Controlled/living polymerization of 2‐(diethylamino)ethyl methacrylate and its block copolymer with tert‐butyl methacrylate by atom transfer radical polymerization

Polymerization of 2‐(diethylamino)ethyl methacrylate (DEAEMA) via homogeneous atom transfer radical polymerization under various reaction conditions is described. The effects of the initiators and solvents were examined. With 1,1,4,7,10,10‐hexamethyl triethylenetetramine/copper(I) chloride/p‐toluenesulfonyl chloride as the ligand/catalyst/initiator system in methanol, poly(DEAEMA) with a polydispersity index as low as 1.07 was synthesized. Kinetic studies demonstrated the polymerization was very well controlled and exhibited the living characteristic of the process. Well‐defined block copolymers of DEAEMA and tert‐butyl methacrylate (tBMA) were successfully synthesized. The copolymers could be synthesized with equally good results by starting with either p(DEAEMA) or p(tBMA) as the macroinitiators. However, only the macroinitiators terminated with chlorine should be used. The corresponding macroinitiators with bromine as a transferable group did not yield well‐defined copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2688–2695, 2003     

Annealing behavior of gel‐spun polyethylene fibers at temperatures lower than needed for significant shrinkage

The annealing at 373 K of ultrastrong, gel‐spun polyethylene (PE) has been studied. At this temperature, the fibers show no significant shrinkage. Still, a significant decrease in the mechanical properties is observed. The fibers have been analyzed with differential scanning calorimetry (DSC), temperature‐modulated differential scanning calorimetry (TMDSC), atomic force microscopy (AFM), and small‐angle X‐ray scattering (SAXS). During the annealing, the glass transition of the intermediate phase is exceeded, as shown by DSC. When split for structure analysis by AFM, the annealed fibers undergo plastic deformation around the base fibrils instead of brittle fracture. The quasi‐isothermal TMDSC experiments are compared to the minor structural changes seen with SAXS and AFM. The loss of performance of the PE fibers at 373 K is suggested to be caused by the oriented intermediate phase, and not by major changes in the structure or morphology. The overall metastable, semicrystalline structure is shown by TMDSC to posses local regions that can melt reversibly. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 403–417, 2003     

Dynamic mechanical thermal analysis transitions of partially and fully substituted cellulose fatty esters

The main transitions of cellulose fatty esters with different degrees of substitution (DSs) were investigated with dynamic mechanical thermal analysis. Two distinct main relaxations were observed in partially substituted cellulose esters (PSCEs). They were attributed to the glass‐transition temperature and to the chain local motion of the aliphatic substituents. The temperatures of both transitions decreased when DS or the number of carbon atoms (n) of the acyl substituent increased. Conversely, all the transitions of fully substituted cellulose esters occurred within a narrow temperature range, and they did not vary significantly with n. This phenomenon was explained by the formation of a crystalline phase of the fatty substituents. The presence of few residual OH groups in PSCEs was responsible for a large increase in the storage bending modulus, and it eliminated the effect of n on damping. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 281–288, 2003     

SASEGASA: A New Generic Parallel Evolutionary Algorithm for Achieving Highest Quality Results

This paper presents a new generic Evolutionary Algorithm (EA) for retarding the unwanted effects of premature convergence. This is accomplished by a combination of interacting generic methods. These generalizations of a Genetic Algorithm (GA) are inspired by population genetics and take advantage of the interactions between genetic drift and migration. In this regard a new selection scheme is introduced, which is designed to directedly control genetic drift within the population by advantageous self-adaptive selection pressure steering. Additionally this new selection model enables a quite intuitive heuristics to detect premature convergence. Based upon this newly postulated basic principle the new selection mechanism is combined with the already proposed Segregative Genetic Algorithm (SEGA), an advanced Genetic Algorithm (GA) that introduces parallelism mainly to improve global solution quality. As a whole, a new generic evolutionary algorithm (SASEGASA) is introduced. The performance of the algorithm is evaluated on a set of characteristic benchmark problems. Computational results show that the new method is capable of producing highest quality solutions without any problem-specific additions.     

