Kinetic features of ethylene polymerization over supported catalysts [2,6‐bis(imino)pyridyl iron dichloride/magnesium dichloride] with AlR3 as an activator

The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl₂/MgCl₂‐Al(i‐Bu)₃ (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007     

长柱形CsI(Tl)闪烁晶体探测器的能量重建

提出了用于TEXONO实验中双端读出的长柱形CsI(Tl)闪烁晶体探测器的两种粒子能量重建方法———“算术平均值能量重建法”和“几何平均值能量重建法”,讨论了两种算法的理论依据和计算方法,并对两种算法进行了比较     

Novel aromatic polyamides bearing pendent diphenylamino or carbazolyl groups

Two new diamines, 2,4‐diaminotriphenylamine ( 3 ) and N‐(2,4‐diaminophenyl)carbazole ( 4 ), were synthesized via the cesium fluoride‐mediated aromatic substitution reactions of 1‐fluoro‐2,4‐dinitrobenzene with diphenylamine and carbazole, followed by palladium‐catalyzed hydrazine reduction. Amorphous and soluble aramids having pendent diphenylamino and carbazolyl groups were prepared by the phosphorylation polycondensation of aromatic dicarboxylic acids with diamines 3 and 4 , respectively. The aramids derived from diamine 3 had sufficiently high molecular weights to permit the casting of flexible and tough films. They exhibited excellent mechanical properties and moderately high softening temperatures in the 221–298 °C range. However, the reactions of diamine 4 with aromatic diacids gave relatively lower molecular weights products that could not afford flexible films. For a comparative purpose, the parent aramids derived from m‐phenylenediamine and aromatic diacids were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3302–3313, 2004     

Synthesis,characterization, and micellization of an epoxy‐based amphiphilic diblock copolymer of ϵ‐caprolactone and glycidyl methacrylate by enzymatic ring‐opening polymerization and atom transfer radical polymerization

Amphiphilic diblock copolymer polycaprolactone‐block‐poly(glycidyl methacrylate) (PCL‐b‐PGMA) was synthesized via enzymatic ring‐opening polymerization (eROP) and atom transfer radical polymerization (ATRP). Methanol first initiated eROP of ?‐caprolactone (?‐CL) in the presence of biocatalyst Novozyme‐435 under anhydrous conditions. The resulting monohydroxyl‐terminated polycaprolactone (PCL–OH) was subsequently converted to a bromine‐ended macroinitiator (PCL–Br) for ATRP by esterification with α‐bromopropionyl bromide. PCL‐b‐PGMA diblock copolymers were synthesized in a subsequent ATRP of glycidyl methacrylate (GMA). A kinetic analysis of ATRP indicated a living/controlled radical process. The macromolecular structures were characterized for PCL–OH, PCL–Br, and the block copolymers by means of nuclear magnetic resonance, gel permeation chromatography, and infrared spectroscopy. Differential scanning calorimetry and wide‐angle X‐ray diffraction analyses indicated that the copolymer composition (?‐CL/GMA) had a great influence on the thermal properties. The well‐defined, amphiphilic diblock copolymer PCL‐b‐PGMA self‐assembled into nanoscale micelles in aqueous solutions, as investigated by dynamic light scattering and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5037–5049, 2007     

Magnetic calorimeter for registration of small energy release

A scheme of magnetic calorimeter for registration of rare events characterized by small energy release (cosmic rays, WIMPs, solitary X-ray quanta) is proposed. The calorimeter is brought to operation by adiabatic demagnetization, and its magnetic response is measured by a quantum interferometer (SQUID, A. Barone and G. Paterno, Physics and applications of Josephson Effect). Special consideration is given to the specific features of calorimeter operation in the ferromagnetic transition region. The trigger registration of ultrasmall energy release by a ferromagnetic system in the metastable state is described.     

Energy crisis or a new soliton in the noncommutative CP(1) model?

The non-commutative (NC) CP(1) model is studied from field theory perspective. Our formalism and definition of the NC CP(1) model differs crucially from the existing one [Phys. Lett. B 498 (2001) 277, hep-th/0203125, hep-th/0303090].

