Laser-induced acoustic wave generation/propagation/interaction in water in various internal channels

Short pulsed laser-induced single acoustic wave generation, propagation, interaction within a water-filled internal channel are experimentally and numerically studied. A large-area, short-duration, single-plane acoustic wave was generated by the thermoelastic interaction of a homogenized nanosecond pulsed laser beam with a liquid–solid interface and propagated at the speed of sound in water. Laser flash Schlieren photography was used to visualize the transient interaction of the plane acoustic wave in various internal channel structures ((a) sudden expansion and contraction channels, (b) bifurcating channels, (c) gradual contraction wall channels and (d) a cylinder). Fairly good agreement between the experimental results and numerical simulation is observed.     

Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory

Neutral phosphidozirconocene complexes [Cp₂Zr(PR₂)Me] (Cp=cyclopentadienyl; 1a : R=cyclohexyl (Cy); 1b : R=mesityl (Mes); 1c : R=tBu) undergo insertion into the Zr?P bond by non‐enolisable carbonyl building blocks (O=CR′R′′), such as benzophenone, aldehydes, paraformaldehyde or CO₂, to give [Cp₂Zr(OCR′R′′PR₂)Me] ( 3 – 7 ). Depending on the steric bulk around P, complexes 3 – 7 react with B(C₆F₅)₃ to give O‐bridged cationic zirconocene dimers that display typical frustrated Lewis pair (FLP)/ambiphilic ligand behaviour. Thus, the reaction of {[Cp₂Zr(μ‐OCHPhPCy₂)][MeB(C₆F₅)₃]}₂ ( 10a ) with chalcone results in 1,4 addition of the Zr⁺/P FLP, whereas the reaction of {[Cp₂Zr(μ‐OCHFcPCy₂)][MeB(C₆F₅)₃]}₂ ( 11a ; Fc=(C₅H₄)CpFe) with [Pd(η³‐C₃H₅)Cl]₂ yields the unique Zr?Fe?Pd trimetallic complex 13a , which has been characterised by XRD analysis.     

Relative Oscillation Theory,Weighted Zeros of the Wronskian,and the Spectral Shift Function

We develop an analog of classical oscillation theory for Sturm–Liouville operators which, rather than measuring the spectrum of one single operator, measures the difference between the spectra of two different operators. This is done by replacing zeros of solutions of one operator by weighted zeros of Wronskians of solutions of two different operators. In particular, we show that a Sturm-type comparison theorem still holds in this situation and demonstrate how this can be used to investigate the number of eigenvalues in essential spectral gaps. Furthermore, the connection with Krein’s spectral shift function is established. Research supported by the Austrian Science Fund (FWF) under Grant No. Y330.     

Duality and Self-Duality (Energy Reflection Symmetry) of Quasi-Exactly Solvable Periodic Potentials

A class of spectral problems with a hidden Lie-algebraic structure is considered. We define a duality transformation which maps the spectrum of one quasi-exactly solvable (QES) periodic potential to that of another QES periodic potential. The self-dual point of this transformation corresponds to the energy-reflection symmetry found previously for certain QES systems. The duality transformation interchanges bands at the bottom (top) of the spectrum of one potential with gaps at the top (bottom) of the spectrum of the other, dual, potential. Thus, the duality transformation provides an exact mapping between the weak coupling (perturbative) and semiclassical (nonperturbative) sectors.     

Functionalization of monofluoroallene and the synthesis of aryl-substituted conjugated fluorodienes

[reaction: see text] 4-Fluoroallenol 3a, prepared from 1, cyclized easily to 4 but preserved its fluoroallenyl integrity under oxidation and S(N)2 displacement to yield aldehyde, amine, mesylate, and halide 6. Allylic isomerization yielded 2-halo-1-fluoro-1,3-butadiene 7, which underwent a Suzuki coupling to give aryl-substituted conjugated diene 8.     

