Origin and Use of Hydroxyl Group Tolerance in Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Catalysts

The origin of hydroxyl group tolerance in neutral and especially cationic molybdenum imido alkylidene N-heterocyclic carbene (NHC) complexes has been investigated. A wide range of catalysts was prepared and tested. Most cationic complexes can be handled in air without difficulty and display an unprecedented stability towards water and alcohols. NHC complexes were successfully used with substrates containing the hydroxyl functionality in acyclic diene metathesis polymerization, homo-, cross and ring-opening cross metathesis reactions. The catalysts remain active even in 2-PrOH and are applicable in ring-opening metathesis polymerization and alkene homometathesis using alcohols as solvent. The use of weakly basic bidentate, hemilabile anionic ligands such as triflate or pentafluorobenzoate and weakly basic aromatic imido ligands in combination with a sterically demanding 1,3-dimesitylimidazol-2-ylidene NHC ligand was found essential for reactive and yet robust catalysts.     

Chromophore and spectrum of the glycogen–iodine complex

The experimental UV-vis spectrum of the glycogen-iodine (GI) complex shows certain features remarkably similar to that of the amylopectin-iodine (API) complex [J. Polymer. Chem. 32, 2257 (1994)], suggesting a strong similarity between the API and the GI structures. As in the API complex, a nearly linear polyiodine unit, I₄, at an interiodine distance of around 3 Å is expected to exist within the helix of 11 anhydroglucose units (AGUs). There are several other spectral features that suggest the presence of another similar but more loosely bound iodine species with a longer interiodine distance of 3.1 Å. These findings suggest the involvement of two different types of glycogen chains in binding iodine molecules. © 1996 John Wiley & Sons, Inc.     

Micellar and microemulsion electrokinetic chromatography of hop bitter acids

The elution order of the hop α- and β-acids has been studied under different modes of electrokinetic separation. A model is advanced to explain the shorter migration times of the more hydrophobic β-acids compared to the α-acids in micellar electrokinetic chromatography (MEKC). For quality control of the bitter principles in hops, the ruggedness of electrokinetic separation could be improved by replacing MEKC by microemulsion electrokinetic chromatography (MEEKC).     

Dust-Acoustic Nonlinear Waves in a Nanoparticle Fraction of Ultracold (2K) Multicomponent Dusty Plasma

The nonlinear dust-acoustic instability in the condensed submicron fraction of dust particles in the low-pressure glow discharge at ultra-low temperatures is experimentally and theoretically investigated. The main discharge parameters are estimated on the basisof the dust-acoustic wave analysis. In particular, the temperature and density of ions, as well as the Debye radius, are determined. It is shown that the ion temperature exceeds the temperature of the neutral gas. The drift characteristics of all plasma fractions are estimated. The reasons for the instability excitation are considered.     

Observation of entanglement between two light beams spanning an octave in optical frequency

We have experimentally demonstrated how two beams of light separated by an octave in frequency can become entangled after their interaction in a chi;{(2)} nonlinear medium. The entangler was a nonlinear optical resonator that was strongly driven by coherent light at the fundamental and second-harmonic wavelengths. An interconversion between the fields created quantum correlations in the amplitude and phase quadratures, which were measured by two independent homodyne detectors. Analysis of the resulting correlation matrix revealed a wave function inseparability of 0.74(1)<1, thereby satisfying the criterion of entanglement.     

On-Surface Synthesis and Characterization of Acene-Based Nanoribbons Incorporating Four-Membered Rings

A bottom up method for the synthesis of unique tetracene-based nanoribbons, which incorporate cyclobutadiene moieties as linkers between the acene segments, is reported. These structures were achieved through the formal [2+2] cycloaddition reaction of ortho-functionalized tetracene precursor monomers. The formation mechanism and the electronic and magnetic properties of these nanoribbons were comprehensively studied by means of a multitechnique approach. Ultra-high vacuum scanning tunneling microscopy showed the occurrence of metal-coordinated nanostructures at room temperature and their evolution into nanoribbons through formal [2+2] cycloaddition at 475 K. Frequency-shift non-contact atomic force microscopy images clearly proved the presence of bridging cyclobutadiene moieties upon covalent coupling of activated tetracene molecules. Insight into the electronic and vibrational properties of the so-formed ribbons was obtained by scanning tunneling microscopy, Raman spectroscopy, and theoretical calculations. Magnetic properties were addressed from a computational point of view, allowing us to propose promising candidates to magnetic acene-based ribbons incorporating four-membered rings. The reported findings will increase the understanding and availability of new graphene-based nanoribbons with high potential in future spintronics.     

Reversible C=C Bond Activation by an Intramolecularly Coordinated Antimony(I) Compound

The reaction of N,C,N-chelated stibinidene ArSb ( 1 ) (Ar=C₆H₃-2,6-(CH=NtBu)₂) with selected N-alkyl/aryl-maleimides RN(C(O)CH)₂ (R=Me, tBu, Ph) gave the addition products with bridged bicyclic [2.2.1] structure containing an antimony atom at the bridgehead position, fused with a 6-membered benzene and a 5-membered N-alkyl/aryl-pyrrolidine ring. These compounds were completely characterized. More importantly, additional studies showed that these reactions are reversible in solution, thereby representing an unprecedented reversible activation of a C=C bond by an antimony(I) compound.     

Effective bimetallic composite catalysts for the synthesis of arylated furans and thiophenes in aqueous media

Chemistry of Heterocyclic Compounds - N-(4,6-Dimethylpyrimidin-2-yl)-5-phenylisoxazole-3-carboxamide was used as a ligand for obtaining bimetallic boron-containing heterogeneous catalysts...     

Statistical maps and generalized random walks

We continue our study of statistical maps (equivalently, fuzzy random variables in the sense of Gudder and Bugajski). In the realm of fuzzy probability theory, statistical maps describe the transportation of probability measures on one measurable space into probability measures on another measurable space. We show that for discrete probability spaces each statistical map can be represented via a special matrix the rows of which are probability functions related to conditional probabilities and the columns are related to fuzzy n-partitions of the domain. Discrete statistical maps sending a probability measure p to a probability measure q can be represented via conditional distributions and correspond to joint probabilities on the product. The composition of statistical maps provide a tool to describe and to study generalized random walks and Markov chains.