Selective reductions. 56. Exploration of the B-haloisopinocampheylboranes for asymmetric reduction of ketones

A series of diisopinocampheylhaloboranes and monoisopinocampheyldihaloboranes were synthesized by the reaction of the corresponding boranes with the respective HX or X₂ (X = halogen) or by the hydroboration of α-pinene with the corresponding haloboranes. Stabilities of these haloboranes in various solvents were studied. Most of these haloboranes proved capable of reducing prochiral ketones to the alcohols with significant optical induction. When tested against a representative aromatic and aliphatic prochiral ketone, acetophenone and 3-methyl-2-butanone, respectively, α-phenethyl alcohol in 65–98% ee and 3-methyl-2-butanol in 28–59% ee were obtained. Some of them exhibited anomalous behavior.     

Automated Synthesis of 68Ga-Labeled DOTA-MGS8 and Preclinical Characterization of Cholecystokinin-2 Receptor Targeting

The new minigastrin analog DOTA-MGS8 targeting the cholecystokinin-2 receptor (CCK2R) used in this study displays the combination of two site-specific modifications within the C-terminal receptor binding sequence together with an additional N-terminal amino acid substitution preventing fast metabolic degradation. Within this study, the preparation of ⁶⁸Ga-labeled DOTA-MGS8 was validated using an automated synthesis module, describing the specifications and analytical methods for quality control for possible clinical use. In addition, preclinical studies were carried out to characterize the targeting potential. [⁶⁸Ga]Ga-DOTA-MGS8 showed a high receptor-specific cell internalization into AR42J rat pancreatic cells (~40%) with physiological expression of rat CCK2R as well as A431-CCK2R cells transfected to stably express human CCK2R (~47%). A favorable biodistribution profile was observed in BALB/c nude mice xenografted with A431-CCK2R cells and mock-transfected A431 cells as control. The high tumor uptake of ~27% IA/g together with low background activity and limited uptake in non-target tissue confirms the potential for high-sensitivity positron emission tomography of stabilized MG analogs in patients with MTC and other CCK2R-related malignancies.     

Tracer diffusion in lattice gases

It has been proved that a tracer particle in a reversible lattice gas converges to Brownian motion. However, only in a few particular cases has a strictly positive self-diffusion coefficientD been established. Here we supply the missing piece and show thatD>0 in general. The exceptions are one-dimensional lattice gases with nearest neighbor jumps only, for whichD=0. The proof establishes a variational formula forD which could be used to obtain realistic bounds.     

Generating Metallic Amorphous Core–Shell Nanoparticles by a Solid‐State Amorphization Process

Metallic crystalline/amorphous core–shell nanoparticles consisting of a crystalline Pd core (c‐Pd) surrounded by an amorphous Fe₂₅Sc₇₅ shell (a‐FeSc) are prepared by inert‐gas condensation. A phase transformation of the c‐Pd by a solid‐state diffusion process resulting in an amorphous core (a‐PdSc) surrounded by an amorphous FeSc shell is observed if the core–shell structure is irradiated at ambient temperature with 300 keV electrons. The amorphization process seems to involve the diffusion of irradiation‐induced defects and is presumably driven by the large negative heat of mixing of Pd and Sc, as well as by the excess enthalpy of the interfaces between the c‐Pd regions and the surrounding a‐FeSc. The structural transformation reported here opens a new way to producing metallic amorphous core–shell nanoparticles of different chemical compositions and probably novel properties.