Substituted 1,8-naphthyridin-2(1H)-ones are superior to thymine in the recognition of adenine in duplex as well as triplex structures

The synthesis and evaluation of a series of novel nucleobases based on substituted 1,8-naphthyridin-2(1H)-ones are reported. The nucleobases were designed to meet the requirements for incorporation into peptide nucleic acids (PNAs) and were evaluated as part of PNA duplex and triplex nucleic acid recognition systems. Of the various nucleobases tested, only the 7-chloro-1,8-naphthyridin-2(1H)-one (7-Cl-bT) nucleobase led to consistently increased affinity in all recognition systems, duplex (Watson-Crick) as well as triplex (Hoogsteen). For multiply modified systems, the increase in thermal stability per modification was dependent on the sequence context, ranging from 2.0 degrees C (in separate positions) to 3.5 degrees C (in adjacent positions) in PNA-DNA duplexes and from 1.2 degrees C (in separate positions) to 3.2 degrees C (in adjacent positions) in PNA-RNA duplexes. Singly mismatched oligonucleotide targets were employed to demonstrate uncompromised sequence discrimination. When part of multiply modified triplex (Hoogsteen) recognition systems, the 7-Cl-bT unit gave rise to increases in the thermal stability ranging from 2.7 to 3.5 degrees C when incorporated into separated and adjacent positions, respectively. Our results furthermore indicate that the duplex stabilization is predominantly enthalpic and therefore most likely not a consequence of single-strand preorganization. Finally, and most surprisingly, we find no direct correlation between the end-stacking efficiency of this type of nucleobase and its helix stabilization when involved in Watson-Crick base pairing within a helix.     

Bending of DNA by asymmetric charge neutralization: all-atom energy simulations

DNA dodecamers of the alternating d(CG).d(CG) sequence with six phosphate groups either charge-neutralized or substituted by neutral methylphosphonates across the major or minor groove have been subjected to energy minimization to determine the conformational effect of the asymmetric elimination of phosphate charge. We report bending angles, directions of bending, and detailed structural characteristics such as groove widths and local base-pair parameters. Our principal results are that charge neutralization on one face of the DNA induces significant bending toward the neutralized face, in agreement with theoretical predictions on a simplified model and experimental data on a similar base-pair sequence, and that the DNA conformation averaged over all stereospecific methylphosphonate substitutions is nearly the same as the conformation produced by charge neutralization of the phosphates. Individual isomers, however, cover a wide range of structures, with the magnitude and direction of overall bending sensitive to the precise stereochemical pattern of neutralization. Our simulation does not explicitly contain counterions, and the results therefore suggest that counterions can influence DNA structure by neutralizing the phosphate charge. These data provide new hints into the molecular mechanisms which underlie the deformations of DNA structure induced by the binding of positively charged proteins and other tightly associated cationic species.     

Regiospecific synthesis of bicyclo- and heterobicyclo-gem-difluorocyclobutenes using functionalized fluoroallenes and a novel Mo-catalyzed intramolecular [2 + 2] cycloaddition reaction

The first synthesis of functionalized gem-difluoroallenes 4 served as platform for an unprecedented molybdenum-catalyzed intramolecular allene-alkyne [2 + 2]-cycloaddition that produced 6, a hitherto unknown class of bicyclo- and heterobicyclo-CF2-containing cyclobutenes.     

Novel rearrangements and formation of 2,5-dihydro-1,2,5-oxoniastannaboratolesvia methanolysis of zwitterionic η2-(alkyn-1-yl-borate)alkenyltin compounds

Organo-substituted 2,5-dihydro-1,2,5-oxoniastannaboratoles3 were prepared by methanolysis of zwitterionic ²-(alkyn-l-ylborate)alkenyltin compounds1. Analogously, the bis[²-(alkyn-l-yl-borate)alkenyltin derivative2 reacts with an excess of methanol to give a dimeric MeO-bridged 2,5-dihydro-1,2,5-oxoniastannaboratole (10a)₂. Various intermediates could be identified by NMR spectroscopy, and the molecular structure of(10a) ₂ was determined by X-ray analysis. The structures of several products of the methanolysis indicate that protolysis of an Sn-C=bond occurs first, followed by an MeO/alkenyl exchange reaction.Dedicated to the 100th Anniversary of A. N. Nesmeyanov's birth.Laboratorium für Anorganische Chemie, Universität Bayreuth, D-95440 Bayreuth, Germany Institut für Anorganische Chemie, Universität-GH Essen, Universitätsstr. 5–7, D-45117 Essen, Germany. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1185–1196, September, 1999.