect of Individual Noncovalent Interactions on the Binding Energy.

We introduce the fragment-pairwise Local Energy Decomposition (fp-LED) scheme for precise quantification of individual interactions contributing to the binding energy of arbitrary chemical entities, such as protein-ligand binding energies, lattice energies of molecular crystals, or association energies of large biomolecular assemblies. Using fp-LED, we can assess whether the contribution to the binding energy arising from noncovalent interactions between pairs of molecular fragments in any chemical system is attractive or repulsive, and accurately quantify its magnitude at the coupled cluster level - commonly considered as the "gold standard" of computational chemistry. Such insights are crucial for advancing molecular and material design strategies in fields like catalysis and therapeutic development.

Oxidation States: Intrinsically Ambiguous?

The oxidation state ( ) formalism is a much-appreciated good in chemistry, receiving wide application. However, like all formalisms, limitations are inescapable, some of which have been recently explored. Providing a broader context, we discuss the and its interpretation from a computational perspective for transition metal (TM) complexes.

Integration of primary care and palliative care services to improve equality and equity at the end-of-life: Findings from realist stakeholder workshops.

Background: Inequalities in access to palliative and end of life care are longstanding. Integration of primary and palliative care has the potential to improve equity in the community. Evidence to inform integration is scarce as research that considers integration of primary care and palliative care services is rare.

Valence Tautomerism Induced Proton Coupled Electron Transfer:X-H Bond Oxidation with a Dinuclear Au(II) Hydroxide Complex.

We report the preparation and characterization of the dinuclear Au hydroxide complex Au (L)(OH) (L=N,N'-bis (2,6-dimethyl) phenylformamidinate) and study its reactivity towards weak X-H bonds. Through the interplay of kinetic analysis and computational studies, we demonstrate that the oxidation of cyclohexadiene follows a concerted proton-coupled electron transfer (cPCET) mechanism, a rare type of reactivity for Au complexes. We find that the Au-Au σ-bond undergoes polarization in the PCET event leading to an adjustment of oxidation levels for both Au centers prior to C(sp)-H bond cleavage.

Understanding patient views and experiences of the IDENTIfication of PALLiative care needs (IDENTI-PALL): a qualitative interview study.

Background: Palliative care improves quality of life for people with life-threatening illnesses. There are longstanding inequalities in access to palliative care, with many people never identified as having palliative care needs, particularly frail older people, those with non-malignant disease, and people from ethnic minority backgrounds. Little is known about the process of identification of palliative care needs from a patient perspective.