Structure and Structural Nonrigidity of Tetrachlorodibenzo-p-Dioxin Radical Cations

Ab initio calculations showed that the tetrachlorodibenzo-para-dioxin radical cations (TCDD RCs) with a planar structure have two steady states with asymmetric dioxin cycles. The activation barriers between these states are up to 2 kcal/mole, so that the RCs may be regarded as being structurally nonrigid within the dioxin cycle. The 2,3,7,8-TCDD RC is more stable than the 1,4,6,9-TCDD RC, the energy difference being 5.2 kcal/mole. The adiabatic ionization potential of 2,3,7,8-TCDD (7.54 eV) is 0.1 eV smaller than the corresponding potential of 1,4,6,9-TCDD. These factors account for the increased hemoproteide affinity and hence increased biological activity of 2,3,7,8-TCDD.     

Dicyclopentadienyl complexes of titanium,niobium, and tungsten in the controlled synthesis of poly(methyl methacrylate)

Organometallic compounds Cp₂TiCl₂, (EtC₅H₄)₂NbCl₂, and (PrⁱC₅H₄)₂WCl₂ were assessed as additives that control polymer chain growth in the polymerization of methyl methacrylate. In the presence of compounds mentioned in amounts comparable with that of the initiator, a uniform process with no gel-effect occured and respective linear increase in the molecular weight of the polymer up to high degrees of the monomer conversion was observed.     

Detecting instabilities in flows of viscoelastic fluids

There is a growing interest in developing numerical tools to investigate the onset of physical instabilities observed in experiments involving viscoelastic flows, which is a difficult and challenging task as the simulations are very sensitive to numerical instabilities. Following a recent linear stability analysis carried out in order to better understand qualitatively the origin of numerical instabilities occurring in the simulation of flows viscoelastic fluids, the present paper considers a possible extension for more complex flows. This promising method could be applied to track instabilities in complex (i.e. essentially non‐parallel) flows. In addition, results related to transient growth mechanism indicate that it might be responsible for the development of numerical instabilities in the simulation of viscoelastic fluids. Copyright © 2003 John Wiley & Sons, Ltd.     

Phase behavior at low temperature of poly(tetrafluoroethylene) by temperature-modulated calorimetry

Temperature modulated differential calorimetry (TMDSC) is used to examine the crystal-crystal transitions of poly(tetrafluoroethylene). This study gives new information about the dynamic thermal behavior of such transitions. The involvement of reversible and irreversible processes during the phenomenon is observed, which are related to the order-disorder changes occurring during the transition.This study adds a new example to the response of TMDSC during first order transitions.     

Fluorine containing phosphazene polymers

In this paper we highlighted the synthesis, characterization, and practical exploitation of different types of polyphosphazenes substituted with fluorinated groups. There are several ways in which fluorine atoms can be inserted into polyphosphazenes, all of which leading to different polymers showing a wide range of characteristics. In general it is true that the insertion of fluorine atoms into phosphazene macromolecules leads to an enhancement of the thermal stability, flame resistance, low-temperature elastomericity, and chemical inertness of the phosphazenes obtained. The contribution of Italian research groups to the preparation and exploitation of organic commercial macromolecules grafted onto fluorinated polyphosphazenes is also reviewed.     

The role of As2O3 on the stability and some physical properties of PbO-Sb2O3 glasses

PbO-Sb₂O₃ glasses added with different concentrations of As₂O₃ (10-55 mol%) were prepared to understand their IR spectra, elastic properties (Young's modulus E, Shear modulus G, microhardness H), optical absorption and dielectric properties (constant ε, loss tan δ, ac conductivity σ_ac over a moderately wide range of frequency and temperature and breakdown strength in air medium at room temperature). Results have indicated that the structure of the PbO-Sb₂O₃-As₂O₃ glass is more rigid when the concentration of As₂O₃ is around 40 mol%.     

Vanadium(III) chloride catalyzed Biginelli condensation: solution phase library generation of dihydropyrimidin-(2H)-ones

The three component condensation of an aldehyde, a β-keto ester and urea (thiourea) in the presence of a catalytic amount of VCl₃ is disclosed for the solution phase synthesis of dihydropyrimidinones. The ease of synthesis and work-up allowed the parallel synthesis of a 48-membered library of dihydropyrimidinones quickly and efficiently in good yields.     

Crystal and Molecular Structure of <Emphasis Type="Italic">Bis</Emphasis>(2,3-pentamethylene-3,4-dihydro-4-oxoquinazolinium) Tetrachlorocuprate(II) Sesquihydrate

The structure of bis-(2,3-pentamethylene-3,4-dihydro-4-oxoquinazolinium) tetrachlorocuprate (II) sesquihydrate, (C₁₃H₁₅N₂O)₂[CuCl₄]·1.5H₂O, was determined by single crystal X-ray diffraction. In contrast to the previously studied analogs, the compound contains crystallization water molecules.Original Russian Text Copyright © 2004 by K. K. Turgunov, B. Tashkhodzhaev, L. V. Molchanov, and Kh. M. Shakhidoyatov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 955–959, September–October, 2004.     

Synthesis and conformational investigation of tetrapeptide analogues of the fragment B23-B26 of insulin

Tetrapeptides containing one of a set of four different α,α-dialkyl glycines at the C-terminus were synthesized by conventional methods in solution and their conformational behavior investigated by ¹H NMR spectroscopy in connection with molecular mechanics calculations. The results were consistent with conformations stabilized by a γ-turn in the case of compounds with alkyl groups larger than methyl, while the corresponding Aib derivative did not exhibit intramolecular hydrogen bonding.     

Lithium heptadecafluorooctanesulfonate catalyzed Mannich-type and aza-Diels-Alder reactions in supercritical carbon dioxide

The Mannich-type reaction of imines with (1-methoxy-2-methylpropenyloxy)trimethylsilane and aza-Diels-Alder reaction of imines with Danishefsky's diene can be carried out in scCO₂ in the presence of lithium heptadecafluorooctanesulfonate which offer a way to synthesize β-amino carbonyl compounds and nitrogen-containing six-membered ring compounds under environmentally benign conditions.