Molecular Fe(II)-Ln(III) dyads for luminescence reading of spin-state equilibria at the molecular level.

Due to the primogenic effect, the valence shells of divalent iron Fe(II) ([Ar]3d) and trivalent lanthanides Ln(III) ([Xe]4f) are compact enough to induce spin-state equilibrium for the 3d-block metal and atom-like luminescence for the 4f-block partner in Fe(II)-Ln(III) dyads. In the specific case of homoleptic pseudo-octahedral [Fe(II)N] units, programming spin crossover (SCO) around room temperature at normal pressure requires the design of unsymmetrical didentate five-membered ring chelating NN' ligands, in which a five-membered (benz)imidazole heterocycle (N) is connected to a six-membered pyrimidine heterocycle (N'). Benefiting from the influence, the facial isomer -[Fe(II)(NN')] is suitable for inducing SCO properties at room temperature in solution.

Unravelling Kinetics of Intramolecular Nd → Fe Energy Transfer in Spin Crossover Single Molecules: Dotting the 's and Crossing the 's.

Compared with the ripple of visible Eu-based emission intensity induced by appended [FeN] spin crossover (SCO) units, as detected in the triple-stranded [EuFe()] helicate, the lanthanide-based luminescent detection of Fe spin-state equilibria could be improved significantly if the luminophore emission is shifted toward the near-infrared (NIR) domain. Replacing Eu with Nd in [NdFe()] (i) maintains the favorable SCO properties in acetonitrile [critical temperature = 322(2) K], (ii) saturates nonradiative vibrational relaxation processes in the 233-333 K range, and (iii) boosts the crucial intramolecular Nd → Fe energy transfer rate processes, which are sensitive to the spin state of the Fe metallic center. Consequently, the steady-state NIR Nd(F → I) emission of the luminophore is amplified and linearly correlated with the low-spin-[FeN] and high-spin-[FeN] mole fractions controlled by the SCO equilibrium.

Forensic age estimation at the University Center of Legal Medicine Lausanne-Geneva: a retrospective study over 12 years.

With the undeniable increase in asylum requests from unaccompanied alleged minors, age estimation of living individuals has become an essential part of the routine work in European forensic centers. This study aims to review the forensic age estimations performed in our center since 2010, to evaluate the state-of-the-art of this practice in Switzerland with the evolution of the methodology according to upcoming recommendations. Our institute's expert reports performed between 2010 and 2022 were retrospectively analyzed.

Programming heterometallic 4f-4f' helicates under thermodynamic control: the circle is complete.

Three non-symmetrical segmental ligand strands L4 can be wrapped around a linear sequence of one Zn and two trivalent lanthanide cations Ln to give quantitatively directional [ZnLn(L4)] triple-stranded helicates in the solid state and in solution. NMR speciations in CDCN show negligible decomplexation at a millimolar concentration and the latter helicate can be thus safely considered as a preorganized -symmetrical -[(L4Zn)(Ln)(Ln)] platform in which the thermodynamic properties of (i) lanthanide permutation between the central N and the terminal NO binding sites and (ii) exchange processes between homo- and heterolanthanide helicates are easy to access (Ln = La, Eu, Lu). Deviations from statistical distributions could be programmed by exploiting specific site recognition and intermetallic pair interactions.

Intraoperative esophageal washout reduces free intraluminal tumor cells during resection of carcinomas of the esophagus and cardia.

Objective: Intraluminally shed viable tumor cells might contribute to anastomotic recurrence in cancer of the esophagus and the cardia. The study aimed to establish a method of esophageal washout and, hence, to reduce intraluminal cancer cells before esophageal anastomosis.

Methods: Forty-eight consecutive patients with esophago-gastric resection for histologically proven cancer of the esophagus or the cardia were included in a prospective, interventional study.