Accurate Geometry and Non-Covalent Interactions in 1-Phenylethanol and its Monohydrate: A Rotational Study

The pure rotational spectra of 1-phenylethanol and its monohydrate were measured by using a pulsed jet Fourier transform microwave spectrometer. One conformer of the 1-phenylethanol monomer with the trans form was observed in the pulsed jet. The experimental values of rotational constants of ten isotopologues, including eight mono-substituted ¹³C and one D isotopologues, allow an accurate structure determination of the skeleton of 1-phenylethanol. For its monohydrate, only one isomer has been observed, of which 1-phenylethanol adopts the trans form and binds with water through an O−H⋅⋅⋅O_w and an O_w−H⋅⋅⋅π hydrogen bond. Each rotational transition displays a doublet with a relative intensity ratio of 1 : 3, due to a hindered internal rotation of water around its C₂ axis. This study provides the information on accurate geometry of 1-phenylethanol (PE) and large amplitude motion of water in the PE monohydrate.     

Calcium coordination compounds based on phenoxyacetic acids: microwave synthesis,thermostability and influences on the crystal structures of chlorine substituent group on ligands

Three calcium coordination compounds, [Ca(CPA)(H₂O)₄]·(CPA), 1, [Ca(MCPA)₂(H₂O)₂]·H₂O, 2, and [Ca(TCPA)₂(H₂O)₃]·2H₂O, 3 [HCPA = 3-chlorophenoxyacetic acid, HMCPA = 2-methyl-4-chlorophenoxyacetic acid, and HTCPA = 2,4,6-trichlorophenoxyacetic acid], have been synthesized by the microwave method with advantages that include shorter reaction times, lower energy consumption, and higher product yield. The structures have been characterized by IR, elemental analysis, and single-crystal X-ray diffraction. Influences on the crystal structures by changing the number and position of chlorine substituent group in phenoxyacetic acid are discussed. Steric hindrance effects involving the Cl and an ability to form the O–H?Cl hydrogen bonds enrich the structure diversity. TG analysis reveals that the thermostability for the three compounds is 3 > 1 > 2, which could be influenced by the existence of hydrogen bonds (O–H?Cl and O–H?O).     

Ethylene glycol,an efficient and recoverable medium for copper-catalyzed N-arylation of diazoles under microwave irradiation

Ethylene glycol was used as an efficient and recoverable medium for the reaction of diazoles with aryl iodides and aryl bromides in the presence of CuCl₂ as the catalyst and K₂CO₃ as the base. Consequently, imidazole, benzimidazole, and pyrazole reacted readily under microwave irradiation to give good to excellent yields of their corresponding N-arylated products in relatively short time periods. Apparently, ethylene glycol plays a dual role by activating the catalyst and also providing a homogenous medium for the processes. The reaction medium consisting of the solvent, the base, and the copper salt was recovered and reused successfully in the next several reactions.     

Excluded Minors and the Ribbon Graphs of Knots

In this article we consider minors of ribbon graphs (or, equivalently, cellularly embedded graphs). The theory of minors of ribbon graphs differs from that of graphs in that contracting loops is necessary and doing this can create additional vertices and components. Thus, the ribbon graph minor relation is incompatible with the graph minor relation. We discuss excluded minor characterizations of minor closed families of ribbon graphs. Our main result is an excluded minor characterization of the family of ribbon graphs that represent knot and link diagrams.     

Microwave-assisted transition-metal-catalyzed synthesis of N-shifted and ring-expanded buflavine analogues

Two novel and efficient strategies for the synthesis of hitherto unknown N-shifted and ring-expanded buflavine analogues are presented. Construction of the medium-sized ring system of the title molecules, a difficult task due to the high activation energy needed for the ring-closure with the additional rigidity imposed by the biaryl skeleton, was achieved by using Suzuki-Miyaura biaryl coupling and a ring-closing metathesis reaction as the key steps. The combination of a second-generation Grubbs catalyst and microwave irradiation proved to be highly useful in generating the otherwise difficult to obtain medium-sized ring system of the buflavine analogues.     

Computing boundary slopes of 2-bridge links

We describe an algorithm for computing boundary slopes of 2-bridge links. As an example, we work out the slopes of the links obtained by surgery on one component of the Borromean rings. A table of all boundary slopes of all 2-bridge links with 10 or less crossings is also included.

     

Influence of the soliton in anharmonic molecular crystals with temperature on Mössbauer effect

The influence of a soliton on the properties of the M?ssbauer effect resulting from the gamma-active nuclei situated at lattice sites in quasi-one-dimensional anharmonically organic molecular chains, in which the active nuclei emit gamma-photons, has been theoretically studied by a quantum vibrational model. An expression for the gamma-radiated M?ssbauer transition probability as a function of the temperature and non-linear interaction has been obtained. Finally we give some new properties of this effect from numerical calculation in such a case, which present a way to experimentally confirm the soliton existence in molecular crystals. Received 9 April 1998 and Received in final form 11 December 1998     

Improvement of the standard method for solving the problem of internal rotation in molecules with symmetrical tops

Drawbacks of the standard method for solving the problem of internal rotation (IR) in molecules with symmetrical tops were examined. The drawbacks can be eliminated by taking into account the higher harmonics of the IR potentials. A new calculation procedure based on the approximation of the lower portion of the potential curve by the equationV(φ)=1/2V _n ^* (1-cosn φ), which describes adequately the arrangement of the torsion levels, was proposed. The successfull implementation of the proposed procedure showed that the procedures used currently are incorrect as well as the Herschbach procedure, which includes a systematic error at each iteration step. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 239–244, February, 1999.     

The cosmological constant revisited

I briefly review the observational evidence for a small cosmological constant at the present epoch. This evidence mainly comes from high redshift observations of Type 1a supernovae, which, when combined with CMB observations strongly support a flat Universe with Ω _m + Ω_A ⋍ 1. Theoretically a cosmological constant can arise from zero point vacuum fluctuations. In addition ultra-light scalar fields could also give rise to a Universe which is accelerating driven by a time dependent Λ-term induced by the scalar field potential. Finally a Λ dominated Universe also finds support from observations of galaxy clustering and the age of the Universe.