Effect of temperature and solvent on polymer tacticity in the free‐radical polymerization of styrene and methyl methacrylate

The effect of temperature and solvent on polymer tacticity in free‐radical polymerization of styrene and methyl methacrylate was studied by ¹³C and ¹H NMR, respectively. Polystyrene shows a mild syndiotactic tendency (P_m = 0.36 ± 0.02) that is independent of temperature over a wide range (?10 to 120 °C), while poly(methyl methacrylate) shows a stronger syndiotactic tendency (P_m = 0.17 ± 0.01 at 30 °C) that decreases as temperature is increased (P_m = 0.22 ± 0.02 at 80 °C). None of the polymerization solvents studied (bulk, THF, DMF, DMSO, acetonitrile, and acetone) had a significant effect on polymer tacticity in either system. The triad fractions of both polymers showed deviations from the Bernoulli model, implying that the antepenultimate unit affects the propagation reaction. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3351–3358     

Identification of radiation‐induced radical structure in azocalix[4]arene: an EPR study

A macrocyclic azocalix[4]arene (1) based ester derivative was synthesized. The single crystals of azocalix[4]arene were produced by slow evaporation of concentrated ethyl acetate solutions. These single crystals were exposed to ⁶⁰Co gamma rays with a dose rate of 0.980 kGy h^‐1 for 48 and 72 h to produce a stable free radical. Electron paramagnetic resonance (EPR) measurements were performed in three mutually perpendicular planes of the single crystal in the magnetic field, in addition, temperature dependence of the EPR signal was studied between 120 K and 450 K. The spectra were found to be temperature and angular dependent. Analysis based on the spectra recorded showed that a free radical was formed by fission of a C–H bond. This radical is described as ^?C_aHC_bH₃ The averages of the principal values of the hyperfine parameters and g‐factor are: g = 2.0034, A_Ha = 1.28 mT, A_H1=H2 = 1.00 mT, and A_H3 = 0.49 mT. Copyright © 2013 John Wiley & Sons, Ltd.     

Teil II: Ergebnisse bei der Bestrahlung einzelner Nahrungsmittelgruppen (Zusammenfassender Bericht)

Nachdem im ersten Teil dieser Arbeit [170] einige Grundprobleme der Nahrungsmittelbestrahlung behandelt wurden, sollen nun die bei der Bestrahlung wichtiger Nahrungsmittelgruppen erzielten Ergebnisse dargelet und eine Einschätzung der Entwicklungstendenzen versucht werden.     

Substitution effects in the 15N NMR chemical shifts of heterocyclic azines evaluated at the GIAO‐DFT level

A systematic study of the accuracy factors for the computation of ¹⁵N NMR chemical shifts in comparison with available experiment in the series of 72 diverse heterocyclic azines substituted with a classical series of substituents (CH₃, F, Cl, Br, NH₂, OCH₃, SCH₃, COCH₃, CONH₂, COOH, and CN) providing marked electronic σ‐ and π‐electronic effects and strongly affecting ¹⁵N NMR chemical shifts is performed. The best computational scheme for heterocyclic azines at the DFT level was found to be KT3/pcS‐3//pc‐2 (IEF‐PCM). A vast amount of unknown ¹⁵N NMR chemical shifts was predicted using the best computational protocol for substituted heterocyclic azines, especially for trizine, tetrazine, and pentazine where experimental ¹⁵N NMR chemical shifts are almost totally unknown throughout the series. It was found that substitution effects in the classical series of substituents providing typical σ‐ and π‐electronic effects followed the expected trends, as derived from the correlations of experimental and calculated ¹⁵N NMR chemical shifts with Swain–Lupton's F and R constants.     

