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31.
Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(OtBu)3]2 ( 1 ) and [(THF)4Na2Fe(2,6‐diisopropylphenolate)4] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO4 array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003  相似文献   
32.
We study the infrared emission at 1.54 μm of an organolanthanide complex, Er(III)-tetraphenylporphyrin [Er(TPP)acac], both as a result of direct optical excitation and via energy transfer from host π-conjugate polymers of type poly(arylene–ethynylene) [PAE]. In the first case, the emission of the neat complex is characterized in inert transparent materials and a value of the quantum yield at 1.54 μm φIR=4×10−4 is measured. Then, fluorescence resonance transfer is investigated in blends of Er(TPP)acac with PAEs by monitoring the quenching of the polymer fluorescence along with the enhancement of both the visible emission of the ligand and the near-infrared band of Er3+. These different procedures allow a detailed analysis of the transfer efficiency within a specific implementation of the Förster model for polymeric donors. The experimental values of the critical radius R0, ranging from 1.3 to 2.5 nm for the different blends, are in good agreement with theory for a wide interval of the physical and spectroscopic parameters. This suggests that other mechanisms for excitation transfer do not play a significant role in these materials.  相似文献   
33.
A novel bifunctional acrylamido‐based reversible addition–fragmentation chain transfer (RAFT) chain‐transfer agent (CTA), N,N′‐ethylenebis[2‐(thiobenzoylthio)propionamide] (CTA2), has been synthesized and used for the controlled free‐radical polymerization of N,N‐dimethylacrylamide (DMA). A comparative study of CTA2 and the monofunctional CTA N,N‐dimethyl‐s‐thiobenzoylthiopropionamide (CTA1) has been conducted. Polymerizations mediated by CTA1 result in poly(N,N‐dimethylacrylamide) (PDMA) homopolymers with unimodal molecular weight distributions, whereas CTA2 yields unimodal, bimodal, and trimodal distributions according to the extent of conversion. The multimodal nature of the PDMAs has been attributed to termination events and/or chains initiated by primary radicals. The RAFT polymerization of DMA with CTA2 also results in a prolonged induction period that may be attributed to the higher local concentration of dithioester functionalities early in the polymerization. A series of ω‐ and α,ω‐dithioester‐capped PDMAs have been prepared in organic media and subsequently employed as macro‐CTAs for the synthesis of diblock and triblock copolymers in aqueous media with the zwitterionic monomer 3‐[2‐(N‐methylacrylamido)‐ethyldimethylammonio] propane sulfonate (MAEDAPS). Additionally, an ω‐dithioester‐capped MAEDAPS homopolymer has been used as a macro‐CTA for the block polymerization of DMA. To our knowledge, this is the first example of a near‐monodisperse, sulfobetaine‐containing block copolymer prepared entirely in aqueous media. The diblock and triblock copolymers form aggregates in pure water that can be dissociated by the addition of salt, as determined by 1H NMR spectroscopy and dynamic light scattering. In pure water, highly uniform, micellelike aggregates with hydrodynamic diameters of 71–93 nm are formed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1262–1281, 2003  相似文献   
34.
We show that if G is a definably compact, definably connected definable group defined in an arbitrary o‐minimal structure, then G is divisible. Furthermore, if G is defined in an o‐minimal expansion of a field, k ∈ ? and pk : GG is the definable map given by pk (x ) = xk for all xG , then we have |(pk )–1(x )| ≥ kr for all xG , where r > 0 is the maximal dimension of abelian definable subgroups of G . (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   
35.
The ring‐opening metathesis polymerizations (ROMP), using RuCl2 (PCy3)2CHPh, of a series of peptide‐functionalized norbornene derivatives have been investigated. Incorporation of a PEG‐monomer was found to prevent premature precipitation of polymer strands during the course of polymerization reactions and yield water compatible polymers in high conversions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3178–3190, 2007  相似文献   
36.
