Minimalistic Ditopic Ligands: An α‐S,N‐Donor‐Substituted Alkyne as Effective Intermetallic Conjugation Linker

The capability of donor‐substituted alkynes to link different metal ions in a side‐on carbon donor‐chelate coordination mode is extended from the donor centers S and P to the second period element N. The complex [Tp′W(CO)₂{η²‐C₂(S)(NHBn)}] (Tp′=hydrido‐tris(3,5‐dimethylpyrazolyl)borate, Bn=benzyl) bearing a terminal sulfur atom and a secondary amine substituent is accessible by a metal‐template synthesis. Subsequent deprotonation allowed the formation of remarkably stable heterobimetallic complexes with the [(η⁵‐C₅H₅)Ru(PPh₃)] and the [Ir(ppy)₂] moiety. Electrochemical and spectroscopic investigations (cyclic voltammetry, IR, UV/Vis, luminescence, EPR), as well as DFT calculations, and X‐ray structure determinations of the W–Ru complex in two oxidation states reveal a strong metal–metal coupling but also a limited delocalization of excited states.     

An optimal<Emphasis Type="Italic">L</Emphasis><Superscript><Emphasis Type="Italic">p</Emphasis></Superscript>-bound on the Krein spectral shift function

Let ξ_A,B be the Krein spectral shift function for a pair of operatorsA, B, with C =A-B trace class. We establish the bound

Synthesis of 1,2,7,7a-tetrahydro-1aH-cyclopropa[b]quinoline-1a-carboxylic acid derivatives, doubly constrained ACC derivatives, by a remarkable cyclopropanation process

Reaction of N-benzoyl-1,2,3,4-tetrahydroquinoline-2-carboxylic acid with acetic anhydride resulted in 1H,3H,5H-oxazolo[3,4-a]quinolin-3-one derivative 13. Different cyclopropanation processes were applied to 13, but only diazomethane in the presence of water furnished the hitherto unknown methyl 1,2,7,7a-tetrahydro-1aH-cyclopropa[b]quinoline-1a-carboxylate 14, which can be considered as a doubly constrained 1-aminocyclopropane-1-carboxylic acid system. The mechanism of the cyclopropanation was studied in detail. The new ACC ester 14 was transformed into fused tetracyclic hydantoin derivatives, which comprised a new type of heterocyclic system.     

In Vitro Degradation of Trimethylene Carbonate Based (Co)polymers

Trimethylene carbonate (TMC) was copolymerized with D ,L ‐lactide (DLLA) or with ε‐caprolactone (CL), and the degradation of melt‐pressed solid copolymer films in phosphate‐buffered saline at pH 7.4 and 37 °C was followed for a period of over two years. The parent homopolymers were used as reference materials. The degradation profile of TMC‐DLLA‐ and TMC‐CL based copolymers was similar and was best described by autocatalyzed bulk hydrolysis, preferentially of ester bonds. The hydrolysis rates varied by two orders of magnitude, depending on polymer composition and physical characteristics under the degradation conditions. TMC‐DLLA copolymers degraded faster than the parent homopolymers. The copolymers lost their tensile strength in less than five months, after which mass loss occurred. Copolymers with 50 or 80 mol‐% of TMC underwent total degradation in eleven months. For TMC‐CL copolymers, a slow and gradual decrease in molecular weight and deterioration of the mechanical performance was observed. These copolymers maintained suitable mechanical properties for seventeen months or longer. Chain scission in the semicrystalline copolymers resulted in an increase in crystallinity. In comparison with the CL homopolymer, the introduction of a small amount of TMC (10 mol‐%) significantly reduced the increase in crystallinity during degradation. Poly(TMC) specimens were dimensionally stable and showed a negligible decrease in molecular weight. A 60% decrease in the initial tensile strength of the polymer samples was observed after two years.

     

Characterization and quantification of metallothionein isoforms by capillary electrophoresis–inductively coupled plasma–isotope-dilution mass spectrometry

In a new approach to the characterization and quantification of metallothionein isoforms an on-line isotope-dilution method in combination with the coupling of capillary electrophoresis (CE) to an inductively coupled plasma-sector field mass spectrometer (ICP-SFMS) is reported. Metallothionein (MT) isoforms are separated by CE and the elements Cu, Zn, Cd, and S are detected simultaneously by use of ICP-SFMS in the medium resolution mode. On-line isotope dilution is performed by continuous introduction of an isotopically enriched, species-unspecific spike solution after the separation step. MT from rabbit liver and a further purified MT-1 isoform were quantified by determination of sulfur, and the stoichiometric compositions of the metalloprotein complexes are characterized by determination of their sulfur-to-metal ratios.     

Nickel-BINAP catalyzed enantioselective alpha-arylation of alpha-substituted gamma-butyrolactones

A Ni(0)-BINAP system is utilized for the highly enantioselective alpha-arylation of alpha-substituted gamma-butyrolactones with aryl chlorides and bromides. alpha-Quaternization is achieved in moderate to excellent yields. Furthermore, the rate accelerating effect caused by the addition of Zn(II) salts is investigated.