Modulating the Photochemistry of Bipyridylic Compounds by Symmetric Substitutions

A quantum electronic study of the effect of substituents on (2,2′‐bipyridyl)‐3,3′‐diol and (2,2′‐bipyridyl)‐3,3′‐diamine is presented. A large difference in the photochemical behavior between the original and the substituted selected systems is expected. For the sake of simplicity, the study is restricted to the symmetrically bi‐substituted compounds: fluorine, the more electronegative atom and thus a strong σ‐acceptor but also a weak π‐donor group, and NO₂, a strong π‐acceptor substituent. Among the large set of compounds studied, two receive special attention: 5,5′‐dinitro‐(2,2′‐bipyridyl)‐3,3′‐diamine and 6,6′‐difluoro‐(2,2′‐bipyridyl)‐3,3′‐diol. While in the former case the nitro substitution transforms (2,2′‐bipyridyl)‐3,3′‐diamine, previously suggested to behave as a photomemory material, into a simple fluorescent species, the latter substitution turns (2,2′‐bipyridyl)‐3,3′‐diol into a fresh new candidate for a photomemory device.     

A theory of plasticity for carbon nanotube reinforced composites

Carbon nanotubes (CNTs) possess exceptional mechanical properties, and when introduced into a metal matrix, it could significantly improve the elastic stiffness and plastic strength of the nanocomposite. But current processing techniques often lead to an agglomerated state for the CNTs, and the pristine CNT surface may not be able to fully transfer the load at the interface. These two conditions could have a significant impact on its strengthening capability. In this article we develop a two-scale micromechanical model to analyze the effect of CNT agglomeration and interface condition on the plastic strength of CNT/metal composites. The large scale involves the CNT-free matrix and the clustered CNT/matrix inclusions, and the small scale addresses the property of these clustered inclusions, each containing the randomly oriented, transversely isotropic CNTs and the matrix. In this development the concept of secant moduli and a field fluctuation technique have been adopted. The outcome is an explicit set of formulae that allows one to calculate the overall stress-strain relations of the CNT nanocomposite. It is shown that CNTs are indeed a very effective strengthening agent, but CNT agglomeration and imperfect interface condition can seriously reduce the effective stiffness and elastoplastic strength. The developed theory has also been applied to examine the size (diameter) effect of CNTs on the elastic and elastoplastic response of the composites, and it was found that, with a perfect interface contact, decreasing the CNT radius would enhance the overall stiffness and plastic strength, but with an imperfect interface the size effect is reversed. A comparison of the theory with some experiments on the CNT/Cu nanocomposite serves to verify the applicability of the theory, and it also points to the urgent need of eliminating all CNT agglomeration and improving the interface condition if the full potential of CNT reinforcement is to be realized.     

MHD flow and heat transfer over permeable stretching sheet with slip conditions

The magnetohydrodynamic (MHD) flow and heat transfer characteristics for the boundary layer flow over a permeable stretching sheet are considered. Velocity and thermal slip conditions are taken into account. Problem formulation is developed in the presence of thermal radiation. Governing non‐linear problem is solved by a homotopy analysis method. Convergence of the derived solutions is studied. Numerical values of skin‐friction coefficient and local Nusselt number are tabulated. Effects of pertinent parameters on the velocity and temperature profiles are discussed. Comparison between the present and previous limiting results is shown. Copyright © 2010 John Wiley & Sons, Ltd.     

Magnetic circular dichroism in the luminescence ofF andF A centres in alkali halides

Summary The magnetic circular dichroism has been in the past an excellent tool to clarify the optical cycle of theF centres in alkali halides and the nature of the relaxed excited state. We have used such technique to study the weak doubleF emission found recently in NaI and the luminescence ofF andF _A centres (of both type I and II) in KCl. We have found that the long-wavelengthF emission in NaI and theF _A (I) emission in KCl∶Na⁺ behave like the well-known emission of theF centres, confirming the attribution of the above luminescence in NaI to the normal relaxed excited state. A completely different behaviour is displayed by the short-wavelengthF emission in NaI and by theF _A (II) emission in KCl∶Li⁺. The experimental data have been compared with the Ham and Grevsmuhl vibronic theory of the relaxed excited state.