2‐connected 7‐coverings of 3‐connected graphs on surfaces

An m‐covering of a graph G is a spanning subgraph of G with maximum degree at most m. In this paper, we shall show that every 3‐connected graph on a surface with Euler genus k ≥ 2 with sufficiently large representativity has a 2‐connected 7‐covering with at most 6k ? 12 vertices of degree 7. We also construct, for every surface F² with Euler genus k ≥ 2, a 3‐connected graph G on F² with arbitrarily large representativity each of whose 2‐connected 7‐coverings contains at least 6k ? 12 vertices of degree 7. © 2003 Wiley Periodicals, Inc. J Graph Theory 43: 26–36, 2003     

Mössbauer Study of Ceramic Finds from the Galería de las Ofrendas, Chavín de Huántar

Ceramic finds from the Galería de las Ofrendas at Chavín de Huántar and surface finds from the settlement of Chavín were characterised by combining the results of archaeological typology with archaeometric studies using neutron activation analysis, Mössbauer spectroscopy, X-ray diffraction and thin-section microscopy. Sherds from the pyramid Tello are included in the study as representative of local material. The analyses show that the vessels were made from different raw materials and that different firing procedures were used in their production. Sherds of certain styles largely exhibit similar types of Mössbauer patterns and in many instances also have similar element compositions. This supports the archaeological notion that the vessels were brought to Chavín from the provinces, perhaps on the occasion of a festivity.     

Kinetics of oxygen exchange in strontium titanate

The kinetics of oxygen exchange are of primary importance for the application of titanates as fast resistive oxygen sensors. The sensor’s conductivity is correlated with the oxygen partial pressure pO₂ of the surrounding atmosphere: Due to oxygen surface transfer and subsequent diffusion of oxygen vacancies V _O ^·· , a pO₂ change gives rise to a conductivity change of the sample. While bulk diffusion usually occurs very fast, the surface transfer reaction becomes the rate determining step for thin samples and for low temperatures. We have shown that in the case of acceptor doped SrTiO₃ the kinetics of the surface transfer reaction can be strongly influenced through stoichiometric changes brought about by thin coatings of alkaline earth metal oxides (e.g. SrO). In contrast to the commonly used jump method (conductivity response to a sudden pO₂ change in the time domain), a model is presented which is based on the frequency-domain analysis of amplitude and phase shift of the response signal obtained from a pO₂ modulation in a fast kinetic measurement set-up. This method allows not only for measuring response times in the sub-millisecond range but also for distinguishing between behaviour either controlled by volume diffusion or by surface transfer reaction. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Simple and efficient cleavage reaction of the boc group in heterocyclic compounds

Dedicated to the memory of Pr. Ladjama Daif A series of chiral cyclosulfamides have been synthesized by alkaline cyclisation starting from N‐benzoylamino acids (Ala, Val, Leu, Phe) derivatives and chlorosulfonyl isocyanate. A simplified and regioselective deprotection of the cyclic compounds (cyclosulfamides) containing the tert‐butyloxycarbonyl group (Boc) has been achieved in good yield by fusion under reduced pressure.     

An expedient synthesis of an isofervenulin analogue

An efficient approach has been developed for the synthesis of an isofervenulin analogue 1 employing a one‐pot condensation‐substitution reaction of a chlorocarboethoxytriazine (electrophile) with a urea (nucleophile). The resulting cyclization reaction resulted in the synthesis of a pyrimido‐heterocycle in good yield in either acidic or basic media. The former was assisted by utilizing trimethylsilyl chloride.     

Kristallstruktur des Zinkamids Zn[N(SiMe3)2]2

Crystal Structure of the Zinc Amide Zn[N(SiMe₃)₂]₂ X‐ray quality crystals of Zn[N(SiMe₃)₂]₂ (monoclinic, P2₁/c) are obtained by sublimation of the zinc amide Zn[N(SiMe₃)₂]₂ at —30 °C in vacuo (300 torr). According to the result of the X‐ray structural analysis, Zn[N(SiMe₃)₂]₂ contains an almost linear N‐Zn‐N unit with two short N‐Zn bonds.