Signature of a type-a glass transition and intrinsic confinement effects in a binary glass-forming system

We study dynamically highly asymmetric binary mixtures comprised of small methyl tetrahydrofuran (MTHF) molecules and polystyrene. Combined use of dielectric spectroscopy, ^{2}H nuclear magnetic resonance, incoherent quasielastic neutron scattering, and depolarized dynamic light scattering allows us to selectively probe the dynamics of the components in a broad dynamic range. It turns out that the mixtures exhibit two glass transitions in a wide concentration range although being fully miscible on a macroscopic scale. In between both glass transition temperatures, the dynamics of the small molecules show strong confinement effects, e.g., a crossover from Vogel-Fulcher to Arrhenius behavior of the time constants. Moreover, the dynamical behavior of small molecules close to the slow matrix is consistent with mode coupling theory predictions for a type-A glass transition, which was expected from recent theoretical and simulation studies in comparable systems.     

Stereoselective functionalization of pyrrolidinone moiety towards the synthesis of salinosporamide A

An important feature of the synthesis of salinosporamide A, a potent proteasome inhibitor, is the establishment of the quaternary stereocenter at C3. A new route has been developed based on the methylation of a functionalized pyrrolidinone. Direct methylation reaction led to the unwanted diastereomer; however, by means of a Corey–Chaykovsky reaction followed by LiAlH₄ epoxide opening, the desired alcohol was obtained. The pyrrolidinone was elaborated through a key allylation reaction between a tertiary allyltitanium reagent and an aldehyde bearing a spiroketal moiety in α-position.     

The Effect of UV-Irradiation on Poly(vinyl alcohol) Composites with Bacterial Cellulose

The development of biodegradable packaging materials, especially from renewable resources is a constant preoccupation of nowadays, because of the environmental problems caused by synthetic polymers. The combination of cellulose with other polymeric materials could be an ecologic alternative and a way to use renewable resources for food packaging. Bacterial cellulose which is produced by microbial fermentation is also a promising material which can be used not only in biomedical application, but also as food packaging material. In this research different composite films between poly(vinyl alcohol)-bacterial cellulose (PVA-BC) were obtained by casting method. The obtained films were UV irradiated for different periods of times from 1 to 10 hours, using a mercury lamp, Philips TUV-30, emitting light mainly at 254 nm. Changes in FT-IR spectra before and after UV irradiation and the modification of transparency and of the swelling characteristics of the films were observed. As it was expected the composites materials are sensitive at UV exposure.     

Differentiated Generalized Voronovskaja’s Theorem in Compact Disks

In this paper we obtain the differentiated generalized Voronovskaja’s theorem in complex setting with upper and exact quantitative estimates. The results extend that obtained in the real case on [0, 1] in Gonska and Ra?a (Mat Vesnik 61:53–60, 2009) and generalize those obtained in the complex case in Gal (Results Math 53:257–268, 2009).     

Detonability of THDCPD-exo–air mixtures

In the frame of industrial risk and propulsive application, the detonability study of JP10–air mixtures was performed. The simulation and measurements of detonation parameters were performed for THDCPD-exo/air mixtures at various initial pressure (1 bar < P ₀ < 3 bar) and equivalence ratio (0.8 < Φ < 1.6) in a heated tube (T ₀ ~ 375 K). Numerical simulations of the detonation were performed with the STANJAN code and a detailed kinetic scheme of the combustion of THDCPD. The experimental study deals with the measurements of detonation velocity and cell size λ. The measured velocity is in a good agreement with the calculated theoretical values. The cell size measurements show a minimum value for Φ ~ 1.2 at every level of initial pressure studied and the calculated induction length L _i corresponds to cell size value with a coefficient k = λ/L _i = 24 at P ₀ = 1 bar. Based on the comparison between the results obtained during this study and those available in the literature on the critical initiation energy E _c, critical tube diameter d _c and deflagration to detonation transition length L _DDT, we can conclude that the detonability of THDCPD–air mixtures corresponds to that of hydrocarbon–air mixtures.

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This paper is based on the work presented at the 33rd International Pyrotechnics Seminar, IPS 2006, Fort Collins, July 16–21, 2006.     

Deformations of duality-symmetric theories

We prove that a sum of free non-covariant duality-symmetric actions does not allow consistent, continuous and local self-interactions that deform the gauge transformations. For instance, non-abelian deformations are not allowed, even in 4 dimensions where Yang–Mills type interactions of 1-forms are allowed in the non-manifestly duality-symmetric formulation. This suggests that non-abelian duality should require to leave the standard formalism of perturbative local field theories. The analyticity of self-interactions for a single duality-symmetric gauge field in four dimensions is also analyzed.     

Anionic and ionic coordinative polymerization of ϵ‐caprolactone

The polymerization of ?‐caprolactone initiated by two catalyst systems was studied: (1) carbazole‐potassium in the presence of 18‐crown‐6 ether and (2) NdCl₃/TBP/TIBA (neodymiumtrichloride/tri‐n‐butyl‐phosphate/triisobutylaluminium) at the molar ratio 1/3/1. For both initiator systems conversion/time plots were determined and the polymers were characterized by IR, GPC and by ¹H‐ and ¹³C?NMR spectroscopy. Polyesters with the highest molecular weight (M _n?44 000 g/mol) were obtained for the polymerizations initiated by the carbazole‐potassium/18‐crown‐6 ether system. The features of the polymerization initiated by the carbazole‐potassium/18‐crown‐6 ether system are discussed on the basis of a simple scheme. The nature of this polymerization is non‐living. Copyright © 2000 John Wiley & Sons, Ltd.     

Synthesis and Stereochemistry of Novel Dibrominated 1,5-Dioxaspiro[5.5]undecane Derivatives

Summary.  The synthesis and stereochemistry of new dibrominated spiro-1,3-dioxane derivatives are reported. Investigations by means of NMR methods and single crystal X-ray diffraction for two compounds revealed the high regio- and diastereoselectivity of the bromination reaction of some new spiro-1,3-dioxanes and the asymmetric induction of the chiral carbon atom located in the spiro skeleton. Received July 13, 1999. Accepted October 21, 1999     

An operator approach to zero-sum repeated games

We consider two person zero-sum stochastic games. The recursive formula for the valuesvλ (resp.v _n) of the discounted (resp. finitely repeated) version can be written in terms of a single basic operator Φ(α,f) where α is the weight on the present payoff andf the future payoff. We give sufficient conditions in terms of Φ(α,f) and its derivative at 0 for limv _n and limvλ to exist and to be equal. We apply these results to obtain such convergence properties for absorbing games with compact action spaces and incomplete information games.