We present the novel observation that Duschinsky mixings can lead to the breakdown of Kasha’s rule in a white light phosphor molecule, dibenzo[<i>b,d</i>]thiophen-2-yl (4-chlorophenyl)methanone. Our theoretical analyses show the energy gap between the T₁ and T₂ states (0.48 eV) is too large to allow for any significant population of the T₂ state at room temperature ...

Photo- and thermo- isomerization trajectories of various conversion pathways between nitro-spiropyran and its <i>trans–trans–cis</i> merocyanine form were produced and the role of nπ* states was investigated along the corresponding potential energy surface calculated using the ωB97XD functional and the cc-pVDZ basis set. The nondissociative nπ* states on the photoisomerization trajectories can switch ...

We report a combined experimental-theoretical study on the 31P NMR chemical shift for a number of trans-platinum(II) complexes. Validity and reliability of the 31P NMR chemical shift calculations are examined by comparing with the experimental data. A successful computational protocol for the accurate prediction of the 31P NMR chemical shifts was established for trans-[PtCl2(dma)PPh3] (dma = ...

A combination of quantum chemical calculations and synthetic studies was used to address the possibility of very high (>6) valence states of transition metals in porphyrin‐type complexes. With corrole as a supporting ligand, DFT calculations ruled out Re(VII) and Ir(VII) dioxo complexes as stable species. Attempted rhenium insertion into benzocarbaporphyrin (BCP) ligands on the other hand led to two ...

<i>Background</i> - The discovery of thermostable DNA polymerases such as Taq DNA polymerase revolutionized amplification of DNA by polymerase chain reaction methods that rely on thermal cycling for strand separation. These methods are widely used in the laboratory for medical research, clinical diagnostics, criminal forensics and general molecular biology research. Today there is a growing demand ...

Reduced nitrogen oxide ligands such as NO⁻/HNO or nitroxyl participate in chemistry distinct from nitric oxide (NO). Nitroxyl has been proposed to form at heme centers to generate the Enemark–Feltham designated {FeNO}⁸ system. The synthesis of a thermally stable {FeNO}⁸ species namely, [Co(Cp^*)₂][Fe(LN₄)(NO)] (3), housed in a heme-like ...

The crystal structure of haemoglobin from Atlantic cod has been solved to 2.54 A˚ resolution. The structure consists of two tetramers in the crystallographic asymmetric unit. The structure of haemoglobin obtained from one individual cod suggests polymorphism in the tetrameric assembly.

We present a formulation of relativistic linear response time-dependent density functional theory for the calculation of electronic excitation energies in the framework of the four-component Dirac-Coulomb Hamiltonian. This approach is based on the noncollinear <i>ansatz</i> originally developed by Scalmani and Frisch [J. Chem. Theory Comput. 8, 2193 (2012)] and improves upon the past treatment of ...

The BCR-ABL T315I mutation causes resistance to imatinib, nilotinib and dasatinib in chronic myeloid leukemia. Forty BCR-ABL positive patients with imatinib resistance were analyzed for T315I mutated clones after six months on nilotinib or dasatinib treatment by quantitative allele-specific ligation polymerase chain reaction with a sensitivity of 0.05%. Ligation polymerase chain reaction revealed ...

A caesium fluoride-mediated hydrocarboxylation of olefins is disclosed that does not rely on precious transition metal catalysts and ligands. The reaction occurs at atmospheric pressures of CO₂ in the presence of 9-BBN as a stoichiometric reductant. Stilbenes, β-substituted styrenes and allenes could be carboxylated in good yields. The developed methodology can be used for preparation of ...