Synthesis and characterization of functional gradient copolymers of allyl methacrylate and butyl acrylate

Functional spontaneous gradient copolymers of allyl methacrylate (A) and butyl acrylate (B) were synthesized via atom transfer radical polymerization. The copolymerization reactions were carried out in toluene solutions at 100 °C with methyl 2‐bromopropionate as the initiator and copper bromide with N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalyst system. Different aspects of the statistical reaction copolymerizations, such as the kinetic behavior, crosslinking density, and gel fraction, were studied. The gel data were compared with Flory's gelation theory, and the sol fractions of the synthesized copolymers were characterized by size exclusion chromatography and nuclear magnetic resonance spectroscopy. The copolymer composition, demonstrating the gradient character of the copolymers, and the microstructure were analyzed. The experimental data agreed well with data calculated with the Mayo–Lewis terminal model and Bernoullian statistics, with monomer reactivity ratios of 2.58 ± 0.37 and 0.51 ± 0.05 for A and B, respectively, an isotacticity parameter for A of 0.24, and a coisotacticity parameter of 0.33. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5304–5315, 2006     

飞秒激光脉冲在三能级有机分子介质中传播时的频谱分析

通过采用预估校正的时域有限差分法求解麦克斯韦-布洛赫方程,我们研究了飞秒激光脉冲在三能级有机分子(4,4-二甲氨基二苯乙烯分子)介质中传播时脉冲的频谱演化情况.在单光子共振情况下,即入射脉冲频率等于1、2能级之间的共振频率,对大面积入射脉冲,由于强的二次激发的作用,电场频谱中出现了在ω32附近振荡的频率成分,ω32是2、3能级之间的共振频率,说明对大面积入射脉冲二能级模型已经失效,需要采用多能级模型来描述分子介质.在双光子共振情况下,即入射脉冲频率等于1、3能级之间的共振频率的一半,由于介质中放大的自发辐射和四波混频的作用,部分入射脉冲能量转化为高频和低频电场成分的能量,分子介质表现出了很强的光功率限幅特性.     

Unconventional antiferromagnetic correlations of the doped Haldane gapsystem Y 2 BaNi 1 - x Zn x O 5

We make a new proposal to describe the very low temperature susceptibility of the doped Haldane gap compound Y₂BaNi_1-xZn_xO₅. We propose a new mean field model relevant for this compound. The ground state of this mean field model is unconventional because antiferromagnetism coexists with random dimers. We present new susceptibility experiments at very low temperature. We obtain a Curie-Weiss susceptibility χ( T ) ∼ C /(Θ + T ) as expected for antiferromagnetic correlations but we do not obtain a direct signature of antiferromagnetic long range order. We explain how to obtain the “impurity” susceptibility ( T ) by subtracting the Haldane gap contribution to the total susceptibility. In the temperature range [1 K, 300 K] the experimental data are well fitted by T ( T ) = C _imp 1 + T _imp / T . In the temperature range [100 mK, 1 K] the experimental data are well fitted by T ( T ) = A ln( T / T _c ), where T _c increases with x. This fit suggests the existence of a finite Néel temperature which is however too small to be probed directly in our experiments. We also obtain a maximum in the temperature dependence of the ac-susceptibility ( T ) which suggests the existence of antiferromagnetic correlations at very low temperature. Received 17 July 2001     

Application of the stabilization method to interacting resonances

The stabilization method is applied to the case of interacting resonances in the photo-dissociation of van der Waals clusters composed by a rare gas atom bound to a dihalogen molecule. The study of an illustrative two-dimensional model consisting in a T-shaped NeI₂ molecule shows the adequacy of the method whenever the projection of the stabilization wave functions on the assumed prepared initial state is accounted for. The agreement of the fragmentation cross-sections with some previous results using the effective resolvent method and accurate close-coupling calculations is excellent. The method reveals its utility as a complementary tool since allows, through the analysis of the stabilization wave function in terms of zero-order levels, a precise characterization of the resonant states involved. Received 5 April 2002 / Received in final form 24 May 2002 Published online 19 July 2002     

Rigidity of the scattering length spectrum

In this paper we consider properties of obstacles satisfying some non-degeneracy conditions that can be recovered from the scattering length spectrum (SLS). Clearly the latter tells us whether the obstacle K is trapping or non-trapping. If the set of trapped points is relatively small, then the SLS also determines the volume of the obstacle, the number of its connected components, and whether its boundary is convex everywhere or it has non-trivial concavities. Under the additional assumption that the curvature of the obstacle does not vanish of infinite order, it is proved that from the SLS one can recover certain information about the number of reflection points of any simply reflecting ray in the exterior of the obstacle. Finally, for some special classes of obstacles (e.g. star-shaped ones), it is shown that the SLS completely determines the obstacle. Received: 2 March 1999 / Revised version: 16 January 2001 / Published online: 5 September 2002     

