Valence Delocalization in Prussian Blue Fe[FeII(CN)6]3 · XD2O,by Polarized Neutron Diffraction

Polarized neutron diffraction has been used to investigate the spin delocalization from the high-spin Fe(III) sites to the low-spin Fe(II) in deuteriated Prussian Blue, Fe₄[Fe(CN)₆]₃ · xD₂O. Measurements of the 111, 200, and 400 reflections were made on a powdered sample at 3 K and 4.8 T using a neutron wavelength of 1.074 Å. The expectation value of S at the Fe(II) site is - 0.008 ± 0.028 corresponding to an upper limit of about 5% of an electron for the spin delocalization.     

Monosubstitution von Octa(hydridosilasesquioxan) H8Si8O12 zu R′H7Si8O12 mittels Hydrosilylierung Kurzmitteilung

Monosubstitution of Octa(hydridosilasesquioxane) H₈Si₈O₁₂ to R′H₇Si₈O₁₂ by Hydrosilylation Hydrosilylation of hex-1-ene and of styrene by octa(hydridosilasesquioxanes) catalyzed by hexachloroplatinic acid leads to the first monosubstituted octasilasesquioxane R′H₇Si₈O₁₂ molecules.     

Zinc Detection in Serum by Anodic Stripping Voltammetry on Microfabricated Bismuth Electrodes

Zinc (Zn) homeostasis is required for a functional immune system. Critically ill patients often exhibit decreased Zn serum concentrations and could potentially benefit from Zn supplementation as a therapeutic strategy. However, the conventional approaches to monitoring Zn are time consuming and costly. This work reports on detection of Zn by anodic stripping voltammetry (ASV) on bismuth electrodes in a microfabricated electrochemical cell. The working potential window of the electrodeposited bismuth film electrode was investigated by cyclic voltammetry, while square wave ASV was used for measuring Zn in acetate buffer and blood serum. Conditions critical to sensing, such as preconcentration potential, preconcentration time, and buffer pH, were optimized for Zn detection. The sensor was successfully calibrated with pH 6 acetate buffer in the physiologically‐relevant range of 5 µM to 50 µM Zn and exhibited well‐defined and highly repeatable peaks. The sensor was used to demonstrate measurement of Zn in blood serum digested in HCl. The results of this work show that Zn detection in serum is possible with smaller sample volumes (µL vs. mL) and faster turnaround time (hours vs. days) as compared with the conventional spectroscopic methods.     

New Synthetic Route to Polyhedral Organylsilsesquioxanes

Hydrosilation of methylenecyclohexane and hex-1-ene by octa(hydridosilsesquioxane) catalysed by hexachloroplatinic acid is a new route to polyhedral organylsilsesquioxanes. Quantitative yield of octa(cyclohexylmethylsilsesquioxane) is reached. This reaction opens a vast field of yet unknown polyhedral silsesquioxanes.     

Lévy-type Processes and Besov Spaces

In [6, Théorème VI. 1], it is shown that almost all sample paths of a given stable process (Z_t) of index belong to the Besov spaces with 1 p < . Our aim is to establish a similar result for general Lévy processes (X_t)_{t 0}. It will turn out that if we restrict the paths to compact time intervals (and put them zero elsewhere) then they belong to Besov spaces for a certain choice of parameters s and p. Finally we extend the results obtained for Lévy processes to Markov processes, which are – in a certain sense – comparable with the given Lévy process.     

The circular dichroism of the charge-transfer bands of M(bpy)2+3 (M = Re,Ru, Os)

The absolute configuration of (?)_D-Ru(bpy)₃(ClO₄)₂ has been determined to be the right-hand screw configuration Δ. CD spectra of M(bpy)²⁺₃ (M = Fe, Ru, Os) doped in a uniaxial host. Lattice lead to a new assignment of CD bands in the MLCT region. The CD arises from intrinsically allowed electronic and magnetic transition dipole moments, the latter coming from metal-centered transitions.     

The electronic structure of the metal-to-ligand charge-transfer states of M(bpy)2+3 (M = Fe,Ru, Os)

New spectroscopic absorption and luminescence data for the ions M(bpy)²⁺₃ (M = Fe, Ru, Os) provide the basis for a theoretical model of the electronic structure of these ions. An important aspect of the model is the essential localization of the triplet states, in contrast to the singlet states which are delocalized. The model accounts very well for the new and existing spectroscopic data.     

A Diene‐Containing Noncanonical Amino Acid Enables Dual Functionality in Proteins: Rapid Diels–Alder Reaction with Maleimide or Proximity‐Based Dimerization

Here, we describe a diene‐containing noncanonical amino acid (ncAA) capable of undergoing fast and selective normal electron‐demand Diels–Alder (DA) reactions following its incorporation into antibodies. A cyclopentadiene derivative of lysine (CpHK) served as the reactive handle for DA transformations and the substrate for genetic incorporation. CpHK incorporated into antibodies with high efficiency and was available for maleimide conjugation or self‐reaction depending on position in the amino acid sequence. CpHK at position K274 reacted with the maleimide drug‐linker AZ1508 at a rate of ≈79 m ^?1 s^?1 to produce functional antibody–drug conjugates (ADCs) in a one‐step process. Incorporation of CpHK at position S239 resulted in dimerization, which covalently linked antibody heavy chains together. The diene ncAA described here is capable of producing therapeutic protein conjugates with clinically validated and widely available maleimide compounds, while also enabling proximity‐based stapling through a DA dimerization reaction.     

Zusatz bei der Korrektur

Ohne Zusammenfassung