Potential energy surfaces for HenNe+ ions: ab initio and diatomics-in-molecule results

The potential energy surface of He2Ne+ has been reinvestigated using a combination of ab initio and diatomics-in-molecule (DIM) calculations. In contrast to the reports of two recent studies the ion is found to have an asymmetric linear He-Ne-He structure, with no barrier to formation from the separated atoms on the ground-state surface. The He-Ne+ bond lengths at the potential minimum are 1.51 and 1.81 A, and the total bonding energy is 0.717 eV. Comparing the He2Ne+ energy to that of HeNe+, the bonding energy for the second helium atom is 0.06 eV, about 10% of that of the first He atom. The saddle point between the two equivalent minima is a symmetric structure, 0.0074 eV above the potential minimum. A symmetric geometry becomes the overall potential minimum if the 2s hole on the Ne is excluded from the reference states of a multireference configuration interaction calculation. A DIM potential was created for the HenNe+ family of ions. The DIM potential is consistent with the asymmetric He2Ne+ ion serving as a core; it predicts a slightly more asymmetric geometry than the ab initio results. Additional helium atoms form five-membered rings around the bonds of the core ion to fill the first shell and then add to the ends of the cluster. The asymmetric core ion and the highly compact structure help to account for the lack of apparent shell structure in the mass spectrometry of HenNe+ clusters. Finally, we recommend that the value De=0.63+/-0.04 eV be adopted for the ground state of HeNe+.     

Studium der Reduktion von Resazurin

Zusammenfassung In dieser Arbeit wurden Schlußfolgerungen über den simultanen Verlauf der beiden Reduktionsphasen von Resazurin überprüft.Weiters wurden Bedingungen für die quantitative titanometrische Bestimmung von Resazurin und seiner Derivate ermittelt.

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The conclusions about the simultaneous course of reduction of Resazurin to Resorufin and Resorufin to Dihidroresorufin were verified in this work.The conditions for the quantitative titanometric determination of Resazurin and its derivatives were found.

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Mit 4 Abbildungen     

Einige analytische Eigenschaften von 1,3-Dimethyl-4,5-diaminouracil

Zusammenfassung 1,3-Dimethyl-4,5-diaminouracil (DAL) hat sich als sehr empfindliches Reagens zum selektiven Nachweis von Co²⁺-Ionen im stark alkalischen Medium einer Phosphatpufferlösung (p_H=11,20) erwiesen. Es wurden vier Additionsverbindungen von DAL mit den Zentralatomen Cd(II), Pd(II), Ni(II) und Co(II) im Verhältnis Me DAL=1 2 hergestellt. Spektrophotometrische Untersuchungen weisen darauf hin, daß bei p_H 6 bis 7 eine Komplexverbindung im Verhältnis CoDAL=12 gebildet wird.

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Summary 1,3-dimethyl-4,5-diaminouracil (DAL) has been found to be a very sensitive reagent for the selective detection of Co²⁺ ions in strong alkaline medium of a phosphate buffer solution (p_H=11.20). Four addition compounds of DAL with the central atoms Cd(II), Pd(II), Ni(II) and Co(II) with the ratio MeDal=12 have been prepared. Spectrophotometric studies indicate that at p_H=6–7, complex compound is produced with the ratio CoDAL=12.

     

Syntheses of Novel Isopenam and Isocephem Antibiotics. Preparation of a retinamido derivative of a highly strained β-lactam as potent anticancer agent

Syntheses of the cis-configurated isopenam 9 (Scheme 1), isocephem 14 (Scheme 2), and isocephem 19 (Scheme 3) are described. The key step in the preparation of 14 and 19 involved a Pummerer-type rearrangement of the corresponding sulfoxides 12 and 18 . These β-lactams were found to possess biological activity against several pathogenic microorganisms in vitro. The electronic activation of the lactam moiety of 19 remarkably enhanced its biological activity. A retinoic moiety was attached to 19 via an amino linker. The resultant retinamido-β-lactam 21 showed significant cytostatic activity in tracheal organ cultures obtained from vitamin-A-deficient hamsters.     

Acene-linked conjugated polymers with ratiometric fluorescent response to 1O2

This communication describes new conjugated polymers that bear diarylanthracene or diaryltetracene pendants and respond to singlet oxygen by interrupting energy transfer resulting in blue-shifted fluorescence.     

One-pot redox syntheses of heteronanostructures of Ag nanoparticles on MoO3 nanofibers

A new one-pot redox route has been developed for simultaneous syntheses of Ag nanoparticles on MoO(3) nanofibers. Four different synthetic reactions that have been integrated into the one-pot synthesis include the oxidation of [Na(H(2)O)(2)](0.25)MoO(3) bronze, the reduction of silver ions, and the in situ simultaneous growth of the self-organized Ag nanoparticles and the MoO(3) nanofibers. This new strategy can be generally applicable to grafting various metal nanoparticles on nanofibers for new catalysis-related applications.     

Common system setup for the entire catalytic cycle of cytochrome P450(cam) in quantum mechanical/molecular mechanical studies

We describe a system setup that is applicable to all species in the catalytic cycle of cytochrome P450(cam). The chosen procedure starts from the X-ray coordinates of the ferrous dioxygen complex and follows a protocol that includes the careful assignment of protonation states, comparison between different conceivable hydration schemes, and system preparation through a series of classical minimizations and molecular dynamics (MD) simulations. The resulting setup was validated by quantum mechanical/molecular mechanical (QM/MM) calculations on the resting state, the pentacoordinated ferric and ferrous complexes, Compound I, the transition state and hydroxo intermediate of the C--H hydroxylation reaction, and the product complex. The present QM/MM results are generally consistent with those obtained previously with individual setups. Concerning hydration, we find that saturating the protein interior with water is detrimental and leads to higher structural flexibility and catalytically inefficient active-site geometries. The MD simulations favor a low water density around Asp251 that facilitates side chain rotation of protonated Asp251 during the conversion of Compound 0 to Compound I. The QM/MM results for the two preferred hydration schemes (labeled SE-1 and SE-4) are similar, indicating that slight differences in the solvation close to the active site are not critical as long as camphor and the crystallographic water molecules preserve their positions in the experimental X-ray structures.     

Photo-induced DNA cleavage by (heterocyclo)carbonyl oxime esters of anthraquinone

Various (heterocyclo)carbonyl mono-oxime esters of anthraquinone were synthesized, which exhibited an ability for DNA cleavage upon UV irradiation. Their structure-activity relationship was established, in which the most potent compound was anthraquinone O-9-(1,3-benzothiazole-2-carbonyl)oxime (4j). It can produce radical species and nick DNA at the concentration as low as 1.0 μM.     

Preparation and characterization of a novel adsorbent for removing lipophilic organic from water

The initial twelve persistent organic pollutants (POPs) in Stockholm Convention on Persistent Or-ganic Pollutions include many organochlorinated pes-ticides (OCPs) and some industrial by-products from manufacture processes, most of which are lipophilic or…     

A novel protecting/activating strategy for beta-hydroxy acids and its use in convergent peptide synthesis

beta-Hydroxy acids were reacted with hexafluoroacetone and carbodiimides to give carboxy-activated six-membered lactones in good yields. On reaction with amines, the corresponding amides were obtained. We demonstrate the following applications of this protecting/activating strategy: preparation of carboxamides in solution and on solid phase (both normal and reverse mode); recovery and reuse of the excess material in solid-phase synthesis; and convergent solid-phase peptide synthesis (CSPPS) with peptide segments bearing C-terminal Ser or Thr with very low levels of epimerization (<1%, HPLC).