Solving the Gleason problem on linearly convex domains

Let be a bounded, connected linearly convex set in with boundary. We show that the maximal ideal (both in ) and ) consisting of all functions vanishing at is generated by the coordinate functions . Received: 2 July 2001; in final form: 26 September 2001 / Published online: 28 February 2002     

Non-trivial simple poles at negative integers and mass concentration at singularity

Let (X,0) be the germ of a normal space of dimension n+1 and let f be the germ at 0 of a holomorphic function on X. Assume both X and f have an isolated singularity at 0. Denote by J the image of the restriction map , where F is the Milnor fibre of f at 0. We prove that the canonical Hermitian form on , given by poles of order at in the meromorphic extension of , passes to the quotient by J and is non-degenerate on . We show that any non-zero element in J produces a “mass concentration” at the singularity which is related to a simple pole concentrated at for (in a non-na?ve sense). We conclude with an application to the asymptotic expansion of oscillatory integrals , for , when . Received: 28 May 2001 / Published online: 26 April 2002     

A decomposition heuristics for the container ship stowage problem

In this paper we face the problem of stowing a containership, referred to as the Master Bay Plan Problem (MBPP); this problem is difficult to solve due to its combinatorial nature and the constraints related to both the ship and the containers. We present a decomposition approach that allows us to assign a priori the bays of a containership to the set of containers to be loaded according to their final destination, such that different portions of the ship are independently considered for the stowage. Then, we find the optimal solution of each subset of bays by using a 0/1 Linear Programming model. Finally, we check the global ship stability of the overall stowage plan and look for its feasibility by using an exchange algorithm which is based on local search techniques. The validation of the proposed approach is performed with some real life test cases. This work has been developed within the research area: “The harbour as a logistic node” of the Italian Centre of Excellence on Integrated Logistics (CIELI) of the University of Genoa, Italy     

A comparative XPS and UPS study of VOx layers on mineral TiO2(001)‐anatase supports

Four vanadium oxide layers on mineral TiO₂(001)‐anatase supports with different thickness (3–33 Å) were prepared with reactive d.c. magnetron sputtering and were extensively studied with photoelectron spectroscopy. Al Kα radiation and 150 eV synchrotron radiation were used as excitation sources. The evolution of the 2p, 3s and 3p core level line shapes of V and Ti as a function of the vanadium oxide thickness was studied, as well as the O1s and O2s core lines and the valence band. All the V2p spectra of the deposited vanadium oxide layers consist of at least 60% V⁵⁺, the rest being V⁴⁺. The V3p region is complicated by multiplet splitting, which prevents the determination of the vanadium oxidation state. The V3p multiplet splitting is different for the two excitation energies. No reduction of the titania support surface due to the vanadium oxide deposition was observed. Copyright © 2006 John Wiley & Sons, Ltd.     

Fluorinated,crosslinkable terpolymers based on vinylidene fluoride and bearing sulfonic acid side groups for fuel‐cell membranes

The radical terpolymerization of 8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene with vinylidene fluoride (VDF) and perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride is presented. Changing the feed compositions of these three fluorinated comonomers enabled us to obtain different random‐type poly[vinylidene fluoride‐ter‐perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride‐ter‐8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene] terpolymers containing various sulfonyl fluoride and brominated side groups. Yields higher than 70% were reached in all cases. The hydrolysis of the sulfonyl fluoride group into the ? SO₃Li function in the presence of lithium carbonate was quantitatively achieved without the content of VDF being affected, and so dehydrofluorination of the VDF base unit was avoided. These original terpolymers were then crosslinked via dangling bromine atoms in the presence of a peroxide/triallyl isocyanurate system, which produced films insoluble in organic solvents such as acetone and dimethylformamide (which totally dissolved uncured terpolymers). The acidification of ? SO₃Li into the ? SO₃H function enabled protonic membranes to be obtained. The thermal stabilities of the crosslinked materials were higher than those of the uncured terpolymers, and their electrochemical performances were investigated. According to the contents of the sulfonic acid side functions, the ion‐exchange capacities ranged from 0.6 to 1.5 mequiv of H⁺/g, whereas the water uptake and conductivities ranged from 5–26% (±11%) and from 0.5 to 6.0 mS/cm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4566–4578, 2006