Reaktionsprodukte aus Antimon(V)-chlorid und N,N′-Dimethyloxamid und deren Schwingungsspektren

Reaction Products of Antimony(V) Chloride and N, N′-Dimethyloxamide and their Vibrational Spectra N, N′-Dimethyloxamide reacts with antimony(V) chloride at lower temperatures to the 1:1 resp. 1:2 addition compounds I resp. II. Pyrolysis of these compounds leads to the cyclic tetrachloroantimony(V)-N, N′-dimethyloxamides (III) resp.(V). III yields with antimony(V) chloride the 1:1 adduct IV, which is transformed to V. The vibrational spectra were assigned and discussed.     

Antibacterial and antibiofilm activity of nanochelating based silver nanoparticles against several nosocomial pathogens

The emergence of multi‐drug resistant (MDR) bacteria and dynamic pattern of infectious diseases demand to develop alternative and more effective therapeutic strategies. Silver nanoparticles (AgNPs) are among the most widely commercialized engineered nanomaterials, because of their unique properties and increasing use for various applications in nanomedicine. This study for the first time aimed to evaluate the antibacterial and antibiofilm activities of newly synthesized nanochelating based AgNPs against several Gram‐positive and ‐negative nosocomial pathogens. Nanochelating technology was used to design and synthesize the AgNPs. The cytotoxicity was tested in human cell line using the MTT assay. AgNPs minimal inhibitory concentration (MIC) was determined by standard broth microdilution. Antibiofilm activity was assayed by a microtiter‐plate screening method. The two synthesized AgNPs including AgNPs (A) with the size of about 20‐25 nm, and AgNPs (B) with 30‐35 nm were tested against Staphylococcus aureus, Staphylococcus epidermidis, Acinetobacter baumannii, and Pseudomonas aeruginosa. AgNPs exhibited higher antibacterial activity against Gram‐positive strains. AgNPs were found to significantly inhibit the biofilm formation of tested strains in concentration 0.01 to 10 mg/mL. AgNPs (A) showed significant effective antibiofilm activity compared to AgNPs (B). In summary, our results showed the promising antibacterial and antibiofilm activity of our new nanochelating based synthesized AgNPs against several nosocomial pathogens.     

Total Synthesis and Structural Revision of the Antibiotic Tetrapeptide GE81112A

The total synthesis of the naturally occurring antibiotic GE81112A, a densely functionalized tetrapeptide, is reported. Comparison of spectral data with those of the natural product and the lack of biological activity of the synthesized compound led us to revise the published configuration of the 3‐hydroxypipecolic acid moiety. This hypothesis was fully validated by the synthesis of the corresponding epimer.     

Raman Optical Activity of a Purely σ‐Bonded Helical Chromophore: (−)‐(M)‐σ‐[4]Helicene

The recent synthesis of enantiomerically pure (−)‐(M)‐σ‐[4]helicene has provided an archetype helical model system for vibrational optical activity, comparable to what π‐helicenes represent in the field of electronic optical activity. We present the first measurements and the first calculations of the Raman optical activity (ROA) of this interesting molecule. Observed and calculated ROA is large throughout the vibrational spectrum, in agreement with expectations, and spectacular effects, with Δ values close to 0.5%, occur in the 900‐cm⁻¹ region. Agreement between the experimental spectrum and the theoretical one, calculated with density‐functional theory for the vibrational part and Hartree‐Fock linear response theory for the molecular electronic tensors, is excellent, clearly the best that has been achieved to date in the field. This allows us to place confidence in the results of an analysis of Raman and ROA scattering generation in the molecule, obtained by a newly developed graphical procedure for extracting this kind of information from ab initio calculations. One finds that relative contributions made by carbon and hydrogen atoms can be comparable in size, but can also vary considerably, even between closely lying vibrations, and that, for most vibrations, the generation of ROA difference intensity is distributed rather differently than that of Raman intensity over the shape of the molecule. The sign of the ROA is, for the set of vibrations in the 900‐cm⁻¹ region, which we analyze in detail, determined by coupling terms between the two halves of the molecule, while Raman intensity is primarily generated within the two fragments, with coupling terms between them only adding to or substracting from it.     

Spiro[4.4]nonatetraene and its Positive and Negative Radical Ions: Molectronic Structure Investigations

The electronic structure of spiro[4.4]nonatetraene 1 as well as that of its radical anion and cation were studied by different spectroscopies. The electron‐energy‐loss spectrum in the gas phase revealed the lowest triplet state at 2.98 eV and a group of three overlapping triplet states in the 4.5 – 5.0 eV range, as well as a number of valence and Rydberg singlet excited states. Electron‐impact excitation functions of pure vibrational and triplet states identified various states of the negative ion, in particular the ground state with an attachment energy of 0.8 eV, an excited state corresponding to a temporary electron attachment to the 2b₁ MO at an attachment energy of 2.7 eV, and a core excited state at 4.0 eV. Electronic‐absorption spectroscopy in cryogenic matrices revealed several states of the positive ion, in particular a richly structured first band at 1.27 eV, and the first electronic transition of the radical anion. Vibrations of the ground state of the cation were probed by IR spectroscopy in a cryogenic matrix. The results are discussed on the basis of density‐functional and CASSCF/CASPT2 quantum‐chemical calculations. In their various forms, the calculations successfully rationalized the triplet and the singlet (valence and Rydberg) excitation energies of the neutral molecule, the excitation energies of the radical cation, its IR spectrum, the vibrations excited in the first electronic absorption band, and the energies of the ground and the first excited states of the anion. The difference of the anion excitation energies in the gas and condensed phases was rationalized by a calculation of the Jahn‐Teller distortion of the anion ground state. Contrary to expectations based on a single‐configuration model for the electronic states of 1 , it is found that the gap between the first two excited states is different in the singlet and the triplet manifold. This finding can be traced to the different importance of configuration interaction in the two multiplicity manifolds.