Several composites were prepared on the basis of an ethylene homopolymer and different copolymers of ethylene and 1‐hexene, synthesized with a metallocene catalyst, as matrices and a content of a 5 wt % of short glass fiber. The effect of the fiber incorporation on the structure and mechanical and viscoelastic behaviors was analyzed for the different samples. The glass fibers induced a slightly higher crystallinity, and the crystallite morphology significantly changed (long spacings and crystal orientation). The incorporation of fibers did not reinforce the different matrices under study at this low content; consequently, the mechanical parameters, such as Young's modulus, yielding stress, and microhardness, were lower in the composites as compared with those values found in the neat polyolefins. The location and apparent activation energies of distinct relaxation processes are also discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1244–1255, 2003  相似文献   
37.
An in situ ultrasonic spectroscopy technique was used to study the ring‐opening metathesis polymerization of dicyclopentadiene catalyzed by bis(tricyclohexylphosphine)benzylidene ruthenium dichloride. A reaction cell employing a flexible poly(ethylene terephthalate) window for pulse echo ultrasonic spectroscopy was used to monitor the polymerization. The changes in the density, wave speed, acoustic modulus, and attenuation were all simultaneously monitored. In comparison with Fourier transform infrared (FTIR) spectroscopy data, the changes in the density, velocity, and modulus only accurately measured the rate constant for the metathesis of the cyclopentyl unsaturation. The ultrasonic values were within 6% of the values determined by FTIR. The activation energy for metathesis of the cyclopentyl unsaturation was 84 kJ mol?1, following first‐order kinetics. Rate constants for the polymerization of the norbornyl unsaturation could not be determined by ultrasound. The gel point, vitrification, and qualitative information about the reaction rate could be determined from the change in the attenuation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1323–1333, 2003  相似文献   
38.
Motivated by recent experimental findings, we investigate the possible occurrence and characteristics of quasicrystalline order in two-dimensional mixtures of point dipoles with two sorts of dipole moments. Despite the fact that the dipolar interaction potential does not exhibit an intrinsic length scale and cannot be tuned a priori to support the formation of quasicrystalline order, we find that configurations with long-range quasicrystallinity yield minima in the potential energy surface of the many particle system. These configurations emanate from an ideal or perturbed ideal decoration of a binary tiling by steepest descent relaxation. Ground state energy calculations of alternative ordered states and parallel tempering Monte-Carlo simulations reveal that the quasicrystalline configurations do not correspond to a thermodynamically stable state. On the other hand, steepest descent relaxations and conventional Monte-Carlo simulations suggest that they are rather robust against fluctuations. Local quasicrystalline order in the disordered equilibrium states can be strong.Received: 15 September 2004, Published online: 26 November 2004PACS: 61.44.Br Quasicrystals - 75.50.Kj Amorphous and quasicrystalline magnetic materials - 82.70.Dd Colloids  相似文献   
39.
The mechanisms involved in the formation of n‐butanol during the synthesis of butyl acrylate containing latices were investigated. The experimental results showed that neither the hydrolysis of butyl acrylate nor of the ester bond in the butyl acrylate segments of the polymer played a major role in the formation of n‐butanol, which was mainly generated from the polymer backbone, by transfer reactions to polymer chain followed by cyclization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5838–5846, 2007  相似文献   
40.
This work deals with As determination in marine sediment using ultrasound for sample preparation. It is shown that As can be quantitatively extracted from marine sediment using 20% (v/v) HCl and sonication. The slurry is centrifuged and the analyte is determined in the supernatant by hydride generation atomic absorption spectrometry (HG AAS). A flow injection (FI) system is employed for hydride generation, with 0.5% (m/v) NaBH(4) used as reducdant and a 20% (v/v) HCl used as sample carrier. The limit of quantification is 1.6 microg g(-1) of As, which is based on 800 microl of sample solution and 0.200 g of sample mass in a volume of 50 mL. Certified and non certified marine sediment samples were analyzed; the results were in accordance with the certified or reference values. Speciation analysis by HPLC-ICP-MS showed that As(V) is the only detectable As species present in the supernatant of the centrifuged sample.  相似文献   
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