Due to the U(1) gauge invariance, the Seiberg–Witten map is used to convert the NC action to an action in terms of ordinary spacetime degrees of freedom and the subsequent theory is studied. The NC effects appear as (NC parameter) θ-dependent interaction terms. The expressions for static energy, obtained from both the symmetric and canonical forms of the energy momentum tensor, are identical, when only spatial noncommutativity is present. Bogomolny analysis reveals a lower bound in the energy in an unambiguous way, suggesting the presence of a new soliton. However, the BPS equations saturating the bound are not compatible to the full variational equation of motion. This indicates that the definitions of the energy momentum tensor for this particular NC theory (the NC theory is otherwise consistent and well defined), are inadequate, thus leading to the “energy crisis”.

A collective coordinate analysis corroborates the above observations. It also shows that the above mentioned mismatch between the BPS equations and the variational equation of motion is small.     

Construction of self-assembled monolayer terminated with N-heterocyclic carbene-rhodium(I) complex moiety

Functionalization of self-assembled monolayer (SAM) of alkanethiolate with metal containing unit is one of the versatile methods to obtain functional surfaces such as heterogeneous catalysts. However, organic molecules that strongly bind to transition metals at SAM terminal are limited. Recently N-heterocyclic carbenes (NHCs) such as cyclic diaminocarbenes have emerged as strongly σ-donating ligands forming a robust bond with broad spectrum of transition metals. In the present study, for the purpose of establishment of a new robust basement for heterogeneous metal catalysts, a SAM of the alkanethiolate terminated with NHC-rhodium(I) complex moiety was prepared by utilizing a newly designed disulfide molecule bearing NHC-metal complex terminals. X-ray photoelectron spectroscopy (XPS) analysis and angle resolved XPS measurement revealed successful formation of the Rh-complex-terminated SAM on a gold substrate. Infrared reflection absorption spectroscopy (IRRAS) analysis suggested that the linker methylene chains connecting the rhodium complex moiety and the gold surface are in a loosely packed structure. This unique chemical species, NHC, would be a promising candidate as a basement for the construction of functional surface.     

Difference Families in Z2d+1⊕Z2d+1 and Infinite Translation Designs in Z⊕Z

We analyse 3-subset difference families of Z_2d+1⊕Z_2d+1 arising as reductions (mod 2d+1) of particular families of 3-subsets of Z⊕Z. The latter structures, namely perfect d-families, can be viewed as 2-dimensional analogues of difference triangle sets having the least scope. Indeed, every perfect d-family is a set of base blocks which, under the natural action of the translation group Z⊕Z, cover all edges {(x,y),(x′,y′)} such that |x−x′|, |y−y′|≤d. In particular, such a family realises a translation invariant (G,K₃)-design, where V(G)=Z⊕Z and the edges satisfy the above constraint. For that reason, we regard perfect families as part of the hereby defined translation designs, which comprise and slightly generalise many structures already existing in the literature. The geometric context allows some suggestive additional definitions. The main result of the paper is the construction of two infinite classes of d-families. Furthermore, we provide two sporadic examples and show that a d-family may exist only if d≡0,3,8,11 (mod 12).     

Mechanism of the reaction of neutral and anionic N-nucleophiles with α-halocarbonyl compounds

N-Acylalkylation of neutral and anionic N-nucleophiles with α-halocarbonyl compounds was investigated by quantum chemical methods in terms of the density functional theory and by experimental methods for 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one, its N-anion, and simpler model structures. High reactivity of these reagents is determined primarily by stabilization of transition states (TS) by bridge bonds involving halogen or nitrogen atoms rather than by conjugation, as has been commonly accepted. Bridged TS are formed by both the substitution mechanism S _N 2 and the addition-elimination mechanism. α-Haloalkyl-substituted zwitterions, which are potential intermediates of stepwise N-acylalkylation of neutral N-nucleophiles, do not exist in the isolated state, but they are rather efficiently stabilized upon solvation. These zwitterions, as well as analogous O-anions generated from anionic N-nucleophiles, can serve as intermediates of N-acylalkylation, as was demonstrated by localization of the corresponding TS. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1150–1164, June, 2007.     

Remarks on a theorem of Taskinen on spaces of continuous functions

We clarify and prove in a simpler way a result of Taskinen about symmetric operators on C(Kⁿ), K an uncountable metrizable compact space. To do this we prove that, for any compact space K and any n ∈ ?, the symmetric injective n–tensor product of C(K), , is complemented in C(B_C(K)*), a result of independent interest. The techniques we develop allow us to extend the result in several directions. We also show that the hypothesis of metrizability and uncountability cannot be removed.