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Riassunto Gli effetti di dicroismo magnetico circolare hanno costituito in passato un ottimo mezzo per chiarire il ciclo ottico dei centriF in alogenuri alcalini e la natura dello stato eccitato rilassato. Abbiamo usato tale tecnica per studiare la debole doppia emissioneF trovata recentemente in NaI e la luminescenza dei centriF edF _A (di tipo I e II) in KCl. Si è trovato che l'emissioneF a minore energia in NaI e l'emissioneF _A (I) in KCl∶Na⁺ si comportano come la ben nota emissione dei centriF, il che conferma l'attribuzione di tale luminescenza in NaI allo stato eccitato rilassato normale. L'emissioneF a energia maggiore in NaI e l'emissioneF _A (II) in KCl∶Li⁺ mostrano un comportamento completamente diverso. I dati sperimentali sono stati confrontati con la teoria vibronica di Ham e Grevsmuhl dello stato eccitato rilassato.

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Резюме Магнитный круговой дихроизм ранее применялся как инструмент для выяснения оптического циклаF центров в щелочных галогенидах и природы релаксирующего возбужденного состояния. В этой работе мы используем эту технику для исследования слабого двойного F излучения, обнаруженного недавно в NaI и при люминесценцииF иF _A центров (типа I и типа II) в KCl. Мы обнаружили, что длинноволновоеF излучения в NaI иF _A (I) излучение в KCl∶Na⁺ ведет себя как хорошо известное излучениеF центров, что подтверждает приписывание вышеуказанной люминесценции в NaI нормальному релаксирующему возбужденному состоянию. Полностью отличное поведение обнаруживает коротковолновоеF излучение в NaI иF _A (II) излучение в KCl∶Li⁺. Полученные экспериментальные данные сравниваются с вибрационной теорией Гама и Гревсмула для релаксирующего возбужденного состояния.

     

An optimization model for amorphous solar cells in which optical,electrical and recombination properties are specified

Summary A model for determination and optimization of the fundamental parameters defining the quality of amorphous solar cells in which optical, electrical and recombination properties are specified is developed. It can be applied to any amorphous solar-cell systems. This paper gives theoretical expressions and describes an iterative method of numerical calculation for the current density of different cells. Results of computer calculations based on this model are presented.

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Riassunto In questo lavoro si presenta un modello per la determinazione e l'ottimizzazione dei parametri fondamentali atti a definire la qualità delle celle solari amorfe, specificando le proprietà ottiche, elettriche e di ricombinazione. Esso può essere applicato a qualunque sistema di celle solari amorfe. Sono fornite le espressioni teoriche ed è descritto un metodo iterativo per il calcolo numerico della densità di corrente di alcuni tipi di celle. Sono anche presentati i risultati ottenuti da calcoli eseguiti col computer e basati su questo modello.

     

Isomers of astrophysical interest in neutron-deficient nuclei at masses A = 81, 85 and 86

Decay properties of neutron-deficient exotic nuclei close to A=80 have been investigated at the IGISOL facility. The studied nuclei, ⁸¹Y, ⁸¹Sr, ^81mKr, ⁸⁵Nb, ⁸⁵Zr, ⁸⁶Mo and ⁸⁶Nb, were produced by a ³²S beam from the Jyv?skyl? isochronous cyclotron on ⁵⁴Fe and ^natNi targets. The internal conversion coefficient for a 190.5 keV isomeric transition in ^81mKr has been measured and the internal transition rate has been determined. The internal transition rate has been used to estimate a neutrino capture rate on ⁸¹Br, which yields a log ft of 5.13±0.09 for the reaction ⁸¹Br( ν, e ^-)^81mKr. A new isomer with a half-life of 3.3±0.9 s has been observed in ⁸⁵Nb. The existence of an earlier reported isomer with a half-life of 56 s in ⁸⁶Nb has not been confirmed.