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Background: Personalized medicine offers targeted therapy options for cancer treatment. However, the decision whether to include a patient into next-generation sequencing (NGS) testing is not standardized. This may result in some patients receiving unnecessary testing while others who could benefit from it are not tested. Typically, patients who have exhausted conventional treatment options are of interest for consideration in molecularly targeted therapy. To assist clinicians in decision-making, we developed a decision support tool using routine data from a precision oncology program. Methods: We trained a machine learning model on clinical data to determine whether molecular profiling should be performed for a patient. To validate the model, the model’s predictions were compared with decisions made by a molecular tumor board (MTB) using multiple patient case vignettes with their characteristics. Results: The prediction model included 440 patients with molecular profiling and 13,587 patients without testing. High area under the curve (AUC) scores indicated the importance of engineered features in deciding on molecular profiling. Patient age, physical condition, tumor type, metastases, and previous therapies were the most important features. During the validation MTB experts made the same decision of recommending a patient for molecular profiling only in 10 out of 15 of their previous cases but there was agreement between the experts and the model in 9 out of 15 cases. Conclusion: Based on a historical cohort, our predictive model has the potential to assist clinicians in deciding whether to perform molecular profiling. [ABSTRACT FROM AUTHOR]

Orange-red trinuclear nickel(II) complexes are obtained by reacting Ni(ClO4)2(H2O)6 with 3(5)-arylpyrazoles in the presence of a base. Herein, the diamagnetic nickel centers are coordinated in a square-pyramidal manner by four pyrazolato ligands, each of which bridges two nickel sites. The structurally unique complexes were investigated by NMR, IR, fluorescence, and X-ray spectroscopy. All seven compounds described here were structurally elucidated by single-crystal X-ray diffraction. With 3(5)-ferrocenylpyrazole as the substrate, a nonametallic system that possesses six redox-active ferrocenyl moieties was obtained. [ABSTRACT FROM AUTHOR]

The spectral properties of fluorescencesensors such as 3-hydroxychromone(3-HC) and its derivatives are sensitive to interaction with the surroundingmedium as well as to substitution. 3-HC is a prototype system forother derivatives because it is the basic unit of all flavonoidesundergoing ESIPT and is not perturbed by a substituent. In this study,the elementary processes and intermediate states in the photocycleof 3-HC as well as its anion were identified and characterized bythe use of static and femtosecond time-resolved spectroscopy in differentsolvents (methylcyclohexane, acetonitrile, ethanol, and water at differentpH). Electronic absorption and fluorescence spectra and lifetimesof the intermediate states were obtained for the normal, tautomerand anionic excited state, while mid-IR vibrational spectra yieldedstructural information on ground and excited states of 3-HC. A highsensitivity on hydrogen-bonding perturbations was observed, leadingto photoinduced anion formation in water, while in organic solvents,different processes are suggested, including slow picosecond ESIPTand contribution of the trans-structure excited state or a differentstable solvation state with different direction of OH. The formationof the latter could be favored by the lack of a substituent increasingcontact points for specific solute–solvent interactions atthe hydroxyl group compared to substituted derivatives. The effectof substituents has to be considered for the design of future fluorescencesensors based on 3-HC. [ABSTRACT FROM AUTHOR]

A series of bimetallic silyl halido cuprates consisting of the new tripodal silicon-based metalloligand [κ3 N-Si(3,5-Me2pz)3Mo(CO)3]− is presented (pz=pyrazolyl). This metalloligand is straightforwardly accessible by reacting the ambidentate ligand tris(3,5-dimethylpyrazolyl)silanide ({Si(3,5-Me2pz)3}−) with [Mo(CO)3(η6-toluene)]. The compound features a fac-coordinated tripodal chelating ligand and an outward pointing, 'free' pyramidal silyl donor, which is easily accessible for a secondary coordination to other metal centers. Several bimetallic silyl halido cuprates of the general formula [CuX{μ-κ1 Si:κ3 N-Si(3,5-Me2pz)3Mo(CO)3}]− (X=Cl, Br, I) have been synthesized. The electronic and structural properties of these complexes were probed in detail by X-ray diffraction analysis, electrospray mass spectrometry, infrared-induced multiphoton dissociation studies, cyclic voltammetry, spectroelectrochemistry, gas-phase photoelectron spectroscopy, as well as UV/Vis and fluorescence spectroscopy. The heterobimetallic complexes contain linear two-coordinate copper(I) entities with the shortest silicon-copper distances reported so far. Oxidation of the anionic complexes in methylene chloride and acetonitrile solutions at ${E{{0\hfill \atop 1/2\hfill}}}$=−0.60 and −0.44 V (vs. ferrocene/ferrocenium (Fc/Fc+)), respectively, shows substantial reversibility. Based on various results obtained from different characterization methods, as well as density functional theory calculations, these oxidation events were attributed to the Mo0/MoI redox couple. [ABSTRACT FROM AUTHOR]