Chemical bonding in view of electron charge density and kinetic energy density descriptors

Stalke's dilemma, stating that different chemical interpretations are obtained when one and the same density is interpreted either by means of natural bond orbital (NBO) and subsequent natural resonance theory (NRT) application or by the quantum theory of atoms in molecules (QTAIM), is reinvestigated. It is shown that within the framework of QTAIM, the question as to whether for a given molecule two atoms are bonded or not is only meaningful in the context of a well‐defined reference geometry. The localized‐orbital‐locator (LOL) is applied to map out patterns in covalent bonding interaction, and produces results that are consistent for a variety of reference geometries. Furthermore, LOL interpretations are in accord with NBO/NRT, and assist in an interpretation in terms of covalent bonding. © 2008 Wiley Periodicals, Inc.J Comput Chem, 2009.     

Fe-contacts on InAs(100) and InP(100) characterised by conversion electron Mössbauer spectroscopy

We have grown 4 nm thin films of ⁵⁷Fe on InAs(100) and InP(100) surfaces by use of MBE and studied the samples by ⁵⁷Fe conversion electron Mössbauer spectroscopy. In the case of InAs, the Mössbauer spectrum showed a sextet due to α-Fe and a further magnetically split component with slightly smaller hyperfine field, which is attributed to interface components. This result indicates that there is a relatively sharp interface between Fe and InAs. On the contrary, the spectrum of the InP sample showed a sextet with very broad lines and a smaller average hyperfine field. This suggests a strong chemical reaction between iron and the substrate, which results in the formation of a poorly crystalline phase.     

Determination of ionic metabolites from ethylene glycol in human blood by isotachophoresis

Conditions for isotachophoretic determination of anionic metabolites in blood from ethylene glycol in poisoned humans were established. Leading electrolytes with 5 mM chloride and and 2.5 gave good separation. Optimal separation was found with leading electrolytes at pH 2.5, and 10 mM acetic acid as terminating electrolyte. Separation and quantification of four out of six metabolites were possible. The four were glycolic acid, glyoxylic acid, oxalic acid and formic acid. Besides these compounds, citric acid, lactic acid, and alpha- and beta-hydroxybutyric acid were separated and quantified. The formation of mixed zones did not give any serious problems, although in samples with high amounts of glycolic acid we had to reduce the maximum injected amount from 3 to 1 microliter. This method might be valuable in further studies of the mechanism of ethylene glycol toxicity and as an important supplement in the diagnosis of late stages of ethylene glycol poisoning in which the glycol has been metabolized to glycolic acid.     

Transition‐Metal‐Free Formal Sonogashira Coupling and α‐Carbonyl Arylation Reactions

Transition‐metal‐free formal Sonogashira coupling and α‐carbonyl arylation reactions have been developed. These transformations are based on the nucleophilic aromatic substitution (S_NAr) of β‐carbonyl sulfones to electron‐deficient aryl fluorides, producing a key intermediate that, depending on the reaction conditions, gives the aromatic alkynes or α‐aryl carbonyl compounds. The development of these reactions is presented and, based on investigations under basic and acidic conditions, mechanisms have been proposed. To develop the formal Sonogashira coupling further, a milder, two‐step protocol is also disclosed that expands the reaction concept. The scope of these reactions is demonstrated for the synthesis of Sonogashira and α‐carbonyl arylated products from a range of electron‐deficient aryl fluorides with a variety of functional groups and aryl‐, heteroaryl‐, alkyl‐, and alkoxy‐substituted sulfone nucleophiles. These transition‐metal‐free reactions complement the metal‐catalyzed versions in terms of substitution patterns, simplicity, and reaction conditions.     

Ring Opening of Pymisyl‐Protected Aziridines with Organocuprates

The pyrimidine‐2‐sulfonyl (pymisyl) group is introduced as a new protecting group that can be used to activate aziridines towards ring opening. It is readily introduced and removed under mild conditions. Regioselective ring opening of pymisyl‐protected 2‐methyl‐aziridine with organocuprates gives the corresponding sulfonamides in high yields, and the pymisyl group can subsequently be removed upon treatment with a thiolate. The versatility of this new nitrogen protecting group is illustrated with a new synthesis of Selegiline, a monoamine oxidase‐B inhibitor marketed for the treatment of Parkinson’s disease.     

Coordination of imidazoles by Cu(II) and Zn(II) as studied by NMR relaxometry, EPR, far-FTIR vibrational spectroscopy and ab initio calculations: effect of methyl substitution

Synthetic imidazole ligands are typically substituted at the N(1) ((1)-Im) position while natural imidazole ligands are substituted at the C(4) ((4)-Im) position. To outline the difference in coordination properties, the methyl-substituted imidazoles Me(4)-Im and Me(1)-Im were complexed with CuCl(2) and ZnCl(2) and investigated by NMR relaxometry, electron paramagnetic resonance, far-Fourier transform IR vibrational spectroscopy, and ab initio calculations. Me(4)-Im, Me(1)-Im, and Im in excess form the usual tetragonal D(4h) [CuL(4)X(2)] complexes with CuCl(2) whereas the methylated imidazoles form pseudotetrahedral C(2v) complexes instead of the usual octahedral O(h) [ZnIm(6)](2+) complex. All imidazoles display a high degree of covalence in the M-L σ- and π-bonds and the π-interaction strength affects the relative energies of complexation. Opportunities to tailor complexes by the chemical properties of the substituents are envisaged due to the role of the inductive and hyperconjugative effects, rather than position.     

Extracting the invariant model from the feedback paths of digital hearing aids

Feedback whistling is a severe problem with hearing aids. A typical acoustical feedback path represents a wave propagation path from the receiver to the microphone and includes many complicated effects among which some are invariant or nearly invariant for all users and in all acoustical environments given a specific type of hearing aids. Based on this observation, a feedback path model that consists of an invariant model and a variant model is proposed. A common-acoustical-pole and zero model-based approach and an iterative least-square search-based approach are used to extract the invariant model from a set of impulse responses of the feedback paths. A hybrid approach combining the two methods is also proposed. The general properties of the three methods are studied using artificial datasets, and the methods are cross-validated using the measured feedback paths. The results show that the proposed hybrid method gives the best overall performance, and the extracted invariant model is effective in modeling the feedback path.